A model framework for actuation and sensing of ionic polymer-metal composites: prospective on frequency and shear response through simulation tools

NASA Astrophysics Data System (ADS)

Stalbaum, Tyler; Shen, Qi; Kim, Kwang J.

2017-04-01

Ionic polymer-metal composite (IPMC) is a promising material for soft-robotic actuator and sensor applications. This material system offers large deformation response for low input voltage and has an aptitude for operation in hydrated environments. Researchers have been developing IPMC actuators and sensors for applications with examples of self-sensing actuators, artificial fish fins and biomimicry of other aquatic lifeforms, and in medical operations such as in guided catheter devices. IPMCs have been developed in a range of geometric configurations, with tube or cylindrical and flat-plate rectangular as the most common shapes. Several mathematical and physics-based models have been developed for describing the transduction effects of IPMCs. In this work, the underlying theories of electromechanical and mechanoelectrical transduction in IPMCs are discussed, and simulated results of frequency response and shear response are presented. A model backbone is utilized which is primarily based on ion-transport and charge dynamics within the polymer membrane. The electromechanical model, that is with an IPMC as an actuator, is caused when an electric field is applied across the membrane causing ionic migration and swelling in the polymer membrane, which is based on the Poisson-Nernst-Planck equations and solid mechanics models. The mechanoelectric model is similar in underlying physics; however, the primary mechanisms of transduction are of different significance, where anion concentrations are as important as cations. COMSOL Multiphysics is utilized for simulations. Example applications of the modeling framework are presented. The simulated results provide additional support for the underlying physics theories discussed.

Biomimetic Beetle-Inspired Flapping Air Vehicle Actuated by Ionic Polymer-Metal Composite Actuator.

PubMed

Zhao, Yang; Xu, Di; Sheng, Jiazheng; Meng, Qinglong; Wu, Dezhi; Wang, Lingyun; Xiao, Jingjing; Lv, Wenlong; Chen, Qinnan; Sun, Daoheng

2018-01-01

During the last decades, the ionic polymer-metal composite (IPMC) received much attention because of its potential capabilities, such as large displacement and flexible bending actuation. In this paper, a biomimetic flapping air vehicle was proposed by combining the superiority of ionic polymer metal composite with the bionic beetle flapping principle. The blocking force was compared between casted IPMC and IPMC. The flapping state of the wing was investigated and the maximum displacement and flapping angle were measured. The flapping displacement under different voltage and frequency was tested. The flapping displacement of the wing and the support reaction force were measured under different frequency by experiments. The experimental results indicate that the high voltage and low frequency would get large flapping displacement.

Command Surface of Self-Organizing Structures by Radical Polymers with Cooperative Redox Reactivity.

PubMed

Sato, Kan; Mizuma, Takahiro; Nishide, Hiroyuki; Oyaizu, Kenichi

2017-10-04

Robust radical-substituted polymers with ideal redox capability were used as "command surfaces" for liquid crystal orientation. The alignment of the smectic liquid crystal electrolytes with low-dimensional ion conduction pathways was reversible and readily switched in response to the redox states of the polymers. In one example, a charge storage device with a cooperative redox effect was fabricated. The bulk ionic conductivity of the cell was significantly decreased only after the electrode was fully charged, due to the anisotropic ionic conductivity of the electrolytes (ratio >10 3 ). The switching enabled both a rapid cell response and long charge retention. Such a cooperative command surface of self-assembled structures will give rise to new highly energy efficient supramolecular-based devices including batteries, charge carriers, and actuators.

An experimental and numerical approach to understand the effect of the IPMC composition on its sensing and energy harvesting behavior

NASA Astrophysics Data System (ADS)

Akle, Barbar; Khairallah, Reef; Challita, Elio

2014-03-01

Ionic Polymer Metal Composite (IPMC) is an Electo-Active Polymer (EAP) that is well-known for its actuation and sensing behavior. It has been shown that in charge sensing mode an IPMC generates one order of magnitude larger current as compared to piezoelectric materials. However the voltage generated is on the order of couple millivolts, making it less attractive as a sensor and energy harvester. Previous numerical work by the author, demonstrated that increasing the ionic concentration of the ionomer will increase the current and voltage generated by an IPMC. Conversely, the previous study showed that the electrode composition and architecture had minimal effects. This paper will present an experimental investigation of the effect of changing the composition of the ionomer, the membrane thickness, and electrode architecture on the sensing and energy harvesting behavior. The response of all IPMC transducers is analyzed and compared to numerical simulations.

Biomimetic Beetle-Inspired Flapping Air Vehicle Actuated by Ionic Polymer-Metal Composite Actuator

PubMed Central

Zhao, Yang; Xu, Di; Sheng, Jiazheng; Meng, Qinglong; Wu, Dezhi; Wang, Lingyun; Xiao, Jingjing; Lv, Wenlong; Sun, Daoheng

2018-01-01

During the last decades, the ionic polymer-metal composite (IPMC) received much attention because of its potential capabilities, such as large displacement and flexible bending actuation. In this paper, a biomimetic flapping air vehicle was proposed by combining the superiority of ionic polymer metal composite with the bionic beetle flapping principle. The blocking force was compared between casted IPMC and IPMC. The flapping state of the wing was investigated and the maximum displacement and flapping angle were measured. The flapping displacement under different voltage and frequency was tested. The flapping displacement of the wing and the support reaction force were measured under different frequency by experiments. The experimental results indicate that the high voltage and low frequency would get large flapping displacement. PMID:29682006

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2016-07-01

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.

Dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pal, P.; Ghosh, A., E-mail: sspag@iacs.res.in

2016-07-28

In this paper, we have studied the dynamics and relaxation of charge carriers in poly(methylmethacrylate)-lithium salt based polymer electrolytes plasticized with ethylene carbonate. Structural and thermal properties have been examined using X-ray diffraction and differential scanning calorimetry, respectively. We have analyzed the complex conductivity spectra by using power law model coupled with the contribution of electrode polarization at low frequencies and high temperatures. The temperature dependence of the ionic conductivity and crossover frequency exhibits Vogel-Tammann-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The scaling of the ac conductivity indicates that relaxation dynamicsmore » of charge carriers follows a common mechanism for all temperatures and ethylene carbonate concentrations. The analysis of the ac conductivity also shows the existence of a nearly constant loss in these polymer electrolytes at low temperatures and high frequencies. The fraction of free anions and ion pairs in polymer electrolyte have been obtained from the analysis of Fourier transform infrared spectra. It is observed that these quantities influence the behavior of the composition dependence of the ionic conductivity.« less

Manufacturing and actuation characterization of ionic polymer metal composites with silver as electrodes

NASA Astrophysics Data System (ADS)

Pandita, Surya D.; Lim, Hyoung Tae; Yoo, Youngtai; Park, Hoon Cheol

2006-03-01

Manufacturing and characterization of ionic polymer metal composites (IPMCs) with silver as electrodes have been investigated. Tollen's reagent that contains ion Ag(NH 3) II + was used as a raw material for silver deposition on the surfaces of the polymer membrane Nafion"R". Two types of inner solvents, namely common water based electrolyte solution (LiOH 1N) and ionic liquid were used and investigated. Compared to IPMCs with platinum electrodes, silver-plated IPMCs with water electrolyte showed higher conductivity. The actuation response of silver-plated IPMCs with the water based electrolyte was faster than that of platinum IPMCs. However, the silver electrode was too brittle and severely damaged during the solvent exchange process from water to ionic liquid, resulted in high resistance and hence very low actuation behavior.

Nano-sponge ionic liquid-polymer composite electrolytes for solid-state lithium power sources

NASA Astrophysics Data System (ADS)

Liao, Kang-Shyang; Sutto, Thomas E.; Andreoli, Enrico; Ajayan, Pulickel; McGrady, Karen A.; Curran, Seamus A.

Solid polymer gel electrolytes composed of 75 wt.% of the ionic liquid, 1- n-butyl-2,3-dimethylimidazolium bis-trifluoromethanesulfonylimide with 1.0 M lithium bis-trifluoromethanesulfonylimide and 25 wt.% poly(vinylidenedifluoro-hexafluoropropene) are characterized as the electrolyte/separator in solid-state lithium batteries. The ionic conductivity of these gels ranges from 1.5 to 2.0 mS cm -1, which is several orders of magnitude more conductive than any of the more commonly used solid polymers, and comparable to the best solid gel electrolytes currently used in industry. TGA indicates that these polymer gel electrolytes are thermally stable to over 280 °C, and do not begin to thermally decompose until over 300 °C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these thin film batteries, 150 charge-discharge cycles are run for Li xCoO 2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects are observed over the charging cycles, indicating the high ionic conductivity of the ionic liquid solid polymer gel electrolyte. The overall cell efficiency is approximately 98%, and no significant loss in battery efficiency is observed over the 150 cycles.

Synthesis and characterization of ionomers as polymer electrolytes for energy conversion devices

NASA Astrophysics Data System (ADS)

Oh, Hyukkeun

Single-ion conducting electrolytes present a unique alternative to traditional binary salt conductors used in lithium-ion batteries. Secondary lithium batteries are considered as one of the leading candidates to replace the combustible engines in automotive technology, however several roadblocks are present which prevent their widespread commercialization. Power density, energy density and safety properties must be improved in order to enable the current secondary lithium battery technology to compete with existing energy technologies. It has been shown theoretically that single-ion electrolytes can eliminate the salt concentration gradient and polarization loss in the cell that develops in a binary salt system, resulting in substantial improvements in materials utilization for high power and energy densities. While attempts to utilize single-ion conducting electrolytes in lithium-ion battery systems have been made, the low ionic conductivities prevented the successful operation of the battery cells in ambient conditions. This work focuses on designing single-ion conducting electrolytes with high ionic conductivities and electrochemical and mechanical stability which enables the stable charge-discharge performance of battery cells. Perfluorosulfonate ionomers are known to possess exceptionally high ionic conductivities due to the electron-withdrawing effect caused by the C-F bonds which stabilizes the negative charge of the anion, leading to a large number of free mobile cations. The effect of perfluorinated sulfonic acid side chains on transport properties of proton exchange membrane polymers was examinated via a comparison of three ionomers, having different side chain structures and a similar polymer backbone. The three different side chain structures were aryl-, pefluoro alkyl-, and alkyl-sulfonic acid groups, respectively. All ionomers were synthesized and characterized by 1H and 19F NMR. A novel ionomer synthesized with a pendant perfluorinated sulfonic acid group and a poly(ether ether ketone) backbone showed the highest proton conductivity and proton diffusion coefficient among the three ionomers, demonstrating the effect of the perfluorinated side chains. The proton conductivity of the novel ionomer was comparable to that of Nafion over a wide humidity range and temperature. A lithium perfluorosulfonate ionomer based on aromatic poly(arylene ether)s with pendant lithium perfluoroethyl sulfonates was prepared by ion exchange of the perlfuorosulfonic acid ionomer, and subsequently incoroporated into a lithium-ion battery cell as a single-ion conducting electrolyte. The microporous polymer film saturated with organic carbonates exhibited a nearly unity Li + transfer number, high ionic conductivity (e.g. > 10-3 S m-1 at room temperature) over a wide range of temperatures, high electrochemical stability, and excellent mechanical properties. Excellent cyclability with almost identical charge and discharge capacities have been demonstrated at ambient temperature in the batteries assembled from the prepared single-ion conductors. The mechanical stability of the polymer film was attributed to the rigid polymer backbone which was largely unaffected by the presence of plasticizing organic solvents, while the porous channels with high concentration of the perfluorinated side chains resulted in high ionic conductivity. The expected high charge-rate performance was not achieved, however, due to the high interfacial impedance present between the polymer electrolyte and the electrodes. Several procedural modifications were employed in order to decrease the interfacial impedance of the battery cell. The poly(arylene ether) based ionomer was saturated with an ionic liquid mixture, in order to explore the possibility of its application as a safe, inflammable electrolyte. A low-viscosity ionic liquid with high ionic conductivity, 1-butyl-3-methylimidazolium thiocyanate which has never been successfully utilized as an electrolyte for lithium-ion batteries was incorporated into a battery cell as a solvent mixture with propylene carbonate and lithium bis(trifluoromethane)sulfonimide impregnated in a free-standing hybrid electrolyte film. Outstanding ionic conductivity was achieved and the lithium half cell comprising a LTO cathode and a lithium metal anode separated by the solid polymer electrolyte showed good cyclability at room temperature and even at 0°C. The presence of a sufficient amount of propylene carbonate, which resulted in flammability of the polymer electrolyte, was discovered to be critical in the electrochemical stability of the polymer electrolyte.

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community to develop innovative ways to improve energy storage and find more efficient methods of transporting the energy. Polymers containing charged species that show high ionic conductivity and good mechanical integrity are the essential components of these energy storage and transport systems. In this talk, first, I will present a fundamental understanding of the thermodynamics and transport in ion-containing block copolymers with a focus on the structure-property relationships. Tailoring the intermolecular interactions between the polymer matrix and the embedded charges appeared to be vital for controlling the transport properties. Particularly, the achievement of well-defined self-assembled morphologies with three-dimensional symmetries has proven to facilitate fast ion transport by constructing less tortuous ion-conducting pathways. Examples of attained morphologies include disorder, lamellae, gyroid, Fddd, hexagonal cylinder, body-centered cubic, face-centered cubic, and A15 phases. Second, various strategies for accessing high cation transference number as well as improved ionic conductivity from ionic-containing polymers are enclosed; (1) the inclusion of terminal ionic units as a new means to control the nanoscale morphologies and the transport efficiency of block copolymer electrolytes and (2) the addition of zwitterions that offered a polar medium close to water, and accordingly increased the charge density and ionic conductivity. The obtained knowledge on polymer electrolytes could be used in a wide range of emerging nanotechnologies such as fuel cells, lithium batteries, and electro-active actuators.

Radiation-grafted fluoropolymers soaked with imidazolium-based ionic liquids for high-performance ionic polymer-metal composite actuators.

PubMed

Lee, Jang Yeol; Wang, Hyuck Sik; Yoon, Bye Ri; Han, Man Jae; Jho, Jae Young

2010-11-01

On purpose to develop a polymer actuator with high stability in air-operation as well as large bending displacement, a series of ionic polymer-metal composites (IPMC) was constructed with poly(styrene sulfonate)-grafted fluoropolymers as ionomeric matrix and immidazolium-based ionic liquids (IL) as inner solvent. The prepared IPMC actuators exhibited greatly enhanced bending displacement compared to Nafion-based actuators. The actuators were stable in air-operation, maintaining initial displacement for up to 10(4) cycles or 24 h. Investigating the material parameters and morphology of the IPMCs, high ion exchange capacity of the ionomers resulted in high ion conductivity and robust electrode of IPMC, which synergistically contributed to the high bending performance. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

PubMed

Yan, Yunsong; Santaniello, Tommaso; Bettini, Luca Giacomo; Minnai, Chloé; Bellacicca, Andrea; Porotti, Riccardo; Denti, Ilaria; Faraone, Gabriele; Merlini, Marco; Lenardi, Cristina; Milani, Paolo

2017-06-01

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm -2 ), high electrochemical capacitance (≈mF g -1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

NASA Astrophysics Data System (ADS)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN decreases its utility as a molecular solvent for polymers such as PEO.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

For Stimul-Responsive Polymers with Enhanced Efficiency in Reservoir Recovery Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charles McCormick; Roger Hester

Acrylamide-based hydrophobically modified (HM) polybetaines containing N-butylphenylacrylamide (BPAM) and varying amounts of either sulfobetaine (3-(2-acrylamido-2-methylpropanedimethylammonio)-1-propanesulfonate, AMPDAPS) or carboxybetaine (4-(2-acrylamido-2-methylpropyldimethylammonio) butanoate, AMPDAB) comonomers were synthesized via micellar copolymerization. The terpolymers were characterized via {sup 13}C NMR and UV spectroscopies, classical and dynamic light scattering, and potentiometric titration. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH, electrolyte concentration, and the addition of small molecule surfactants, was investigated using surface tension and rheological measurements. Low charge density terpolymers were found to show greater viscosity enhancement upon the addition of surfactant compared to the high charge densitymore » terpolymers. The addition of sodium dodecyl sulfate (SDS) produced the largest maximum in solution viscosity, while N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), N-dodecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-12), and Triton X-100 tended to show reduced viscosity enhancement. In most cases, the high charge density carboxybetaine terpolymer exhibited diminished solution viscosities upon surfactant addition. In our last report, we discussed solution thermodynamic theory that described changes in polymer coil conformation as a function of solution temperature and polymer molecular weight. These polymers contained no ionic charges. In this report, we expand polymer solution theory to account for the electrostatic interactions present in solutions of charged polymers. Polymers with ionic charges are referred to as polyions or polyelectrolytes.« less

Fluid flow sensing with ionic polymer-metal composites

NASA Astrophysics Data System (ADS)

Stalbaum, Tyler; Trabia, Sarah; Shen, Qi; Kim, Kwang J.

2016-04-01

Ionic polymer-metal composite (IPMC) actuators and sensors have been developed and modeled over the last two decades for use as soft-robotic deformable actuators and sensors. IPMC devices have been suggested for application as underwater actuators, energy harvesting devices, and medical devices such as in guided catheter insertion. Another interesting application of IPMCs in flow sensing is presented in this study. IPMC interaction with fluid flow is of interest to investigate the use of IPMC actuators as flow control devices and IPMC sensors as flow sensing devices. An organized array of IPMCs acting as interchanging sensors and actuators could potentially be designed for both flow measurement and control, providing an unparalleled tool in maritime operations. The underlying physics for this system include the IPMC ion transport and charge fundamental framework along with fluid dynamics to describe the flow around IPMCs. An experimental setup for an individual rectangular IPMC sensor with an externally controlled fluid flow has been developed to investigate this phenomenon and provide further insight into the design and application of this type of device. The results from this portion of the study include recommendations for IPMC device designs in flow control.

A Novel Ionic Polymer Metal ZnO Composite (IPMZC)

PubMed Central

Kim, Sang-Mun; Tiwari, Rashi; Kim, Kwang J.

2011-01-01

The presented research introduces a new Ionic Polymer-Metal-ZnO Composite (IPMZC) demonstrating photoluminescence (PL)-quenching on mechanical bending or application of an electric field. The newly fabricated IPMZC integrates the optical properties of ZnO and the electroactive nature of Ionic Polymer Metal Composites (IPMC) to enable a non-contact read-out of IPMC response. The electro-mechano-optical response of the IPMZC was measured by observing the PL spectra under mechanical bending and electrical regimes. The working range was measured to be 375–475 nm. It was noted that the PL-quenching increased proportionally with the increase in curvature and applied field at 384 and 468 nm. The maximum quenching of 53.4% was achieved with the membrane curvature of 78.74/m and 3.01% when electric field (12.5 × 103 V/m) is applied. Coating IPMC with crystalline ZnO was observed to improve IPMC transduction. PMID:22163869

Mechanical and thermal behavior of ionic polymer metal composites: effects of electroded metals

NASA Astrophysics Data System (ADS)

Park, Il-Seok; Kim, Sang-Mun; Kim, Kwang J.

2007-08-01

In this study, we investigated the mechanical properties of various types of ionic polymer-metal composites (IPMCs) and Pt, Au, Pd, and Pt electroded ionic liquid (IL-Pt) IPMCs, by testing tensile modulus and dynamic mechanical behavior. The SEM was utilized to investigate the characteristics of the doped electroding layer, and the DSC was probed in order to look into the thermal behavior of various types of IPMCs. Au IPMCs, having a 5-7 µm-doped layer and nanosized Au particles (ca. 10 nm), showed the highest tensile strength (56 MPa) and modulus (602 MPa) in dried conditions. With regards to thermal behavior, Au IPMC had the highest Tg (153 °C) and Tm (263 °C) in both the DMA and DSC results. The fracture behavior of various types of IPMCs followed the behavior of the base material, Nafion™, which is represented as the semicrystalline polymer characteristic.

Structure-Antibacterial Activity Relationships of Imidazolium-Type Ionic Liquid Monomers, Poly(ionic liquids) and Poly(ionic liquid) Membranes: Effect of Alkyl Chain Length and Cations.

PubMed

Zheng, Zhiqiang; Xu, Qiming; Guo, Jiangna; Qin, Jing; Mao, Hailei; Wang, Bin; Yan, Feng

2016-05-25

The structure-antibacterial activity relationship between the small molecular compounds and polymers are still elusive. Here, imidazolium-type ionic liquid (IL) monomers and their corresponding poly(ionic liquids) (PILs) and poly(ionic liquid) membranes were synthesized. The effect of chemical structure, including carbon chain length of substitution at the N3 position and charge density of cations (mono- or bis-imidazolium) on the antimicrobial activities against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was investigated by determination of minimum inhibitory concentration (MIC). The antibacterial activities of both ILs and PILs were improved with the increase of the alkyl chain length and higher charge density (bis-cations) of imidazolium cations. Moreover, PILs exhibited lower MIC values relative to the IL monomers. However, the antibacterial activities of PIL membranes showed no correlation to those of their analogous small molecule IL monomers and PILs, which increased with the charge density (bis-cations) while decreasing with the increase of alkyl chain length. The results indicated that antibacterial property studies on small molecules and homopolymers may not provide a solid basis for evaluating that in corresponding polymer membranes.

Structural and Dielectric Properties of Ionic Liquid Doped Metal Organic Framework based Polymer Electrolyte Nanocomposites

NASA Astrophysics Data System (ADS)

Dutta, Rituraj; Kumar, Ashok

2016-10-01

Metal Organic Frameworks (MOFs) are mesoporous materials that can be treated as potential hosts for trapping guest molecules in their pores. Ion conduction and phase behavior dynamics of Ionic Liquids (ILs) can be controlled by tunable interactions of MOFs with the ILs. MOFs incorporated with ionic liquid can be dispersed in the polymers to synthesize polymer electrolyte nanocomposites with high ionic conductivity, electrochemical and thermal stability for applications in energy storage and conversion devices such as rechargeable Li-ion batteries. In the present work we have synthesized Cu-based MOF [Cu3(l,3,5-benzene tricarboxylate)2(H2O)] incorporated with the ionic liquid 1-Butyl-3-methylimidazolium bromide at different weight ratios of MOF and IL. The synthesized MOF-IL composites are dispersed in Poly (ethylene oxide) (PEO). Frequency dependent behavior of permittivity and dielectric loss of the nanocomposites depict the non-Debye dielectric relaxation mechanism. The room temperature Nyquist plots reveal decreasing bulk resistance upto 189 Ω with optimum ionic conductivity of 1.3×10-3S cm-1at maximum doping concentration of IL in the nanocomposite system.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

Iacob, Ciprian; Matusmoto, Atsushi; Inoue, Tadashi; Runt, James

Polymerized ionic liquids (PILs) combine the attractive mechanical characteristics of polymers and unique physico-chemical properties of low molecular weight ionic liquids in the same material. PILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells and lithium batteries, among others. Understanding their ionic transport mechanism is the key for designing highly conductive PILs. In the current study, the correlation between morphology and charge transport in two homologous series of PILs with systematic variation of the alkyl chain length and anions is investigated using broadband dielectric spectroscopy, rheology, differential scanning calorimetry and X-ray scattering. As the alkyl chain length increases, the backbone-to-backbone separation increases, and dc-conductivity consequently decreases. The cations dominate structural dynamics since they are attached to the polymer chains, while the anions are smaller and more mobile ionic species thereby controlling the ionic conductivity. Further interpretation of decoupling of dc conductivity from the segmental relaxation enabled the correlation between polymer morphology and dc conductivity. Supported by the National Science Foundation, Polymers Program.

Enhanced photophysics of conjugated polymers

DOEpatents

Chen, Liaohai [Argonne, IL; Xu, Su [Santa Clara, CA; McBranch, Duncan [Santa Fe, NM; Whitten, David [Santa Fe, NM

2003-05-27

The addition of oppositely charged surfactant to fluorescent ionic conjugated polymer forms a polymer-surfactant complex that exhibits at least one improved photophysical property. The conjugated polymer is a fluorescent ionic polymer that typically has at least one ionic side chain or moiety that interacts with the specific surfactant selected. The photophysical property improvements may include increased fluorescence quantum efficiency, wavelength-independent emission and absorption spectra, and more stable fluorescence decay kinetics. The complexation typically occurs in a solution of a polar solvent in which the polymer and surfactant are soluble, but it may also occur in a mixture of solvents. The solution is commonly prepared with a surfactant molecule:monomer repeat unit of polymer ratio ranging from about 1:100 to about 1:1. A polymer-surfactant complex precipitate is formed as the ratio approaches 1:1. This precipitate is recoverable and usable in many forms.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystal at imperfect metals

PubMed Central

Kaiser, V.; Comtet, J.; Niguès, A.; Siria, A.; Coasne, B.; Bocquet, L.

2017-01-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon the approach by [Kornyshev et al. Zh. Eksp. Teor. Fiz., 78(3):1008–1019, 1980] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allow for an estimate of interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. A counterintuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length ℓTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement. PMID:28436506

Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

2017-10-01

Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

Rapid Polymer Transport in a Single Nanometer-Scale Pore

NASA Astrophysics Data System (ADS)

Kasianowicz, J. J.

1998-03-01

Protein ion channels are nanometer-scale pores that control the transport of ions and polymers across cell membranes. We compared the ability of charged and nonelectrolyte linear polymers to partition into a single channel reconstituted into a planar lipid bilayer membrane. The entry of each polymer (e.g. monodisperse length single-stranded homopolymeric RNA1 or poly(ethylene glycol)2,3) into the pore caused characteristic transient decreases in the channel's ionic conductance. The ionic current blockades yield detailed information about the physical properties of the polymers and the pore. The biological and technological significance of the results will be discussed.

Electroactive polymer actuator based on a reduced graphene electrode

NASA Astrophysics Data System (ADS)

Im, Ki Hong; Choi, Hyonkwang

2014-03-01

We report an electroactive polymer (EAP) actuator using a reduced graphene electrode for a ionic polymer-metal composite actuator. Aqueous-reduced graphene is deposited to both sides of the ionic polymer membranes by using a simple inkjet printing process. The electrical and the optical properties of the reduced graphene were evaluated by using a four-point probe system, Raman spectroscopy, and Fourier-transform infrared attenuated total reflection spectroscopy. The actuator properties were evaluated from the curvatures of the ionic polymer graphene composite (IPGC) for various input voltages. From the results, we propose a new and simple isosceles trapezoidal element model for analyzing the relations among the input voltage, thickness, and curvature of IPGC.

Use of Ionic Liquids in Rod-Coil Block Copolyimides for Improved Lithium Ion Conduction

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.; Chapin, Kara; Bennett, William R.

2007-01-01

Solvent-free, solid polymer electrolytes (SPE) have the potential to improve safety, increase design flexibility and enhance performance of rechargeable lithium batteries. Solution based electrolytes are flammable and typically incompatible with lithium metal anodes, limiting energy density. We have previously demonstrated use of polyimide rod coil block copolymers doped with lithium salts as electrolytes for lithium polymer batteries. The polyimide rod blocks provide dimensional stability while the polyethylene oxide (PEO) coil portions conduct ions. Phase separation of the rods and coils in these highly branched polymers provide channels with an order of magnitude improvement in lithium conduction over polyethylene oxide itself at room temperature. In addition, the polymers have been demonstrated in coin cells to be compatible with lithium metal. For practical use at room temperature and below, however, at least an order of magnitude improvement in ion conduction is still required. The addition of nonvolatile, room temperature ionic liquids has been shown to improve the ionic conductivity of high molecular weight PEO. Herein we describe use of these molten salts to improve ionic conductivity in the rod-coil block copolymers.

Self Assembly and Interface Engineering of Organic Functional Materials for High Performance Polymer Solar Cells

NASA Astrophysics Data System (ADS)

Jen, Alex

2010-03-01

The performance of polymer solar cells are strongly dependent on the efficiency of light harvesting, exciton dissociation, charge transport, and charge collection at the metal/organic, metal/metal oxide, and organic/metal oxide interfaces. To improve the device performance, two parallel approaches were used: 1) developing novel low band gap conjugated polymers with good charge-transporting properties and 2) modifying the interfaces between the organic/metal oxide and organic/metal layers with functional self-assembling monolayers to tune their energy barriers. Moreover, the molecule engineering approach was also used to tune the energy level, charge mobility, and morphology of organic semiconductors.

Mixed system of Eudragit s-100 with a designed amphipathic peptide: control of interfacial elasticity by solution composition.

PubMed

Dexter, Annette F; Malcolm, Andrew S; Zeng, Biyun; Kennedy, Debora; Middelberg, Anton P J

2008-04-01

We report an interfacially active system based on an informational peptide surfactant mixed with an oppositely charged polyelectrolyte. The 21-residue cationic peptide, AM1, has previously been shown to respond reversibly to pH and metal ions at fluid interfaces, forming elastic films that can be rapidly switched to collapse foams or emulsions on demand. Here we report the reversible association of AM1 with the methacrylate-based anionic polymer Eudragit S-100. The strength of the association, in bulk aqueous solution, is modulated by added metal ions and by ionic strength. Addition of zinc ions to the peptide-polymer system promotes complex formation and phase separation, while addition of a chelating agent reverses the association. The addition of salt weakens peptide-polymer interactions in the presence or absence of zinc. At the air-water interface, Eudragit S-100 forms an elastic mixed film with AM1 in the absence of metal, under conditions where the peptide alone does not show interfacial elasticity. When zinc is present, the elasticity of the mixed film is increased, but the rate of interfacial adsorption slows due to formation of peptide-polymer complexes in bulk solution. An understanding of these interactions can be used to identify favorable foam-forming conditions in the mixed system.

Electrochemical and morphological studies of ionic polymer metal composites as stress sensors

DOE PAGES

Hong, Wangyujue; Almomani, Abdallah; Montazami, Reza

2016-10-04

Ionic polymer metal composites (IPMCs) are the backbone of a wide range of ionic devices. IPMC mechanoelectric sensors are advanced nanostructured transducers capable of converting mechanical strain into easily detectable electric signal. Such attribute is realized by ion mobilization in and through IPMC nanostructure. In this study we have investigated electrochemical and morphological characteristics of IPMCs by varying the morphology of their metal composite component (conductive network composite (CNC)). We have demonstrated the dependence of electrochemical properties on CNC nanostructure as well as mechanoelectrical performance of IPMC sensors as a function of CNC morphology. Lastly, it is shown that themore » morphology of CNC can be used as a means to improve sensitivity of IPMC sensors by 3–4 folds.« less

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

PubMed

Kaiser, V; Comtet, J; Niguès, A; Siria, A; Coasne, B; Bocquet, L

2017-07-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length l TF , profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

NASA Astrophysics Data System (ADS)

Kwon, Ha-Kyung; Olvera de La Cruz, Monica

2015-03-01

Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

Solubilization of octane in cationic surfactant-anionic polymer complexes: Effect of ionic strength.

PubMed

Zhang, Hui; Deng, Lingli; Sun, Ping; Que, Fei; Weiss, Jochen

2016-01-01

Polymers may alter the ability of oppositely charged surfactant micelles to solubilize hydrophobic molecules depending on surfactant-polymer interactions. This study was conducted to investigate the effect of ionic strength on the solubilization thermodynamics of an octane oil-in-water emulsion in mixtures of an anionic polymer (carboxymethyl cellulose) and cationic cetyltrimethylammonium bromide (CTAB) surfactant micelles using isothermal titration calorimetry (ITC). Results indicated that the CTAB binding capacity of carboxymethyl cellulose increased with increasing NaCl concentrations up to 100 mM, and the thermodynamic behavior of octane solubilization in CTAB micelles, either in the absence or presence of polymer, was found to have a strong dependence on ionic strength. The increasing ionic strength caused the solubilization in CTAB micelles to be less endothermic or even exothermic, but increased the solubilization capacity. Based on the phase separation model, the solubilization was suggested to be driven by enthalpy. It is indicated that increasing ionic strength gave rise to a larger Gibbs energy decrease but a smaller unfavorable entropy increase for octane solubilization in cationic surfactant micelles. Copyright © 2015 Elsevier Inc. All rights reserved.

Reliability of ionic polymer metallic composite for opto-mechanical applications

NASA Astrophysics Data System (ADS)

Yu, Chung-Yi; Su, Guo-Dung J.

2014-09-01

Electroactive polymer (EAP) is capable of exhibiting large shape changes in response to electrical stimulation. EAPs can produce large deformation with lower applied voltage for actuation applications. IPMC (Ionic Polymer Metal Composite) is a well-known ionic EAPs. It has numerous attractive advantages, such as low electrical energy consumption and light weight. The mechanism of IPMC actuator is due to the ionic diffusion when the voltage gradient is applied, so that the type of ionic solution has a large impact on the physical properties of IPMC. In this paper, the reliability tests of IPMC with non-aqueous ionic solution are demonstrated. Pt-IPMC with LiOH aqueous solution exhibits the best maximum displacement, but the water in LiOH solution is electrolyzed because of the low electrolysis voltage 1.23 V of water. To improve electrolysis problems and the operation time in the air, proper solvents including high electrolysis voltage and low vapor pressure should be considered. The reliability tests focus on the durability of IPMC in the air. The surface resistance, tip displacement and response time of IPMC are presented. More improvements of IPMC fabrication, such as Ag-IPMC, was developed in this paper.

Thermotropic Ionic Liquid Crystals

PubMed Central

Axenov, Kirill V.; Laschat, Sabine

2011-01-01

The last five years’ achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed. PMID:28879986

Thermotropic Ionic Liquid Crystals.

PubMed

Axenov, Kirill V; Laschat, Sabine

2011-01-14

The last five years' achievements in the synthesis and investigation of thermotropic ionic liquid crystals are reviewed. The present review describes the mesomorphic properties displayed by organic, as well as metal-containing ionic mesogens. In addition, a short overview on the ionic polymer and self-assembled liquid crystals is given. Potential and actual applications of ionic mesogens are also discussed.

Spacecraft dielectric material properties and spacecraft charging

NASA Technical Reports Server (NTRS)

Frederickson, A. R.; Wall, J. A.; Cotts, D. B.; Bouquet, F. L.

1986-01-01

The physics of spacecraft charging is reviewed, and criteria for selecting and testing semiinsulating polymers (SIPs) to avoid charging are discussed and illustrated. Chapters are devoted to the required properties of dielectric materials, the charging process, discharge-pulse phenomena, design for minimum pulse size, design to prevent pulses, conduction in polymers, evaluation of SIPs that might prevent spacecraft charging, and the general response of dielectrics to space radiation. SIPs characterized include polyimides, fluorocarbons, thermoplastic polyesters, poly(alkanes), vinyl polymers and acrylates, polymers containing phthalocyanine, polyacene quinones, coordination polymers containing metal ions, conjugated-backbone polymers, and 'metallic' conducting polymers. Tables summarizing the results of SIP radiation tests (such as those performed for the NASA Galileo Project) are included.

Characteristics of ionic polymer-metal composite with chemically doped TiO2 particles

NASA Astrophysics Data System (ADS)

Jung, Youngsoo; Kim, Seong Jun; Kim, Kwang J.; Lee, Deuk Yong

2011-12-01

Many studies have investigated techniques to improve the bending performance of ionic polymer-metal composite (IPMC) actuators, including 'doping' of metal particles in the polymer membrane usually by means of physical processes. This study is mainly focused on the characterization of the physical, electrochemical and electromechanical properties of TiO2-doped ionic polymer membranes and IPMCs prepared by the sol-gel method, which results in a uniform distribution of the particles inside the polymer membrane. X-ray and UV-visible spectra indicate the presence of anatase-TiO2 in the modified membranes. TiO2-doped membranes (0.16 wt%) exhibit the highest level of water uptake. The glass transition temperature of these membranes, measured using differential scanning calorimetry (DSC), increases with the increase of the amount of TiO2 in the membrane. Dynamic mechanical analysis (DMA) demonstrated that the storage modulus of dried TiO2-doped ionic polymer membranes increases as the amount of TiO2 in the membrane increases, whereas the storage modulus of hydrated samples is closely related to the level of water uptake. Electrochemical impedance spectroscopy (EIS) shows that the conductivity of TiO2-doped membranes decreases with increasing TiO2 content in spite of an internal resistance drop in the samples. Above all, bending deflection of TiO2-doped IPMC decreased with higher TiO2 content in the membrane while the blocking force of each sample increased with the higher TiO2 content. Additionally, it was determined that the lifetime of IPMC is strongly dependent on the level of water uptake.

Polymer Ni-MH battery based on PEO-PVA-KOH polymer electrolyte

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen

An alkaline polymer electrolyte film has been prepared by a solvent-casting method. Poly(vinyl alcohol), PVA is added to improve the ionic conductivity of the electrolyte. The ionic conductivity increases from 10 -7 to 10 -2 S cm -1 at room temperature when the weight percent ratio of poly(ethylene oxide), PEO to PVA is increased from 10:0 to 5:5. The activation energy of the ionic conductivity for the PEO-PVA-KOH polymer electrolyte is 3-8 kJ mol -1. The properties of the electrolyte film are characterized by a wide variety of techniques and it is found that the film exhibits good mechanical stability and high ionic conductivity at room temperature. The application of such electrolyte films to nickel-metal-hydride (Ni-MH) batteries is examined and the electrochemical characteristics of a polymer Ni-MH battery are obtained.

Studies of Surface Charging of Polymers by Indirect Triboelectrification

NASA Astrophysics Data System (ADS)

Mantovani, James; Calle, Carlos; Groop, Ellen; Buehler, Martin

2001-03-01

Charge is known to develop on the surface of an insulating polymer by frictional charging through direct physical contact with another material. We will present results of recent triboelectrification studies of polymer surfaces that utilized an indirect method of frictional charging. This method first involves placing a grounded thin metal foil in stationary contact over the polymer surface. The exposed metal foil is then rubbed with the surface of the material that generates the triboelectric charge. Data is presented for five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). The amount of charge that develops on an insulator's surface is measured using the MECA Electrometer, which was developed jointly by NASA Kennedy Space Center and the Jet Propulsion Laboratory to study the electrostatic properties of soil on the surface of Mars. Even though the insulator's surface is electrically shielded from the rubbing material by the grounded metal foil, charge measurements obtained by the MECA Electrometer after the metal foil is separated from the insulator's surface reveal that the insulator's surface does accumulate charge by indirect frictional charging. A possible explanation of the observations will be presented based on a simple contact barrier model.

Carbon nanotube-graphene composite for ionic polymer actuators

NASA Astrophysics Data System (ADS)

Yang, Woosung; Choi, Hyonkwang; Choi, Suho; Jeon, Minhyon; Lee, Seung-Yop

2012-05-01

In this paper, we develop a new ionic polymer-metal composite (IPMC) by replacing a typical platinum or gold electrode with a multi-walled carbon nanotube (MWNT)-graphene based electrode. A solvent of MWNT and graphene is formed on both sides of the ionic polymer membranes as electrodes by means of spray coating and baking. Then, the ionic liquid process is performed for actuating in air. The four kinds of IPMC samples with different MWNT-graphene ratios are fabricated with the same solid Nafion film. Experimental results show that the IPMC with a pure MWNT based electrode exhibits higher displacement compared to the conventional IPMC with a platinum electrode. Also, the increment of the ratio of graphene to the MWNT-graphene electrode decreases the resultant displacement but increases the fundamental natural frequency of the polymer actuator.

The mechanical properties of ionic polymer-metal composites

NASA Astrophysics Data System (ADS)

Park, Il-Seok; Kim, Sang-Mun; Kim, Doyeon; Kim, Kwang J.

2007-04-01

In this study, we investigated the mechanical properties of various type ionic polymer-metal composites (IPMCs) and Pt, Au, Pd, and Pt electroded ionic liquid (IL-Pt) IPMCs, by testing tensile modulus and dynamic mechanical behavior. The SEM was utilized to investigate the characteristics of the doped electroding layer, and the DSC was probed in order to look into the thermal behavior of various types of IPMCs. Au IPMCs, having a 5~7 μm doped layer and nano-sized Au particles (ca. 10 nm), showed the highest tensile strength (56 MPa) and modulus (602 MPa) in a dried condition. In a thermal behavior, Au IPMC has the highest T g (153°C) and T m (263°C) in both the DMA and DSC results. The fracture behavior of various types IPMCs followed base material's behavior, Nafion TM, which is represented as the semicrystalline polymer characteristic.

Focus tunable device actuator based on ionic polymer metal composite

NASA Astrophysics Data System (ADS)

Zhang, Yi-Wei; Su, Guo-Dung J.

2015-09-01

IPMC (Ionic Polymer Metallic Composite) is a kind of electroactive polymer (EAP) which is used as an actuator because of its low driving voltage and small size. The mechanism of IPMC actuator is due to the ionic diffusion when the voltage gradient is applied. In this paper, the complex IPMC fabrication such as Ag-IPMC be further developed in this paper. The comparison of response time and tip bending displacement of Pt-IPMC and Ag-IPMC will also be presented. We also use the optimized IPMC as the lens actuator integrated with curvilinear microlens array, and use the 3D printer to make a simple module and spring stable system. We also used modeling software, ANSYS Workbench, to confirm the effect of spring system. Finally, we successfully drive the lens system in 200μm stroke under 2.5V driving voltage within 1 seconds, and the resonant frequency is approximately 500 Hz.

Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

PubMed

Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

2016-01-14

In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

``Smart'' Surfaces of Polymer Brushes

NASA Astrophysics Data System (ADS)

Wang, Qiang; Meng, Dong

2009-03-01

``Smart'' surfaces, also known as stimuli-responsive surfaces, can change their properties (e.g., wettability, adhesion, friction, elasticity, and biocompatibility) in response to external stimuli (e.g., temperature, pressure, light, solvent selectivity, ionic strength, type of salt, pH, applied electric field, etc.). In this work, we use numerical self-consistent field calculations to study in detail the structure and stimuli- responses of various polymer brushes, including (1) the thermo- response of PNIPAM brushes in water, (2) solvent-response of uncharged diblock copolymer brushes, and (3) the stimuli- response of charged two-component polymer brushes (including both the binary A/B brushes and diblock copolymer A-B brushes) to ionic strength, pH, and applied electric field. Among the many design parameters (e.g., chain lengths, grafting densities, A-B incompatibility, degree of ionization of charged polymers, etc.) we identify those that strongly affect the surface switchability. Such knowledge is useful to the experimental design of these smart polymer brushes for their applications.

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy harvesting from the tail beating of a carangiform swimmer using ionic polymer-metal composites.

PubMed

Cha, Youngsu; Verotti, Matteo; Walcott, Horace; Peterson, Sean D; Porfiri, Maurizio

2013-09-01

In this paper, we study energy harvesting from the beating of a biomimetic fish tail using ionic polymer-metal composites. The design of the biomimetic tail is based on carangiform swimmers and is specifically inspired by the morphology of the heterocercal tail of thresher sharks. The tail is constituted of a soft silicone matrix molded in the form of the heterocercal tail and reinforced by a steel beam of rectangular cross section. We propose a modeling framework for the underwater vibration of the biomimetic tail, wherein the tail is assimilated to a cantilever beam with rectangular cross section and heterogeneous physical properties. We focus on base excitation in the form of a superimposed rotation about a fixed axis and we consider the regime of moderately large-amplitude vibrations. In this context, the effect of the encompassing fluid is described through a hydrodynamic function, which accounts for inertial, viscous and convective phenomena. The model is validated through experiments in which the base excitation is systematically varied and the motion of selected points on the biomimetic tail tracked in time. The feasibility of harvesting energy from an ionic polymer-metal composite attached to the vibrating structure is experimentally and theoretically assessed. The response of the transducer is described using a black-box model, where the voltage output is controlled by the rate of change of the mean curvature. Experiments are performed to elucidate the impact of the shunting resistance, the frequency of the base excitation and the placement of the ionic polymer-metal composite on energy harvesting from the considered biomimetic tail.

Superior Blends Solid Polymer Electrolyte with Integrated Hierarchical Architectures for All-Solid-State Lithium-Ion Batteries.

PubMed

Zhang, Dechao; Zhang, Long; Yang, Kun; Wang, Hongqiang; Yu, Chuang; Xu, Di; Xu, Bo; Wang, Li-Min

2017-10-25

Exploration of advanced solid electrolytes with good interfacial stability toward electrodes is a highly relevant research topic for all-solid-state batteries. Here, we report PCL/SN blends integrating with PAN-skeleton as solid polymer electrolyte prepared by a facile method. This polymer electrolyte with hierarchical architectures exhibits high ionic conductivity, large electrochemical windows, high degree flexibility, good flame-retardance ability, and thermal stability (workable at 80 °C). Additionally, it demonstrates superior compatibility and electrochemical stability toward metallic Li as well as LiFePO 4 cathode. The electrolyte/electrode interfaces are very stable even subjected to 4.5 V at charging state for long time. The LiFePO 4 /Li all-solid-state cells based on this electrolyte deliver high capacity, outstanding cycling stability, and superior rate capability better than those based on liquid electrolyte. This solid polymer electrolyte is eligible for next generation high energy density all-solid-state batteries.

Thermal Conductivity Changes Due to Degradation of Cathode Film Subjected to Charge-Discharge Cycles in a Li Ion Battery

NASA Astrophysics Data System (ADS)

Jagannadham, K.

2018-05-01

A battery device with graphene platelets as anode, lithium nickel manganese oxide as cathode, and solid-state electrolyte consisting of layers of lithium phosphorous oxynitride and lithium lanthanum titanate is assembled on the stainless steel substrate. The battery in a polymer enclosure is subjected to several electrical tests consisting of charge and discharge cycles at different current and voltage levels. Thermal conductivity of the cathode layer is determined at the end of charge-discharge cycles using transient thermoreflectance. The microstructure and composition of the cathode layer and the interface between the cathode, the anode, and the electrolyte are characterized using scanning electron microscopy and elemental mapping. The decrease in the thermal conductivity of the same cathode observed after each set of electrical test cycles is correlated with the volume changes and formation of low ionic and thermal conductivity lithium oxide and lithium oxychloride at the interface and along porous regions. The interface between the metal current collector and the cathode is also found to be responsible for the increase in thermal resistance. The results indicate that changes in the thermal conductivity of the electrodes provide a measure of the resistance to heat transfer and degradation of ionic transport in the cathode accompanying the charge-discharge cycles in the batteries.

Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

PubMed

Han, Mengwei; Espinosa-Marzal, Rosa M

2017-09-07

We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

2011-04-01

Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

"JCE" Classroom Activity Connections: NaCl or CaCl[subscript 2], Smart Polymer Gel Tells More

ERIC Educational Resources Information Center

Chen, Yueh-Huey; Lin, Jia-Ying; Wang, Yu-Chen; Yaung, Jing-Fun

2010-01-01

This classroom activity connection demonstrates the differences between the effects of NaCl (a salt of monovalent metal ions) and CaCl[subscript 2] (a salt of polyvalent metal ions) on swollen superabsorbent polymer gels. Being ionic compounds, NaCl and CaCl[subscript 2] both collapse the swollen polymer gels. The gel contracted by NaCl reswells…

Oxyphosphorus-containing polymers as binders for battery cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, Russell Clayton; Mullin, Scott Allen; Eitouni, Hany Basam

A class of polymeric phosphorous esters can be used as binders for battery cathodes. Metal salts can be added to the polymers to provide ionic conductivity. The polymeric phosphorous esters can be formulated with other polymers either as mixtures or as copolymers to provide additional desirable properties. Examples of such properties include even higher ionic conductivity and improved mechanical properties. Furthermore, cathodes that include the polymeric phosphorous esters can be assembled with a polymeric electrolyte separator and an anode to form a complete battery.

Effect of porosity and tortuosity of electrodes on carbon polymer soft actuators

NASA Astrophysics Data System (ADS)

S, Sunjai Nakshatharan; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2018-01-01

This work presents an electro-mechanical model and simulation of ionic electroactive polymer soft actuators with a porous carbon electrode, polymer membrane, and ionic liquid electrolyte. An attempt is made to understand the effects of specific properties of the porous electrodes such as porosity and tortuosity on the charge dynamics and mechanical performance of the actuator. The model uses porous electrode theory to study the electrochemical response of the system. The mechanical response of the whole laminate is attributed to the evolution of local stresses caused by diffusion of ions (diffusion-induced stresses or chemical stresses). The model indicates that in actuators with porous electrode, the diffusion coefficient of ions, conductivity of the electrodes, and ionic conductivity in both electrodes and separator are altered significantly. In addition, the model leads to an obvious deduction that the ions that are highly active in terms of mobility will dominate the whole system in terms of resulting mechanical deformation direction and rate of deformation. Finally, to validate the model, simulations are conducted using the finite element method, and the outcomes are compared with the experimental data. Significant effort has been put forward to experimentally measure the key parameters essential for the validation of the model. The results show that the model developed is able to well predict the behavior of the actuator, providing a comprehensive understanding of charge dynamics in ionic polymer actuator with porous electrodes.

Insulator to metal transition in WO 3 induced by electrolyte gating

DOE PAGES

Leng, X.; Pereiro, J.; Strle, J.; ...

2017-07-03

Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO 3 films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge accumulation near the interface) and oxygen-related mechanisms. Wemore » propose instead that hydrogen intercalation is responsible for doping WO 3 into a highly conductive ground state and provide evidence that it can be described as a dense polaronic gas.« less

Ionic polymer metal composites with nanoporous carbon electrodes

NASA Astrophysics Data System (ADS)

Palmre, Viljar; Brandell, Daniel; Mäeorg, Uno; Torop, Janno; Volobujeva, Olga; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2010-04-01

Ionic Polymer Metal Composites (IPMCs) are soft electroactive polymer materials that bend in response to the voltage stimulus (1 - 4 V). They can be used as actuators or sensors. In this paper, we introduce two new highly-porous carbon materials for assembling high specific area electrodes for IPMC actuators and compare their electromechanical performance with recently reported IPMCs based on RuO2 electrodes. We synthesize ionic liquid (Emi-Tf) actuators with either Carbide-Derived Carbon (CDC) (derived from TiC) or coconut shell based activated carbon electrodes. The carbon electrodes are applied onto ionic liquid-swollen Nafion membranes using the direct assembly process. Our results show that actuators assembled with CDC electrodes have the greatest peak-to-peak strain output, reaching up to 20.4 mɛ (equivalent to >2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also revealed significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

Immobilization of yeast cells with ionic hydrogel carriers by adhesion-multiplication.

PubMed

Zhaoxin, L; Fujimura, T

2000-12-01

The mixture of an ionic monomer, 2-acrylamido 2-methylpropanesulfonic acid (TBAS), and a series of poly(ethylene glycol) dimethacrylate (nG) monomers were copolymerized with 60Co gamma-rays, and the produced ionic hydrogel polymers were used for immobilization of yeast cells. The cells were adhered onto the surface of the hydrogel polymers and intruded into the interior of the polymers with growing. The immobilized yeast cells with these hydrogel polymers had higher ethanol productivity than that of free cells. The yield of ethanol with poly(TBAS-14G) carrier was the highest and increased by 3.5 times compared to the free cells. It was found that the ethanol yield increased with the increase of glycol number in poly(ethylene glycol) dimethacrylate. The state of the immobilized cells was observed with microscope, and it was also found that the difference in the ethanol productivity is mainly due to the difference in the internal structure and properties of polymer carrier, such as surface charge, hydrophilicity, and swelling ability of polymer carrier.

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

NASA Astrophysics Data System (ADS)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Modeling of robotic fish propelled by an ionic polymer-metal composite caudal fin

NASA Astrophysics Data System (ADS)

Chen, Zheng; Shatara, Stephan; Tan, Xiaobo

2009-03-01

In this paper, a model is proposed for a biomimetic robotic fish propelled by an ionic polymer metal composite (IPMC) actuator with a rigid passive fin at the end. The model incorporates both IPMC actuation dynamics and the hydrodynamics, and predicts the steady-state speed of the robot under a periodic actuation voltage. Experimental results have shown that the proposed model can predict the fish motion for different tail dimensions. Since its parameters are expressed in terms of physical properties and geometric dimensions, the model is expected to be instrumental in optimal design of the robotic fish.

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

Soft actuator based on Kraton with GO/Ag/Pani composite electrodes for robotic applications

NASA Astrophysics Data System (ADS)

Khan, Ajahar; Kant Jain, Ravi; Banerjee, Priyabrata; Inamuddin; Asiri, Abdullah M.

2017-11-01

In this work, electrochemically-driven Kraton/graphene oxide/Ag/polyaniline (Kraton/GO/Ag/Pani) polymer composite based ionic polymer metal composite (IPMC) was fabricated as a soft actuator. Silver nanopowder with polyaniline coating used as an electrode material is a novel approach in the fabrication of IPMC, which gives new opportunities for development of the electrode on ionic polymer actuator surfaces directly without electroless plating of Pt or Au metal. The Kraton/GO/Ag/Pani membrane showed much higher water-uptake (WU), ion exchange capacity (IEC), proton conductivity than those of several reported IPMC membranes. The enhanced actuation performance indicates that the Kraton/GO/Ag/Pani is a better alternative to the highly expensive commercialized IPMC actuator.

Preparation of ionic membranes for zinc/bromine storage batteries

NASA Astrophysics Data System (ADS)

Assink, R. A.; Arnold, C., Jr.

Zinc/bromine flow batteries are being developed for vehicular and utility load leveling applications. During charge, an aqueous zinc bromide salt is electrolyzed to zinc metal and molecular bromine. During discharge, the zinc and bromine react to again form the zinc bromide salt. One serious disadvantage of the microporous separators presently used in the zinc/bromine battery is that modest amounts of bromine and negatively charged bromine moieties permeate through these materials and react with the zinc anode. This results in partial self-discharge of the battery and low coulombic efficiencies. Our approach to this problem is to impregnate the microporous separators with a soluble cationic polyelectrolyte. In laboratory screening tests a sulfonated polysulfone resin and fully fluorinated sulfonic acid polymer substantially reduced bromine permeation with only modest increases in the area resistance.

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids.

PubMed

Lin, Junhong; Liu, Yang; Zhang, Q M

2011-01-21

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10(-2) mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids

PubMed Central

Lin, Junhong; Liu, Yang; Zhang, Q. M.

2011-01-01

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10−2 mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed. PMID:21339839

Mass and charge transport in IPMC actuators with fractal interfaces

NASA Astrophysics Data System (ADS)

Chang, Longfei; Wu, Yucheng; Zhu, Zicai; Li, Heng

2016-04-01

Ionic Polymer-Metal Composite (IPMC) actuators have been attracting a growing interest in extensive applications, which consequently raises the demands on the accuracy of its theoretical modeling. For the last few years, rough landscape of the interface between the electrode and the ionic membrane of IPMC has been well-documented as one of the key elements to ensure a satisfied performance. However, in most of the available work, the interface morphology of IPMC was simplified with structural idealization, which lead to perplexity in the physical interpretation on its interface mechanism. In this paper, the quasi-random rough interface of IPMC was described with fractal dimension and scaling parameters. And the electro-chemical field was modeled by Poisson equation and a properly simplified Nernst-Planck equation set. Then, by simulation with Finite Element Method, a comprehensive analysis on he inner mass and charge transportation in IPMC actuators with different fractal interfaces was provided, which may be further adopted to instruct the performance-oriented interface design for ionic electro-active actuators. The results also verified that rough interface can impact the electrical and mechanical response of IPMC, not only from the respect of the real surface increase, but also from mass distribution difference caused by the complexity of the micro profile.

Luminescent tunable polydots: Charge effects in confined geometry

DOE PAGES

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; ...

2017-06-28

Long-lived soft nanoparticles, formed by conjugated polymers, constitute a new class of far-from-equilibrium responsive structures for nano-medicine. Tethering ionizable groups to the polymers enables functionality. However concurrently, the ionic groups perturb the delicate balance of interactions that governs these particles. Using fully atomistic molecular dynamics simulations, this study probed the effects of charged groups tethered to poly para phenylene ethynylene substituted by alkyl groups on the polymer conformation and dynamics in confined geometry. As a result, we find that the ionizable groups affect the entire shape of the polydots and impact the conformation and dynamics of the polymer.

Charge carrier dynamics and relaxation in (polyethylene oxide-lithium-salt)-based polymer electrolyte containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as ionic liquid

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

In this paper we report the dynamics of charge carriers and relaxation in polymer electrolytes based on polyethylene oxide (PEO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPTFSI) ionic liquid prepared by solution cast technique. It has been observed that the incorporation of BMPTFSI into PEO-LiTFSI electrolyte is an effective way for increasing the amorphous phase to a large extent. It has also been observed that both the glass transition and melting temperatures decrease with the increase of BMPTFSI concentration. The ionic conductivity of these polymer electrolytes increases with the increase of BMPTFSI concentration. The highest ionic conductivity obtained at 25 °C is ˜3×10-4 S cm-1 for the electrolyte containing 60 wt % BMPTFSI and ethylene oxide (EO)/Li ratio of 20. The temperature dependence of the dc conductivity and the hopping frequency show Vogel-Tamman-Fulcher type behavior indicating a strong coupling between the ionic and the polymer chain segmental motions. The frequency dependence of the ac conductivity exhibits a power law with an exponent n which decreases with the increase of temperature. The scaling of the ac conductivity indicates that relaxation dynamics of charge carriers follows a common mechanism for all temperatures and BMPTFSI concentrations. We have also presented the electric modulus data which have been analyzed in the framework of a Havriliak-Negami equation and the shape parameters obtained by the analysis show slight temperature dependence, but change sharply with BMPTFSI concentration. The stretched exponent β obtained from Kohlrausch-Williams-Watts fit to the modulus data is much lower than unity signifying that the relaxation is highly nonexponential. The decay function obtained from analysis of experimental modulus data is highly asymmetric with time.

Charge Density Dependent Hole Mobility and Density of States Throughout the Entire Finite Potential Window of Conductivity in Ionic Liquid Gated Poly(3-hexylthiophene)

NASA Astrophysics Data System (ADS)

Paulsen, Bryan D.; Frisbie, C. Daniel

2012-02-01

Ionic liquids, used in place of traditional gate dielectric materials, allow for the accumulation of very high 2D and 3D charge densities (>10^14 #/cm^2 and >10^21 #/cm^3 respectively) at low voltage (<5 V). Here we study the electrochemical gating of the benchmark semiconducting polymer poly(3-hexylthiophene) (P3HT) with the ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMI][FAP]). The electrochemical stability of [EMI][FAP] allowed the reproducible accumulation of 2 x 10^21 hole/cm^3, or one hole (and stabilizing anion dopant) per every two thiophene rings. A finite potential/charge density window of high electrical conductivity was observed with hole mobility reaching a maximum of 0.86 cm^2/V s at 0.12 holes per thiophene ring. Displacement current measurements, collected versus a calibrated reference electrode, allowed the mapping of the highly structured and extremely broad density of states of the P3HT/[EMI][FAP] doped composite. Variable temperature and charge density hole transport measurements revealed hole transport to be thermally activated and non-monotonic, displaying a activation energy minimum of ˜20 meV in the region of maximum conductivity and hole mobility. To show the generality of this result, the study was extended to an additional four ionic liquids and three semiconducting polymers.

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody

2016-06-15

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10{sup −3} S cm{sup −1}. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providingmore » flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g{sup −1} for standard metallic current collectors and (ii) 99.5 mAh g{sup −1} for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.« less

Poly(vinylidene fluoride-hexafluoropropylene) polymer electrolyte for paper-based and flexible battery applications

NASA Astrophysics Data System (ADS)

Aliahmad, Nojan; Shrestha, Sudhir; Varahramyan, Kody; Agarwal, Mangilal

2016-06-01

Paper-based batteries represent a new frontier in battery technology. However, low-flexibility and poor ionic conductivity of solid electrolytes have been major impediments in achieving practical mechanically flexible batteries. This work discuss new highly ionic conductive polymer gel electrolytes for paper-based battery applications. In this paper, we present a poly(vinylidene fluoride-hexafluoropropylene) (PVDH-HFP) porous membrane electrolyte enhanced with lithium bis(trifluoromethane sulphone)imide (LiTFSI) and lithium aluminum titanium phosphate (LATP), with an ionic conductivity of 2.1 × 10-3 S cm-1. Combining ceramic (LATP) with the gel structure of PVDF-HFP and LiTFSI ionic liquid harnesses benefits of ceramic and gel electrolytes in providing flexible electrolytes with a high ionic conductivity. In a flexibility test experiment, bending the polymer electrolyte at 90° for 20 times resulted in 14% decrease in ionic conductivity. Efforts to further improving the flexibility of the presented electrolyte are ongoing. Using this electrolyte, full-cell batteries with lithium titanium oxide (LTO) and lithium cobalt oxide (LCO) electrodes and (i) standard metallic current collectors and (ii) paper-based current collectors were fabricated and tested. The achieved specific capacities were (i) 123 mAh g-1 for standard metallic current collectors and (ii) 99.5 mAh g-1 for paper-based current collectors. Thus, the presented electrolyte has potential to become a viable candidate in paper-based and flexible battery applications. Fabrication methods, experimental procedures, and test results for the polymer gel electrolyte and batteries are presented and discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leng, X.; Pereiro, J.; Strle, J.

Tungsten oxide and its associated bronzes (compounds of tungsten oxide and an alkali metal) are well known for their interesting optical and electrical characteristics. We have modified the transport properties of thin WO 3 films by electrolyte gating using both ionic liquids and polymer electrolytes. We are able to tune the resistivity of the gated film by more than five orders of magnitude, and a clear insulator-to-metal transition is observed. To clarify the doping mechanism, we have performed a series of incisive operando experiments, ruling out both a purely electronic effect (charge accumulation near the interface) and oxygen-related mechanisms. Wemore » propose instead that hydrogen intercalation is responsible for doping WO 3 into a highly conductive ground state and provide evidence that it can be described as a dense polaronic gas.« less

Analysis and experiment on a self-sensing ionic polymer-metal composite actuator

NASA Astrophysics Data System (ADS)

Nam, Doan Ngoc Chi; Ahn, Kyoung Kwan

2014-07-01

An ionic polymer-metal composite (IPMC) actuator is an electro-active polymer (EAP) that bends in response to a small applied electrical field as a result of the mobility of cations in the polymer network. This paper aims to develop a self-sensing actuator for practical use, since current sensing methods generally face limitations due to the compact size and mobility of the IPMC actuator. Firstly, the variation of surface resistance during bending operations is investigated. Then, the behavior of IPMC corresponding to the variation of surface resistance is mathematically analyzed. Based on the analysis results, a simple configuration to realize the self-sensing behavior is introduced. In this technique, the bending curvature of an IPMC can be obtained accurately by employing several feedback voltage signals along with the IPMC length. Finally, experimental evaluations proved the ability of the proposed scheme to estimate the bending behavior of IPMC actuators.

Interaction of slow highly charged ions with a metal surface covered with a thin dielectric film. The role of the neutralization energy in the nanostructures formation

NASA Astrophysics Data System (ADS)

Majkić, M. D.; Nedeljković, N. N.; Dojčilović, R. J.

2017-09-01

We consider the slow highly charged ions impinging upon a metal surface covered with a thin dielectric film, and formation of the surface nanostructures (craters) from the standpoint of the required energy. For the moderate ionic velocities, the size of the surface features depends on the deposited kinetic energy of the projectile and the ionic neutralization energy. The neutralization energy is calculated by employing the recently developed quasi-resonant two-state vector model for the intermediate Rydberg state population and the micro-staircase model for the cascade neutralization. The electron interactions with the ionic core, polarized dielectric and charge induced on the metal surface are modelled by the appropriate asymptotic expressions and the method for calculation of the effective ionic charges in the dielectric is proposed. The results are presented for the interaction of \\text{X}{{\\text{e}}Z+} ions (velocity v=0.25 a.u.; 25) with the metal surface (Co) covered with a thin dielectric film, for model values of dielectric constant inside the interaction region. In the absence of dielectric film, the neutralization energy is lower than the potential (ionization) energy due to the incomplete neutralization. The presence of dielectric film additionally decreases the neutralization energy. We calculate the projectile neutralization energy in the perturbed dielectric (perturbation is caused by the ionic motion and the surface structure formation). We correlate the neutralization energy added to the deposited kinetic energy with the experimentally obtained energy necessary for the formation of the nano-crater of a given depth.

Effect of Charge Patterning on the Phase Behavior of Polymer Coacervates for Charge Driven Self Assembly

NASA Astrophysics Data System (ADS)

Radhakrishna, Mithun; Sing, Charles E.

Oppositely charged polymers can undergo associative liquid-liquid phase separation when mixed under suitable conditions of ionic strength, temperature and pH to form what are known as `polymeric complex coacervates'. Polymer coacervates find use in diverse array of applications like microencapsulation, drug delivery, membrane filtration and underwater adhesives. The similarity between complex coacervate environments and those in biological systems has also found relevance in areas of bio-mimicry. Our previous works have demonstrated how local charge correlations and molecular connectivity can drastically affect the phase behavior of coacervates. The precise location of charges along the chain therefore dramatically influences the local charge correlations, which consequently influences the phase behavior of coacervates. We investigate the effect of charge patterning along the polymer chain on the phase behavior of coacervates in the framework of the Restricted Primitive Model using Gibbs Ensemble Monte Carlo simulations. Our results show that charge patterning dramatically changes the phase behavior of polymer coacervates, which contrasts with the predictions of the classical Voorn-Overbeek theory. This provides the basis for designing new materials through charge driven self assembly by controlling the positioning of the charged monomers along the chain.

Elucidating the correlation between morphology and ion dynamics in polymerized ionic liquids.

NASA Astrophysics Data System (ADS)

Heres, Maximilian; Cosby, Tyler; Iacob, Ciprian; Runt, James; Benson, Roberto; Liu, Hongjun; Paddison, Stephen; Sangoro, Joshua

Charge transport and dynamics are investigated for a series of poly-ammonium and poly-imidazolium-based polymerized ionic liquids (polyIL) with a common bis(trifluoromethylsulfonyl)imide anion using broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry. A significant enhancement of the Tg independent ionic conductivity is observed for ammonium based polyIL with shorter pendant groups, in comparison to imidazolium based systems. These results emphasize the importance of polymer backbone spacing as well as counter-ion size on ionic conductivity in polymerized ionic liquids. NSF DMR 1508394.

Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Diaz, Mariana; ...

2017-09-05

Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as an ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature - a charge transport faster than the segmental dynamics. Here, to address this issue, we have studied three novel polymer electrolyte membrane for fuel cells as well as four single-ion conductors including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting propertiesmore » of the examined systems. Finally, we demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.« less

Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojnarowska, Zaneta; Feng, Hongbo; Diaz, Mariana

Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as an ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature - a charge transport faster than the segmental dynamics. Here, to address this issue, we have studied three novel polymer electrolyte membrane for fuel cells as well as four single-ion conductors including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting propertiesmore » of the examined systems. Finally, we demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.« less

An ionic liquid-gated polymer thin film transistor with exceptionally low "on" resistance

NASA Astrophysics Data System (ADS)

Algarni, Saud A.; Althagafi, Talal M.; Smith, Patrick J.; Grell, Martin

2014-05-01

We report the ionic liquid (IL) gating of a solution processed semiconducting polymer, poly(2,5-bis(3-hexadecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT). IL gating relies on the poor solubility of PBTTT, which requires hot chlorinated benzenes for solution processing. PBTTT, thus, resists dissolution even in IL, which otherwise rapidly dissolves semiconducting polymers. The resulting organic thin film transistors (OTFTs) display low threshold, very high carrier mobility (>3 cm2/Vs), and deliver high currents (in the order of 1 mA) at low operational voltages. Such OTFTs are interesting both practically, for the addressing of current-driven devices (e.g., organic LEDs), and for the study of charge transport in semiconducting polymers at very high carrier density.

The effect of ionic membrane properties on the performance of ionic polymer-metal composite (IPMC) actuator

NASA Astrophysics Data System (ADS)

Jho, Jae Y.; Han, Man J.; Park, Jong H.; Lee, Jang Y.; Wang, Hyuck S.

2005-05-01

On purpose to overcome the limit of conventional ionic polymer-metal composites (IPMC) using the commercial ionic membranes, novel IPMCs with radiation-grafted ion-exchange membranes were prepared. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(ethylene-co-tetrafluoroethylene) (ETFE) were radiation-grafted with styrene, and then sulfonated. The properties of the membranes were modulated by controlling the amount of polystyrene sulfonic acid (PSSA) groups in the membranes. The amount of PSSA groups were tuned by controlling the total absorbed dose of γ-ray. The membranes were characterized by measuring the water-uptake, the ion-exchange capacity, and the ion conductivity. The performance of the IPMCs using these membranes were analyzed with laser displacement meter. They exhibited much larger bending displacement in comparison with Nafion-based IPMC. With increasing the amount of PSSA groups, the maximum displacement and the bending speed were remarkably increased. The results made sure that the property of ion-exchange membrane was the key element affecting the actuation performance of IPMC.

Dispersions of polymer ionomers: I.

PubMed

Capek, Ignác

2004-12-31

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.

Electrically and chemically tunable soft-solid block copolymer structural color (Conference Presentation)

NASA Astrophysics Data System (ADS)

Park, Cheolmin

2016-09-01

1D photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied due to their potential use in low-power reflective mode displays, e-books and sensors, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid swollen block copolymer films. Placement of a polymer/ionic liquid (IL) film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2vinyl pyridine) (PS-b-QP2VP) copolymer SC film allowed the development of R, G and B full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3V to +6V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

Searching for a new ionomer for 3D printable ionic polymer-metal composites: Aquivion as a candidate

NASA Astrophysics Data System (ADS)

Trabia, Sarah; Olsen, Zakai; Kim, Kwang J.

2017-11-01

The work presented in this paper introduces Aquivion as a potential candidate for additive manufacturing of ionomeric polymers for the application of IPMCs. First, Aquivion was characterized and compared with Nafion to show that it has the similar qualities, with the major difference being the ionic conductivity. Ionic polymer-metal composites (IPMCs) were fabricated using off-the-shelf membranes of Nafion and Aquivion. The actuation tests showed improved performance for an IPMC with Aquivion as the base compared to an IPMC with a Nafion base. With these results in mind, additive manufacturing of unique shapes using Aquivion filament was studied. A 3D printer was modified to work with Aquivion filament and the polymer was printed into various shapes. Using the printed membranes, IPMCs were fabricated using an electroless plating process. Nafion-based and printed Aquivion-based IPMCs were tested for their performance in back relaxation, frequency driven actuation, blocking force, and mechano-electric sensing. The printed Aquivion-based IPMCs performed comparably to Nafion-based IPMC in back relaxation and showed significantly improved performance in frequency driven actuation, blocking force generation, and mechano-electric sensing.

Label-free biosensing with functionalized nanopipette probes.

PubMed

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W; Pourmand, Nader

2009-03-24

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research.

An ionic polymer-metal composite actuator based on PSMI-incorporated PVDF with chemical stability and performance durability

NASA Astrophysics Data System (ADS)

Lu, Jun; Kim, Sang-Gyun; Lee, Sunwoo; Oh, Il-Kwon

2009-07-01

To develop artificial muscles with improved performance, a novel ionic polymer-metal composite (IPMC) actuator was developed by employing the newly-synthesized ionic networking film of poly (styrene-alt-maleimide) (PSMI)- incorporated poly (vinylidene fluoride) (PVDF). Scanning electron microscope and transmission electron microscopy revealed that much smaller and more uniform nano-sized platinum particles were formed on the surfaces of the film as well as within its polymer matrix after the electroless-plating process. Fourier transform infrared results suggested that no hydrolysis occurred for the as-prepared film actuator before and after the exposure to the elevated PH solutions at 25°C for 48h. The new actuator showed much larger tip displacement than that of a Nafion-based counterpart under the applied electrical stimulus, and overcame the back relaxation of the traditional IPMC actuator under the constant voltage. The current actuator was operated over 6.5h at high-frequency sinusoidal excitation, and its tip displacement was still comparable to that of the referenced Nafion actuator when the test was terminated. The excellent electromechanical performance is due to the inherent large ionic-exchange capacity and the unique hydrophilic nano-channels of the ionic networking film. Furthermore, the working principle of the developed IPMC actuator is thought to be based on a combination of piezoelectricity and ionic transport. The film of PSMI-incorporated PVDF has some advantages over the most widely-used Nafion-based one by diversifying niche applications in biomimetic motion, and the present study is believed to open a new avenue for the design and fabrication of the electro-active polymer film with unique functional properties.

Tuning the metal-insulator crossover and magnetism in SrRuO 3 by ionic gating

DOE PAGES

Yi, Hee Taek; Gao, Bin; Xie, Wei; ...

2014-10-13

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. We report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO 3. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90–250 K and 70–100 K,more » respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications.« less

Tuning the metal-insulator crossover and magnetism in SrRuO₃ by ionic gating.

PubMed

Yi, Hee Taek; Gao, Bin; Xie, Wei; Cheong, Sang-Wook; Podzorov, Vitaly

2014-10-13

Reversible control of charge transport and magnetic properties without degradation is a key for device applications of transition metal oxides. Chemical doping during the growth of transition metal oxides can result in large changes in physical properties, but in most of the cases irreversibility is an inevitable constraint. Here we report a reversible control of charge transport, metal-insulator crossover and magnetism in field-effect devices based on ionically gated archetypal oxide system - SrRuO₃. In these thin-film devices, the metal-insulator crossover temperature and the onset of magnetoresistance can be continuously and reversibly tuned in the range 90-250 K and 70-100 K, respectively, by application of a small gate voltage. We infer that a reversible diffusion of oxygen ions in the oxide lattice dominates the response of these materials to the gate electric field. These findings provide critical insights into both the understanding of ionically gated oxides and the development of novel applications.

Charge injection and transport in regioregular poly(3-hexylthiophene)-based field-effect transistors

NASA Astrophysics Data System (ADS)

Singh, Kumar Abhishek

Organic (semi)conductors are poised as never before to transform the electronics industry towards unprecedented versatility. In this thesis, we have taken an experimental approach to address the effect of nanostructure and the energy-level alignment at the metal/polymer interface on charge injection and transport in regioregular poly(3-hexylthiophene) (rr-P3HT) based field-effect transistors (FETs). We found that the mobility and contact resistance in rr-P3HT based FETs show an inverse relationship, and that both properties were affected by the nanostructure of the polymer proving that that charge injection, in addition to charge transport, is significantly affected by the bulk-transport properties of rr-P3HT. Thereafter we successfully recessed the contacts into the SiO 2 dielectric to minimize the effect of the step between the metal contacts and the dielectric on the polymer nanomorphology. The planarization of the devices resulted in a dramatic improvement of the nanomorphology of rr-P3HT reflected as an improvement in charge injection as evident from the decrease in contact resistance values. Gold contacts were also modified by treating them with self-assembled monolayers (SAMs) of aromatic thiols. Electron-poor (electron-rich) SAMs resulted in an increase (decrease) in the Au work function because of the electron-withdrawing (-donating) tendency of the polar molecules. The change in metal work-function by SAM modification also resulted in a modulation of the contact resistance. While there was a clear effect on charge injection upon modification of the contacts, either by SAMs or planarization, the mobility values improved only in the short-channel devices indicating that at longer channels the OFETs are channel-limited because of grain-boundary limited charge transport. Photoemission spectroscopy was also conducted to investigate the energy level alignment at bottom-contact (polymer-on-metal) and top-contact (metal-on-polymer) geometries for high work function metals (Au, Pt) and rr-P3HT. The Fermi energy level was found to be pinned at the polaronic energy level within the band gap of rr-P3HT resulting in barrier-less interfaces for charge injection. Photoemission spectroscopy studies of the metal-on-polymer configuration also provided insight into the chemical structure of the metal/polymer interface. Platinum was found to react with sulfur from the thiophene ring whereas Au was found to be relatively unreactive.

Like-charge attraction and opposite-charge decomplexation between polymers and DNA molecules

NASA Astrophysics Data System (ADS)

Buyukdagli, Sahin

2017-02-01

We scrutinize the effect of polyvalent ions on polymer-DNA interactions. We extend a recently developed test-charge theory [S. Buyukdagli et al., Phys. Rev. E 94, 042502 (2016), 10.1103/PhysRevE.94.042502] to the case of a stiff polymer interacting with a DNA molecule in an electrolyte mixture. The theory accounts for one-loop level electrostatic correlation effects such as the ionic cloud deformation around the strongly charged DNA molecule as well as image-charge forces induced by the low DNA permittivity. Our model can reproduce and explain various characteristics of the experimental phase diagrams for polymer solutions. First, the addition of polyvalent cations to the electrolyte solution results in the attraction of the negatively charged polymer by the DNA molecule. The glue of the like-charge attraction is the enhanced shielding of the polymer charges by the dense counterion layer at the DNA surface. Second, through the shielding of the DNA-induced electrostatic potential, mono- and polyvalent cations of large concentration both suppress the like-charge attraction. Within the same formalism, we also predict a new opposite-charge repulsion effect between the DNA molecule and a positively charged polymer. In the presence of polyvalent anions such as sulfate or phosphate, their repulsion by the DNA charges leads to the charge screening deficiency of the region around the DNA molecule. This translates into a repulsive force that results in the decomplexation of the polymer from DNA. This opposite-charge repulsion phenomenon can be verified by current experiments and the underlying mechanism can be beneficial to gene therapeutic applications where the control over polymer-DNA interactions is the key factor.

The Impact of Template Types on Polyeugenol to the Adsorption Selectivity of Ionic Imprinted Polymer (IIP) Fe Metal Ion

NASA Astrophysics Data System (ADS)

Djunaidi, M. C.; Haris, A.; Pardoyo; Rosdiana, K.

2018-04-01

The synthesis of IIP was carried out by variation of Fe(III) ion templates from Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 compounds which then tested IIP selectivity to the Fe metal ions through adsorption process. Ionic Imprinted Polymer (IIP) is a method of printing metal ions bound in a polymer, subsequently released from the polymer matrix to produce a suitable imprint for the target ion. The purposes of this study were to produce IIP from Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 templates, to know the effect of templates on adsorption selectivity of IIP involving imprint cavity, and to know the impact of metal competitor on the selectivity adsorption of IIP to the Fe metals. The results obtained showed that IIP synthesized by variations of Fe(NO3)3, K3[Fe(CN)6] and NH4Fe(SO4)2 templates were successfully synthesized. The adsorption selectivity of Fe (III) metal ion in the Fe(NO3)3 template was greater than that of in the K3[Fe(CN)6] and NH4Fe(SO4)2 templates. The adsorption selectivity of Fe was greater on Fe-Cr compared to on Fe-Cd and Fe-Pb.

Volatile chemical reagent detector

DOEpatents

Chen, Liaohai; McBranch, Duncan; Wang, Rong; Whitten, David

2004-08-24

A device for detecting volatile chemical reagents based on fluorescence quenching analysis that is capable of detecting neutral electron acceptor molecules. The device includes a fluorescent material, a contact region, a light source, and an optical detector. The fluorescent material includes at least one polymer-surfactant complex. The polymer-surfactant complex is formed by combining a fluorescent ionic conjugated polymer with an oppositely charged surfactant. The polymer-surfactant complex may be formed in a polar solvent and included in the fluorescent material as a solution. Alternatively, the complex may be included in the fluorescent material as a thin film. The use of a polymer-surfactant complex in the fluorescent material allows the device to detect both neutral and ionic acceptor molecules. The use of a polymer-surfactant complex film allows the device and the fluorescent material to be reusable after exposing the fluorescent material to a vacuum for limited time.

Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation.

PubMed

Lin, Rijia; Ge, Lei; Diao, Hui; Rudolph, Victor; Zhu, Zhonghua

2016-11-23

Obtaining strong interfacial affinity between filler and polymer is critical to the preparation of mixed matrix membranes (MMMs) with high separation efficiency. However, it is still a challenge for micron-sized metal organic frameworks (MOFs) to achieve excellent compatibility and defect-free interface with polymer matrix. Thin layer of ionic liquid (IL) was immobilized on micron-sized HKUST-1 to eliminate the interfacial nonselective voids in MMMs with minimized free ionic liquid (IL) in polymer matrix, and then the obtained IL decorated HKUST-1 was incorporated into 4,4'-(hexafluoroisopropylidene)diphthalic anhydride-2,3,5,6-tetramethyl-1,3-phenyldiamine (6FDA-Durene) to fabricate MMMs. Acting as a filler/polymer interfacial binder, the favorable MOF/IL and IL/polymer interaction can facilitate the enhancement of MOF/polymer affinity. Compared to MMM with only HKUST-1 incorporation, MMM with IL decorated HKUST-1 succeeded in restricting the formation of nonselective interfacial voids, leading to an increment in CO 2 selectivity. The IL decoration method can be an effective approach to eliminate interfacial voids in MMMs, extending the filler selection to a wide range of large-sized fillers.

Estimation of the ionic charge of non-metallic species into an electrical discharge through a web application

NASA Astrophysics Data System (ADS)

Pérez Gutiérrez, B. R.; Vera-Rivera, F. H.; Niño, E. D. V.

2016-08-01

Estimate the ionic charge generated in electrical discharges will allow us to know more accurately the concentration of ions implanted on the surfaces of nonmetallic solids. For this reason, in this research a web application was developed to allow us to calculate the ionic charge generated in an electrical discharge from the experimental parameters established in an ion implantation process performed in the JUPITER (Joint Universal Plasma and Ion Technologies Experimental Reactor) reactor. The estimated value of the ionic charge will be determined from data acquired on an oscilloscope, during startup and shutdown of electrical discharge, which will then be analyzed and processed. The study will provide best developments with regard to the application of ion implantation in various industrial sectors.

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

Synthesis and Properties of Highly Dispersed Ionic Silica–Poly(ethylene oxide) Nanohybrids

PubMed Central

2013-01-01

We report an ionic hybrid based on silica nanoparticles as the anion and amine-terminated poly(ethylene oxide) (PEO) as a cation. The charge on the nanoparticle anion is carried by the surface hydroxyls. SAXS and TEM reveal an exceptional degree of dispersion of the silica in the polymer and high degree of order in both thin film and bulk forms. In addition to better dispersion, the ionic hybrid shows improved flow characteristics compared to silica/PEO mixtures in which the ionic interactions are absent. PMID:23351113

Ionic Liquid Epoxy Resin Monomers

NASA Technical Reports Server (NTRS)

Paley, Mark S. (Inventor)

2013-01-01

Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

Molecular dynamics simulation of the polymer electrolyte poly(ethylene oxide)/LiClO(4). II. Dynamical properties.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2006-12-07

The dynamical properties of the polymer electrolyte poly(ethylene oxide) (PEO)LiClO(4) have been investigated by molecular dynamics simulations. The effect of changing salt concentration and temperature was evaluated on several time correlation functions. Ionic displacements projected on different directions reveal anisotropy in short-time (rattling) and long-time (diffusive) dynamics of Li(+) cations. It is shown that ionic mobility is coupled to the segmental motion of the polymeric chain. Structural relaxation is probed by the intermediate scattering function F(k,t) at several wave vectors. Good agreement was found between calculated and experimental F(k,t) for pure PEO. A remarkable slowing down of polymer relaxation is observed upon addition of the salt. The ionic conductivity estimated by the Nernst-Einstein equation is approximately ten times higher than the actual conductivity calculated by the time correlation function of charge current.

Printable polymer actuators from ionic liquid, soluble polyimide, and ubiquitous carbon materials.

PubMed

Imaizumi, Satoru; Ohtsuki, Yuto; Yasuda, Tomohiro; Kokubo, Hisashi; Watanabe, Masayoshi

2013-07-10

We present here printable high-performance polymer actuators comprising ionic liquid (IL), soluble polyimide, and ubiquitous carbon materials. Polymer electrolytes with high ionic conductivity and reliable mechanical strength are required for high-performance polymer actuators. The developed polymer electrolytes comprised a soluble sulfonated polyimide (SPI) and IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([C2mim][NTf2]), and they exhibited acceptable ionic conductivity up to 1 × 10(-3) S cm(-1) and favorable mechanical properties (elastic modulus >1 × 10(7) Pa). Polymer actuators based on SPI/[C2mim][NTf2] electrolytes were prepared using inexpensive activated carbon (AC) together with highly electron-conducting carbon such as acetylene black (AB), vapor grown carbon fiber (VGCF), and Ketjen black (KB). The resulting polymer actuators have a trilaminar electric double-layer capacitor structure, consisting of a polymer electrolyte layer sandwiched between carbon electrode layers. Displacement, response speed, and durability of the actuators depended on the combination of carbons. Especially the actuators with mixed AC/KB carbon electrodes exhibited relatively large displacement and high-speed response, and they kept 80% of the initial displacement even after more than 5000 cycles. The generated force of the actuators correlated with the elastic modulus of SPI/[C2mim][NTf2] electrolytes. The displacement of the actuators was proportional to the accumulated electric charge in the electrodes, regardless of carbon materials, and agreed well with the previously proposed displacement model.

Manufacturing of ionic polymer-metal composites (IPMCs) that can actuate into complex curves

NASA Astrophysics Data System (ADS)

Stoimenov, Boyko L.; Rossiter, Jonathan M.; Mukai, Toshiharu

2007-04-01

Ionic polymer-metal composites (IPMC) are soft actuators with potential applications in the fields of medicine and biologically inspired robotics. Typically, an IPMC bends with approximately constant curvature when voltage is applied to it. More complex shapes were achieved in the past by pre-shaping the actuator or by segmentation and separate actuation of each segment. There are many applications for which fully independent control of each segment of the IPMC is not required and the use of external wiring is objectionable. In this paper we propose two key elements needed to create an IPMC, which can actuate into a complex curve. The first is a connection between adjacent segments, which enables opposite curvature. This can be achieved by reversing the polarity applied on each side of the IPMC, for example by a through-hole connection. The second key element is a variable curvature segment. The segment is designed to bend with any fraction of its full bending ability under given electrical input by changing the overlap of opposite charge electrodes. We demonstrated the usefulness of these key elements in two devices. One is a bi-stable buckled IPMC beam, also used as a building block in a linear actuator device. The other one is an IPMC, actuating into an S-shaped curve with gradually increasing curvature near the ends. The proposed method of manufacturing holds promise for a wide range of new applications of IPMCs, including applications in which IPMCs are used for sensing.

Synthesis and application of ion-imprinted polymer nanoparticles for the extraction and preconcentration of copper ions in environmental water samples.

PubMed

Roushani, Mahmoud; Abbasi, Shahryar; Khani, Hossein

2015-04-01

Novel Cu(II) ion-imprinted polymers (Cu-IIP) nanoparticles were prepared by using Cu(II) ion-thiosemicarbazide complex as the template molecule and methacrylic acid, ethylene glycol dimethacrylate (EGDMA), and 2,2'azobisisobutyronitrile (AIBN) as the functional monomer, cross-linker, and the radical initiator, respectively. The synthesized polymer nanoparticles were characterized by using infrared spectroscopy (IR), thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopic (SEM) techniques. Some parameters such as pH, weight of the polymer, adsorption time, elution time, eluent type, and eluent volume which affect the extraction efficiency of the polymer were studied. In the proposed method, the maximum sorbent capacity of the ion-imprinted polymer was calculated to be 38.8 mg g(-1). The preconcentration factor, relative standard deviation, and limit of detection of the method were found to be 80, 1.7%, and 0.003 μg mL(-1), respectively. The prepared ion-imprinted polymer nanoparticles have an increased selectivity toward Cu(II) ions over a range of competing metal ions with the same charge and similar ionic radius. The method was applied to the determination of ultra trace levels of Cu2+ in environmental water samples with satisfactory results.

Electro-osmotic flow in coated nanocapillaries: a theoretical investigation.

PubMed

Marini Bettolo Marconi, Umberto; Monteferrante, Michele; Melchionna, Simone

2014-12-14

Motivated by recent experiments, we present a theoretical investigation of how the electro-osmotic flow occurring in a capillary is modified when its charged surfaces are coated with charged polymers. The theoretical treatment is based on a three-dimensional model consisting of a ternary fluid-mixture, representing the solvent and two species for the ions, confined between two parallel charged plates decorated with a fixed array of scatterers representing the polymer coating. The electro-osmotic flow, generated by a constant electric field applied in a direction parallel to the plates, is studied numerically by means of Lattice Boltzmann simulations. In order to gain further understanding we performed a simple theoretical analysis by extending the Stokes-Smoluchowski equation to take into account the porosity induced by the polymers in the region adjacent to the walls. We discuss the nature of the velocity profiles by focusing on the competing effects of the polymer charges and the frictional forces they exert. We show evidence of the flow reduction and of the flow inversion phenomenon when the polymer charge is opposite to the surface charge. By using the density of polymers and the surface charge as control variables, we propose a phase diagram that discriminates the direct and the reversed flow regimes and determines their dependence on the ionic concentration.

Solid polymer electrolyte compositions

DOEpatents

Garbe, James E.; Atanasoski, Radoslav; Hamrock, Steven J.; Le, Dinh Ba

2001-01-01

An electrolyte composition is featured that includes a solid, ionically conductive polymer, organically modified oxide particles that include organic groups covalently bonded to the oxide particles, and an alkali metal salt. The electrolyte composition is free of lithiated zeolite. The invention also features cells that incorporate the electrolyte composition.

Label-free biosensing with functionalized nanopipette probes

PubMed Central

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W.; Pourmand, Nader

2009-01-01

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research. PMID:19264962

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride- co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Zhao, Xiaohui; Shin, Chorong; Baek, Dong-Ho; Choi, Jae-Won; Manuel, James; Heo, Min-Yeong; Ahn, Jou-Hyeon; Nah, Changwoon

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride- co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10 -3 S cm -1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.

(1-Butyl-4-methyl-pyridinium)[Cu(SCN)2]: a coordination polymer and ionic liquid.

PubMed

Spielberg, Eike T; Edengeiser, Eugen; Mallick, Bert; Havenith, Martina; Mudring, Anja-Verena

2014-04-25

The compound (C4C1py)[Cu(SCN)2], (C4C1py = 1-Butyl-4-methyl-pyridinium), which can be obtained from CuSCN and the ionic liquid (C4C1py)(SCN), turns out to be a new organic-inorganic hybrid material as it qualifies both, as a coordination polymer and an ionic liquid. It features linked [Cu(SCN)2](-) units, in which the thiocyanates bridge the copper ions in a μ1,3-fashion. The resulting one-dimensional chains run along the a axis, separated by the C4C1py counterions. Powder X-ray diffraction not only confirms the single-crystal X-ray structure solution but proves the reformation of the coordination polymer from an isotropic melt. However, the materials shows a complex thermal behavior often encountered for ionic liquids such as a strong tendency to form a supercooled melt. At a relatively high cooling rate, glass formation is observed. When heating this melt in differential scanning calorimetry (DSC) and temperature-dependent polarizing optical microscopy (POM), investigations reveal the existence of a less thermodynamically stable crystalline polymorph. Raman measurements conducted at 10 and 100 °C point towards the formation of polyanionic chain fragments in the melt. Solid-state UV/Vis spectroscopy shows a broad absorption band around 18,870 cm(-1) (530 nm) and another strong one below 20,000 cm(-1) (<500 nm). The latter is attributed to the d(Cu(I))→π*(SCN)-MLCT (metal-to-ligand charge transfer) transition within the coordination polymer yielding an energy gap of 2.4 eV. At room temperature and upon irradiation with UV light, the material shows a weak fluorescence band at 15,870 cm(-1) (630 nm) with a quantum efficiency of 0.90(2) % and a lifetime of 131(2) ns. Upon lowering the temperature, the luminescence intensity strongly increases. Simultaneously, the band around 450 nm in the excitation spectrum decreases. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of the influence of polyaspartic acid and polylysine functional groups on the adsorption at the Cr2O3-Aqueous polymer solution interface

NASA Astrophysics Data System (ADS)

Ostolska, Iwona; Wiśniewska, Małgorzata

2014-08-01

Polyamino acids are a group of synthesized polymers obtained by polymerization of a given kind of amino acid monomer. Because of high biodegradability of this class of polymers, they can be used as flocculation or stabilization agents in the environmental aspects. Therefore determination of their influence on the stability of the aqueous suspension of metal oxides is important. An influence of different functional groups of polyamino acids, their molecular weight and concentration on the adsorption at the chromium (III) oxide (Cr2O3)-aqueous solution interface was determined. Experiments were carried out for four values of solution pH varying from 3 to 10 (3, 4, 7.6 and 10, respectively). Two polymers were used: anionic polyaspartic acid (ASP) of 6800 and 27,000 as well as polylysine (LYS) of 4900 and 33,000 molecular weights. Changes of surface charge density of colloidal Cr2O3 in the presence and in the absence of macromolecular substances were determined using potentiometric titration. In these studies the influence of the concentration and molecular weight of the ionic polymers on the pHpzc value was determined. Additionally, due to the lack of appropriate literature data, potentiometric titration of the selected polymers was performed to determine pKa values.

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Optimizing Ionic Electrolytes for Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Fan, Xiaojuan; Hall, Sarah

2009-03-01

Dye-sensitized solar cells DSSCs provide next generation, low cost, and easy fabrication photovoltaic devices based on organic sensitizing molecules, polymer gel electrolyte, and metal oxide semiconductors. One of the key components is the solvent-free ionic liquid electrolyte that has low volatility and high stability. We report a rapid and low cost method to fabricate ionic polymer electrolyte used in DSSCs. Poly(ethylene oxide) (PEO) is blended with imidazolinium salt without any chemical solvent to form a gel electrolyte. Uniform and crack-free porous TiO2 thin films are sensitized by porphrine dye covered by the synthesized gel electrolyte. The fabricated DSSCs are more stable and potentially increase the photo-electricity conversion efficiency.

Applications of positron annihilation spectroscopy in materials research

NASA Technical Reports Server (NTRS)

Singh, Jag J.

1988-01-01

Positron Annihilation Spectroscopy (PAS) has emerged as a powerful technique for research in condensed matter. It has been used extensively in the study of metals, ionic crystals, glasses and polymers. The present review concentrates on applications of positron lifetime measurements for elucidation of the physicochemical structure of polymers.

Quantification of amino acids and peptides in an ionic liquid based aqueous two-phase system by LC-MS analysis.

PubMed

Oppermann, Sebastian; Oppermann, Christina; Böhm, Miriam; Kühl, Toni; Imhof, Diana; Kragl, Udo

2018-04-25

Aqueous two-phase systems (ATPS) occur by the mixture of two polymers or a polymer and an inorganic salt in water. It was shown that not only polymers but also ionic liquids in combination with inorganic cosmotrophic salts are able to build ATPS. Suitable for the formation of ionic liquid-based ATPS systems are hydrophilic water miscible ionic liquids. To understand the driving force for amino acid and peptide distribution in IL-ATPS at different pH values, the ionic liquid Ammoeng 110™ and K 2 HPO 4 have been chosen as a test system. To quantify the concentration of amino acids and peptides in the different phases, liquid chromatography and mass spectrometry (LC-MS) technologies were used. Therefore the peptides and amino acids have been processed with EZ:faast™-Kit from Phenomenex for an easy and reliable quantification method even in complex sample matrices. Partitioning is a surface-dependent phenomenon, investigations were focused on surface-related amino acid respectively peptide properties such as charge and hydrophobicity. Only a very low dependence between the amino acids or peptides hydrophobicity and the partition coefficient was found. Nevertheless, the presented results show that electrostatic respectively ionic interactions between the ionic liquid and the amino acids or peptides have a strong impact on their partitioning behavior.

Efficient barrier for charge injection in polyethylene by silver nanoparticles/plasma polymer stack

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milliere, L.; Makasheva, K., E-mail: kremena.makasheva@laplace.univ-tlse.fr; Laurent, C.

2014-09-22

Charge injection from a metal/insulator contact is a process promoting the formation of space charge in polymeric insulation largely used in thick layers in high voltage equipment. The internal charge perturbs the field distribution and can lead to catastrophic failure either through its electrostatic effects or through energetic processes initiated under charge recombination and/or hot electrons effects. Injection is still ill-described in polymeric insulation due to the complexity of the contact between the polymer chains and the electrodes. Barrier heights derived from the metal work function and the polymer electronic affinity do not provide a good description of the measurementsmore » [Taleb et al., IEEE Trans. Dielectr. Electr. Insul. 20, 311–320 (2013)]. Considering the difficulty to describe the contact properties and the need to prevent charge injection in polymers for high voltage applications, we developed an alternative approach by tailoring the interface properties by the silver nanoparticles (AgNPs)/plasma polymer stack, deposited on the polymer film. Due to their small size, the AgNPs, covered by a very thin film of plasma polymer, act as deep traps for the injected charges thereby stabilizing the interface from the point of view of charge injection. After a quick description of the method for elaborating the nanostructured layer near the contact, it is demonstrated how the AgNPs/plasma polymer stack effectively prevents, in a spectacular way, the formation of bulk space charge.« less

Charge-flow structures as polymeric early-warning fire alarm devices. M.S. Thesis; [metal oxide semiconductors

NASA Technical Reports Server (NTRS)

Sechen, C. M.; Senturia, S. D.

1977-01-01

The charge-flow transistor (CFT) and its applications for fire detection and gas sensing were investigated. The utility of various thin film polymers as possible sensing materials was determined. One polymer, PAPA, showed promise as a relative humidity sensor; two others, PFI and PSB, were found to be particularly suitable for fire detection. The behavior of the charge-flow capacitor, which is basically a parallel-plate capacitor with a polymer-filled gap in the metallic tip electrode, was successfully modeled as an RC transmission line. Prototype charge-flow transistors were fabricated and tested. The effective threshold voltage of this metal oxide semiconductor was found to be dependent on whether surface or bulk conduction in the thin film was dominant. Fire tests with a PFI-coated CFT indicate good sensitivity to smouldering fires.

Effects of anisotropic surface texture on the performance of ionic polymer-metal composite (IPMC)

NASA Astrophysics Data System (ADS)

He, Qingsong; Yu, Min; Ding, Haitao; Guo, Dongjie; Dai, Zhendong

2010-04-01

Ionic polymer metal composite (IPMC), an electrically activated polymer (EAP), has attracted great attention for the excellent properties such as large deformation, light weight, low noise, flexibility and low driving voltages, which makes the material a possible application as artificial muscle if the output force can be increased. To improve the property, we manufactured the Nafion membrane by casting from liquid solution, modified the surface by sandblasting or polishing, and obtained the isotropic and anisotropic surface texture respectively. The microstructure of the Nafion surface and metal electrode, effects of surface texture on the output force and displacement of IPMC were studied. Results show that the output force of IPMC with the anisotropic surface texture is 2~4 times higher than that with the isotropic surface texture without enormous sacrifice of the displacement. The output force may reach to 6.63gf (Sinusoidal 3.5V and 0.1Hz, length 20mm, width 5mm and thickness 0.66mm), which suggest an effective way to improve the mechanical properties of IPMC.

Poly(1-Vinyl-1,2,4-triazolium) Poly(Ionic Liquid)s: Synthesis and the Unique Behavior in Loading Metal Ions.

PubMed

Zhang, Weiyi; Yuan, Jiayin

2016-07-01

Herein, the synthesis of a series of poly(4-alkyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid)s is reported either via straightforward free radical polymerization of their corresponding ionic liquid monomers or via anion metathesis of the polymer precursors bearing halide as counter anion. The ionic liquid monomers are first prepared via N-alkylation reaction of commercially available 1-vinyl-1,2,4-triazole with alkyl iodides, followed by anion metathesis with targeted fluorinated anions. The thermal properties and solubilities of these poly(ionic liquid)s have been systematically investigated. Interestingly, it is found that the poly(4-ethyl-1-vinyl-1,2,4-triazolium) poly(ionic liquid) exhibited an improved loading capacity of transition metal ions in comparison with its imidazolium counterpart. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of MWCNT nanofiller incorporated polymer composite for lithium battery applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pradeepa, P.; Raj, S. Edwin; Selvakumar, K.

Poly (ethyl methacrylate) based polymer electrolyte films were prepared by solution casting technique incorporating multi-walled carbon nanotube (MWCNT) as filler and characterized using XRD and Ac impedance analysis. The electrical conductivity is increased with increasing filler concentration (upto 6wt %), which is attributed to the formation of charge transfer complexes. The maximum ionic conductivity value is found to be 1.171×10{sup −3} Scm{sup −1} at 303K for PEMA (19wt %) -LiClO{sub 4} (8wt %) -MWCNT (6wt %) -PC (67wt %) electrolyte system. The temperature dependent ionic conductivity plot seems to obey Vogel -Tamman-Fulcher relation.

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results inmore » highly aligned, highly crystalline donor-acceptor polymer thin films over large area (41cm 2) and promoted charge transport along both the polymer backbone and the π-π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment.« less

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

PubMed Central

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei; Qu, Ge; Zhang, Fengjiao; Zhao, Xikang; Mei, Jianguo; Zuo, Jian-Min; Shukla, Diwakar; Diao, Ying

2017-01-01

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results in highly aligned, highly crystalline donor–acceptor polymer thin films over large area (>1 cm2) and promoted charge transport along both the polymer backbone and the π–π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment. PMID:28703136

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films

DOE PAGES

Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei; ...

2017-07-13

Solution processable semiconducting polymers have been under intense investigations due to their diverse applications from printed electronics to biomedical devices. However, controlling the macromolecular assembly across length scales during solution coating remains a key challenge, largely due to the disparity in timescales of polymer assembly and high-throughput printing/coating. Herein we propose the concept of dynamic templating to expedite polymer nucleation and the ensuing assembly process, inspired by biomineralization templates capable of surface reconfiguration. Molecular dynamic simulations reveal that surface reconfigurability is key to promoting template–polymer interactions, thereby lowering polymer nucleation barrier. Employing ionic-liquid-based dynamic template during meniscus-guided coating results inmore » highly aligned, highly crystalline donor-acceptor polymer thin films over large area (41cm 2) and promoted charge transport along both the polymer backbone and the π-π stacking direction in field-effect transistors. We further demonstrate that the charge transport anisotropy can be reversed by tuning the degree of polymer backbone alignment.« less

Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

PubMed

Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

2018-03-19

By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Fused filament 3D printing of ionic polymer-metal composites (IPMCs)

NASA Astrophysics Data System (ADS)

Carrico, James D.; Traeden, Nicklaus W.; Aureli, Matteo; Leang, Kam K.

2015-12-01

This paper describes a new three-dimensional (3D) fused filament additive manufacturing (AM) technique in which electroactive polymer filament material is used to build soft active 3D structures, layer by layer. Specifically, the unique actuation and sensing properties of ionic polymer-metal composites (IPMCs) are exploited in 3D printing to create electroactive polymer structures for application in soft robotics and bio-inspired systems. The process begins with extruding a precursor material (non-acid Nafion precursor resin) into a thermoplastic filament for 3D printing. The filament is then used by a custom-designed 3D printer to manufacture the desired soft polymer structures, layer by layer. Since at this stage the 3D-printed samples are not yet electroactive, a chemical functionalization process follows, consisting in hydrolyzing the precursor samples in an aqueous solution of potassium hydroxide and dimethyl sulfoxide. Upon functionalization, metal electrodes are applied on the samples through an electroless plating process, which enables the 3D-printed IPMC structures to be controlled by voltage signals for actuation (or to act as sensors). This innovative AM process is described in detail and the performance of 3D printed IPMC actuators is compared to an IPMC actuator fabricated from commercially available Nafion sheet material. The experimental results show comparable performance between the two types of actuators, demonstrating the potential and feasibility of creating functional 3D-printed IPMCs.

Rational material, interface, and device engineering for high-performance polymer and perovskite solar cells (Presentation Recording)

NASA Astrophysics Data System (ADS)

Jen, Alex K.

2015-10-01

The performance of polymer and hybrid solar cells is also strongly dependent on their efficiency in harvesting light, exciton dissociation, charge transport, and charge collection at the metal/organic/metal oxide or the metal/perovskite/metal oxide interfaces. Our laboratory employs a molecular engineering approach to develop processible low band-gap polymers with high charge carrier mobility that can enhance power conversion efficiency of the single junction solar cells to values as high as ~11%. We have also developed several innovative strategies to modify the interface of bulk-heterojunction devices and create new device architectures to fully explore their potential for solar applications. In this talk, the integrated approach of combining material design, interface, and device engineering to significantly improve the performance of polymer and hybrid perovskite photovoltaic cells will be discussed. Specific emphasis will be placed on the development of low band-gap polymers with reduced reorganizational energy and proper energy levels, formation of optimized morphology of active layer, and minimized interfacial energy barriers using functional conductive surfactants. At the end, several new device architectures and optical engineering strategies to make tandem cells and semitransparent solar cells will be discussed to explore the full promise of polymer and perovskite hybrid solar cells.

Ionic electroactive hybrid transducers

NASA Astrophysics Data System (ADS)

Akle, Barbar J.; Bennett, Matthew D.; Leo, Donald J.

2005-05-01

Ionic electroactive actuators have received considerable attention in the past ten years. Ionic electroactive polymers, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typical types of ionic electroactive polymer transducers include ionic polymers, conducting polymers, and carbon nanotubes. Preliminary research combining multiple types of materials proved to enhance certain transduction properties such as speed of response, maximum strain, or quasi-static actuation. Recently it was demonstrated that ionomer-ionic liquid transducers can operate in air for long periods of time (>250,000 cycles) and showed potential to reduce or eliminate the back-relaxation issue associated with ionomeric polymers. In addition, ionic liquids have higher electrical stability window than those operated with water as the solvent thereby increasing the maximum strain that the actuator can produce. In this work, a new technique developed for plating metal particulates on the surface of ionomeric materials is applied to the development of hybrid transducers that incorporate carbon nanotubes and conducting polymers as electrode materials. The new plating technique, named the direct assembly process, consists of mixing a conducting powder with an ionomer solution. This technique has demonstrated improved response time and strain output as compared to previous methods. Furthermore, the direct assembly process is less costly to implement than traditional impregnation-reduction methods due to less dependence on reducing agents, it requires less time, and is easier to implement than other processes. Electrodes applied using this new technique of mixing RuO2 (surface area 45~65m2/g) particles and Nafion dispersion provided 5x the displacement and 10x the force compared to a transducer made with conventional methods. Furthermore, the study illustrated that the response speed of the transducer is optimized by varying the vol% of metal in the electrode. For RuO2, the optimal loading was approximately 45%. This study shows that carbon nanotubes electrodes have an optimal performance at loadings around 30 vol%, while PANI electrodes are optimized at 95 vol%. Due to low percolation threshold, carbon nanotubes actuators perform better at lower loading than other conducting powders. The addition of nanotubes to the electrode tends to increase both the strain rate and the maximum strain of the hybrid actuator. SWNT/RuO2 hybrid transducer has a strain rate of 2.5%/sec, and a maximum attainable peak-to-peak strain of 9.38% (+/- 2V). SWNT/PANI hybrid also increased both strain and strain rate but not as significant as with RuO2. PANI/RuO2 actuator had an overwhelming back relaxation.

Multivalent Ion Transport in Polymers via Metal-Ligand Coordination

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Schauser, Nicole; Evans, Christopher; Majumdar, Shubhaditya; Segalman, Rachel

Elucidating design rules for multivalent ion conducting polymers is critical for developing novel high-performance materials for electrochemical devices. Herein, we molecularly engineer multivalent ion conducting polymers based on metal-ligand interactions and illustrate that both segmental dynamics and ion coordination kinetics are essential for ion transport through polymers. We present a novel statistical copolymer, poly(ethylene oxide-stat-imidazole glycidyl ether) (i.e., PEO-stat-PIGE), that synergistically combines the structural hierarchy of PEO with the Lewis basicity of tethered imidazole ligands (xIGE = 0.17) required to coordinate a series of transition metal salts containing bis(trifluoromethylsulfonyl)imide anions. Complexes of PEO-stat-PIGE with salts exhibit a nanostructure in which ion-enriched regions alternate with ion-deficient regions, and an ionic conductivity above 10-5 S/cm. Novel normalization schemes that account for ion solvation kinetics are presented to attain a universal scaling relationship for multivalent ion transport in polymers via metal-ligand coordination. AFOSR MURI program under FA9550-12-1.

Carbohydrate gel beads as model probes for quantifying non-ionic and ionic contributions behind the swelling of delignified plant fibers.

PubMed

Karlsson, Rose-Marie Pernilla; Larsson, Per Tomas; Yu, Shun; Pendergraph, Samuel Allen; Pettersson, Torbjörn; Hellwig, Johannes; Wågberg, Lars

2018-06-01

Macroscopic beads of water-based gels consisting of uncharged and partially charged β-(1,4)-d-glucan polymers were developed to be used as a novel model material for studying the water induced swelling of the delignified plant fiber walls. The gel beads were prepared by drop-wise precipitation of solutions of dissolving grade fibers carboxymethylated to different degrees. The internal structure was analyzed using Solid State Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance and Small Angle X-ray Scattering showing that the internal structure could be considered a homogeneous, non-crystalline and molecularly dispersed polymer network. When beads with different charge densities were equilibrated with aqueous solutions of different ionic strengths and/or pH, the change in water uptake followed the trends expected for weak polyelectrolyte gels and the trends found for cellulose-rich fibers. When dried and subsequently immersed in water the beads also showed an irreversible loss of swelling depending on the charge and type of counter-ion which is commonly also found for cellulose-rich fibers. Taken all these results together it is clear that the model cellulose-based beads constitute an excellent tool for studying the fundamentals of swelling of cellulose rich plant fibers, aiding in the elucidation of the different molecular and supramolecular contributions to the swelling. Copyright © 2018 Elsevier Inc. All rights reserved.

Intelligent control of an IPMC actuated manipulator using emotional learning-based controller

NASA Astrophysics Data System (ADS)

Shariati, Azadeh; Meghdari, Ali; Shariati, Parham

2008-08-01

In this research an intelligent emotional learning controller, Takagi- Sugeno- Kang (TSK) is applied to govern the dynamics of a novel Ionic-Polymer Metal Composite (IPMC) actuated manipulator. Ionic-Polymer Metal Composites are active actuators that show very large deformation in existence of low applied voltage. In this research, a new IPMC actuator is considered and applied to a 2-dof miniature manipulator. This manipulator is designed for miniature tasks. The control system consists of a set of neurofuzzy controller whose parameters are adapted according to the emotional learning rules, and a critic with task to assess the present situation resulted from the applied control action in terms of satisfactory achievement of the control goals and provides the emotional signal (the stress). The controller modifies its characteristics so that the critic's stress decreased.

A model for ionic polymer metal composites as sensors

NASA Astrophysics Data System (ADS)

Bonomo, C.; Fortuna, L.; Giannone, P.; Graziani, S.; Strazzeri, S.

2006-06-01

This paper introduces a comprehensive model of sensors based on ionic polymer metal composites (IPMCs) working in air. Significant quantities ruling the sensing properties of IPMC-based sensors are taken into account and the dynamics of the sensors are modelled. A large amount of experimental evidence is given for the excellent agreement between estimations obtained using the proposed model and the observed signals. Furthermore, the effect of sensor scaling is investigated, giving interesting support to the activities involved in the design of sensing devices based on these novel materials. We observed that the need for a wet environment is not a key issue for IPMC-based sensors to work well. This fact allows us to put IPMC-based sensors in a totally different light to the corresponding actuators, showing that sensors do not suffer from the same drawbacks.

NMR study on mechanisms of ionic polymer-metal composites deformation with water content

NASA Astrophysics Data System (ADS)

Zhu, Zicai; Chen, Hualing; Wang, Yongquan; Luo, Bin; Chang, Longfei; Li, Bo; Chen, Luping

2011-10-01

Ionic polymer-metal composites (IPMCs) exhibit a large dynamic bending deformation under exterior electric field. The states and proportions of water within the IPMCs have great effect on the IPMCs deformation properties. This letter investigates the influence of the proportion changes of different types of water on the deformation, which may disclose the working mechanisms of the IPMCs. We give a deformation trend of IPMCs with the reduction of water content firstly. Then by the method of nuclear magnetic resonance, various water types (water bonded to sulfonates, loosely bound water and free water) of IPMCs and their proportions are investigated in the drying process which corresponds to their different deformation states. It is obtained that the deformation properties of IPMCs depend strongly on their water content and the excess free water is responsible for the relaxation deformation.

Improving the light-emitting properties of single-layered polyfluorene light-emitting devices by simple ionic liquid blending

NASA Astrophysics Data System (ADS)

Horike, Shohei; Nagaki, Hiroto; Misaki, Masahiro; Koshiba, Yasuko; Morimoto, Masahiro; Fukushima, Tatsuya; Ishida, Kenji

2018-03-01

This paper describes an evaluation of ionic liquids (ILs) as potential electrolytes for single-layered light-emitting devices with good emission performance. As optoelectronic devices continue to grow in abundance, high-performance light-emitting devices with a single emission layer are becoming increasingly important for low-cost production. We show that a simple technique of osmosing IL into the polymer layer can result in high luminous efficiency and good response times of single-layered light-emitting polymers, even without the additional stacking of charge carrier injection and transport layers. The IL contributions to the light-emission of the polymer are discussed from the perspectives of energy diagrams and of the electric double layers on the electrodes. Our findings enable a faster, cheaper, and lower-in-waste production of light-emitting devices.

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE PAGES

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao; ...

2017-08-21

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wojnarowska, Zaneta; Feng, Hongbo; Fu, Yao

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less

Carbon Redox-Polymer-Gel Hybrid Supercapacitors.

PubMed

Vlad, A; Singh, N; Melinte, S; Gohy, J-F; Ajayan, P M

2016-02-26

Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances.

Particle transport through hydrogels is charge asymmetric.

PubMed

Zhang, Xiaolu; Hansing, Johann; Netz, Roland R; DeRouchey, Jason E

2015-02-03

Transport processes within biological polymer networks, including mucus and the extracellular matrix, play an important role in the human body, where they serve as a filter for the exchange of molecules and nanoparticles. Such polymer networks are complex and heterogeneous hydrogel environments that regulate diffusive processes through finely tuned particle-network interactions. In this work, we present experimental and theoretical studies to examine the role of electrostatics on the basic mechanisms governing the diffusion of charged probe molecules inside model polymer networks. Translational diffusion coefficients are determined by fluorescence correlation spectroscopy measurements for probe molecules in uncharged as well as cationic and anionic polymer solutions. We show that particle transport in the charged hydrogels is highly asymmetric, with diffusion slowed down much more by electrostatic attraction than by repulsion, and that the filtering capability of the gel is sensitive to the solution ionic strength. Brownian dynamics simulations of a simple model are used to examine key parameters, including interaction strength and interaction range within the model networks. Simulations, which are in quantitative agreement with our experiments, reveal the charge asymmetry to be due to the sticking of particles at the vertices of the oppositely charged polymer networks. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Ionic liquids as lubricants of metal-polymer contacts. Preparation and properties of the first dispersions of ionic liquids and nanoparticles in polymers

NASA Astrophysics Data System (ADS)

Sanes Molina, Jose

Room-temperature ionic liquids (ILs) are high performance fluids that stand out because of a wide range of functional properties and exhibit a great potential for engineering applications. Although they have been employed as lubricants in metal-metal, metal-ceramic and ceramic-ceramic contacts, in this thesis we present the first study about the use of ILs as pure lubricants in polymer/steel contacts. The tests have established the efficacy of the ILs to reduce friction coefficient and wear rates in a variety of kinds of contacts, and criogenic to high temperature performance. Novel dispersions of ILs in polymers have been obtained with epoxy resin and thermoplastics as matrix. Therefore, the thermal, mechanical and tribological properties of the materials have studied and are discussed in the present thesis. Furthermore, the contents of ILs in the polymer matrix have been studied in relation to the tribological properties using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Spectrometry (EDS), the wear mechanisms that operated in the contacts were established. The novel dispersions showed a reduction in the friction coefficient and wear in comparison with neat polymers, reaching in some cases a decrease of 79%. In the case of thermoplastics such as polystyrene and polyamide 6, the new dispersions showed a reduction in friction coefficient and wear in the same range as that of the ILs when used as external lubricants in the steel/polymer contact. In addition nanoparticles of zinc oxide were used to obtain polycarbonate based nanohybrids with the purpose of improving the tribological properties. Novel nanohybrids of zinc oxide and modified zinc oxide were obtained. The mechanical, thermal and tribological properties were studied. The results of experiments clearly demonstrated that the use of ILs modifies the shape and size of the ZnO nanoparticles, increasing the tribological properties of the novel nanohybrids. Different techniques such as EDS, Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectrometry (XPS) were used to examine and establish the surface interactions and mechanism that operated between ILs and ZnO. In summary, the results reveal the importance of the processing parameters on the stability of the nature of the anion in the ILs.

A theoretical framework for the study of compression sensing in ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Volpini, Valentina; Bardella, Lorenzo; Rodella, Andrea; Cha, Youngsu; Porfiri, Maurizio

2017-04-01

Ionic Polymer Metal Composites (IPMCs) are electro-responsive materials for sensing and actuation, consisting of an ion-exchange polymeric membrane with ionized units, plated within noble metal electrodes. In this work, we investigate the sensing response of IPMCs that are subject to a through-the-thickness compression, by specializing the continuum model introduced by Cha and Porfiri,1 to this one-dimensional problem. This model modifies the classical Poisson-Nernst-Plank system governing the electrochemistry in the absence of mechanical effects, by accounting for finite deformations underlying the actuation and sensing processes. With the aim of accurately describing the IPMC dynamic compressive behavior, we introduce a spatial asymmetry in the properties of the membrane, which must be accounted for to trigger a sensing response. Then, we determine an analytical solution by applying the singular perturbation theory, and in particular the method of matched asymptotic expansions. This solution shows a good agreement with experimental findings reported in literature.

Aggregation and Charge Behavior of Metallic and Nonmetallic Nanoparticles in the Presence of Competing Similarly-Charged Inorganic Ions

EPA Science Inventory

The influence of competing, similarly charged, inorganic ions on the size and charge behavior of suspended titanium-dioxide (nTiO2), silver (nAg) and fullerene (nC60) nanoparticles (NPs) was investigated. Under pH and ionic conditions similar to natural water bodies, Ca2+ induced...

Healable supramolecular polymers as organic metals.

PubMed

Armao, Joseph J; Maaloum, Mounir; Ellis, Thomas; Fuks, Gad; Rawiso, Michel; Moulin, Emilie; Giuseppone, Nicolas

2014-08-13

Organic materials exhibiting metallic behavior are promising for numerous applications ranging from printed nanocircuits to large area electronics. However, the optimization of electronic conduction in organic metals such as charge-transfer salts or doped conjugated polymers requires high crystallinity, which is detrimental to their processability. To overcome this problem, the combination of the electronic properties of metal-like materials with the mechanical properties of soft self-assembled systems is attractive but necessitates the absence of structural defects in a regular lattice. Here we describe a one-dimensional supramolecular polymer in which photoinduced through-space charge-transfer complexes lead to highly coherent domains with delocalized electronic states displaying metallic behavior. We also reveal that diffusion of supramolecular polarons in the nanowires repairs structural defects thereby improving their conduction. The ability to access metallic properties from mendable self-assemblies extends the current understanding of both fields and opens a wide range of processing techniques for applications in organic electronics.

Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

2016-10-01

A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Electrochemical testing of industrially produced PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, G. B.; Alessandrini, F.; Duan, R. G.; Arzu, A.; Passerini, S.

The present report describes the results of the electrochemical tests performed on polyethyleneoxide-based polymer electrolyte thin films industrially manufactured by blown-extrusion. The polymer electrolyte composition was PEO 20 LiCF 3SO 3: 16.7% γLiAlO 2. The polymer electrolyte film was tested to evaluate the ionic conductivity as well as the interfacial properties with lithium metal anodes. The work was developed within the advanced lithium polymer electrolyte (ALPE) project, an Italian project devoted to the realization of lithium polymer batteries for electric vehicle applications, in collaboration with Union Carbide.

Mechanistic Studies in Friction and Wear of Bulk Materials

NASA Astrophysics Data System (ADS)

Sawyer, W. Gregory; Argibay, Nicolas; Burris, David L.; Krick, Brandon A.

2014-07-01

From the context of a contemporary understanding of the phenomenological origins of friction and wear of materials, we review insightful contributions from recent experimental investigations of three classes of materials that exhibit uniquely contrasting tribological behaviors: metals, polymers, and ionic solids. We focus on the past decade of research by the community to better understand the correlations between environment parameters, materials properties, and tribological behavior in systems of increasingly greater complexity utilizing novel synthesis and in situ experimental techniques. In addition to such review, and a half-century after seminal publications on the subject, we present recently acquired evidence linking anisotropy in friction response with anisotropy in wear behavior of crystalline ionic solids as a function of crystallographic orientation. Although the tribological behaviors of metals, polymers, and ionic solids differ widely, it is increasingly more evident that the mechanistic origins (such as fatigue, corrosion, abrasion, and adhesion) are essentially the same. However, we hope to present a clear and compelling argument favoring the prominent and irreplaceable role of in situ experimental techniques as a bridge between fundamental atomistic and molecular processes and emergent behaviors governing tribological contacts.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, Terje A.; Okamoto, Yoshiyuki; Lee, Hung S.

1989-01-01

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10.sup.-4 to 10.sup.-7 S cm.sup.-1 at room temperature.

Preparation of metallic cation conducting polymers based on sterically hindered phenols containing polymeric systems

DOEpatents

Skotheim, T.A.; Okamoto, Yoshiyuki; Lee, H.S.

1989-11-21

The present invention relates to ion-conducting solvent-free polymeric systems characterized as being cationic single ion conductors. The solvent-free polymer electrolytes comprise a flexible polymer backbone to which is attached a metal salt, such as a lithium, sodium or potassium salt, of a sterically hindered phenol. The solid polymer electrolyte may be prepared either by (1) attaching the hindered phenol directly to a flexible polymeric backbone, followed by neutralization of the phenolic OH's or (2) reacting the hindered phenol with a polymer precursor which is then polymerized to form a flexible polymer having phenolic OH's which are subsequently neutralized. Preferably the hindered phenol-modified polymeric backbone contains a polyether segment. The ionic conductivity of these solvent-free polymer electrolytes has been measured to be in the range of 10[sup [minus]4] to 10[sup [minus]7] S cm[sup [minus]1] at room temperature.

Conductivity through Polymer Electrolytes and Its Implications in Lithium-Ion Batteries: Real-World Application of Periodic Trends

ERIC Educational Resources Information Center

Compton, Owen C.; Egan, Martin; Kanakaraj, Rupa; Higgins, Thomas B.; Nguyen, SonBinh T.

2012-01-01

Periodic conductivity trends are placed in the scope of lithium-ion batteries, where increases in the ionic radii of salt components affect the conductivity of a poly(ethyleneoxide)-based polymer electrolyte. Numerous electrolytes containing varying concentrations and types of metal salts are prepared and evaluated in either one or two laboratory…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pasaribu, Marvin H., E-mail: marvin-shady88@yahoo.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id; Wahyuningrum, Deana, E-mail: deana@chem.itb.ac.id

Lithium ion battery has been currently developed and produced because it has a longer life time, high energycapacity, and the efficient use of lithium ion battery that is suitable for storing electrical energy. However, this battery has some drawbacks such as use liquid electrolytes that are prone to leakage and flammability during the battery charging process in high temperature. In this study, an ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) containing Li{sup +} ions was synthesized and combined with chitosan polymer host as a polymer electrolyte membrane for lithium-ion batteries to solve this problems. This ionic liquid was obtained from the anionmore » metathesis reaction between EMImBr and LiBF4 salt, while EMImBr was synthesized from the reaction between 1-methylimidazole and ethyl bromide utilizing Microwave Assisted Organic Synthesis (MAOS) method. The ionic liquid obtained was characterized by microstructure analysis with using NMR and FTIR spectroscopy. The polymer electrolyte membrane was characterized by analysis functional groups (FTIR), ionic conductivity (EIS), and surface morphology (SEM). The analysis results of ion conductivity by the EIS method showed the increase the ionic conductivity value of membranes from 1.30 × 10{sup −2} S cm{sup −1} for chitosan to 1.30 × 10{sup −2} S cm{sup −1} for chitosan with EMImBF4/Li{sup +}, and this result was supported by analysis the surface morphology (SEM)« less

Immobilization of Anions on Polymer Matrices for Gel Electrolytes with High Conductivity and Stability in Lithium Ion Batteries.

PubMed

Wang, Shih-Hong; Lin, Yong-Yi; Teng, Chiao-Yi; Chen, Yen-Ming; Kuo, Ping-Lin; Lee, Yuh-Lang; Hsieh, Chien-Te; Teng, Hsisheng

2016-06-15

This study reports on a high ionic-conductivity gel polymer electrolyte (GPE), which is supported by a TiO2 nanoparticle-decorated polymer framework comprising poly(acrylonitrile-co-vinyl acetate) blended with poly(methyl methacrylate), i.e. , PAVM: TiO2. High conductivity TiO2 is achieved by causing the PAVM:TiO2 polymer framework to swell in 1 M LiPF6 in carbonate solvent. Raman analysis results demonstrate that the poly(acrylonitrile) (PAN) segments and TiO2 nanoparticles strongly adsorb PF6(-) anions, thereby generating 3D percolative space-charge pathways surrounding the polymer framework for Li(+)-ion transport. The ionic conductivity of TiO2 is nearly 1 order of magnitude higher than that of commercial separator-supported liquid electrolyte (SLE). TiO2 has a high Li(+) transference number (0.7), indicating that most of the PF6(-) anions are stationary, which suppresses PF6(-) decomposition and substantially enlarges the voltage that can be applied to TiO2 (to 6.5 V vs Li/Li(+)). Immobilization of PF6(-) anions also leads to the formation of stable solid-electrolyte interface (SEI) layers in a full-cell graphite|electrolyte|LiFePO4 battery, which exhibits low SEI and overall resistances. The graphite|electrolyte|LiFePO4 battery delivers high capacity of 84 mAh g(-1) even at 20 C and presents 90% and 71% capacity retention after 100 and 1000 charge-discharge cycles, respectively. This study demonstrates a GPE architecture comprising 3D space charge pathways for Li(+) ions and suppresses anion decomposition to improve the stability and lifespan of the resulting LIBs.

Fused filament 3D printing of ionic polymer-metal composites for soft robotics

NASA Astrophysics Data System (ADS)

Carrico, James D.; Leang, Kam K.

2017-04-01

Additive manufacturing techniques are used to create three-dimensional structures with complex shapes and features from polymer and/or metal materials. For example, fused filament three-dimensional (3D) printing utilizes non-electroactive polymers, such as acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA), to build structures and components in a layer-by-layer fashion for a wide variety of applications. Presented here is a summary of recent work on a fused filament 3D-printing technique to create 3D ionic polymer-metal composite (IPMC) structures for applications in soft robotics. The 3D printing technique overcomes some of the limitations of existing manufacturing processes for creating IPMCs, such as limited shapes and sizes and time-consuming manufacturing steps. In the process described, first a precursor material (non-acid Nafion precursor resin) is extruded into a thermoplastic filament for 3D printing. Then, a custom-designed 3D printer is described that utilizes the precursor filament to manufacture custom-shaped structures. Finally, the 3D-printed samples are functionalized by hydrolyzing them in an aqueous solution of potassium hydroxide and dimethyl sulfoxide, followed by application of platinum electrodes. Presented are example 3D-printed single and multi-degree-of-freedom IPMC actuators and characterization results, as well as example soft-robotic devices to demonstrate the potential of this process.

Towards flexible solid-state supercapacitors for smart and wearable electronics.

PubMed

Dubal, Deepak P; Chodankar, Nilesh R; Kim, Do-Heyoung; Gomez-Romero, Pedro

2018-03-21

Flexible solid-state supercapacitors (FSSCs) are frontrunners in energy storage device technology and have attracted extensive attention owing to recent significant breakthroughs in modern wearable electronics. In this study, we review the state-of-the-art advancements in FSSCs to provide new insights on mechanisms, emerging electrode materials, flexible gel electrolytes and novel cell designs. The review begins with a brief introduction on the fundamental understanding of charge storage mechanisms based on the structural properties of electrode materials. The next sections briefly summarise the latest progress in flexible electrodes (i.e., freestanding and substrate-supported, including textile, paper, metal foil/wire and polymer-based substrates) and flexible gel electrolytes (i.e., aqueous, organic, ionic liquids and redox-active gels). Subsequently, a comprehensive summary of FSSC cell designs introduces some emerging electrode materials, including MXenes, metal nitrides, metal-organic frameworks (MOFs), polyoxometalates (POMs) and black phosphorus. Some potential practical applications, such as the development of piezoelectric, photo-, shape-memory, self-healing, electrochromic and integrated sensor-supercapacitors are also discussed. The final section highlights current challenges and future perspectives on research in this thriving field.

Partial Ionic Character beyond the Pauling Paradigm: Metal Nanoparticles

DOE PAGES

Duanmu, Kaining; Truhlar, Donald G.

2014-11-12

A canonical perspective on the chemical bond is the Pauling paradigm: a bond in a molecule containing only identical atoms has no ionic character. However, we show that homonuclear silver clusters have very uneven charge distributions (for example, the C 2v structure of Ag 4 has a larger dipole moment than formaldehyde or acetone), and we show how to predict the charge distribution from coordination numbers and Hirshfeld charges. The new charge model is validated against Kohn–Sham calculations of dipole moments with four approximations for the exchange–correlation functional. We report Kohn–Sham studies of the binding energies of CO on silvermore » monomer and silver clusters containing 2–18 atoms. We also find that an accurate charge model is essential for understanding the site dependence of binding. In particular we find that atoms with more positive charges tend to have higher binding energies, which can be used for guidance in catalyst modeling and design. Furthermore, the nonuniform charge distribution of silver clusters predisposes the site preference of binding of carbon monoxide, and we conclude that nonuniform charge distributions are an important property for understanding binding of metal nanoparticles in general.« less

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

Mayes, Anne M.; Ceder, Gerbrand; Chiang, Yet-Ming; Sadoway, Donald R.; Aydinol, Mehmet K.; Soo, Philip P.; Jang, Young-Il; Huang, Biying

2006-04-11

Solid battery components are provided. A block copolymeric electrolyte is non-crosslinked and non-glassy through the entire range of typical battery service temperatures, that is, through the entire range of at least from about 0.degree. C. to about 70.degree. C. The chains of which the copolymer is made each include at least one ionically-conductive block and at least one second block immiscible with the ionically-conductive block. The chains form an amorphous association and are arranged in an ordered nanostructure including a continuous matrix of amorphous ionically-conductive domains and amorphous second domains that are immiscible with the ionically-conductive domains. A compound is provided that has a formula of Li.sub.xM.sub.yN.sub.zO.sub.2. M and N are each metal atoms or a main group elements, and x, y and z are each numbers from about 0 to about 1. y and z are chosen such that a formal charge on the M.sub.yN.sub.z portion of the compound is (4-x). In certain embodiments, these compounds are used in the cathodes of rechargeable batteries. The present invention also includes methods of predicting the potential utility of metal dichalgogenide compounds for use in lithium intercalation compounds. It also provides methods for processing lithium intercalation oxides with the structure and compositional homogeneity necessary to realize the increased formation energies of said compounds. An article is made of a dimensionally-stable, interpenetrating microstructure of a first phase including a first component and a second phase, immiscible with the first phase, including a second component. The first and second phases define interphase boundaries between them, and at least one particle is positioned between a first phase and a second phase at an interphase boundary. When the first and second phases are electronically-conductive and ionically-conductive polymers, respectively, and the particles are ion host particles, the arrangement is an electrode of a battery.

Underwater energy harvesting from a turbine hosting ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Cellini, Filippo; Pounds, Jason; Peterson, Sean D.; Porfiri, Maurizio

2014-08-01

In this study, we explore the possibility of energy harvesting from fluid flow through a turbine hosting ionic polymer metal composites (IPMCs). Specifically, IPMC harvesters are embedded in the blades of a small-scale vertical axis water turbine to convert flow kinetics into electrical power via low-frequency flow-induced IPMC deformations. An in-house fabricated Savonius-Darrieus hybrid active turbine with three IPMCs is tested in a laboratory water tunnel to estimate the energy harvesting capabilities of the device as a function of the shunting electrical load. The turbine is shown to harvest a few nanowatt from a mean flow of 0.43\\;m\\;{{s}^{-1}} for shunting resistances in the range 100-1000\\;\\Omega . To establish a first understanding of the energy harvesting device, we propose a quasi-static hydroelastic model for the bending of the IPMCs and we utilize a black-box model to study their electromechanical response.

Ionic polymer-metal composite torsional sensor: physics-based modeling and experimental validation

NASA Astrophysics Data System (ADS)

Aidi Sharif, Montassar; Lei, Hong; Khalid Al-Rubaiai, Mohammed; Tan, Xiaobo

2018-07-01

Ionic polymer-metal composites (IPMCs) have intrinsic sensing and actuation properties. Typical IPMC sensors are in the shape of beams and only respond to stimuli acting along beam-bending directions. Rod or tube-shaped IPMCs have been explored as omnidirectional bending actuators or sensors. In this paper, physics-based modeling is studied for a tubular IPMC sensor under pure torsional stimulus. The Poisson–Nernst–Planck model is used to describe the fundamental physics within the IPMC, where it is hypothesized that the anion concentration is coupled to the sum of shear strains induced by the torsional stimulus. Finite element simulation is conducted to solve for the torsional sensing response, where some of the key parameters are identified based on experimental measurements using an artificial neural network. Additional experimental results suggest that the proposed model is able to capture the torsional sensing dynamics for different amplitudes and rates of the torsional stimulus.

A resonant force sensor based on ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Bonomo, Claudia; Fortuna, Luigi; Giannone, Pietro; Graziani, Salvatore; Strazzeri, Salvatore

2008-02-01

In this paper a novel force sensor, based on ionic polymer metal composites (IPMCs), is presented. The system has DC sensing capabilities and is able to work in the range of a few millinewtons. IPMCs are emerging materials used to realize motion actuators and sensors. An IPMC strip is activated in a beam fixed/simply-supported configuration. The beam is tightened at the simply-supported end by a force. This influences the natural resonant frequency of the beam; the value of the resonant frequency is used in the proposed system to estimate the force applied in the axial direction. The performance of the system based on the IPMC material has proved to be comparable with that of sensors based on other sensing mechanisms. This suggests the possibility of using this class of polymeric devices to realize PMEMS (plastic micro electrical mechanical systems) sensors.

Alkaline polymer electrolyte fuel cells stably working at 80 °C

NASA Astrophysics Data System (ADS)

Peng, Hanqing; Li, Qihao; Hu, Meixue; Xiao, Li; Lu, Juntao; Zhuang, Lin

2018-06-01

Alkaline polymer electrolyte fuel cells are a new class of polymer electrolyte fuel cells that fundamentally enables the use of nonprecious metal catalysts. The cell performance mostly relies on the quality of alkaline polymer electrolytes, including the ionic conductivity and the chemical/mechanical stability. For a long time, alkaline polymer electrolytes are thought to be too weak in stability to allow the fuel cell to be operated at elevated temperatures, e.g., above 60 °C. In the present work, we report a progress in the state-of-the-art alkaline polymer electrolyte fuel cell technology. By using a newly developed alkaline polymer electrolyte, quaternary ammonia poly (N-methyl-piperidine-co-p-terphenyl), which simultaneously possesses high ionic conductivity and excellent chemical/mechanical stability, the fuel cell can now be stably operated at 80 °C with high power density. The peak power density reaches ca. 1.5 W/cm2 at 80 °C with Pt/C catalysts used in both the anode and the cathode. The cell works stably in a period of study over 100 h.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces.

PubMed

Limmer, David T

2015-12-18

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces

NASA Astrophysics Data System (ADS)

Limmer, David T.

2015-12-01

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

PubMed

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

Morphology of Block Copolymer Electrolytes: A Numerical Self-Consistent Field Theory Study

NASA Astrophysics Data System (ADS)

Hou, Kevin; Qin, Jian

Engineering the morphology of ion-containing block copolymers is imperative for the optimization of their charge-transport and mechanical properties. Existing experiments have demonstrated that the addition of ions has a dramatic effect on the morphology and thermodynamic behavior of these structured electrolytes. We have developed an efficient, symmetry-adapted algorithm to calculate the ionic interactions in the SCFT for ion-containing polymers. We present the results of a numerical SCFT study examining how dielectric heterogeneity, ion concentration, and ion solvation affect morphology, domain spacing, ion distribution, and polymer density profiles. Particular attention is given to the detailed morphological analysis of the bicontinuous gyroidal phase, as well as the relevance of the aforementioned results to ionic conductivity.

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE PAGES

Guardado, Jesus O.; Salleo, Alberto

2017-07-17

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guardado, Jesus O.; Salleo, Alberto

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Carbon Redox-Polymer-Gel Hybrid Supercapacitors

PubMed Central

Vlad, A.; Singh, N.; Melinte, S.; Gohy, J.-F.; Ajayan, P.M.

2016-01-01

Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances. PMID:26917470

Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

PubMed

Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

2018-01-31

Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

NASA Astrophysics Data System (ADS)

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-12-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

PubMed

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

2015-12-04

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

PubMed Central

Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

2015-01-01

Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries. PMID:26634644

Method for conversion of carbohydrate polymers to value-added chemical products

DOEpatents

Zhang, Zongchao C [Norwood, NJ; Brown, Heather M [Kennewick, WA; Su, Yu [Richland, WA

2012-02-07

Methods are described for conversion of carbohydrate polymers in ionic liquids, including cellulose, that yield value-added chemicals including, e.g., glucose and 5-hydroxylmethylfurfural (HMF) at temperatures below 120.degree. C. Catalyst compositions that include various mixed metal halides are described that are selective for specified products with yields, e.g., of up to about 56% in a single step process.

Polymeric Ionic Networks with High Charge Density: Solid-like Electrolytes in Lithium Metal Batteries

DOE PAGES

Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; ...

2015-11-02

Polymerized ionic networks (PINs) with six ion pairs per repeating unit are synthesized by nucleophilic-substitution-mediated polymerization or radical polymerization of monomers bearing six 1-vinylimidazolium cations. PIN-based solid-like electrolytes show good ionic conductivities (up to 5.32 × 10 -3 S cm -1 at 22 °C), wide electrochemical stability windows (up to 5.6 V), and good interfacial compatibility with the electrodes.

Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

NASA Astrophysics Data System (ADS)

Liu, Libin; Wu, Xiwen; Li, Tianduo

2014-03-01

A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application

NASA Astrophysics Data System (ADS)

Parameswaran, V.; Nallamuthu, N.; Devendran, P.; Nagarajan, E. R.; Manikandan, A.

2017-06-01

Solid polymer blend electrolytes are widely studied due to their extensive applications particularly in electrochemical devices. Blending polymer makes the thermal stability, higher mechanical strength and inorganic salt provide ionic charge carrier to enhance the conductivity. In these studies, 50% polyvinyl alcohol (PVA), 50% poly (N-vinyl pyrrolidone) (PVP) and 2.5% L-Asparagine mixed with different ratio of the Ammonium bromide (NH4Br), have been synthesized using solution casting technique. The prepared PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films have been characterized by various analytical methods such as FT-IR, XRD, impedance spectroscopy, TG-DSC and scanning electron microscopy. FT-IR, XRD and TG/DSC analysis revealed the structural and thermal behavior of the complex formation between PVA/PVP/L-Asparagine/doped-NH4Br. The ionic conductivity and the dielectric properties of PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films were examined using impedance analysis. The highest ionic conductivity was found to be 2.34×10-4 S cm-1 for the m.wt. composition of 50%PVA:50%PVP:2.5%L-Asparagine:doped 0.15 g NH4Br at ambient temperature. Solid state proton battery is fabricated and the observed open circuit voltage is 1.1 V and its performance has been studied.

Determining equilibrium osmolarity in poly(ethylene glycol)/chondrotin sulfate gels mimicking articular cartilage.

PubMed

Sircar, S; Aisenbrey, E; Bryant, S J; Bortz, D M

2015-01-07

We present an experimentally guided, multi-phase, multi-species polyelectrolyte gel model to make qualitative predictions on the equilibrium electro-chemical properties of articular cartilage. The mixture theory consists of two different types of polymers: poly(ethylene gylcol) (PEG), chondrotin sulfate (ChS), water (acting as solvent) and several different ions: H(+), Na(+), Cl(-). The polymer chains have covalent cross-links whose effect on the swelling kinetics is modeled via Doi rubber elasticity theory. Numerical studies on equilibrium polymer volume fraction and net osmolarity (difference in the solute concentration across the gel) show a complex interplay between ionic bath concentrations, pH, cross-link fraction and the average charge per monomer. Generally speaking, swelling is aided due to a higher average charge per monomer (or a higher particle fraction of ChS, the charged component of the polymer), low solute concentration in the bath, a high pH or a low cross-link fraction. A peculiar case arises at higher values of cross-link fraction, where it is observed that increasing the average charge per monomer leads to gel deswelling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Polymer Micelles with Cross-Linked Polyanion Core for Delivery of a Cationic Drug Doxorubicin

PubMed Central

Kim, Jong Oh; Kabanov, Alexander V.; Bronich, Tatiana K.

2009-01-01

Polymer micelles with cross-linked ionic cores were prepared by using block ionomer complexes of poly(ethylene oxide)-b-poly(methacrylic acid) (PEO-b-PMA) copolymer and divalent metal cations as templates. Doxorubicin (DOX), an anthracycline anticancer drug, was successfully incorporated into the ionic cores of such micelles via electrostatic interactions. A substantial drug loading level (up to 50 w/w %) was achieved and it was strongly dependent on the structure of the cross-linked micelles and pH. The drug-loaded micelles were stable in aqueous dispersions exhibiting no aggregation or precipitation for a prolonged period of time. The DOX-loaded polymer micelles exhibited noticeable pH-sensitive behavior with accelerated release of DOX in acidic environment due to the protonation of carboxylic groups in the cores of the micelles. The attempt to protect the DOX-loaded core with the polycationic substances resulted in the decrease of loading efficacy and had a slight effect on the release characteristics of the micelles. The DOX-loaded polymer micelles exhibited a potent cytotoxicity against human A2780 ovarian carcinoma cells. These results point to a potential of novel polymer micelles with cross-linked ionic cores to be attractive carriers for the delivery of DOX. PMID:19386272

Developing a polymeric sensor to monitor intracellular conditions

NASA Astrophysics Data System (ADS)

Mudarri, Timothy C.; Leo, Donald J.; Wood, Brett C.; Shires, Peter K.

2004-07-01

Ionic electroactive polymers have been developed as mechanical sensors or actuators, taking advantage of the electromechanical coupling of the materials. This research attempts to take advantage of the chemomechanical and chemoelectrical coupling by characterizing the transient response as the polymer undergoes an ion exchange, thus using the polymer for ionic sensing. Nafion is a biocompatible material, and an implantable polymeric ion sensor which has applications in the biomedical field for bone healing research. An ion sensor and a strain gauge could determine the effects of motion allowed at the fracture site, thus improving rehabilitation procedures for bone fractures. The charge sensitivity of the material and the capacitance of the material were analyzed to determine the transient response. Both measures indicate a change when immersed in ionic salt solutions. It is demonstrated that measuring the capacitance is the best indicator of an ion exchange. Relative to a flat response in deionized water (+/-2%), the capacitance of the polymer exhibits an exponential decay of ~25% of its peak when placed in a salt solution. A linear correlation between the time constant of the decay and the ionic size of the exchanging ion was developed that could reasonably predict a diffusing ion. Tests using an energy dispersive spectrometer (EDS) indicate that 90% of the exchange occurs in the first 20 minutes, shown by both capacitance decay and an atomic level scan. The diffusion rate time constant was found to within 0.3% of the capacitance time constant, confirming the ability of capacitance to measure ion exchange.

Fused electron deficient semiconducting polymers for air stable electron transport.

PubMed

Onwubiko, Ada; Yue, Wan; Jellett, Cameron; Xiao, Mingfei; Chen, Hung-Yang; Ravva, Mahesh Kumar; Hanifi, David A; Knall, Astrid-Caroline; Purushothaman, Balaji; Nikolka, Mark; Flores, Jean-Charles; Salleo, Alberto; Bredas, Jean-Luc; Sirringhaus, Henning; Hayoz, Pascal; McCulloch, Iain

2018-01-29

Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare polymers where double bonds lock-in a rigid backbone conformation, thus eliminating free rotation along the conjugated backbone. This polymerisation route requires neither organometallic monomers nor transition metal catalysts and offers a reliable design strategy to facilitate delocalisation of frontier molecular orbitals, elimination of energetic disorder arising from rotational torsion and allowing closer interchain electronic coupling. These characteristics are desirable for high charge carrier mobilities. Our polymers with a high electron affinity display long wavelength NIR absorption with air stable electron transport in solution processed organic thin film transistors.

Capacitance of the Double Layer Formed at the Metal/Ionic-Conductor Interface: How Large Can It Be?

NASA Astrophysics Data System (ADS)

Skinner, Brian; Loth, M. S.; Shklovskii, B. I.

2010-03-01

The capacitance of the double layer formed at a metal/ionic-conductor interface can be remarkably large, so that the apparent width of the double layer is as small as 0.3 Å. Mean-field theories fail to explain such large capacitance. We propose an alternate theory of the ionic double layer which allows for the binding of discrete ions to their image charges in the metal. We show that at small voltages the capacitance of the double layer is limited only by the weak dipole-dipole repulsion between bound ions, and is therefore very large. At large voltages the depletion of bound ions from one of the capacitor electrodes triggers a collapse of the capacitance to the mean-field value.

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V.; West, William C.; Kindler, Andrew; Smart, Marshall C.

2013-01-01

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes.

PubMed

Fong, Kara D; Wang, Tiesheng; Kim, Hyun-Kyung; Kumar, R Vasant; Smoukov, Stoyan K

2017-09-08

Conducting polymers show great promise as supercapacitor materials due to their high theoretical specific capacitance, low cost, toughness, and flexibility. Poor ion mobility, however, can render active material more than a few tens of nanometers from the surface inaccessible for charge storage, limiting performance. Here, we use semi-interpenetrating networks (sIPNs) of a pseudocapacitive polymer in an ionically conductive polymer matrix to decrease ion diffusion length scales and make virtually all of the active material accessible for charge storage. Our freestanding poly(3,4-ethylenedioxythiophene)/poly(ethylene oxide) (PEDOT/PEO) sIPN films yield simultaneous improvements in three crucial elements of supercapacitor performance: specific capacitance (182 F/g, a 70% increase over that of neat PEDOT), cycling stability (97.5% capacitance retention after 3000 cycles), and flexibility (the electrodes bend to a <200 μm radius of curvature without breaking). Our simple and controllable sIPN fabrication process presents a framework to develop a range of polymer-based interpenetrated materials for high-performance energy storage technologies.

Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

NASA Technical Reports Server (NTRS)

Thompson, David W.

1993-01-01

Lanthanide metal ions were incorporated into the polyimide derived from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 1,3-bis(aminophenoxy) benzene (APB) in an attempt to produce molecular level metal-polymer composites. The lanthanide series of metal ions (including aluminum, scandium, and yttrium) provide discrete and stable metal ions in the 3+ oxidation state. Throughout the series there is a uniform variation in ionic size ranging from 50 pm for aluminum to a maximum of 103.4 pm for cerium and gradually decreasing again to 84.8 pm for lutetium. The high charge-to-size ratio for these ions as well as the ability to obtain large coordination numbers makes them excellent candidates for interacting with the polymer substructure. The distinct lack of solubility of simple lanthanide salts such as the acetates and halides has made it difficult to obtain metal ions distributed in the polymer framework as discrete ions or metal complexes rather than microcomposites of metal clusters. (Lanthanum nitrates are quite soluble, but the presence of the strongly oxidizing nitrate ion leads to serious degradation of the polymer upon thermal curing. This work was successful at extending the range of soluble metals salts by using chelating agents derived from the beta-diketones dipivaloylmethane, dibenzoylmethane, trifluoroacetylacetone, and hexafluoroacetylacetone. Metal acetates which are insoluble in dimethylacetamide dissolve readily in the presence of the diketones. Addition of the polyimide yields a homogeneous resin which is then cast into a clear film. Upon curing clear films were obtained with the dibenzoylmethane and trifluoroacetylacetone ligands. The dipavaloylmethane precipitates the metal during the film casting process, and hexafluoroacetylacetone gives cured films which are deformed and brittle. These clear films are being evaluated for the effect of the metal ions on the coefficient of thermal expansion, resistance to atomic oxygen, and on selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

Competition between excluded-volume and electrostatic interactions for nanogel swelling: effects of the counterion valence and nanogel charge.

PubMed

Adroher-Benítez, Irene; Martín-Molina, Alberto; Ahualli, Silvia; Quesada-Pérez, Manuel; Odriozola, Gerardo; Moncho-Jordá, Arturo

2017-03-01

In this work the equilibrium distribution of ions around a thermo-responsive charged nanogel particle in an electrolyte aqueous suspension is explored using coarse-grained Monte Carlo computer simulations and the Ornstein-Zernike integral equation theory. We explicitly consider the ionic size in both methods and study the interplay between electrostatic and excluded-volume effects for swollen and shrunken nanogels, monovalent and trivalent counterions, and for two different nanogel charges. We find good quantitative agreement between the ionic density profiles obtained using both methods when the excluded repulsive force exerted by the cross-linked polymer network is taken into account. For the shrunken conformation, the electrostatic repulsion between the charged groups provokes a heterogeneous polymer density profile, leading to a nanogel structure with an internal low density hole surrounded by a dense corona. The results show that the excluded-volume repulsion strongly hinders the ion permeation for shrunken nanogels, where volume exclusion is able to significantly reduce the concentration of counterions in the more dense regions of the nanogel. In general, we demonstrate that the thermosensitive behaviour of nanogels, as well as their internal structure, is strongly influenced by the valence of the counterions and also by the charge of the particles. On the one hand, an increase of the counterion valence moves the swelling transition to lower temperatures, and induces a major structuring of the charged monomers into internal and external layers around the crown for shrunken nanogels. On the other hand, increasing the particle charge shifts the swelling curve to larger values of the effective radius of the nanogel.

Recent Advances in Fast Ion Conducting Materials and Devices - Proceedings of the 2nd Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Liu, Qingguo; Chen, Liquan

The Table of Contents for the book is as follows: * Preface * Invited Papers * Recent Trends in Solid State Ionics * Theoretical Aspects of Fast Ion Conduction in Solids * Chemical Bonding and Intercalation Processes in Framework Structures * Extra-Large Near-Electrode Regions and Diffusion Length on the Solid Electrolyte-Electrode Interface as Studied by Photo-EMF Method * Frequency Response of Glasses * XPS Studies on Ion Conducting Glasses * Characterization of New Ambient Temperature Lithium Polymer-Electrolyte * Recent Development of Polymer Electrolytes: Solid State Voltammetry in Polymer Electrolytes * Secondary Solid State Batteries: From Material Properties to Commercial Development * Silver Vanadium Oxide Bronze and its Applications for Electrochemical Devices * Study on β''-Alumina Solid Electrolyte and β Battery in SIC * Materials for Solid Oxide Fuel Cells * Processing for Super Superionic Ceramics * Hydrogen Production Using Oxide Ionic or Protonic Conductor * Ionically Conductive Sulfide-Based Lithium Glasses * Relation of Conductivity to Structure and Structural Relaxation in Ion-Conducting Glasses * The Mechanism of Ionic Conductivity in Glass * The Role of Synthesis and Structure in Solid State Ionics - Electrodes to Superconductors * Electrochromism in Spin-Coated Thin Films from Peroxo-Poly tungstate Solutions * Electrochemical Studies on High Tc Superconductors * Multivalence Fast Ionic Conductors - Montmorillonites * Contributed Papers * Volt-Ampere Characteristics and Interface Charge Transport in Solid Electrolytes * Internal Friction of Silver Chalcogenides * Thermal Expansion of Ionic and Superionic Solids * Improvement of PEO-LiCF3SO3 Complex Electrolytes Using Additives * Ionic Conductivity of Modified Poly (Methoxy Polyethylene Glycol Methacrylate) s-Lithium Salt Complexes * Solid Polymer Electrolytes of Crosslinked Polyethylene Glycol and Lithium Salts * Single Ionic Conductors Prepared by in Situ Polymerization of Methacrylic Acid Alkali Metal Salts in Polyethylene Oxide * Redox Behavior of Alkyl Viologens in Ion Conductive Polymer Solid * Ionic Conductivity of Interpenetrating Polymer Networks Containing LiClO4 * Electrochemical Behaviors of Porphyrins Incorporated into Solid Polymer Electrolytes * Lithium Ion Conducting Polymer Electrolytes * Electrochemical Synthesis of Polyaniline Thin Film * Electrochemical Aspect of Polyaniline Electrode in Aqueous Electrolyte * Mixed Cation Effect in Epoxy Resin - PEO-IPN Containing Perchlorate Salts * Conductivity, Raman and IR Studies on the Doped PEO-PPG Polymer Blends * Proton Conducting Polymeric Electrolytes from Poly (Ethyleneoxide) System * Surface Structure of Polymer Solid Ionic Conductors Based on Segmented Polyether Polyurethaneureas * Study on Addition Products of LiI and Diethylene Glycol etc. * Solid State Rechargeable Battery Using Paper Form Copper Ion Conductive Solid Electrolyte * Characterization of Electrode/Electrolyte Interfaces in Battery Li/PVAC-Li-Mont./Li1+xV3O8 by AC Impedance Method * Investigation on Reversibility of Vanadium Oxide Cathode Materials in Solid-State Battery * Preparation and Characterization of Silver Boromolybdate Solid State Batteries * The Electric Properties of the Trinary Cathode Material and its Application in Magnisium Solid State Cell * Electrical Properties and Phase Relation of Na2Mo0.1S0.9O4 Doped with Rare Earth Sulfate * New Electrochemical Probe for Rapid Determination of Silicon Concentration in Hot Metals * A New Theoretical EMF Expression for SOx(x = 2, 3) Sensors Based on Na2SO4 Solid Electrolyte * Evaluation of the Electrochemical SOx(x = 2, 3) Sensor with a Tubular Nasicon Electrolyte * The Response Time of a Modified Oxygen Sensor Using Zirconia Electrolyte * Preparation, Characteristics and Sintering Behavior of MgO-PSZ Powder * Reaction between La0.9MnO3 and Yttria Doped Zirconia * Development of the Extended-Life Oxygen Sensor of Caβ''-Al2O3 * Caβ''-Al2O3 Ultra-Low Oxygen Sensor * Measurement of Sulfur Concentration with Zirconia-Based Electrolyte Cell in Molten Iron * Influence of SO2 on the Conductivity of Calcia Stabilized Zirconia * Reactions between YSZ and La1-xCaxMnO3 as a Cathode for SOFC * Preparation and Electrical Properties of Lithium β''-Alumina * Influence of Lithia Content on Properties of β''-Alumina Ceramics * Electrical Conductivity of Solid Solutions of Na2SO4 with Na2SeO4 * Effect of Antagonist XO42- = MoO42- and WO42- Ion Substitution on the Electrical Conductivity of Li2SO4 : Li2CO3 Eutectic System * Study on the Electrical Properties and Structure of Multicrystal Materials Li5+xGe1-xCrxV3O12 * Preliminary Study on Synthesis of Silver Zirconium Silicophosphates by Sol - Gel Process * Sodium Ion Conduction in Iron(III) Exchanged Y Zeolite * Electrical Properties of V5O9+x (x = 0, 1) and CuxV5O9.1 * Electrical Properties of the Tetragonal ZrO2 Stabilized with CeO2, CeO2 + Gd2O3 * Study of Preparation and Ionic Conduction of Doped Barium Cerate Perovskite * Preparing Fine Alumina Powder by Homogeneous Precipitation Method for Fabricating β''-Al2O3 * Amorphous Lithium Ion Conductors in Li2S-SiS2-LiBO2 System * Mixed Alkali Effect of Glass Super Ionic Conductors * Electrical Property and Phase Separation, Crystallization Behavior of A Cu+-Conducting Glass * Investigation of Phase Separation and Crystallization for 0.4CuI-0.3 Cu2O-0.3P2O5 Glass by SEM and XRD * Study on the Lithium Solid Electrolytes of Li3N-LiX(X = F, Cl, Br, I)-B2O3 Ternary Systems * Synthesis and Characterization of the Li2O : P2O5 : WO3 Glasses * The Electrochromic Properties of Electrodeposited Ni-O Films in Nonaqueous Electrolytes * All Solid-State WO3-MnO2 Based Electrochromic Window * Electrochromism in Nickel Oxide Films * E S R of X-Irradiated Melt Quenched Li2SO4 * Mixed-Alkali Effect in the Li2O-Na2O-TeO2 Glass System * Electrical and Thermal Studies on Silver Tellurite Glasses * Late Entries (Invited Papers) * Proton Conducting Polymers * Light Scattering Studies on Superionic Conductor YSZ * Development of Thin Film Surface Modified Solid State Electrochemical Gas Sensors * Author Index * List of Participants

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Tracking Ionic Rearrangements and Interpreting Dynamic Volumetric Changes in Two-Dimensional Metal Carbide Supercapacitors: A Molecular Dynamics Simulation Study.

PubMed

Xu, Kui; Lin, Zifeng; Merlet, Céline; Taberna, Pierre-Louis; Miao, Ling; Jiang, Jianjun; Simon, Patrice

2017-12-06

We present a molecular dynamics simulation study achieved on two-dimensional (2D) Ti 3 C 2 T x MXenes in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] + [TFSI] - ) electrolyte. Our simulations reproduce the different patterns of volumetric change observed experimentally for both the negative and positive electrodes. The analysis of ionic fluxes and structure rearrangements in the 2D material provide an atomic scale insight into the charge and discharge processes in the layer pore and confirm the existence of two different charge-storage mechanisms at the negative and positive electrodes. The ionic number variation and the structure rearrangement contribute to the dynamic volumetric changes of both electrodes: negative electrode expansion and positive electrode contraction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel hybrid metal-organic framework-polymeric monolith for solid-phase microextraction.

PubMed

Lin, Chen-Lan; Lirio, Stephen; Chen, Ya-Ting; Lin, Chia-Her; Huang, Hsi-Ya

2014-03-17

This study describes the fabrication of a novel hybrid metal-organic framework- organic polymer (MOF-polymer) for use as a stationary phase in fritless solid-phase microextraction (SPME) for validating analytical methods. The MOF-polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium-based ionic liquid as porogenic solvent followed by microwave-assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF-polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF-organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63-96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

NASA Astrophysics Data System (ADS)

Pandian, Amaresh Samuthira; Chen, X. Chelsea; Chen, Jihua; Lokitz, Bradley S.; Ruther, Rose E.; Yang, Guang; Lou, Kun; Nanda, Jagjit; Delnick, Frank M.; Dudney, Nancy J.

2018-06-01

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtain composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. A remarkable Li+ transference number of 0.79 is discovered for the composite electrolyte.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Do Membranes Dream of Electric Tubes? Advanced Membranes Using Carbon Nanotube - Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

de Lannoy, Charles-Francois Pedro Claude Karolek Ghislain

Membrane technologies represent an energy efficient, effective solution for treating municipal and commercial waters/wastewaters. Membranes are predominantly polymer-based and despite steady advances in polymeric materials, they continue to suffer from operational problems including biofouling and breakages. This work addresses these two disparate problems by developing novel CNT-polymer nanocomposite materials that contain variously functionalized carbon nanotubes (fCNTs) in low quantities (<0.5wt%). Several strategies have been employed to achieve highly functional CNT-polymer nanocomposite membranes including blend mixing, ionic charge association, and covalent cross-linking with monomer and oligomer constituents. These CNT-polymer nanocomposite membranes were compared to traditional polymer membranes across various properties including increased Young's Modulus, changes in surface hydrophilicity, fine control over molecular weight cut-off and flux, and surface electrical conductivity. Membranes with high surface electrical conductivity were further tested for their anti-biofouling properties. Finally, CNT stability and polymer compatibility were evaluated throughout membrane manufacture, use, and cleaning. The incorporation of CNTs mixed in bulk phase and linked through ionic associations in polymer matrices showed significant (50%) increases in Young's modulus for certain CNT functionalizations and derivatization percent. Membranes formed with high surface electrical conductivity demonstrated almost complete resistance to biofouling (> 95%) in long-term bacterially challenged experiments. CNTs and polymer mixtures that lacked covalent or ionic bonds were susceptible to significant (up to 10%) loss of CNTs during membrane non-solvent gelation and aggressive chemical cleaning treatment. Functionalized carbon nanotubes endow polymer membranes with their unique strength and electrically conductive properties. These added properties were demonstrated to greatly improve membrane operational efficiency and membrane longevity. CNT-polymer nanocomposite membranes offer low-energy, high-efficiency, and long-lifetime alternatives to traditional polymer membranes. With further advances in polymeric nanomaterials, membrane technology has the potential for wide applicability across many fields outside of water filtration and desalination.

Lattice model of ionic liquid confined by metal electrodes

NASA Astrophysics Data System (ADS)

Girotto, Matheus; Malossi, Rodrigo M.; dos Santos, Alexandre P.; Levin, Yan

2018-05-01

We study, using Monte Carlo simulations, the density profiles and differential capacitance of ionic liquids confined by metal electrodes. To compute the electrostatic energy, we use the recently developed approach based on periodic Green's functions. The method also allows us to easily calculate the induced charge on the electrodes permitting an efficient implementation of simulations in a constant electrostatic potential ensemble. To speed up the simulations further, we model the ionic liquid as a lattice Coulomb gas and precalculate the interaction potential between the ions. We show that the lattice model captures the transition between camel-shaped and bell-shaped capacitance curves—the latter characteristic of ionic liquids (strong coupling limit) and the former of electrolytes (weak coupling). We observe the appearance of a second peak in the differential capacitance at ≈0.5 V for 2:1 ionic liquids, as the packing fraction is increased. Finally, we show that ionic size asymmetry decreases substantially the capacitance maximum, when all other parameters are kept fixed.

Contribution of capillary electrophoresis to an integrated vision of humic substances size and charge characterizations

DOE Office of Scientific and Technical Information (OSTI.GOV)

D'Orlye, Fanny; Reiller, Pascal E.

2014-02-15

The physicochemical properties of three different humic substances (HS) are probed using capillary zone electrophoresis in alkaline carbonate buffers, pH 10. Special attention is drawn to the impact of the electrolyte ionic strength and counter-ion nature, chosen within the alkali-metal series, on HS electrophoretic mobility. Taylor-Aris dispersion analysis provides insights into the hydrodynamic radius (R-H) distributions of HS. The smallest characterized entities are of nano-metric dimensions, showing neither ionic strength- nor alkali-metal-induced aggregation. These results are compared with the entities evidenced in dynamic light scattering measurements, the size of which is two order of magnitude higher, ca. 100 nm. Themore » extended Onsager model provides a reasonable description of measured electrophoretic mobilities in the ionic strength range 1-50 mM, thus allowing the estimation of limiting mobilities and ionic charge numbers for the different HS samples. An unexpected HS electrophoretic mobility increase (in absolute value) is observed in the order Li{sup +} ≤ Na{sup +} ≤ K{sup +} ≤ Cs{sup +} and discussed either in terms of retarding forces or in terms of ion-ion interactions. (authors)« less

Electrical research on solar cells and photovoltaic materials

NASA Technical Reports Server (NTRS)

Orehotsky, J.

1984-01-01

The flat-plate solar cell array program which increases the service lifetime of the photovoltaic modules used for terrestrial energy applications is discussed. The current-voltage response characteristics of the solar cells encapsulated in the modules degrade with service time and this degradation places a limitation on the useful lifetime of the modules. The most desirable flat-plate array system involves solar cells consisting of highly polarizable materials with similar electrochemical potentials where the cells are encapsulated in polymers in which ionic concentrations and mobilities are negligibly small. Another possible mechanism limiting the service lifetime of the photovoltaic modules is the gradual loss of the electrical insulation characteristics of the polymer pottant due to water absorption or due to polymer degradation from light or heat effects. The mechanical properties of various polymer pottant materials and of electrochemical corrosion mechanisms in solar cell material are as follows: (1) electrical and ionic resistivity; (2) water absorption kinetics and water solubility limits; and (3) corrosion characterization of various metallization systems used in solar cell construction.

Ion imprinted polymeric nanoparticles for selective separation and sensitive determination of zinc ions in different matrices

NASA Astrophysics Data System (ADS)

Shamsipur, Mojtaba; Rajabi, Hamid Reza; Pourmortazavi, Seied Mahdi; Roushani, Mahmoud

2014-01-01

Preparation of Zn2+ ion-imprinted polymer (Zn-IIP) nanoparticles is presented in this report. The Zn-IIP nanoparticles are prepared by dissolving stoichiometric amounts of zinc nitrate and selected chelating ligand, 3,5,7,20,40-pentahydroxyflavone, in 15 mL ethanol-acetonitrile (2:1; v/v) mixture as a porogen solvent in the presence of ethylene glycol-dimethacrylate (EGDMA) as cross-linking, methacrylic acid (MAA) as functional monomer, and 2,2-azobisisobutyronitrile (AIBN) as initiator. After polymerization, Cavities in the polymer particles corresponding to the Zn2+ ions were created by leaching the polymer in HCl aqueous solution. The synthesized IIPs were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal analysis techniques. Also, the pH range for rebinding of Zn2+ ion on the IIP and equilibrium binding time were optimized, using flame atomic absorption spectrometry. In selectivity study, it was found that imprinting results increased affinity of the material toward Zn2+ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for six times without any significant decrease in polymer binding affinities. Finally, the prepared sorbent was successfully applied to the selective recognition and determination of zinc ion in different real samples.

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on-off" ratio in electrochemical activity at elevated temperatures. Overall, solution pH and conductivity were altered by an order of magnitude and device performance (ability to store charge) decreased by over 70%. After demonstration of a model responsive electrolyte in an aqueous system, ionic liquid (IL) based electrolytes were developed as a means of controlling the electrochemical performance in the non-aqueous environments that batteries, specifically Li-ion, require. Here, two systems were developed: (1) an electrolyte comprising poly(ethylene oxide) (PEO), the IL, [EMIM][BF4], and a lithium salt and (2) an electrolyte comprising poly(benzyl methacrylate) (PBzMA), the IL, [EMIM][TFSI], and a lithium salt. In each system, the polymer-IL phase separation inhibited device operation at elevated temperatures. For the PEO/IL electrolyte, the thermally induced liquid-liquid phase separation was shown to decrease the ionic conductivity, thereby affecting the concentration of ions at the electrode. Additionally, an increasing charge transfer resistance associated with the phase separated polymer coating the porous electrode was shown to limit electrochemical activity significantly. For the PBzMA/IL electrolyte, the solid-liquid phase separation did not show a change in conductivity, but did cause a drastic increase in charge transfer resistance, effectively shutting off Li-ion battery operation at high temperatures. Such responsive mixtures provide a transformative approach to regulating electrochemical processes, which is necessary to achieve inherently safe operation in large format energy storage with EDLCs, supercapacitors and Li-ion batteries.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

Role of charge separation mechanism and local disorder at hybrid solar cell interfaces

NASA Astrophysics Data System (ADS)

Ehrenreich, Philipp; Pfadler, Thomas; Paquin, Francis; Dion-Bertrand, Laura-Isabelle; Paré-Labrosse, Olivier; Silva, Carlos; Weickert, Jonas; Schmidt-Mende, Lukas

2015-01-01

Dye-sensitized metal oxide polymer hybrid solar cells deliver a promising basis in organic solar cell development due to many conceptual advantages. Since the power conversion efficiency is still in a noncompetitive state, it has to be understood how the photocurrent contribution can be maximized (i.e., which dye-polymer properties are most beneficial for efficient charge generation in hybrid solar cells). By the comparison of three model systems for hybrid solar cells with Ti O2 -dye-polymer interfaces, this paper was aimed at elucidating the role of the exact mechanism of charge generation. In the exciton dissociation (ED) case, an exciton that is generated in the polymer is split at the dye-polymer interface. Alternatively, this exciton can be transferred to the dye via an energy transfer (ET), upon which charge separation occurs between dye and Ti O2 . For comparison, the third case is included in which the high lowest unoccupied molecular orbital of the dye does not allow exciton separation or ET from the dye to the polymer, so that the dye only is responsible for charge generation. To separate effects owing to differences in energy levels of the involved materials from the impact of local order and disorder in the polymer close to the interface, this paper further comprises a detailed analysis of the polymer crystallinity based on the H-aggregate model. While the massive impact of the poly(3-hexylthiophene) crystallinity on device function has been outlined for bare metal oxide-polymer interfaces, it has not been considered for hybrid solar cells with dye-sensitized Ti O2 . The results presented here indicate that all dye molecules in general influence the polymer morphology, which has to be taken into account for future optimization of hybrid solar cells. Apart from that, it can be suggested that ED on the polymer needs an additional driving force to work efficiently; thus, energy transfer seems to be currently the most promising strategy to increase the polymer photocurrent contribution.

A review on robotic fish enabled by ionic polymer-metal composite artificial muscles.

PubMed

Chen, Zheng

2017-01-01

A novel actuating material, which is lightweight, soft, and capable of generating large flapping motion under electrical stimuli, is highly desirable to build energy-efficient and maneuverable bio-inspired underwater robots. Ionic polymer-metal composites are important category of electroactive polymers, since they can generate large bending motions under low actuation voltages. IPMCs are ideal artificial muscles for small-scale and bio-inspired robots. This paper takes a system perspective to review the recent work on IPMC-enabled underwater robots, from modeling, fabrication, and bio-inspired design perspectives. First, a physics-based and control-oriented model of IPMC actuator will be reviewed. Second, a bio-inspired robotic fish propelled by IPMC caudal fin will be presented and a steady-state speed model of the fish will be demonstrated. Third, a novel fabrication process for 3D actuating membrane will be introduced and a bio-inspired robotic manta ray propelled by two IPMC pectoral fins will be demonstrated. Fourth, a 2D maneuverable robotic fish propelled by multiple IPMC fin will be presented. Last, advantages and challenges of using IPMC artificial muscles in bio-inspired robots will be concluded.

Polymer stability and function for electrolyte and mixed conductor applications

NASA Astrophysics Data System (ADS)

Hammond, Paula; Davis, Nicole; Liu, David; Amanchukwu, Chibueze; Lewis, Nate; Shao-Horn, Yang

2015-03-01

Polymers exhibit a number of attractive properties as solid state electrolytes for electrochemical energy devices, including the light weight, flexibility, low cost and adaptive transport properties that polymeric materials can exhibit. For a number of applications, mixed ionic and electronic conducting materials are of interest to achieve transport of electrons and holes or ions within an electrode or at the electrode-electrolyte interface (e.g. aqueous batteries, solar water splitting, lithium battery electrode). Using layer-by-layer assembly, a mode of alternating adsorption of charged or complementary hydrogen bonding group, we can design composite thin films that contain bicontinuous networks of electronically and ionically conducting polymers. We have found that manipulation of salt concentration and the use of divalent ions during assembly can significantly enhance the number of free acid anions available for ion hopping. Unfortunately, for certain electrochemical applications, polymer stability is a true challenge. In separate studies, we have been investigating macromolecular systems that may provide acceptable ion transport properties, but withstand the harsh oxidative environment of lithium air systems. An investigation of different polymeric materials commonly examined for electrochemical applications provides insight into polymer design for these kinds of environments. NSF Center for Chemical Innovation, NDSEG Fellowship and Samsung Corporation.

Porous Ionic Polymers as a Robust and Efficient Platform for Capture and Chemical Fixation of Atmospheric CO2.

PubMed

Sun, Qi; Jin, Yingyin; Aguila, Briana; Meng, Xiangju; Ma, Shengqian; Xiao, Feng-Shou

2017-03-22

Direct use of atmospheric CO 2 as a C 1 source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO 2 are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO 2 , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO 2 , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO 2 uptake capacity of the PIPs facilitates the enrichment of CO 2 molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO 2 can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO 2 . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Rajeev

2017-02-14

Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes frommore » the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.« less

Simulation of Ionic Aggregation and Ion Dynamics in Model Ionomers

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie L.

2012-02-01

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. A single-ion conducting polymer electrolyte would be safer and have higher efficiency than the currently-used liquid electrolytes. However, to date ionomeric materials do not have sufficiently high conductivities for practical application. This is most likely because the ions tend to form aggregates, leading to slow ion transport. A key question is therefore how molecular structure affects the ionic aggregation and ion dynamics. To probe these structure-property relationships, we have performed molecular simulations of a set of recently synthesized poly(ethylene-co-acrylic acid) copolymers and ionomers, with a focus on the morphology of the ionic aggregates. The ionomers have a precise, constant spacing of charged groups, making them ideal for direct comparisons with simulations. Ab initio calculations give insight into the expected coordination of cations with fragments of the ionomers. All-atom molecular dynamics (MD) simulations of the ionomer melt show aggregation of the ionic groups into extended string-like clusters. An extensive set of coarse-grained molecular dynamics simulations extend the results to longer times and larger length scales. The structure factors calculated from the MD simulations compare favorably with x-ray scattering data. Furthermore, the simulations give a detailed picture of the sizes, shapes, and composition of the ionic aggregates, and how they depend on polymer architecture. Implications for ion transport will be discussed. [Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Soft Ionic Electroactive Polymer Actuators with Tunable Non-Linear Angular Deformation

PubMed Central

Hong, Wangyujue; Almomani, Abdallah; Chen, Yuanfen; Jamshidi, Reihaneh; Montazami, Reza

2017-01-01

The most rational approach to fabricate soft robotics is the implementation of soft actuators. Conventional soft electromechanical actuators exhibit linear or circular deformation, based on their design. This study presents the use of conjugated polymers, Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) to locally vary ion permeability of the ionic electroactive polymer actuators and manipulate ion motion through means of structural design to realize intrinsic angular deformation. Such angular deformations are closer to biomimetic systems and have potential applications in bio-robotics. Electrochemical studies reveal that the mechanism of actuation is mainly associated with the charging of electric double layer (EDL) capacitors by ion accumulation and the PEDOT:PSS layer’s expansion by ion interchange and penetration. Dependence of actuator deformation on structural design is studied experimentally and conclusions are verified by analytical and finite element method modeling. The results suggest that the ion-material interactions are considerably dominated by the design of the drop-cast PEDOT:PSS on Nafion. PMID:28773036

Soft Ionic Electroactive Polymer Actuators with Tunable Non-Linear Angular Deformation.

PubMed

Hong, Wangyujue; Almomani, Abdallah; Chen, Yuanfen; Jamshidi, Reihaneh; Montazami, Reza

2017-06-21

The most rational approach to fabricate soft robotics is the implementation of soft actuators. Conventional soft electromechanical actuators exhibit linear or circular deformation, based on their design. This study presents the use of conjugated polymers, Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) to locally vary ion permeability of the ionic electroactive polymer actuators and manipulate ion motion through means of structural design to realize intrinsic angular deformation. Such angular deformations are closer to biomimetic systems and have potential applications in bio-robotics. Electrochemical studies reveal that the mechanism of actuation is mainly associated with the charging of electric double layer (EDL) capacitors by ion accumulation and the PEDOT:PSS layer's expansion by ion interchange and penetration. Dependence of actuator deformation on structural design is studied experimentally and conclusions are verified by analytical and finite element method modeling. The results suggest that the ion-material interactions are considerably dominated by the design of the drop-cast PEDOT:PSS on Nafion.

Adsorption of surfactants and polymers at interfaces

NASA Astrophysics Data System (ADS)

Rojas, Orlando Jose

Surface tension and high-resolution laser light scattering experiments were used to investigate the adsorption of isomeric sugar-based surfactants at the air/liquid interface in terms of surfactant surface packing and rheology. Soluble monolayers of submicellar surfactant solutions exhibited a relatively viscous behavior. It was also proved that light scattering of high-frequency thermally-induced capillary waves can be utilized to study surfactant exchange between the surface and the bulk solution. Such analysis revealed the existence of a diffusional relaxation mechanism. A procedure based on XPS was developed for quantification, on an absolute basis, of polymer adsorption on mica and Langmuir-Blodgett cellulose films. The adsorption of cationic polyelectrolytes on negatively-charged solid surfaces was highly dependent on the polymer ionicity. It was found that the adsorption process is driven by electrostatic mechanisms. Charge overcompensation (or charge reversal) of mica occurred after adsorption of polyelectrolytes of ca. 50% charge density, or higher. It was demonstrated that low-charge-density polyelectrolytes adsorb on solid surfaces with an extended configuration dominated by loops and tails. In this case the extent of adsorption is limited by steric constraints. The conformation of the polyelectrolyte in the adsorbed layer is dramatically affected by the presence of salts or surfactants in aqueous solution. The phenomena which occur upon increasing the ionic strength are consistent with the screening of the electrostatic attraction between polyelectrolyte segments and solid surface. This situation leads to polyelectrolyte desorption accompanied by both an increase in the layer thickness and the range of the steric force. Adsorbed polyelectrolytes and oppositely charged surfactants readily associate at the solid/liquid interface. Such association induces polyelectrolyte desorption at a surfactant concentration which depends on the polyelectrolyte charge density. In practical systems the adsorption phenomena were found to be far more complex. Electrostatic and hydrogen bonding interactions play a major role in the adsorption of cationic polyelectrolytes on cellulosic substrates. Cationic and underivatized guar gum macromolecules form complexes with fines and dissolved and colloidal carbohydrates which are then retained on the cellulose fibers. The extent of the adsorption and association depends on the charge and nature of all the components present in pulp suspensions.

Safe Direct Current Stimulation to Expand Capabilities of Neural Prostheses

PubMed Central

Fridman, Gene Y.; Della Santina, Charles C.

2014-01-01

While effective in treating some neurological disorders, neuroelectric prostheses are fundamentally limited because they must employ charge-balanced stimuli to avoid evolution of irreversible electrochemical reactions and their byproducts at the interface between metal electrodes and body fluids. Charge-balancing is typically achieved by using brief biphasic alternating current (AC) pulses, which typically excite nearby neural tissues but cannot efficiently inhibit them. In contrast, direct current (DC) applied via a metal electrode in contact with body fluids can excite, inhibit and modulate sensitivity of neurons; however, DC stimulation is biologically unsafe because it violates “safe charge injection” limits that have long been considered unavoidable constraints. In this report, we describe the design and fabrication of a safe DC stimulator (SDCS) that overcomes this constraint. The SCDS drives DC ionic current into target tissue via salt-bridge micropipette electrodes by switching valves in phase with AC square waves applied to metal electrodes contained within the device. This approach achieves DC ionic flow through tissue while still adhering to charge-balancing constraints at each electrode-saline interface. We show the SDCS’s ability to both inhibit and excite neural activity to achieve improved dynamic range during prosthetic stimulation of the vestibular part of the inner ear in chinchillas. PMID:23476007

Polyelectrolyte multilayer capsules as vehicles with tunable permeability.

PubMed

Antipov, Alexei A; Sukhorukov, Gleb B

2004-11-29

This review is devoted to a novel type of polymer micro- and nanocapsules. The shell of the capsule is fabricated by alternate adsorption of oppositely charged polyelectrolytes (PEs) onto the surface of colloidal particles. Cores of different nature (organic or inorganic) with size varied from 0.1 to 10 mum can be used for templating such PE capsules. The shell thickness can be tuned in nanometer range by assembling of defined number of PE layers. The permeability of capsules depends on the pH, ionic strength, solvent, polymer composition, and shell thickness; it can be controlled and varied over wide range of substances regarding their molecular weight and charge. Including functional polymers into capsule wall, such as weak PEs or thermosensitive polymers, makes the capsule permeability sensitive to correspondent external stimuli. Permeability of the capsules is of essential interest in diverse areas related to exploitation of systems with controlled and sustained release properties. The envisaged applications of such capsules/vesicles cover biotechnology, medicine, catalysis, food industry, etc.

Selective and Responsive Nanopore-Filled Membranes

DTIC Science & Technology

2011-03-14

Materials Science and Engineering Poster Competition 15. Chen, H.; Elabd, Y.A. Ionic Liquid Polymers: Electrospinning and Solution Properties. Fall...hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project include (1) synthesizing stimuli...on polymer-polymer nanocomposites of hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project

Prominent roles of impurities in ionic liquid for catalytic conversion of carbohydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Haibo; Brown, Heather M.; Holladay, Johnathan E.

2012-02-07

In the last two decades, ionic liquids have emerged as new and versatile solvents, and many of them are also catalysts for a broad range of catalytic reactions. Certain ionic liquids have been found to possess the unique capability of dissolving cellulosic biomass. The potential of such ionic liquids as solvent to enable catalytic conversion of cellulosic polymers was first explored and demonstrated by Zhao et al. This field of research has since experienced a rapid growth. Most ionic liquids have negligible vapor pressure and excellent thermal stability over a wide temperature range. For example, ionic liquids composed of 1-ethyl-3-methylimidazoliummore » (EMIM+) cation and Cl- anion was reported to be stable up to 285 C, while salts of the same cation with other anions such as BF4- and PF6- are thermally stable above 380 C under inert atmosphere. It is well known that presence of impurities in ionic liquids typically causes changes in physical properties, e.g. decreasing in melting point and viscosity. Addition of Lewis acidic metal chlorides, e.g. AlCl3 to 1-alkyl-3-methylimidazolium chloride, [AMIM]Cl, is an exothermic reaction and considerably reduces the melting point by forming [AMIM]AlCl4 or [AMIM]Al2Cl7 that are also ionic liquids but have much lower melting point than the parent [AMIM]Cl. While most early research on catalysis of ionic liquids involving metallohalide anions were typically conducted from stoichiometric ratio of such anions to organic cations, e.g. [AMIM]+, the use of pure ionic liquids only as a solvent to carry out catalysis by a catalytic amount of a metal halide as catalyst truly displayed the solvent property of such ionic liquids.4 In such reaction systems, catalytic amounts of metal halides were used to catalyze the conversion of glucose and cellulose.4,11,12 The metal chloride catalyst concentration was in the order of 10-3 M. The presence of another metal chloride in the ionic liquids, even in the order of 10-5 M concentration was found to bring a dramatic synergistic effect. Therefore, the catalytic performance of the metal halide catalyst for the conversion of carbohydrates in the ionic liquid systems is highly sensitive to the presence of impurities. This work presents findings on the role of impurities that were present in some commercially available ionic liquids used for the conversion of the cellulose.« less

Relaxation and transport properties of Li+ ion conducting biocompatible material for battery application

NASA Astrophysics Data System (ADS)

Hegde, Shreedatta; Ravindrachary, V.; Praveena, S. D.; Guruswamy, B.; Sagar, Rohan N.; Sanjeev, Ganesh

2018-04-01

Solid polymer electrolyte based on lithium chloride doped Poly (vinyl) alcohol composites are prepared by solution casting method. XRD results show that the crystallinity of the polymer interrupted upon LiCl doping and amorphous nature increases with dopant concentration. Impedance analysis revealed that conductivity of PVA increases with doping level and maximum ionic conductivity is observed to be 6.69 × 10-3 S/cm for 15 wt% LiCl doped PVA composite at 353K. Wagner's polarization technique has been followed to calculate ion transport number for high conducting electrolyte and transient study confirmed the presence of single charge species within the polymer electrolyte.

Dynamics in Complex Coacervates

NASA Astrophysics Data System (ADS)

Perry, Sarah

Understanding the dynamics of a material provides detailed information about the self-assembly, structure, and intermolecular interactions present in a material. While rheological methods have long been used for the characterization of complex coacervate-based materials, it remains a challenge to predict the dynamics for a new system of materials. Furthermore, most work reports only qualitative trends exist as to how parameters such as charge stoichiometry, ionic strength, and polymer chain length impact self-assembly and material dynamics, and there is little information on the effects of polymer architecture or the organization of charges within a polymer. We seek to link thermodynamic studies of coacervation phase behavior with material dynamics through a carefully-controlled, systematic study of coacervate linear viscoelasticity for different polymer chemistries. We couple various methods of characterizing the dynamics of polymer-based complex coacervates, including the time-salt superposition methods developed first by Spruijt and coworkers to establish a more mechanistic strategy for comparing the material dynamics and linear viscoelasticity of different systems. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

Metal-chelating active packaging film enhances lysozyme inhibition of Listeria monocytogenes.

PubMed

Roman, Maxine J; Decker, Eric A; Goddard, Julie M

2014-07-01

Several studies have demonstrated that metal chelators enhance the antimicrobial activity of lysozyme. This study examined the effect of metal-chelating active packaging film on the antimicrobial activity of lysozyme against Listeria monocytogenes. Polypropylene films were surface modified by photoinitiated graft polymerization of acrylic acid (PP-g-PAA) from the food contact surface of the films to impart chelating activity based on electrostatic interactions. PP-g-PAA exhibited a carboxylic acid density of 113 ± 5.4 nmol cm(-2) and an iron chelating activity of 53.7 ± 9.8 nmol cm(-2). The antimicrobial interaction of lysozyme and PP-g-PAA depended on growth media composition. PP-g-PAA hindered lysozyme activity at low ionic strength (2.48-log increase at 64.4 mM total ionic strength) and enhanced lysozyme activity at moderate ionic strength (5.22-log reduction at 120 mM total ionic strength). These data support the hypothesis that at neutral pH, synergy between carboxylate metal-chelating films (pKa(bulk) 6.45) and lysozyme (pI 11.35) is optimal in solutions of moderate to high ionic strength to minimize undesirable charge interactions, such as lysozyme absorption onto film. These findings suggest that active packaging, which chelates metal ions based on ligand-specific interactions, in contrast to electrostatic interactions, may improve antimicrobial synergy. This work demonstrates the potential application of metal-chelating active packaging films to enhance the antimicrobial activity of membrane-disrupting antimicrobials, such as lysozyme.

Ionic-liquid materials for the electrochemical challenges of the future.

PubMed

Armand, Michel; Endres, Frank; MacFarlane, Douglas R; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Ionic-liquid materials for the electrochemical challenges of the future

NASA Astrophysics Data System (ADS)

Armand, Michel; Endres, Frank; Macfarlane, Douglas R.; Ohno, Hiroyuki; Scrosati, Bruno

2009-08-01

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

Protein Corona Composition of Superparamagnetic Iron Oxide Nanoparticles with Various Physico-Chemical Properties and Coatings

NASA Astrophysics Data System (ADS)

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Salaklang, Jatuporn; Hofmann, Heinrich

2014-05-01

Because of their biocompatibility and unique magnetic properties, superparamagnetic iron oxide nanoparticles NPs (SPIONs) are recognized as some of the most prominent agents for theranostic applications. Thus, understanding the interaction of SPIONs with biological systems is important for their safe design and efficient applications. In this study, SPIONs were coated with 2 different polymers: polyvinyl alcohol polymer (PVA) and dextran. The obtained NPs with different surface charges (positive, neutral, and negative) were used as a model study of the effect of surface charges and surface polymer materials on protein adsorption using a magnetic separator. We found that the PVA-coated SPIONs with negative and neutral surface charge adsorbed more serum proteins than the dextran-coated SPIONs, which resulted in higher blood circulation time for PVA-coated NPs than the dextran-coated ones. Highly abundant proteins such as serum albumin, serotransferrin, prothrombin, alpha-fetoprotein, and kininogen-1 were commonly found on both PVA- and dextran-coated SPIONs. By increasing the ionic strength, soft- and hard-corona proteins were observed on 3 types of PVA-SPIONs. However, the tightly bound proteins were observed only on negatively charged PVA-coated SPIONs after the strong protein elution.

Platinated DNA oligonucleotides: new probes forming ultrastable conjugates with graphene oxide

NASA Astrophysics Data System (ADS)

Wang, Feng; Liu, Juewen

2014-05-01

Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials.Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials. Electronic supplementary information (ESI) available: Methods, additional gels, kinetics, mass spectrum. See DOI: 10.1039/c4nr00867g

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Facile and scalable fabrication of polymer-ceramic composite electrolyte with high ceramic loadings

DOE PAGES

Pandian, Amaresh Samuthira; Chen, Xi Chelsea; Chen, Jihua; ...

2018-04-24

Solid state electrolytes are a promising alternative to flammable liquid electrolytes for high-energy lithium battery applications. In this work polymer-ceramic composite electrolyte membrane with high ceramic loading (greater than 60 vol%) is fabricated using a model polymer electrolyte poly(ethylene oxide) + lithium trifluoromethane sulfonate and a lithium-conducting ceramic powder. The effects of processing methods, choice of plasticizer and varying composition on ionic conductivity of the composite electrolyte are thoroughly investigated. The physical, structural and thermal properties of the composites are exhaustively characterized. We demonstrate that aqueous spray coating followed by hot pressing is a scalable and inexpensive technique to obtainmore » composite membranes that are amazingly dense and uniform. The ionic conductivity of composites fabricated using this protocol is at least one order of magnitude higher than those made by dry milling and solution casting. The introduction of tetraethylene glycol dimethyl ether further increases the ionic conductivity. The composite electrolyte's interfacial compatibility with metallic lithium and good cyclability is verified by constructing lithium symmetrical cells. As a result, a remarkable Li + transference number of 0.79 is discovered for the composite electrolyte.« less

Ionic Liquids in Polymer Design: From Energy to Health

DTIC Science & Technology

2016-10-19

SECURITY CLASSIFICATION OF: ACS Symposium: Ionic Liquids in Polymer Design: From Energy to Health at Fall 2015 ACS Meeting in Boston, MA The...combination of ionic liquids and polymers has emerged as an active field of exploration in polymer science, where new materials have be realized for...2016 Final Report: Ionic Liquids in Polymer Design: From Energy to Health The views, opinions and/or findings contained in this report are those of

Study of microstructural characterization and ionic conductivity of a chemical-covalent polyether-siloxane hybrid doped with LiClO4.

PubMed

Liang, Wuu-Jyh; Chen, Ying-Pin; Wu, Chien-Pang; Kuo, Ping-Lin

2005-12-29

The chemical-covalent polyether-siloxane hybrids (EDS) doped with various amounts of LiClO4 salt were characterized by FT-IR, DSC, TGA, and solid-state NMR spectra as well as impedance measurements. These observations indicate that different types of complexes by the interactions of Li+ and ClO4- ions are formed within the hybrid host, and the formation of transient cross-links between Li+ ions and ether oxygens results in the increase in T(g) of polyether segments and the decrease in thermal stability of hybrid electrolyte. Initially a cation complexation dominated by the oxirane-cleaved cross-link site and PEO block is present, and after the salt-doped level of O/Li+ = 20, the complexation through the PPO block becomes more prominent. Moreover, a significant degree of ionic association is examined in the polymer-salt complexes at higher salt uptakes. A VTF-like temperature dependence of ionic conductivity is observed in all of the investigated salt concentrations, implying that the diffusion of charge carrier is assisted by the segmental motions of the polymer chains. The behavior of ion transport in these hybrid electrolytes is further correlated with the interactions between ions and polymer host.

Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

PubMed

Zhang, Zhiyue; Maji, Samarendra; da Fonseca Antunes, André B; De Rycke, Riet; Hoogenboom, Richard; De Geest, Bruno G

2016-06-13

Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks.

PubMed

Vaid, Thomas P; Kelley, Steven P; Rogers, Robin D

2017-07-01

Traditional synthesis of metal-organic frameworks (MOFs) involves the reaction of a metal-containing precursor with an organic linker in an organic solvent at an elevated temperature, in what is termed a 'solvothermal' reaction. More recently, many examples have been reported of MOF synthesis in ionic liquids (ILs), rather than an organic solvent, in 'ionothermal' reactions. The high concentration of both cations and anions in an ionic liquid allows for the formation of new MOF structures in which the IL cation or anion or both are incorporated into the MOF. Most commonly, the IL cation is included in the open cavities of the MOF, countering the anionic charge of the MOF framework itself and acting as a template around which the MOF structure forms. Ionic liquids can also serve other structure-directing roles, for example, when an IL containing a single enantiomer of a chiral anion leads to a homochiral MOF, even though the IL anion is not itself incorporated into the MOF. A comprehensive review of ionothermal syntheses of MOFs, and the structure-directing effects of the ILs, is given.

Ionic-Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?

PubMed

Kerner, Ross A; Rand, Barry P

2018-01-04

Ambipolar transport describes the nonequilibrium, coupled motion of positively and negatively charged particles to ensure that internal electric fields remain small. It is commonly invoked in the semiconductor community where the motion of excess electrons and holes drift and diffuse together. However, the concept of ambipolar transport is not limited to semiconductor physics. Materials scientists working on ion conducting ceramics understand ambipolar transport dictates the coupled diffusion of ions and the rate is limited by the ion with the lowest diffusion coefficient. In this Perspective, we review a third application of ambipolar transport relevant to mixed ionic-electronic conducting materials for which the motion of ions is expected to be coupled to electronic carriers. In this unique situation, the ambipolar diffusion model has been successful at explaining the photoenhanced diffusion of metal ions in chalcogenide glasses and other properties of materials. Recent examples of photoenhanced phenomena in metal halide perovskites are discussed and indicate that mixed ionic-electronic ambipolar transport is similarly important for a deep understanding of these emerging materials.

Ultrahigh Ionic Conduction in Water-Stable Close-Packed Metal-Carbonate Frameworks.

PubMed

Manna, Biplab; Desai, Aamod V; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K

2017-08-21

Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion-conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10 -2 S cm -1 along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Chemoelectronic circuits based on metal nanoparticles

NASA Astrophysics Data System (ADS)

Yan, Yong; Warren, Scott C.; Fuller, Patrick; Grzybowski, Bartosz A.

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the ‘jammed’ nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems ‘chemoelectronic’. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also ‘green’, in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Chemoelectronic circuits based on metal nanoparticles.

PubMed

Yan, Yong; Warren, Scott C; Fuller, Patrick; Grzybowski, Bartosz A

2016-07-01

To develop electronic devices with novel functionalities and applications, various non-silicon-based materials are currently being explored. Nanoparticles have unique characteristics due to their small size, which can impart functions that are distinct from those of their bulk counterparts. The use of semiconductor nanoparticles has already led to improvements in the efficiency of solar cells, the processability of transistors and the sensitivity of photodetectors, and the optical and catalytic properties of metal nanoparticles have led to similar advances in plasmonics and energy conversion. However, metals screen electric fields and this has, so far, prevented their use in the design of all-metal nanoparticle circuitry. Here, we show that simple electronic circuits can be made exclusively from metal nanoparticles functionalized with charged organic ligands. In these materials, electronic currents are controlled by the ionic gradients of mobile counterions surrounding the 'jammed' nanoparticles. The nanoparticle-based electronic elements of the circuitry can be interfaced with metal nanoparticles capable of sensing various environmental changes (humidity, gas, the presence of various cations), creating electronic devices in which metal nanoparticles sense, process and ultimately report chemical signals. Because the constituent nanoparticles combine electronic and chemical sensing functions, we term these systems 'chemoelectronic'. The circuits have switching times comparable to those of polymer electronics, selectively transduce parts-per-trillion chemical changes into electrical signals, perform logic operations, consume little power (on the scale of microwatts), and are mechanically flexible. They are also 'green', in the sense that they comprise non-toxic nanoparticles cast at room temperature from alcohol solutions.

Effects of compatibility of polymer binders with solvate ionic liquid electrolytes on discharge and charge reactions of lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Nakazawa, Toshitada; Ikoma, Ai; Kido, Ryosuke; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

2016-03-01

Electrochemical reactions in Li-S cells with a solvate ionic liquid (SIL) electrolyte composed of tetraglyme (G4) and Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) are studied. The sulfur cathode (S cathode) comprises sulfur, carbon powder, and a polymer binder. Poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA-x) with different degrees of saponification (x%) are used as binders to prepare the composite cathodes. For the Li-S cell containing PEO binder, lithium polysulfides (Li2Sm, 2 ≤ m ≤ 8), reaction intermediates of the S cathode, dissolve into the electrolyte, and Li2Sm acts as a redox shuttle in the Li-S cell. In contrast, in the Li-S cell with PVA-x binder, the dissolution of Li2Sm is suppressed, leading to high columbic efficiencies during charge-discharge cycles. The compatibility of the PVA-x binder with the SIL electrolyte changes depending on the degree of saponification. Decreasing the degree of saponification leads to increased electrolyte uptake by the PVA-x binder, increasing the charge and discharge capacities of Li-S cell. The rate capability of Li-S cell is also enhanced by the partial swelling of the PVA-x binder. The enhanced performance of Li-S cell containing PVA-x is attributed to the lowering of resistance of Li+ ion transport in the composite cathode.

Dynamic NMR studies of polymer electrolyte materials for application to lithium-ion batteries and fuel cells

NASA Astrophysics Data System (ADS)

Khalfan, Amish N.

This dissertation investigates the structural and dynamical properties of polymer electrolyte materials for applications to lithium-ion batteries and fuel cells. The nuclear magnetic resonance (NMR) technique was used to characterize these materials. NMR aids in understanding the local environments of nuclei and the mobility of a molecular/ionic species. Five research projects were carried out, and they have been outlined in this work. NASA has developed rod-coil block copolymers for use as electrolytes in lithium-ion batteries. The copolymers exhibit a microphase separation within their structure leading to the formation of ionically conducting channels. We studied ion transport properties of the copolymers, and determined the predominant mechanism for transport to occur in the amorphous phase. Seven gel polymer electrolytes, each containing a mixture of LiBETI salt and organic solvents, were studied. Two of them incorporated BMI (1-n-butyl-3-methylimidazolium) ionic liquid. Ionic liquids are room temperature molten salts. BMI had been thought to enhance ion mobility. However, the BMI component was observed to restrict ion mobility. Gel polymer electrolytes containing LiTFSI salt and P13TFSI ionic liquid with or without the inclusion of ethylene carbonate (EC) were studied for application to lithium metal/air batteries, which have high theoretical energy densities. The addition of EC was found to improve lithium ion transport. The gels with EC therefore prove to be favorable for use as electrolytes in lithium metal/air batteries. Highly sulfonated poly(arylenethioethersulfone) (SPTES) membranes were examined for use in direct methanol fuel cells (DMFCs) as an alternative to the Nafion membrane. DMFCs use methanol as a fuel instead of reformed hydrogen as in conventional proton exchange membrane fuel cells. Compared to Nafion, the SPTES membranes were shown to retain water better at high temperatures and yield lower methanol diffusion. SPTES membranes with the addition of fluorine groups (6F-SPTES) were also studied, and these membranes had been thought to show an improvement in water transport properties over SPTES. However, water diffusion studies of the 6F-SPTES membranes revealed the fluorinated membranes to be unfavorable. The morphology of the FSPTES is suspected to be more susceptible to the loss of bound water at higher temperatures than SPTES.

Ionic Liquid-Doped Gel Polymer Electrolyte for Flexible Lithium-Ion Polymer Batteries

PubMed Central

Zhang, Ruisi; Chen, Yuanfen; Montazami, Reza

2015-01-01

Application of gel polymer electrolytes (GPE) in lithium-ion polymer batteries can address many shortcomings associated with liquid electrolyte lithium-ion batteries. Due to their physical structure, GPEs exhibit lower ion conductivity compared to their liquid counterparts. In this work, we have investigated and report improved ion conductivity in GPEs doped with ionic liquid. Samples containing ionic liquid at a variety of volume percentages (vol %) were characterized for their electrochemical and ionic properties. It is concluded that excess ionic liquid can damage internal structure of the batteries and result in unwanted electrochemical reactions; however, samples containing 40–50 vol % ionic liquid exhibit superior ionic properties and lower internal resistance compared to those containing less or more ionic liquids.

Efficient and Stable Photovoltaic Characteristics of Quasi-Solid State DSSC using Polymer Gel Electrolyte Based on Ionic Liquid in Organosiloxane Polymer Gels

NASA Astrophysics Data System (ADS)

Pujiarti, H.; Arsyad, W. S.; Shobih; Muliani, L.; Hidayat, R.

2018-04-01

Dye-Sensitized Solar Cell (DSSC) is still one of the promising solar cell types among the third generation of solar cells because of easiness of fabrication and variety of available materials. In this type of solar cell, the electrolyte is one of the important components for regenerating excited dyes and transporting electric charge carriers to the counter electrode. Indeed, the power conversion efficiency of DSSC can be then significantly affected by the chemical and physical properties of the electrolyte. The simplest electrolyte system of an I-/I3 - redox couple in an organic solvent, however, has some drawbacks due to corrosive properties, volatile and leakage problem. Use of solid phase or gel phase electrolyte may overcome those problems, but it is often considered to suppress the efficiency due to low ion diffusion. Here, we report the photovoltaic characteristics of DSSC using polymer gel electrolyte (PGE), which is composed of ionic liquid and an organosiloxane polymer gel. The better cell performance with power conversion efficiency of about 6% has been obtained by optimizing the mesoporous size of the TiO2 layer and the PGE viscosity.

An accurate coarse-grained model for chitosan polysaccharides in aqueous solution.

PubMed

Tsereteli, Levan; Grafmüller, Andrea

2017-01-01

Computational models can provide detailed information about molecular conformations and interactions in solution, which is currently inaccessible by other means in many cases. Here we describe an efficient and precise coarse-grained model for long polysaccharides in aqueous solution at different physico-chemical conditions such as pH and ionic strength. The Model is carefully constructed based on all-atom simulations of small saccharides and metadynamics sampling of the dihedral angles in the glycosidic links, which represent the most flexible degrees of freedom of the polysaccharides. The model is validated against experimental data for Chitosan molecules in solution with various degree of deacetylation, and is shown to closely reproduce the available experimental data. For long polymers, subtle differences of the free energy maps of the glycosidic links are found to significantly affect the measurable polymer properties. Therefore, for titratable monomers the free energy maps of the corresponding links are updated according to the current charge of the monomers. We then characterize the microscopic and mesoscopic structural properties of large chitosan polysaccharides in solution for a wide range of solvent pH and ionic strength, and investigate the effect of polymer length and degree and pattern of deacetylation on the polymer properties.

An accurate coarse-grained model for chitosan polysaccharides in aqueous solution

PubMed Central

Tsereteli, Levan

2017-01-01

Computational models can provide detailed information about molecular conformations and interactions in solution, which is currently inaccessible by other means in many cases. Here we describe an efficient and precise coarse-grained model for long polysaccharides in aqueous solution at different physico-chemical conditions such as pH and ionic strength. The Model is carefully constructed based on all-atom simulations of small saccharides and metadynamics sampling of the dihedral angles in the glycosidic links, which represent the most flexible degrees of freedom of the polysaccharides. The model is validated against experimental data for Chitosan molecules in solution with various degree of deacetylation, and is shown to closely reproduce the available experimental data. For long polymers, subtle differences of the free energy maps of the glycosidic links are found to significantly affect the measurable polymer properties. Therefore, for titratable monomers the free energy maps of the corresponding links are updated according to the current charge of the monomers. We then characterize the microscopic and mesoscopic structural properties of large chitosan polysaccharides in solution for a wide range of solvent pH and ionic strength, and investigate the effect of polymer length and degree and pattern of deacetylation on the polymer properties. PMID:28732036

Control of gel swelling and phase separation of weakly charged thermoreversible gels by salt addition

PubMed Central

Solis, Francisco J.; Vernon, Brent

2009-01-01

Doping of thermoreversible polymer gels with charged monomers provides a way to control phase separation and gelation conditions by coupling the properties of the gel with a tunable ionic environment. We analyze the dependence of the gelation and phase separation conditions on the amount of salt present using a mean field model of weakly charged associative polymers. The ions and co-ions present are explicitly considered at the mean field level, and we determine their concentrations in the different equilibrium phases when the system undergoes phase separation. For weak polymer charge, the entropic contributions of the ions to the free energy of the system play a central role in the determination of the location of phase equilibrium. In the simplest case, when the associative interaction responsible for gel formation is independent of the electrostatic interaction, the addition of salt changes the polymer equilibrium concentrations and indirectly changes the measurable swelling of the gel. We construct phase diagrams of these systems showing the location of the coexistence region, the gel-sol boundary and the location of the tie-lines. We determine the swelling of the gel within the co-existence region. Our main result is that the description of the effect of the salt on the properties of the weakly charged gel can be described through an extra contribution to the effective immiscibility parameter χ proportional to the square of the doping degree f2 and to the inverse square of the added salt concentration s−2. PMID:19759854

A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

PubMed Central

Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

2016-01-01

Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm−1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

PubMed Central

Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei; Devaux, Didier; Wong, Dominica H. C.; DeSimone, Joseph M.; Balsara, Nitash P.

2016-01-01

Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10−4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li+/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries. PMID:26699512

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Villaluenga, Irune; Wujcik, Kevin H.; Tong, Wei

2015-12-22

Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. Here, we have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10 -4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Limore » +/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.« less

Fabrication and characterization of a micromachined swirl-shaped ionic polymer metal composite actuator with electrodes exhibiting asymmetric resistance.

PubMed

Feng, Guo-Hua; Liu, Kim-Min

2014-05-12

This paper presents a swirl-shaped microfeatured ionic polymer-metal composite (IPMC) actuator. A novel micromachining process was developed to fabricate an array of IPMC actuators on a glass substrate and to ensure that no shortcircuits occur between the electrodes of the actuator. We demonstrated a microfluidic scheme in which surface tension was used to construct swirl-shaped planar IPMC devices of microfeature size and investigated the flow velocity of Nafion solutions, which formed the backbone polymer of the actuator, within the microchannel. The unique fabrication process yielded top and bottom electrodes that exhibited asymmetric surface resistance. A tool for measuring surface resistance was developed and used to characterize the resistances of the electrodes for the fabricated IPMC device. The actuator, which featured asymmetric electrode resistance, caused a nonzero-bias current when the device was driven using a zero-bias square wave, and we propose a circuit model to describe this phenomenon. Moreover, we discovered and characterized a bending and rotating motion when the IPMC actuator was driven using a square wave. We observed a strain rate of 14.6% and a displacement of 700 μm in the direction perpendicular to the electrode surfaces during 4.5-V actuation.

Fabrication and Characterization of a Micromachined Swirl-Shaped Ionic Polymer Metal Composite Actuator with Electrodes Exhibiting Asymmetric Resistance

PubMed Central

Feng, Guo-Hua; Liu, Kim-Min

2014-01-01

This paper presents a swirl-shaped microfeatured ionic polymer-metal composite (IPMC) actuator. A novel micromachining process was developed to fabricate an array of IPMC actuators on a glass substrate and to ensure that no shortcircuits occur between the electrodes of the actuator. We demonstrated a microfluidic scheme in which surface tension was used to construct swirl-shaped planar IPMC devices of microfeature size and investigated the flow velocity of Nafion solutions, which formed the backbone polymer of the actuator, within the microchannel. The unique fabrication process yielded top and bottom electrodes that exhibited asymmetric surface resistance. A tool for measuring surface resistance was developed and used to characterize the resistances of the electrodes for the fabricated IPMC device. The actuator, which featured asymmetric electrode resistance, caused a nonzero-bias current when the device was driven using a zero-bias square wave, and we propose a circuit model to describe this phenomenon. Moreover, we discovered and characterized a bending and rotating motion when the IPMC actuator was driven using a square wave. We observed a strain rate of 14.6% and a displacement of 700 μm in the direction perpendicular to the electrode surfaces during 4.5-V actuation. PMID:24824370

Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon

Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which aremore » anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.« less

Ionic Liquid Activation of Amorphous Metal-Oxide Semiconductors for Flexible Transparent Electronic Devices

DOE PAGES

Pudasaini, Pushpa Raj; Noh, Joo Hyon; Wong, Anthony T.; ...

2016-02-09

To begin this abstract, amorphous metal-oxide semiconductors offer the high carrier mobilities and excellent large-area uniformity required for high performance, transparent, flexible electronic devices; however, a critical bottleneck to their widespread implementation is the need to activate these materials at high temperatures which are not compatible with flexible polymer substrates. The highly controllable activation of amorphous indium gallium zinc oxide semiconductor channels using ionic liquid gating at room temperature is reported. Activation is controlled by electric field-induced oxygen migration across the ionic liquid-semiconductor interface. In addition to activation of unannealed devices, it is shown that threshold voltages of a transistormore » can be linearly tuned between the enhancement and depletion modes. Finally, the first ever example of transparent flexible thin film metal oxide transistor on a polyamide substrate created using this simple technique is demonstrated. Finally, this study demonstrates the potential of field-induced activation as a promising alternative to traditional postdeposition thermal annealing which opens the door to wide scale implementation into flexible electronic applications.« less

Investigation of ionic conduction in PEO-PVDF based blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Patla, Subir Kumar; Ray, Ruma; Asokan, K.; Karmakar, Sanat

2018-03-01

We investigate the effect of blend host polymer on solid polymer electrolyte (SPE) films doped with ammonium iodide (NH4I) salt using a variety of experimental techniques. Structural studies on the composite SPEs show that the blending of Poly(ethylene oxide) (PEO)-Poly(vinylidene fluoride) (PVDF) polymers in a suitable ratio enhances the amorphous fraction of the polymer matrix and facilitates fast ion conduction through it. We observe that the addition of a small amount of PVDF in the PEO host polymer enhances the ion - polymer interaction leading to more ion dissociation. As a result, the effective number of mobile charge carriers within the polymer matrix increases. Systematic investigation in these blend SPEs shows that the maximum conductivity (1.01 × 10-3 S/cm) is obtained for PEO - rich (80 wt. % PEO, 20 wt. % PVDF) composites at 35 wt. % NH4I concentration at room temperature. Interestingly, at higher salt concentrations (above 35 wt. %), the conductivity is found to decrease in this system. The reduction of conductivity at higher salt concentrations is the consequence of decrease in the carrier concentration due to the formation of an ion pair and ion aggregates. PVDF-rich compositions (20 wt. % PEO and 80 wt. % PVDF), on the other hand, show a very complex porous microstructure. We also observe a much lower ionic conductivity (maximum ˜ 10-6 S/cm at 15 wt. % salt) in these composite systems relative to PEO-rich composites.

One molecule of ionic liquid and tert-alcohol on a polystyrene-support as catalysts for efficient nucleophilic substitution including fluorination.

PubMed

Shinde, Sandip S; Patil, Sunil N

2014-12-07

The tert-alcohol and ionic liquid solvents in one molecule [mim-(t)OH][OMs] was immobilized on polystyrene and reported to be a highly efficient catalyst in aliphatic nucleophilic substitution using alkali metal salts. Herein, we investigated the catalytic activity of a new structurally modified polymer-supported tert-alcohol functionalized imidazolium salt catalyst in nucleophilic substitution of 2-(3-methanesulfonyloxypropyoxy)naphthalene as a model substrate with various metal nucleophiles. The tert-alcohol moiety of the ionic liquid with a hexyl chain distance from polystyrene had a better catalytic activity compared to the other resin which lacked an alkyl linker and tert-alcohol moiety. We found that the maximum [mim-(t)OH][OMs] loading had the best catalytic efficacy among the tested polystyrene-based ionic liquids (PSILs) in nucleophilic fluorination. The catalytic efficiency of the PS[him-(t)OH][OMs] as a phase transfer catalyst (PTC) was determined by carrying out various nucleophilic substitutions using the corresponding alkali metal salts from the third to sixth periodic in CH3CN or tert-BuOH media. The scope of this protocol with primary and secondary polar substrates containing many heteroatoms is also reported. This PS[him-(t)OH][OMs] catalyst not only enhances the reactivity of alkali metal salts and reduces the formation of by-products but also affords high yield with easy isolation.

Quantitative structure-activity relationships for green algae growth inhibition by polymer particles.

PubMed

Nolte, Tom M; Peijnenburg, Willie J G M; Hendriks, A Jan; van de Meent, Dik

2017-07-01

After use and disposal of chemical products, many types of polymer particles end up in the aquatic environment with potential toxic effects to primary producers like green algae. In this study, we have developed Quantitative Structure-Activity Relationships (QSARs) for a set of highly structural diverse polymers which are capable to estimate green algae growth inhibition (EC50). The model (N = 43, R 2  = 0.73, RMSE = 0.28) is a regression-based decision tree using one structural descriptor for each of three polymer classes separated based on charge. The QSAR is applicable to linear homo polymers as well as copolymers and does not require information on the size of the polymer particle or underlying core material. Highly branched polymers, non-nitrogen cationic polymers and polymeric surfactants are not included in the model and thus cannot be evaluated. The model works best for cationic and non-ionic polymers for which cellular adsorption, disruption of the cell wall and photosynthesis inhibition were the mechanisms of action. For anionic polymers, specific properties of the polymer and test characteristics need to be known for detailed assessment. The data and QSAR results for anionic polymers, when combined with molecular dynamics simulations indicated that nutrient depletion is likely the dominant mode of toxicity. Nutrient depletion in turn, is determined by the non-linear interplay between polymer charge density and backbone flexibility. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ionic polymer-metal composite enabled robotic manta ray

NASA Astrophysics Data System (ADS)

Chen, Zheng; Um, Tae I.; Bart-Smith, Hilary

2011-04-01

The manta ray, Manta birostris, demonstrates excellent swimming capabilities; generating highly efficient thrust via flapping of dorsally flattened pectoral fins. In this paper, we present an underwater robot that mimics the swimming behavior of the manta ray. An assembly-based fabrication method is developed to create the artificial pectoral fins, which are capable of generating oscillatory with a large twisting angle between leading and trailing edges. Ionic polymer-metal composite (IPMC) actuators are used as artificial muscles in the fin. Each fin consists of four IPMC beams bonded with a compliant poly(dimethylsiloxane) (PDMS) membrane. By controlling each individual IPMC strips, we are able to generate complex flapping motions. The fin is characterized in terms of tip deflection, tip blocking force, twist angle, and power consumption. Based on the characteristics of the artificial pectoral fin, a small size and free-swimming robotic manta ray is developed. The robot consists of two artificial pectoral fins, a rigid body, and an on-board control unit with a lithium ion rechargeable battery. Experimental results show that the robot swam at a speed of up to 0.055 body length per second (BL/sec).

Bio-applications of ionic polymer metal composite transducers

NASA Astrophysics Data System (ADS)

Aw, K. C.; McDaid, A. J.

2014-07-01

Traditional robotic actuators have advanced performance which in some aspects can surpass that of humans, however they are lacking when it comes to developing devices which are capable of operating together with humans. Bio-inspired transducers, for example ionic polymer metal composites (IPMC), which have similar properties to human tissue and muscle, demonstrate much future promise as candidates for replacing traditional robotic actuators in medical robotics applications. This paper outlines four biomedical robotics applications, an IPMC stepper motor, an assistive glove exoskeleton/prosthetic hand, a surgical robotic tool and a micromanipulation system. These applications have been developed using mechanical design/modelling techniques with IPMC ‘artificial muscle’ as the actuation system. The systems are designed by first simulating the performance using an IPMC model and dynamic models of the mechanical system; the appropriate advanced adaptive control schemes are then implemented to ensure that the IPMCs operate in the correct manner, robustly over time. This paper serves as an overview of the applications and concludes with some discussion on the future challenges of developing real-world IPMC applications.

A nonlinear model for ionic polymer metal composites as actuators

NASA Astrophysics Data System (ADS)

Bonomo, C.; Fortuna, L.; Giannone, P.; Graziani, S.; Strazzeri, S.

2007-02-01

This paper introduces a comprehensive nonlinear dynamic model of motion actuators based on ionic polymer metal composites (IPMCs) working in air. Significant quantities ruling the acting properties of IPMC-based actuators are taken into account. The model is organized as follows. As a first step, the dependence of the IPMC absorbed current on the voltage applied across its thickness is taken into account; a nonlinear circuit model is proposed to describe this relationship. In a second step the transduction of the absorbed current into the IPMC mechanical reaction is modelled. The model resulting from the cascade of both the electrical and the electromechanical stages represents a novel contribution in the field of IPMCs, capable of describing the electromechanical behaviour of these materials and predicting relevant quantities in a large range of applied signals. The effect of actuator scaling is also investigated, giving interesting support to the activities involved in the design of actuating devices based on these novel materials. Evidence of the excellent agreement between the estimations obtained by using the proposed model and experimental signals is given.

Design and control of 2-axis tilting actuator for endoscope using ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Kim, Sung-Joo; Kim, Chul-Jin; Park, No-Cheol; Yang, Hyun-Seok; Park, Young-Pil

2009-03-01

In field of endoscopy, in order to overcome limitation in conventional endoscopy, capsule endoscope has been developed and has been recently applied in medical field in hospital. However, since capsule endoscope moves passively through GI tract by peristalsis, it is not able to control direction of head including camera. It is possible to miss symptoms of disease. Therefore, in this thesis, 2-Axis Tilting Actuator for Endoscope, based on Ionic Polymer Metal Composites (IPMC), is presented. In order to apply to capsule endoscope, the actuator material should satisfy a size, low energy consumption and low working voltage. Since IPMC is emerging material that exhibits a large bending deflection at low voltage, consume low energy and it can be fabricated in any size or any shape, IPMC are selected as an actuator. The system tilts camera module of endoscope to reduce invisible area of the intestines and a goal of tilting angle is selected to be an angle of 5 degrees for each axis. In order to control tiling angle, LQR controller and the full order observer is designed.

Hydrated Cations in the General Chemistry Course.

ERIC Educational Resources Information Center

Kauffman, George B.; Baxter, John F., Jr.

1981-01-01

Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

REMOVAL OF RADIONUCLIDES BY ELECTROKINETIC SOIL PROCESSING

EPA Science Inventory

Electrokinetics promises to be an innovative treatment process for in-situ treatment of soils and groundwater contaminated with heavy metals and radionuclides. Electrokinetics refers to the movement of ionic liquids and charged particles relative to one another under the action ...

Composite Electrolytes for Lithium Batteries: Ionic Liquids in APTES Crosslinked Polymers

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Bennett, William R.

2007-01-01

Solvent free polymer electrolytes were made consisting of Li(+) and pyrrolidinium salts of trifluoromethanesulfonimide added to a series of hyperbranched poly(ethylene oxide)s (PEO). The polymers were connected by triazine linkages and crosslinked by a sol-gel process to provide mechanical strength. The connecting PEO groups were varied to help understand the effects of polymer structure on electrolyte conductivity in the presence of ionic liquids. Polymers were also made that contain poly(dimethylsiloxane) groups, which provide increased flexibility without interacting with lithium ions. When large amounts of ionic liquid are added, there is little dependence of conductivity on the polymer structure. However, when smaller amounts of ionic liquid are added, the inherent conductivity of the polymer becomes a factor. These electrolytes are more conductive than those made with high molecular weight PEO imbibed with ionic liquids at ambient temperatures, due to the amorphous nature of the polymer.

The influence of chain rigidity and the degree of sulfonation on the morphology of block copolymers as nano reactor

NASA Astrophysics Data System (ADS)

Hong, K.; Zhang, X.

2005-03-01

Polyelectrolyte block copolymer was used to form an ordered domain of ionic block as a ``nanoreactor'' due to its ability to bind oppositely charged metal ion, Zn^2+, Fe^2+ etc. The purpose of our research is to investigate the controllability of the size and morphology of domains (inorganic nano particles) by changing backbone stiffness, the charge density and the volume fraction of ionic block. Poly(styrene sulfonate) (PSS), which backbone is flexible, and poly(cyclohexadiene sulfonate) (PCHDS), which backbone is ``semiflexible'', were used as ionic blocks. We synthesized PtBS-PSS and PS-PCHDS with various degree of sulfonation and the volume fraction. Zinc oxide (ZnO) nano particles successfully formed in the ionic domain of microphase separated block copolymers. We used SANS to characterize the morphology of block copolymers and TEM for block copolymer containing ZnO nano particles. Our experimental results show that the chemistry of ``sulfonation'' of block copolymers can be successfully used to synthesize nano composite materials.

Development of safe, green and high performance ionic liquids-based batteries (ILLIBATT project)

NASA Astrophysics Data System (ADS)

Balducci, A.; Jeong, S. S.; Kim, G. T.; Passerini, S.; Winter, M.; Schmuck, M.; Appetecchi, G. B.; Marcilla, R.; Mecerreyes, D.; Barsukov, V.; Khomenko, V.; Cantero, I.; De Meatza, I.; Holzapfel, M.; Tran, N.

This manuscript presents the work carried out within the European project ILLIBATT, which was dedicated to the development of green, safe and high performance ionic liquids-based lithium batteries. Different types of ionic liquids-based electrolytes were developed in the project, based on different ionic liquids and polymers. Using these electrolytes, the performance of several anodic and cathodic materials has been tested and promising results have been obtained. Also, electrodes were formulated using water soluble binders. Using these innovative components, lithium-ion and lithium-metal battery prototypes (0.7-0.8 Ah) have been assembled and cycled between 100% and 0% SOC. The results of these tests showed that such ionic liquids-based prototypes are able to display high capacity, high coulombic efficiency and high cycle life. Moreover, safety tests showed that the introduction of these alternative electrolytes positively contribute to the safety of the batteries.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids

NASA Astrophysics Data System (ADS)

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K. G.

2009-05-01

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids.

PubMed

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K G

2009-05-28

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Optimization of PEDOT films in ionic liquid supercapacitors: demonstration as a power source for polymer electrochromic devices.

PubMed

Österholm, Anna M; Shen, D Eric; Dyer, Aubrey L; Reynolds, John R

2013-12-26

We report on the optimization of the capacitive behavior of poly(3,4-ethylenedioxythiophene) (PEDOT) films as polymeric electrodes in flexible, Type I electrochemical supercapacitors (ESCs) utilizing ionic liquid (IL) and organic gel electrolytes. The device performance was assessed based on figures of merit that are critical to evaluating the practical utility of electroactive polymer ESCs. PEDOT/IL devices were found to be highly stable over hundreds of thousands of cycles and could be reversibly charged/discharged at scan rates between 500 mV/s and 2 V/s depending on the polymer loading. Furthermore, these devices exhibit leakage currents and self-discharge rates that are comparable to state of the art electrochemical double-layer ESCs. Using an IL as device electrolyte allowed an extension of the voltage window of Type I ESCs by 60%, resulting in a 2.5-fold increase in the energy density obtained. The efficacies of tjese PEDOT ESCs were assessed by using them as a power source for a high-contrast and fast-switching electrochromic device, demonstrating their applicability in small organic electronic-based devices.

Fixed Junction Light Emitting Electrochemical Cells based on Polymerizable Ionic Liquids

NASA Astrophysics Data System (ADS)

Brown, Erin; Limanek, Austin; Bauman, James; Leger, Janelle

Organic photovoltaic (OPV) devices are of interest due to ease of fabrication, which increases their cost-effectiveness. OPV devices based on fixed-junction light emitting electrochemical cells (LECs) in particular have shown promising results. LECs are composed of a layer of polymer semiconductor blended with a salt sandwiched between two electrodes. As a forward bias is applied, the ions within the polymer separate, migrate to the electrodes, and enable electrochemical doping, thereby creating a p-n junction analog. In a fixed junction device, the ions are immobilized after the desired distribution has been established, allowing for operation under reverse bias conditions. Fixed junctions can be established using various techniques, including chemically by mixing polymerizable salts that will bond to the polymer under a forward bias. Previously we have demonstrated the use of the polymerizable ionic liquid allyltrioctylammonium allysulfonate (ATOAAS) as an effective means of creating a chemically fixed junction in an LEC. Here we present the application of this approach to the creation of photovoltaic devices. Devices demonstrate higher open circuit voltages, faster charging, and an overall improved device performance over previous chemically-fixed junction PV devices.

The Structures of Fibronectin Adsorbed on Polyelectrolyte Thin Films

NASA Astrophysics Data System (ADS)

Shin, Kwanwoo; Satija, Sushil; Fang, Xiao-Hua; Li, Bin-Quan; Nadine, Pernodet; Miriam, Rafailovich; Sokolov, Jonathan; Arach, Goldar; Roser, Steve

2002-03-01

We have shown that it is possible to form a fibrilar network of fibronectin on a polyelectrolyte polymer film whose dimensions are similar to those reported on the extra cellular matrix. The fibronectin network was observed to form only when the charge density of the polymer was in excess of the natural charge density of the cell wall. Furthermore, the self-organized fibronectin layer was much thicker than the polymer film, indicating that long ranged interaction may play a key role in the assembly process. It is therefore important to understand the structure of the polymer layer/protein interface. Here we report on a neutron reflectivity study where we explore the structure of the polyelectrolyte layer, in this case sulfonated polystyrene (PSS_x.), with varying degree of sulfonation (x<30%), as a function of sulfur content and counter ion concentration. These results are then correlated with systemic study of the adsorption and the multilayer formation of fibronectin as a function of incubation time for various sulfonation levels of PSS_x. Furthermore, the surface charge on the substrates can be strongly influenced by the presence of salt ions, it is important to understand changes due to electrostatic interactions occurring in the various salt conditions. Complementary X-ray reflection was used to determine the salt density profile associating with the internal ionic polymer matrix. This work was funded in part of the NSF-MRSEC program.

A Highly Aromatic and Sulfonated Ionomer for High Elastic Modulus Ionic Polymer Membrane Micro-Actuators

DTIC Science & Technology

2012-05-01

fluorophenyl)sulfone (DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL... ionic liquid Q M Zhang, Gokhan Hatipoglu, Yang Liu, Ran Zhao, Mitra Yoonessi, Dean M Tigelaar, Srinivas Tadigadapa Virginia Polytechnic Institute...DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL) uptake and

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

DOE PAGES

Varenyk, O. V.; Silibin, M. V.; Kiselev, Dmitri A.; ...

2015-08-19

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. Furthermore, the obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers,more » which are of potential interest for flexible and high-density non-volatile memory devices.« less

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

NASA Astrophysics Data System (ADS)

Varenyk, O. V.; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V.; Morozovska, A. N.

2015-08-01

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

A study of water electrolysis using ionic polymer-metal composite for solar energy storage

NASA Astrophysics Data System (ADS)

Keow, Alicia; Chen, Zheng

2017-04-01

Hydrogen gas can be harvested via the electrolysis of water. The gas is then fed into a proton exchange membrane fuel cell (PEMFC) to produce electricity with clean emission. Ionic polymer-metal composite (IPMC), which is made from electroplating a proton-conductive polymer film called Nafion encourages ion migration and dissociation of water under application of external voltage. This property has been proven to be able to act as catalyst for the electrolysis of pure water. This renewable energy system is inspired by photosynthesis. By using solar panels to gather sunlight as the source of energy, the generation of electricity required to activate the IPMC electrolyser is acquired. The hydrogen gas is collected as storable fuel and can be converted back into energy using a commercial fuel cell. The goal of this research is to create a round-trip energy efficient system which can harvest solar energy, store them in the form of hydrogen gas and convert the stored hydrogen back to electricity through the use of fuel cell with minimal overall losses. The effect of increasing the surface area of contact is explored through etching of the polymer electrolyte membrane (PEM) with argon plasma or manually sanding the surface and how it affects the increase of energy conversion efficiency of the electrolyser. In addition, the relationship between temperature and the IPMC is studied. Experimental results demonstrated that increases in temperature of water and changes in surface area contact correlate with gas generation.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

PubMed

Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

2013-04-10

Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore

NASA Astrophysics Data System (ADS)

Wells, Craig C.; Melnikov, Dmitriy V.; Gracheva, Maria E.

2017-08-01

We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

Brownian dynamics of a protein-polymer chain complex in a solid-state nanopore.

PubMed

Wells, Craig C; Melnikov, Dmitriy V; Gracheva, Maria E

2017-08-07

We study the movement of a polymer attached to a large protein inside a nanopore in a thin silicon dioxide membrane submerged in an electrolyte solution. We use Brownian dynamics to describe the motion of a negatively charged polymer chain of varying lengths attached to a neutral protein modeled as a spherical bead with a radius larger than that of the nanopore, allowing the chain to thread the nanopore but preventing it from translocating. The motion of the protein-polymer complex within the pore is also compared to that of a freely translocating polymer. Our results show that the free polymer's standard deviations in the direction normal to the pore axis is greater than that of the protein-polymer complex. We find that restrictions imposed by the protein, bias, and neighboring chain segments aid in controlling the position of the chain in the pore. Understanding the behavior of the protein-polymer chain complex may lead to methods that improve molecule identification by increasing the resolution of ionic current measurements.

Single-Walled Carbon Nanotubes: Mimics of Biological Ion Channels.

PubMed

Amiri, Hasti; Shepard, Kenneth L; Nuckolls, Colin; Hernández Sánchez, Raúl

2017-02-08

Here we report on the ion conductance through individual, small diameter single-walled carbon nanotubes. We find that they are mimics of ion channels found in natural systems. We explore the factors governing the ion selectivity and permeation through single-walled carbon nanotubes by considering an electrostatic mechanism built around a simplified version of the Gouy-Chapman theory. We find that the single-walled carbon nanotubes preferentially transported cations and that the cation permeability is size-dependent. The ionic conductance increases as the absolute hydration enthalpy decreases for monovalent cations with similar solid-state radii, hydrated radii, and bulk mobility. Charge screening experiments using either the addition of cationic or anionic polymers, divalent metal cations, or changes in pH reveal the enormous impact of the negatively charged carboxylates at the entrance of the single-walled carbon nanotubes. These observations were modeled in the low-to-medium concentration range (0.1-2.0 M) by an electrostatic mechanism that mimics the behavior observed in many biological ion channel-forming proteins. Moreover, multi-ion conduction in the high concentration range (>2.0 M) further reinforces the similarity between single-walled carbon nanotubes and protein ion channels.

Design of ultra-thin high frequency trilayer conducting polymer micro-actuators for tactile feedback interfaces

NASA Astrophysics Data System (ADS)

Ebrahimi Takalloo, Saeedeh; Seifi, Hasti; Madden, John D. W.

2017-04-01

Fast actuation of conducting polymer trilayers has been achieved by reducing the thickness of the device to as little as 6 μm. Reducing size also reduces force and displacement. Here the tradeoffs between speed of response, force and deformation angle are explored, and related to an example application - a tactile feedback interface that aims to make use of the very high sensitivity of our fingertip skin to vibrations of about 150 Hz. In general, the actuation rate in these devices is limited by the speed of charging, and by inertia. Here we use an established transmission line model to simulate charging speed. By making use of the empirical relationship between strain and charge, and using beam bending theory, the extent of charging enables estimation of the degree of actuator deformation and the forces that can be generated. In seeking to achieve non-resonant actuation at frequencies of 150 Hz or more, while also generating the forces and displacements needed for tactile stimulation, it is found that electronic and ionic conductivities of the conducting polymer electrodes needs to be on the order of 24,000 S/m and 0.04 S/m, respectively. These values along with the required dimensions appear to be feasible.

Bucky gel actuators optimization towards haptic applications

NASA Astrophysics Data System (ADS)

Bubak, Grzegorz; Ansaldo, Alberto; Ceseracciu, Luca; Hata, Kenji; Ricci, Davide

2014-03-01

An ideal plastic actuator for haptic applications should generate a relatively large displacement (minimum 0.2-0.6 mm, force (~50 mN/cm2) and a fast actuation response to the applied voltage. Although many different types of flexible, plastic actuators based on electroactive polymers (EAP) are currently under investigation, the ionic EAPs are the only ones that can be operated at low voltage. This property makes them suitable for applications that require inherently safe actuators. Among the ionic EAPs, bucky gel based actuators are very promising. Bucky gel is a physical gel made by grounding imidazolium ionic liquids with carbon nanotubes, which can then be incorporated in a polymeric composite matrix to prepare the active electrode layers of linear and bending actuators. Anyhow, many conflicting factors have to be balanced to obtain required performance. In order to produce high force a large stiffness is preferable but this limits the displacement. Moreover, the bigger the active electrode the larger the force. However the thicker an actuator is, the slower the charging process becomes (it is diffusion limited). In order to increase the charging speed a thin electrolyte would be desirable, but this increases the probability of pinholes and device failure. In this paper we will present how different approaches in electrolyte and electrode preparation influence actuator performance and properties taking particularly into account the device ionic conductivity (which influences the charging speed) and the electrode surface resistance (which influences both the recruitment of the whole actuator length and its speed).

Interatomic interactions in M2(C8H4O4)2C6H12N2 (M = Zn, Cu, Co, Ni) metal-organic framework polymers: X-ray photoelectron spectroscopy, QTAIM and ELF study

NASA Astrophysics Data System (ADS)

Kozlova, S. G.; Ryzhikov, M. R.; Samsonenko, D. G.; Kalinkin, A. V.

2017-12-01

Interatomic interactions in M2(C8H4O4)2C6H12N2 (M = Co, Ni, Cu, Zn) metal-organic framework polymers have been studied with the methods of quantum chemistry and X-ray photoelectron spectroscopy. Interactions of C6H12N2 molecules and C8H4O42- anions with metal atoms are shown to be of closed-shell type. C6H12N2 molecules are positively charged, the value of the charge slightly depends on the type of the metal atoms. Msbnd M interactions are described as "intermediate interactions" with some covalence contribution which reaches maximum for the interactions between cobalt atoms. The obtained quantum-chemical data agree with those obtained from photoelectron spectroscopy measurements.

PDADMAC flocculation of Chinese hamster ovary cells: enabling a centrifuge-less harvest process for monoclonal antibodies.

PubMed

McNerney, Thomas; Thomas, Anne; Senczuk, Anna; Petty, Krista; Zhao, Xiaoyang; Piper, Rob; Carvalho, Juliane; Hammond, Matthew; Sawant, Satin; Bussiere, Jeanine

2015-01-01

High titer (>10 g/L) monoclonal antibody (mAb) cell culture processes are typically achieved by maintaining high viable cell densities over longer culture durations. A corresponding increase in the solids and sub-micron cellular debris particle levels are also observed. This higher burden of solids (≥15%) and sub-micron particles typically exceeds the capabilities of a continuous centrifuge to effectively remove the solids without a substantial loss of product and/or the capacity of the harvest filtration train (depth filter followed by membrane filter) used to clarify the centrate. We discuss here the use of a novel and simple two-polymer flocculation method used to harvest mAb from high cell mass cell culture processes. The addition of the polycationic polymer, poly diallyldimethylammonium chloride (PDADMAC) to the cell culture broth flocculates negatively-charged cells and cellular debris via an ionic interaction mechanism. Incorporation of a non-ionic polymer such as polyethylene glycol (PEG) into the PDADMAC flocculation results in larger flocculated particles with faster settling rate compared to PDADMAC-only flocculation. PDADMAC also flocculates the negatively-charged sub-micron particles to produce a feed stream with a significantly higher harvest filter train throughput compared to a typical centrifuged harvest feed stream. Cell culture process variability such as lactate production, cellular debris and cellular densities were investigated to determine the effect on flocculation. Since PDADMAC is cytotoxic, purification process clearance and toxicity assessment were performed.

PDADMAC flocculation of Chinese hamster ovary cells: Enabling a centrifuge-less harvest process for monoclonal antibodies

PubMed Central

McNerney, Thomas; Thomas, Anne; Senczuk, Anna; Petty, Krista; Zhao, Xiaoyang; Piper, Rob; Carvalho, Juliane; Hammond, Matthew; Sawant, Satin; Bussiere, Jeanine

2015-01-01

High titer (>10 g/L) monoclonal antibody (mAb) cell culture processes are typically achieved by maintaining high viable cell densities over longer culture durations. A corresponding increase in the solids and sub-micron cellular debris particle levels are also observed. This higher burden of solids (≥15%) and sub-micron particles typically exceeds the capabilities of a continuous centrifuge to effectively remove the solids without a substantial loss of product and/or the capacity of the harvest filtration train (depth filter followed by membrane filter) used to clarify the centrate. We discuss here the use of a novel and simple two-polymer flocculation method used to harvest mAb from high cell mass cell culture processes. The addition of the polycationic polymer, poly diallyldimethylammonium chloride (PDADMAC) to the cell culture broth flocculates negatively-charged cells and cellular debris via an ionic interaction mechanism. Incorporation of a non-ionic polymer such as polyethylene glycol (PEG) into the PDADMAC flocculation results in larger flocculated particles with faster settling rate compared to PDADMAC-only flocculation. PDADMAC also flocculates the negatively-charged sub-micron particles to produce a feed stream with a significantly higher harvest filter train throughput compared to a typical centrifuged harvest feed stream. Cell culture process variability such as lactate production, cellular debris and cellular densities were investigated to determine the effect on flocculation. Since PDADMAC is cytotoxic, purification process clearance and toxicity assessment were performed. PMID:25706650

Binding in alkali and alkaline-earth tetrahydroborates: Special position of magnesium tetrahydroborate

NASA Astrophysics Data System (ADS)

Łodziana, Zbigniew; van Setten, Michiel J.

2010-01-01

Compounds of light elements and hydrogen are currently extensively studied due to their potential application in the field of hydrogen or energy storage. A number of new interesting tetrahydroborates that are especially promising due to their very high gravimetric hydrogen content were recently reported. However, the determination and understanding of their complex crystalline structures has created considerable debate. Metal tetrahydroborates, in general, form a large variety of structures ranging from simple for NaBH4 to very complex for Mg(BH4)2 . Despite the extensive discussion in the literature no clear explanation has been offered for this variety so far. In this paper we analyze the structural and electronic properties of a broad range of metal tetrahydroborates and reveal the factors that determine their structure: ionic bonding, the orientation of the BH4 groups, and the coordination number of the metal cation. We show, in a simple way, that the charge transfer in the metal tetrahydroborates rationally explains the structural diversity of these compounds. Being ionic systems, the metal tetrahydroborates fall into the classification of Linus Pauling. By using the ionic radius for the BH4 group as determined in this paper, this allows for structural predictions for new and mixed compounds.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

Computer-aided design of polymers and composites

NASA Technical Reports Server (NTRS)

Kaelble, D. H.

1985-01-01

This book on computer-aided design of polymers and composites introduces and discusses the subject from the viewpoint of atomic and molecular models. Thus, the origins of stiffness, strength, extensibility, and fracture toughness in composite materials can be analyzed directly in terms of chemical composition and molecular structure. Aspects of polymer composite reliability are considered along with characterization techniques for composite reliability, relations between atomic and molecular properties, computer aided design and manufacture, polymer CAD/CAM models, and composite CAD/CAM models. Attention is given to multiphase structural adhesives, fibrous composite reliability, metal joint reliability, polymer physical states and transitions, chemical quality assurance, processability testing, cure monitoring and management, nondestructive evaluation (NDE), surface NDE, elementary properties, ionic-covalent bonding, molecular analysis, acid-base interactions, the manufacturing science, and peel mechanics.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

Lithium secondary batteries: Role of polymer cathode morphology

NASA Astrophysics Data System (ADS)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

DNA binding and biological studies of some novel water-soluble polymer-copper(II)-phenanthroline complexes.

PubMed

Kumar, Rajendran Senthil; Arunachalam, Sankaralingam; Periasamy, Vaiyapuri Subbarayan; Preethy, Christo Paul; Riyasdeen, Anvarbatcha; Akbarsha, Mohammad Abdulkader

2008-10-01

Some novel water-soluble polymer-copper(II)-phenanthroline complex samples, [Cu(phen)2(BPEI)]Cl(2).4H2O (phen=1,10-phenanthroline, BPEI=branched polyethyleneimine), with different degrees of copper complex content in the polymer chain have been prepared by ligand substitution method in water-ethanol medium and characterized by infrared, UV-visible, EPR spectral and elemental analysis methods. The binding of these complex samples with DNA has been investigated by electronic absorption spectroscopy, emission spectroscopy and gel retardation assay. Electrostatic interactions between DNA molecule and polymer-copper(II) complex molecule containing many high positive charges have been observed. Besides these ionic interactions, van der Waals interactions, hydrogen bonding and other partial intercalation binding modes may also exist in this system. The polymer-copper(II) complex with higher degree of copper complex content was screened for its antimicrobial activity and antitumor activity.

Complex coacervation of supercharged proteins with polyelectrolytes.

PubMed

Obermeyer, Allie C; Mills, Carolyn E; Dong, Xue-Hui; Flores, Romeo J; Olsen, Bradley D

2016-04-21

Complexation of proteins with polyelectrolytes or block copolymers can lead to phase separation to generate a coacervate phase or self-assembly of coacervate core micelles. However, many proteins do not coacervate at conditions near neutral pH and physiological ionic strength. Here, protein supercharging is used to systematically explore the effect of protein charge on the complex coacervation with polycations. Four model proteins were anionically supercharged to varying degrees as quantified by mass spectrometry. Proteins phase separated with strong polycations when the ratio of negatively charged residues to positively charged residues on the protein (α) was greater than 1.1-1.2. Efficient partitioning of the protein into the coacervate phase required larger α (1.5-2.0). The preferred charge ratio for coacervation was shifted away from charge symmetry for three of the four model proteins and indicated an excess of positive charge in the coacervate phase. The composition of protein and polymer in the coacervate phase was determined using fluorescently labeled components, revealing that several of the coacervates likely have both induced charging and a macromolecular charge imbalance. The model proteins were also encapsulated in complex coacervate core micelles and micelles formed when the protein charge ratio α was greater than 1.3-1.4. Small angle neutron scattering and transmission electron microscopy showed that the micelles were spherical. The stability of the coacervate phase in both the bulk and micelles improved to increased ionic strength as the net charge on the protein increased. The micelles were also stable to dehydration and elevated temperatures.

Reliability of high-strain ionomeric polymer transducers fabricated using the novel direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2006-03-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typically, ionic polymer actuators are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique named the Direct Assembly Process (DAP), which allowed good control on electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. A single- walled carbon nanotubes (SWNT) and ruthenium dioxide (RuO II) hybrid electrode was sprayed on a Formamide hydrated Nafion-117 membrane using the DAP method. This transducer was shown to generate 9.4% peak-peak strain under the application of +/-2V at a strain rate of 1%/sec. Furthermore using the DAP one is capable of incorporating several types of diluents in ionomeric polymer transducers. Transducers with ionic liquid diluents are demonstrated to operate in air for long periods of time. In this work we will present a reliability study of transducers fabricated using the DAP. Each transducer is tested under a frequency range of 0.2Hz to 1Hz, and a potential of +/-1V to +/-3V. Water hydrated transducers dehydrates and stop moving within 5 minutes while operating in air under +/-2V. Transducers with Formamide diluents operate for 20,000 cycles under +/-1.5V and 0.5Hz (around 11hrs), while they degrade in less than 3000 cycles under +/-2V and 0.5Hz. Ionic liquid based transducers are demonstrated to operate in air for over 400,000 with little loss in performance, and over 1 million cycle with a loss of only 43%. Actuators with several electrode compositions are fabricated and a correlation between the reliability of ionic liquid-ionic polymer transducers and maximum strain will be presented. This correlation will be used to assess the adhesion between the high surface area electrodes and the Nafion membrane. SEM images of tested transducers will be presented.

Synthesis of new solid polymer electrolyte and actuator based on PEDOT/NBR/ionic liquid

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2006-03-01

The conducting polymer actuator was presented. The solid polymer electrolyte based on nitrile rubber (NBR) activated with different ionic liquids was prepared. The three different grades of NBR films were synthesized by emulsion polymerization with different amount of acrylonitrile, 23, 35, and 40 mol. %, respectively. The effect of acrylonitrile content on the ionic conductivity and dielectric constant of solid polymer electrolytes was characterized. A conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique, and room temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X [where X= BF 4 -, PF 6 -, (CF 3SO II) IIN -], were absorbed into the composite film. The effects of the anion size of the ionic liquids on the displacement of the actuator were examined. The displacement increased with increasing the anion-size of the ionic liquids.

Statistical field theory description of inhomogeneous polarizable soft matter

NASA Astrophysics Data System (ADS)

Martin, Jonathan M.; Li, Wei; Delaney, Kris T.; Fredrickson, Glenn H.

2016-10-01

We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

Synthesis and characterization of ion containing polymers

NASA Astrophysics Data System (ADS)

Dou, Shichen

Two types of ion-containing polymers are included in this dissertation. The first was focused on the rheology, solvation, and correlation length of polyelectrolyte solutions in terms of charge density, solvent dielectric constant, and solvent quality. The second was focused on the PEO-based polyester ionomers as single ion conductors. A series of polyelectrolytes with varied charge density (0.03 < alpha < 0.6) and counterions (Cl- and I-) were investigated in good solvent (EG, NMF, and GC) and poor solvent (DW and F). The concentration dependence of the specific viscosity and relaxation time of polyelectrolytes in solution agrees with Dobrynin's theoretical predictions at c < c**. Effective charge density greatly impacts the viscosity of polyelectrolyte semidilute solutions, while residual salt significantly reduces the viscosity of polyelectrolyte solutions at concentrations c < 2cs/f. For polyelectrolyte solutions with less condensed counterions, the correlation length obtained from SAXS and rheology perfectly matches and agrees with de Gennes prediction. Dobrynin scaling model successfully predicts the rheology of polyelectrolyte solutions in all cases: without salt, with low residual salt, and with high residual salt concentration. PEO-based polyester ionomers were synthesized by melt polycondensation. Mn was determined using the 1H NMR of ionomers. No ion-cluster was observed from the DSC, SAXS, and rheology measurements. Ionic conductivity greatly depends on the Tg, T-T g and ion content of the ionomers. PEG600-PTMO650 (z)-Li copolyester ionomers show microphase separation and much lower ionic conductivity, compared to that of PE600-Li. PTMO650-Li shows nonconductor behavior.

Statistical field theory description of inhomogeneous polarizable soft matter.

PubMed

Martin, Jonathan M; Li, Wei; Delaney, Kris T; Fredrickson, Glenn H

2016-10-21

We present a new molecularly informed statistical field theory model of inhomogeneous polarizable soft matter. The model is based on fluid elements, referred to as beads, that can carry a net monopole of charge at their center of mass and a fixed or induced dipole through a Drude-type distributed charge approach. The beads are thus polarizable and naturally manifest attractive van der Waals interactions. Beyond electrostatic interactions, beads can be given soft repulsions to sustain fluid phases at arbitrary densities. Beads of different types can be mixed or linked into polymers with arbitrary chain models and sequences of charged and uncharged beads. By such an approach, it is possible to construct models suitable for describing a vast range of soft-matter systems including electrolyte and polyelectrolyte solutions, ionic liquids, polymerized ionic liquids, polymer blends, ionomers, and block copolymers, among others. These bead models can be constructed in virtually any ensemble and converted to complex-valued statistical field theories by Hubbard-Stratonovich transforms. One of the fields entering the resulting theories is a fluctuating electrostatic potential; other fields are necessary to decouple non-electrostatic interactions. We elucidate the structure of these field theories, their consistency with macroscopic electrostatic theory in the absence and presence of external electric fields, and the way in which they embed van der Waals interactions and non-uniform dielectric properties. Their suitability as a framework for computational studies of heterogeneous soft matter systems using field-theoretic simulation techniques is discussed.

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Zhang, Heng; Piszcz, Michał; Oteo, Uxue; Rodriguez-Martinez, Lide M.; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2017-04-01

We report a simple synthesis route towards a new type of comb polymer material based on polyether amines oligomer side chains (i.e., Jeffamine® compounds) and a poly(ethylene-alt-maleic anhydride) backbone. Reaction proceeds by imide ring formation through the NH2 group allowing for attachment of side chains. By taking advantage of the high configurational freedoms and flexibility of propylene oxide/ethylene oxide units (PO/EO) in Jeffamine® compounds, novel polymer matrices were obtained with good elastomeric properties. Fully amorphous solid polymer electrolytes (SPEs) based on lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and Jeffamine®-based polymer matrices show low glass transition temperatures around -40 °C, high ionic conductivities and good electrochemical stabilities. The ionic conductivities of Jeffamine-based SPEs (5.3 × 10-4 S cm-1 at 70 °C and 4.5 × 10-5 S cm-1 at room temperature) are higher than those of the conventional SPEs comprising of LiTFSI and linear poly(ethylene oxide) (PEO), due to the amorphous nature and the high concentration of mobile end-groups of the Jeffamine-based polymer matrices rather than the semi-crystalline PEO The feasibility of Jeffamine-based compounds in lithium metal batteries is further demonstrated by the implementation of Jeffamine®-based polymer as a binder for cathode materials, and the stable cycling of Li|SPE|LiFePO4 and Li|SPE|S cells using Jeffamine-based SPEs.

Crystalline, Glassy and Polymeric Electrolytes:. Similarities and Differences in Ionic Transport Mechanisms

NASA Astrophysics Data System (ADS)

Souquet, Jean Louis

2006-06-01

Ionocovalent crystals or glasses as well as molten salts or salt polymer complexes are currently studied as electrolytes for high energy density batteries. Their large Red/Ox stability range results from their thermodynamic or kinetic characteristics. For all these electrolytes, charge carriers are the consequence of local deviations from electroneutrality, identified as point defects for ionic crystals or partial dissociation in disordered structures. The charge carriers formation derives from a similar activated process. The main difference comes from the migration process, which depends on the dynamic properties of the surrounding medium. When the structural relaxation time is large, an activated process, mainly enthalpic, prevails for charge carriers migration. It is the usual case for ionic crystals or glasses. In the liquid or overcooled liquid states, the structural relaxation time of the medium is shorter that the time required for the activated migration process to occur and a local reorganization of the medium vanishes the energy barrier and provides the free volume necessary to ionic migration. In that case, the migration is mainly an entropic process. The configurational entropy necessary to this process decreases with temperature and vanishes at the so called ideal glass transition temperature which can be estimated by extrapolation of the transport properties or of the thermodynamic characteristics of the medium. However, at the experiment time scale, this configurational entropy disappears at a somewhat higher temperature, the glass transition temperature at which the structural relaxation time corresponds to the measurement time. Some glass forming ionic melts studied in a large temperature scale, over and below the glass transition temperature, evidence the two, enthalpic and entropic, migration mechanisms, allowing the determination of the thermodynamic characteristics of the charge carriers formation and migration. Some recent results indicate that entropic process, associated to long scale deformations, may also exist in crystalline structures.

An electroactive conducting polymer actuator based on NBR/RTIL solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Cho, M. S.; Seo, H. J.; Nam, J. D.; Choi, H. R.; Koo, J. C.; Lee, Y.

2007-04-01

This paper reports the fabrication of a dry-type conducting polymer actuator using nitrile rubber (NBR) as the base material in a solid polymer electrolyte. The conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), was synthesized on the surface of the NBR layer by using a chemical oxidation polymerization technique. Room-temperature ionic liquids (RTIL) based on imidazolium salts, e.g. 1-butyl-3-methyl imidazolium X (where X = BF4-, PF6-, (CF3SO2)2N-), were absorbed into the composite film. The compatibility between the ionic liquids and the NBR polymer was confirmed by DMA. The effect of the anion size of the ionic liquids on the displacement of the actuator was examined. The displacement increased with increasing anion size of the ionic liquids. The cyclic voltammetry responses and the redox switching dynamics of the actuators were examined in different ionic liquids.

Correlation between ion diffusional motion and ionic conductivity for different electrolytes based on ionic liquid.

PubMed

Kaur, Dilraj Preet; Yamada, K; Park, Jin-Soo; Sekhon, S S

2009-04-23

Room temperature ionic liquid 2,3-dimethyl-1-hexylimidazolium bis(trifluoromethane sulfonyl)imide (DMHxImTFSI) has been synthesized and used in the preparation of polymer gel electrolytes containing polymethylmethacrylate and propylene carbonate (PC). The onset of ion diffusional motion has been studied by (1)H and (19)F NMR spectroscopy and the results obtained for ionic liquid, liquid electrolytes, and polymer gel electrolytes have been correlated with the ionic conductivity results for these electrolytes in the 100-400 K temperature range. The temperature at which (1)H and (19)F NMR lines show motional narrowing and hence ion diffusional motion starts has been found to be closely related to the temperature at which a large increase in ionic conductivity has been observed for these electrolytes. Polymer gel electrolytes have high ionic conductivity over a wide range of temperatures. Thermogravimetric analysis/differential scanning calorimetry studies show that the ionic liquid (DMHxImTFSI) used in the present study is thermally stable up to 400 degrees C, whereas the addition of PC lowers the thermal stability of polymer gel electrolytes containing the ionic liquid. Different electrolytes have been observed to show high ionic conductivity in different range of temperatures, which can be helpful in the design of polymer gel electrolytes for specific applications.

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

Finite element modeling of the electromechanical coupling in ionic polymer transducers

NASA Astrophysics Data System (ADS)

Akle, Barbar; Habchi, Wassim; Wallmersperger, Thomas; Leo, Donald

2010-04-01

Several researchers are actively studying Ionomeric polymer transducers (IPT) as a large strain low voltage Electro- Active Polymer (EAP) actuator. EAPs are devices that do not contain any moving parts leading to a potential large life time. Furthermore, they are light weight and flexible. An IPT is made of an ion saturated polymer usually Nafion, sandwiched between two electrodes made of a mixture of Nafion and electrically conductive particles usually RuO2 or platinum. Nafion is an acid membrane in which the cations are mobile while the anions are covalently fixed to the polymer structure. Upon the application of an electric potential on the order of 2V at the electrodes the mobile positive ions migrate towards the cathode leading to bending strains in the order of 5%. Our earlier studies demonstrate that the cations develop thin boundary layers around the electrode. Later developments in this finite element model captured the importance of adding particles in the electrode. This study presents the electromechanical coupling in ionic polymer transducers. Since all our earlier models were restricted to the electro-chemical part, here we will introduce the chemomechanical coupling. This coupling is performed based on previous studies (Akle and Leo) in which the authors experimentally showed that the mechanical strain in IPTs is proportional to a linear term and a quadratic term of the charge accumulated at the electrode. The values of the linear and quadratic terms are extracted from experimental data.

Conductivity-Relaxation Relations in Nanocomposite Polymer Electrolytes Containing Ionic Liquid.

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

In this study, we have used nanocomposite polymer electrolytes, consisting of poly(ethylene oxide) (PEO), δ-Al 2 O 3 nanoparticles, and lithium bis(trifluoromethanesolfonyl)imide (LiTFSI) salt (with 4 wt % δ-Al 2 O 3 and PEO:Li ratios of 16:1 and 8:1), and added different amounts of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesolfonyl)imide (BMITFSI). The aim was to elucidate whether the ionic liquid is able to dissociate the Li-ions from the ether oxygens and thereby decouple the ionic conductivity from the segmental polymer dynamics. The results from DSC and dielectric spectroscopy show that the ionic liquid speeds up both the segmental polymer dynamics and the motion of the Li + ions. However, a close comparison between the structural (α) relaxation process, given by the segmental polymer dynamics, and the ionic conductivity shows that the motion of the Li + ions decouples from the segmental polymer dynamics at higher concentrations of the ionic liquid (≥20 wt %) and instead becomes more related to the viscosity of the ionic liquid. This decoupling increases with decreasing temperature. In addition to the structural α-relaxation, two more local relaxation processes, denoted β and γ, are observed. The β-relaxation becomes slightly faster at the highest concentration of the ionic liquid (at least for the lower salt concentration), whereas the γ-relaxation is unaffected by the ionic liquid, over the whole concentration range 0-40 wt %.

Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

2018-04-01

Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

Block copolymers for alkaline fuel cell membrane materials

NASA Astrophysics Data System (ADS)

Li, Yifan

Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC-b-PS. The incorporation of the hydrophilic polymer allows for an investigation of the effect of hydration on ionic conductivity, resulting in the increase in membrane water affinity, enhancement of conductivity and reduced dependence of conductivity on relative humidity. A study of crosslinking of block copolymers was done wherein the crosslinking occurs in the non-matrix phase in order to maintain mechanical properties. The formation of a cationic crosslinked structure improves the mechanical integrity of the membrane in water while showing little deleterious effect on ionic conductivity and mechanical properties.

Synthesis and characterisation of nano structure lead (II) ion-imprinted polymer as a new sorbent for selective extraction and preconcentration of ultra trace amounts of lead ions from vegetables, rice, and fish samples.

PubMed

Behbahani, Mohammad; Bagheri, Akbar; Taghizadeh, Mohsen; Salarian, Mani; Sadeghi, Omid; Adlnasab, Laleh; Jalali, Kobra

2013-06-01

This paper describes the preparation of new Pb(II)-imprinted polymeric particles using 2-vinylpyridine as a functional monomer, ethylene glycol dimethacrylate as the cross-linker, 2,2'- azobisisobutyronitrile as the initiator, diphenylcarbazone as the ligand, acetonitril as the solvent, and Pb(NO(3))(2) as the template ion, through bulk polymerisation technique. The imprinted lead ions were removed from the polymeric matrix using 5 mL of HCl (2 mol.L(-1)) as the eluting solvent. The lead ion concentration was determined by flame atomic absorption spectrometry. Optimum pH for maximum sorption was obtained at 6.0. Sorption and desorption of Pb(II) ions on the IIP particles were quite fast and achieved fully over 5 min. In the proposed method, the maximum sorbent capacity of the ion-imprinted polymer was calculated to be 75.4 mg g(-1). The preconcentration factor, relative standard deviation, and limit of detection of the method were found to be 245, 2.1%, and 0.42 ng mL(-1), respectively. The prepared ion-imprinted polymer particles have an increased selectivity toward Pb(II) ions over a range of competing metal ions with the same charge and similar ionic radius. This ion-imprinted polymer is an efficient solid phase for extraction and preconcentration of lead ions in complex matrixes. For proving that the proposed method is reliable, a wide range of food samples with different and complex matrixes was used. Copyright © 2012 Elsevier Ltd. All rights reserved.

Use of a chemical equilibrium model to describe surface properties and uptake of cadmium, strontium, and lead by Chlorella (UTEX 252)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassett, J.M.

1988-01-01

Metal-aquatic biota interactions are important in both natural and engineered systems. In this study, the uptake of cadmium, strontium and lead by the unicellular green alga Chlorella (UTEX 252) was investigated. Variables included metal concentration, pH, and ionic strength. Data gathered included dry weights (mg/l), cell counts (cells/ml), electrophoretic mobilities (EPMs, {mu}m/sec/V/cm) of metal-free and metal-exposed cells, and metal uptake - difference in concentration in filtrate of cell-metal and cell-free metal solutions. Derived data included cell volumes and surface area, uptake on a {mu}M/m{sup 2} basis, {zeta}-potentials, diffuse layer potentials and charge densities. Typical uptake values were 1.1, 5.2, andmore » 6 {mu}M/m{sup 2} for Cd, Pb, and Sr, respectively, from solutions of pH 6, ionic strength 0.02M, and metal concentration 10{sup {minus}4} M. Cell EPMs were insensitive to metal; under certain conditions, however, (pM > 4, pH > 8), cadmium exposed cells exhibited a reversal in surface charge from negative to positive. The chemical equilibrium model MINEQL1 + STANFORD was used to model algal surface properties and metal uptake. Input data included site pK, density, and {Delta}pK, estimated from EPM-pH data. The model described surface properties of Chlorella (UTEX 252) as judged by a close fit of {zeta}-potentials and model-derived diffuse layer potentials. Metal uptake was modelled by adjusting site density and/or metal-surface site equilibrium constants. Attempts to model surface properties and metal uptake simultaneously were not successful.« less

Ion Transport via Structural Relaxations in Polymerized Ionic Liquids

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Mogurampelly, Santosh

We study the mechanisms underlying ion transport in poly(1-butyl-3-vinylimidazolium-hexafluorophosphate) polymer electrolytes. We consider polymer electrolytes of varying polymerized ionic liquid to ionic liquid (polyIL:IL) ratios and use atomistic molecular dynamics (MD) simulations to probe the dynamical and structural characteristics of the electrolyte. Our results reveal that anion diffusion along polymer backbone occurs primarily viathe formation and breaking of ion-pairs involving threepolymerized cationic monomers of twodifferent polymer chains. Moreover, we observe that the ionic diffusivities exhibit a direct correlation with the structural relaxation times of the ion-pairs and hydrogen bonds (H-bonds). These results provide new insights into the mechanisms underlying ion transport in polymerized ionic liquid electrolytes.

Polarization effect in the Ionic conductor TlBr

NASA Astrophysics Data System (ADS)

Rocha Leao, Cedric; Lordi, Vincenzo

2012-02-01

TlBr is an ionic crystal that in recent years has been standing out as one of the most promising materials for effective room temperature radiation detection. However, its exceptional performance invariably degrades after operation times that vary from hours to several weeks. This phenomenon, known as polarization, is assigned to the undesirable ionic current that sets in the crystal under an applied bias, leading to the accumulation of oppositely charged Tl+ and Br- ions at the electric contacts of the device. This charge build up induces a field that opposes the applied bias, impairing the collection of the photo-induced carriers. In this presentation, we use parameter free quantum mechanical simulations to discuss the possible origins of the polarization effect in TlBr, showing that ionic mobility in the intrinsic material is not enough to account for effects reported by several groups. We then discuss other possible causes for the degradation of biased TlBr and propose ways to prevent its occurrence, via careful co-doping as well as a judicious choice of the metal contacts to be employed.

Design and Fabrication of a Large-Stroke Deformable Mirror Using a Gear-Shape Ionic-Conductive Polymer Metal Composite

PubMed Central

Wei, Hsiang-Chun; Su, Guo-Dung John

2012-01-01

Conventional camera modules with image sensors manipulate the focus or zoom by moving lenses. Although motors, such as voice-coil motors, can move the lens sets precisely, large volume, high power consumption, and long moving time are critical issues for motor-type camera modules. A deformable mirror (DM) provides a good opportunity to improve these issues. The DM is a reflective type optical component which can alter the optical power to focus the lights on the two dimensional optical image sensors. It can make the camera system operate rapidly. Ionic polymer metal composite (IPMC) is a promising electro-actuated polymer material that can be used in micromachining devices because of its large deformation with low actuation voltage. We developed a convenient simulation model based on Young's modulus and Poisson's ratio. We divided an ion exchange polymer, also known as Nafion®, into two virtual layers in the simulation model: one was expansive and the other was contractive, caused by opposite constant surface forces on each surface of the elements. Therefore, the deformation for different IPMC shapes can be described more easily. A standard experiment of voltage vs. tip displacement was used to verify the proposed modeling. Finally, a gear shaped IPMC actuator was designed and tested. Optical power of the IPMC deformable mirror is experimentally demonstrated to be 17 diopters with two volts. The needed voltage was about two orders lower than conventional silicon deformable mirrors and about one order lower than the liquid lens. PMID:23112648

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf2N ionic liquid.

PubMed

Sandoval, Andrea P; Suárez-Herrera, Marco F; Feliu, Juan M

2015-01-01

Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force microscopy. It was found that the polymer grows faster on Pt(111) than on Pt(110) or Pt(100) and that the redox reactions associated with the PEDOT p-doping process are much more reversible in [EMMIM]Tf2N than in acetonitrile. Finally, the ion exchange and charge carriers' formation during the p-doping reaction of PEDOT were studied using in situ FTIR spectroscopy.

Length scale dependence of the dynamic properties of hyaluronic acid solutions in the presence of salt.

PubMed

Horkay, Ferenc; Falus, Peter; Hecht, Anne-Marie; Geissler, Erik

2010-12-02

In solutions of the charged semirigid biopolymer hyaluronic acid in salt-free conditions, the diffusion coefficient D(NSE) measured at high transfer momentum q by neutron spin echo is more than an order of magnitude smaller than that determined by dynamic light scattering, D(DLS). This behavior contrasts with neutral polymer solutions. With increasing salt content, D(DLS) approaches D(NSE), which is independent of ionic strength. Contrary to theoretical expectation, the ion-polymer coupling, which dominates the low q dynamics of polyelectrolyte solutions, already breaks down at distance scales greater than the Debye-Hückel length.

A moisture and electric coupling stimulated ionic polymer-metal composite actuator with controllable deformation behavior

NASA Astrophysics Data System (ADS)

Ru, Jie; Zhu, Zicai; Wang, Yanjie; Chen, Hualing; Bian, Changsheng; Luo, Bin; Li, Dichen

2018-02-01

Ionic polymer-metal composite (IPMC) actuator can generate large and rapid deformation based on ion migration under a relatively low driving voltage. Under full hydrated conditions, the deformation is always prone to relaxation. At room humidity conditions, the deformation increases substantially at the early stage of actuation, and then decreases gradually. Generally, most researchers considered that the change of water content or relative humidity mainly leads to the deformation instabilities, which severely limits the practical applications of IPMC. In this Letter, a novel actuation mode is proposed to control the deformation behavior of IPMC by employing moisture as an independent or collaborative incentive source together with the electric field. The deformation response is continuously measured under electric field, electric field-moisture coupling stimulus and moisture stimulus. The result shows that moisture can be a favorable driving factor for IPMC actuation. Such an electric field-moisture coupling stimulus can avoid the occurrence of deformation instabilities and guarantee a superior controllable deformation in IPMC actuation. This research provides a new method to obtain stable and large deformation of IPMC, which is of great significance for the guidance of material design and application for IPMC and IPMC-type iEAP materials.

Kinematically stable bipedal locomotion using ionic polymer-metal composite actuators

NASA Astrophysics Data System (ADS)

Hosseinipour, Milad; Elahinia, Mohammad

2013-08-01

Ionic conducting polymer-metal composites (abbreviated as IPMCs) are interesting actuators that can act as artificial muscles in robotic and microelectromechanical systems. Various black or gray box models have modeled the electrochemical-mechanical behavior of these materials. In this study, the governing partial differential equation of the behavior of IPMCs is solved using finite element methods to find the critical actuation parameters, such as strain distribution, maximum strain, and response time. One-dimensional results of the FEM solution are then extended to 2D to find the tip displacement of a flap actuator and experimentally verified. A model of a seven-degree-of-freedom biped robot, actuated by IPMC flaps, is then introduced. The possibility of fast and stable bipedal locomotion using IPMC artificial muscles is the main motivation of this study. Considering the actuator limits, joint path trajectories are generated to achieve a fast and smooth motion. The stability of the proposed gait is then evaluated using the ZMP criterion and motion simulation. The fabrication parameters of each actuator, such as length, platinum plating thickness and installation angle, are then determined using the generated trajectories. A discussion on future studies on force-torque generation of IPMCs for biped locomotion concludes this paper.

Investigation on the Mechanical and Electrical Behavior of a Tuning Fork-Shaped Ionic Polymer Metal Composite Actuator with a Continuous Water Supply Mechanism

PubMed Central

Feng, Guo-Hua; Huang, Wei-Lun

2016-01-01

This paper presents an innovative tuning fork-shaped ionic polymer metal composite (IPMC) actuator. With an integrated soft strain gauge and water supply mechanism (WSM), the surface strain of the actuator can be sensed in situ, and providing a continuous water supply maintains the water content inside the IPMC for long-term operation in air. The actuator was fabricated using a micromachining technique and plated with a nickel electrode. The device performance was experimentally characterized and compared with an actuator without a WSM. A large displacement of 1.5 mm was achieved for a 6 mm-long prong with 7-V dc actuation applied for 30 s. The measured current was analyzed using an electrochemical model. The results revealed that the faradaic current plays a crucial role during operation, particularly after 10 s. The measured strain confirms both the bending and axial strain generation during the open-and-close motion of the actuator prongs. Most of the water loss during device operation was due to evaporation rather than hydrolysis. The constructed WSM effectively maintained the water content inside the IPMC for long-term continuous operation. PMID:27023549

Active Tube-Shaped Actuator with Embedded Square Rod-Shaped Ionic Polymer-Metal Composites for Robotic-Assisted Manipulation

PubMed Central

Liu, Jiayu; Zhu, Denglin; Chen, Hualing

2018-01-01

This paper reports a new technique involving the design, fabrication, and characterization of an ionic polymer-metal composite- (IPMC-) embedded active tube, which can achieve multidegree-of-freedom (MODF) bending motions desirable in many applications, such as a manipulator and an active catheter. However, traditional strip-type IPMC actuators are limited in only being able to generate 1-dimensional bending motion. So, in this paper, we try to develop an approach which involves molding or integrating rod-shaped IPMC actuators into a soft silicone rubber structure to create an active tube. We modified the Nafion solution casting method and developed a complete sequence of a fabrication process for rod-shaped IPMCs with square cross sections and four insulated electrodes on the surface. The silicone gel was cured at a suitable temperature to form a flexible tube using molds fabricated by 3D printing technology. By applying differential voltages to the four electrodes of each IPMC rod-shaped actuator, MDOF bending motions of the active tube can be generated. Experimental results show that such IPMC-embedded tube designs can be used for developing robotic-assisted manipulation. PMID:29770160

Active Tube-Shaped Actuator with Embedded Square Rod-Shaped Ionic Polymer-Metal Composites for Robotic-Assisted Manipulation.

PubMed

Wang, Yanjie; Liu, Jiayu; Zhu, Denglin; Chen, Hualing

2018-01-01

This paper reports a new technique involving the design, fabrication, and characterization of an ionic polymer-metal composite- (IPMC-) embedded active tube, which can achieve multidegree-of-freedom (MODF) bending motions desirable in many applications, such as a manipulator and an active catheter. However, traditional strip-type IPMC actuators are limited in only being able to generate 1-dimensional bending motion. So, in this paper, we try to develop an approach which involves molding or integrating rod-shaped IPMC actuators into a soft silicone rubber structure to create an active tube. We modified the Nafion solution casting method and developed a complete sequence of a fabrication process for rod-shaped IPMCs with square cross sections and four insulated electrodes on the surface. The silicone gel was cured at a suitable temperature to form a flexible tube using molds fabricated by 3D printing technology. By applying differential voltages to the four electrodes of each IPMC rod-shaped actuator, MDOF bending motions of the active tube can be generated. Experimental results show that such IPMC-embedded tube designs can be used for developing robotic-assisted manipulation.

Investigation on the Mechanical and Electrical Behavior of a Tuning Fork-Shaped Ionic Polymer Metal Composite Actuator with a Continuous Water Supply Mechanism.

PubMed

Feng, Guo-Hua; Huang, Wei-Lun

2016-03-25

This paper presents an innovative tuning fork-shaped ionic polymer metal composite (IPMC) actuator. With an integrated soft strain gauge and water supply mechanism (WSM), the surface strain of the actuator can be sensed in situ, and providing a continuous water supply maintains the water content inside the IPMC for long-term operation in air. The actuator was fabricated using a micromachining technique and plated with a nickel electrode. The device performance was experimentally characterized and compared with an actuator without a WSM. A large displacement of 1.5 mm was achieved for a 6 mm-long prong with 7-V dc actuation applied for 30 s. The measured current was analyzed using an electrochemical model. The results revealed that the faradaic current plays a crucial role during operation, particularly after 10 s. The measured strain confirms both the bending and axial strain generation during the open-and-close motion of the actuator prongs. Most of the water loss during device operation was due to evaporation rather than hydrolysis. The constructed WSM effectively maintained the water content inside the IPMC for long-term continuous operation.

The Role of Dissolved Gas in Ionic Liquid Electrolytes for Secondary Lithium Metal Batteries

DTIC Science & Technology

2013-01-07

devices use lithium-ion batteries comprised of a graphite anode and metal oxide cathode . Lithium, being the third-lightest element, is already synonymous...support shuttling lithium ions (battery cycling) such as the separator, electrolyte, and cathode and anode superstructures contribute most of the...ability of electro-deposit lithium non-dendritically. When lithium is electrodeposited , as during battery charging, it tends to form needle-like

Organic transistors making use of room temperature ionic liquids as gating medium

NASA Astrophysics Data System (ADS)

Hoyos, Jonathan Javier Sayago

The ability to couple ionic and electronic transport in organic transistors, based on pi conjugated organic materials for the transistor channel, can be particularly interesting to achieve low voltage transistor operation, i.e. below 1 V. The operation voltage in typical organic transistors based on conventional dielectrics (200 nm thick SiO2) is commonly higher than 10 V. Electrolyte-gated (EG) transistors, i.e. employing an electrolyte as the gating medium, permit current modulations of several orders of magnitude at relatively low gate voltages thanks to the exceptionally high capacitance at the electrolyte/transistor channel interface, in turn due to the low thickness (ca. 3 nm) of the electrical double layers forming at the electrolyte/semiconductor interface. Electrolytes based on room temperature ionic liquids (RTILs) are promising in EG transistor applications for their high electrochemical stability and good ionic conductivity. The main motivation behind this work is to achieve low voltage operation in organic transistors by making use of RTILs as gating medium. First we demonstrate the importance of the gate electrode material in the EG transistor performance. The use of high surface area carbon gate electrodes limits undesirable electrochemical processes and renders unnecessary the presence of a reference electrode to monitor the channel potential. This was demonstrated using activated carbon as gate electrode, the electronic conducting polymer MEH-PPV, poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] channel material, and the ionic liquid [EMIM][TFSI] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), as gating medium. Using high surface area gate electrodes resulted in sub-1 V operation and charge carrier mobilities of (1.0 +/- 0.5) x 10-2 cm2V -1s-1. A challenge in the field of EG transistors is to decrease their response time, a consequence of the slow ion redistribution in the transistor channel upon application of electric biases. We systematically investigated EG transistors employing RTILs belonging to the same family, i.e. based on a common anion and different cations. The transistor characteristics showed a limited cation influence in establishing the p-type doping of the conducting polymer. Interestingly, we observed that the transistor response time depends on at least two processes: the redistribution of ions from the electrolyte into the transistor channel, affecting the gate-source current (I gs); and the redistribution of charges in the transistor channel, affecting the drain-source current (Ids), as a function of time. The two processes have different rates, with the latter being the slowest. Incorporating propylene carbonate in the electrolyte proved to be an effective solution to increase the ionic conductivity, to lower the viscosity and, consequently, to reduce the transistor response time. Finally, we were able to demonstrate a multifunctional device integrating the transistor logic function with that of energy storage in a supercapacitor: the TransCap. The polymer/electrolyte/carbon vertical stacking of the EG transistor features the cell configuration of a hybrid supercapacitor. Supercapacitors are high specific power systems that, for their ability to store/deliver charge within short times may outperform batteries in applications having high power demand. When the TransCap is ON (open transistor channel), the polymer and the carbon gate electrodes store charge (Q) at a given Vgs, hence the stored energy equals Q˙V gs. When the TransCap is switched OFF, the channel and the gate are discharged and the energy can be delivered back to power other electronic components. EG transistors, making use of activated carbon as gate electrode and different RTILs as well as RTIL solvent mixtures as electrolyte gating medium, are interesting towards low voltage printable electronics. The high capacitance at the interface between the electrolyte and the transistor channel enables energy storage within the EG transistor architecture.

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices.

PubMed

Black, Jennifer M; Come, Jeremy; Bi, Sheng; Zhu, Mengyang; Zhao, Wei; Wong, Anthony T; Noh, Joo Hyon; Pudasaini, Pushpa R; Zhang, Pengfei; Okatan, Mahmut Baris; Dai, Sheng; Kalinin, Sergei V; Rack, Philip D; Ward, Thomas Zac; Feng, Guang; Balke, Nina

2017-11-22

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal-insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment and theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.

Sequential growth for lifetime extension in biomimetic polypyrrole actuator systems

NASA Astrophysics Data System (ADS)

Sarrazin, J. C.; Mascaro, Stephen A.

2015-04-01

Electroactive polymers (EAPs) present prospective use in actuation and manipulation devices due to their low electrical activation requirements, biocompatibility, and mechanical performance. One of the main drawbacks with EAP actuators is a decrease in performance over extended periods of operation caused by over-oxidation of the polymer and general polymer degradation. Synthesis of the EAP material, polypyrrole with an embedded metal helix allows for sequential growth of the polymer during operation. The helical metal electrode acts as a scaffolding to support the polymer, and direct the 3-dimensional change in volume of the polymer along the axis of the helix during oxidative and reductive cycling. The metal helix also provides a working metal electrode through the entire length of the polymer actuator to distribute charge for actuation, as well as for sequential growth steps during the lifetime of operation of the polymer. This work demonstrates the method of sequential growth can be utilized after extended periods of use to partially restore electrical and mechanical performance of polypyrrole actuators. Since the actuation must be temporarily stopped to allow for a sequential growth cycle to be performed and reverse some of the polymer degradation, these actuator systems more closely mimic natural muscle in their analogous maintenance and repair.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

NASA Astrophysics Data System (ADS)

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

PubMed Central

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-01-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability. PMID:27080134

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation.

PubMed

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-15

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors' knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties.

PubMed

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-03-16

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.

Ionogels Based on Poly(methyl methacrylate) and Metal-Containing Ionic Liquids: Correlation between Structure and Mechanical and Electrical Properties

PubMed Central

Zehbe, Kerstin; Kollosche, Matthias; Lardong, Sebastian; Kelling, Alexandra; Schilde, Uwe; Taubert, Andreas

2016-01-01

Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs. PMID:26999112

Direct Observation of Ion Distributions near Electrodes in Ionic Polymer Actuators Containing Ionic Liquids

PubMed Central

Liu, Yang; Lu, Caiyan; Twigg, Stephen; Ghaffari, Mehdi; Lin, Junhong; Winograd, Nicholas; Zhang, Q. M.

2013-01-01

The recent boom of energy storage and conversion devices, exploiting ionic liquids (ILs) to enhance the performance, requires an in-depth understanding of this new class of electrolytes in device operation conditions. One central question critical to device performance is how the mobile ions accumulate near charged electrodes. Here, we present the excess ion depth profiles of ILs in ionomer membrane actuators (Aquivion/1-butyl-2,3-dimethylimidazolium chloride (BMMI-Cl), 27 μm thick), characterized directly by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) at liquid nitrogen temperature. Experimental results reveal that for the IL studied, cations and anions are accumulated at both electrodes. The large difference in the total volume occupied by the excess ions between the two electrodes cause the observed large bending actuation of the actuator. Hence we demonstrate that ToF-SIMS experiment provides great insights on the physics nature of ionic devices. PMID:23512124

Charged Covalent Triazine Frameworks for CO2 Capture and Conversion.

PubMed

Buyukcakir, Onur; Je, Sang Hyun; Talapaneni, Siddulu Naidu; Kim, Daeok; Coskun, Ali

2017-03-01

The quest for the development of new porous materials addressing both CO 2 capture from various sources and its conversion into useful products is a very active research area and also critical in order to develop a more sustainable and environmentally-friendly society. Here, we present the first charged covalent triazine framework (cCTF) prepared by simply heating nitrile functionalized dicationic viologen derivatives under ionothermal reaction conditions using ZnCl 2 as both solvent and trimerization catalyst. It has been demonstrated that the surface area, pore volume/size of cCTFs can be simply controlled by varying the synthesis temperature and the ZnCl 2 content. Specifically, increasing the reaction temperature led to controlled increase in the mesopore content and facilitated the formation of hierarchical porosity, which is critical to ensure efficient mass transport within porous materials. The resulting cCTFs showed high specific surface areas up to 1247 m 2 g -1 , and high physicochemical stability. The incorporation of ionic functional moieties to porous organic polymers improved substantially their CO 2 affinity (up to 133 mg g -1 , at 1 bar and 273 K) and transformed them into hierarchically porous organocatalysts for CO 2 conversion. More importantly, the ionic nature of cCTFs, homogeneous charge distribution together with hierarchical porosity offered a perfect platform for the catalytic conversion of CO 2 into cyclic carbonates in the presence of epoxides through an atom economy reaction in high yields and exclusive product selectivity. These results clearly demonstrate the promising aspect of incorporation of charged units into the porous organic polymers for the development of highly efficient porous organocatalysts for CO 2 capture and fixation.

Ionic Adsorption and Desorption of CNT Nanoropes

PubMed Central

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-01-01

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment. PMID:28335306

Ionic Adsorption and Desorption of CNT Nanoropes.

PubMed

Shang, Jun-Jun; Yang, Qing-Sheng; Yan, Xiao-Hui; He, Xiao-Qiao; Liew, Kim-Meow

2016-09-28

A nanorope is comprised of several carbon nanotubes (CNTs) with different chiralities. A molecular dynamic model is built to investigate the ionic adsorption and desorption of the CNT nanoropes. The charge distribution on the nanorope is obtained by using a modified gradient method based on classical electrostatic theory. The electrostatic interactions among charged carbon atoms are calculated by using the Coulomb law. It was found here that the charged nanorope can adsorb heavy metal ions, and the adsorption and desorption can be realized by controlling the strength of applied electric field. The distance between the ions and the nanorope as well as the amount of ions have an effect on the adsorption capacity of the nanorope. The desorption process takes less time than that of adsorption. The study indicates that the CNT nanorope can be used as a core element of devices for sewage treatment.

Electrospun nanocomposite fibrous polymer electrolyte for secondary lithium battery applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padmaraj, O.; Rao, B. Nageswara; Jena, Paramananda

2014-04-24

Hybrid nanocomposite [poly(vinylidene fluoride -co- hexafluoropropylene) (PVdF-co-HFP)/magnesium aluminate (MgAl{sub 2}O{sub 4})] fibrous polymer membranes were prepared by electrospinning method. The prepared pure and nanocomposite fibrous polymer electrolyte membranes were soaked into the liquid electrolyte 1M LiPF{sub 6} in EC: DEC (1:1,v/v). XRD and SEM are used to study the structural and morphological studies of nanocomposite electrospun fibrous polymer membranes. The nanocomposite fibrous polymer electrolyte membrane with 5 wt.% of MgAl{sub 2}O{sub 4} exhibits high ionic conductivity of 2.80 × 10{sup −3} S/cm at room temperature. The charge-discharge capacity of Li/LiCoO{sub 2} coin cells composed of the newly prepared nanocomposite [(16more » wt.%) PVdF-co-HFP+(5 wt.%) MgAl{sub 2}O{sub 4}] fibrous polymer electrolyte membrane was also studied and compared with commercial Celgard separator.« less

Structure and dynamics of single hydrophobic/ionic heteropolymers at the vapor-liquid interface of water.

PubMed

Vembanur, Srivathsan; Venkateshwaran, Vasudevan; Garde, Shekhar

2014-04-29

We focus on the conformational stability, structure, and dynamics of hydrophobic/charged homopolymers and heteropolymers at the vapor-liquid interface of water using extensive molecular dynamics simulations. Hydrophobic polymers collapse into globular structures in bulk water but unfold and sample a broad range of conformations at the vapor-liquid interface of water. We show that adding a pair of charges to a hydrophobic polymer at the interface can dramatically change its conformations, stabilizing hairpinlike structures, with molecular details depending on the location of the charged pair in the sequence. The translational dynamics of homopolymers and heteropolymers are also different, whereas the homopolymers skate on the interface with low drag, the tendency of charged groups to remain hydrated pulls the heteropolymers toward the liquid side of the interface, thus pinning them, increasing drag, and slowing the translational dynamics. The conformational dynamics of heteropolymers are also slower than that of the homopolymer and depend on the location of the charged groups in the sequence. Conformational dynamics are most restricted for the end-charged heteropolymer and speed up as the charge pair is moved toward the center of the sequence. We rationalize these trends using the fundamental understanding of the effects of the interface on primitive pair-level interactions between two hydrophobic groups and between oppositely charged ions in its vicinity.

Entropic and Electrostatic Effects on the Folding Free Energy of a Surface-Attached Biomolecule: An Experimental and Theoretical Study

PubMed Central

Watkins, Herschel M.; Vallée-Bélisle, Alexis; Ricci, Francesco; Makarov, Dmitrii E.; Plaxco, Kevin W.

2012-01-01

Surface-tethered biomolecules play key roles in many biological processes and biotechnologies. However, while the physical consequences of such surface attachment have seen significant theoretical study, to date this issue has seen relatively little experimental investigation. In response we present here a quantitative experimental and theoretical study of the extent to which attachment to a charged –but otherwise apparently inert– surface alters the folding free energy of a simple biomolecule. Specifically, we have measured the folding free energy of a DNA stem loop both in solution and when site-specifically attached to a negatively charged, hydroxyl-alkane-coated gold surface. We find that, whereas surface attachment is destabilizing at low ionic strength it becomes stabilizing at ionic strengths above ~130 mM. This behavior presumably reflects two competing mechanisms: excluded volume effects, which stabilize the folded conformation by reducing the entropy of the unfolded state, and electrostatics, which, at lower ionic strengths, destabilizes the more compact folded state via repulsion from the negatively charged surface. To test this hypothesis we have employed existing theories of the electrostatics of surface-bound polyelectrolytes and the entropy of surface-bound polymers to model both effects. Despite lacking any fitted parameters, these theoretical models quantitatively fit our experimental results, suggesting that, for this system, current knowledge of both surface electrostatics and excluded volume effects is reasonably complete and accurate. PMID:22239220

Understanding the Thermal Properties of Precursor-Ionomers to Optimize Fabrication Processes for Ionic Polymer-Metal Composites (IPMCs)

PubMed Central

Choi, Kisuk; Olsen, Zakai; Hwang, Taeseon; Nam, Jae-Do

2018-01-01

Ionic polymer-metal composites (IPMCs) are one of many smart materials and have ionomer bases with a noble metal plated on the surface. The ionomer is usually Nafion, but recently Aquivion has been shown to be a promising alternative. Ionomers are available in the form of precursor pellets. This is an un-activated form that is able to melt, unlike the activated form. However, there is little study on the thermal characteristics of these precursor ionomers. This lack of knowledge causes issues when trying to fabricate ionomer shapes using methods such as extrusion, hot-pressing, and more recently, injection molding and 3D printing. To understand the two precursor-ionomers, a set of tests were conducted to measure the thermal degradation temperature, viscosity, melting temperature, and glass transition. The results have shown that the precursor Aquivion has a higher melting temperature (240 °C) than precursor Nafion (200 °C) and a larger glass transition range (32–65 °C compared with 21–45 °C). The two have the same thermal degradation temperature (~400 °C). Precursor Aquivion is more viscous than precursor Nafion as temperature increases. Based on the results gathered, it seems that the precursor Aquivion is more stable as temperature increases, facilitating the manufacturing processes. This paper presents the data collected to assist researchers in thermal-based fabrication processes. PMID:29693584

A self-strain feedback tuning-fork-shaped ionic polymer metal composite clamping actuator with soft matter elasticity-detecting capability for biomedical applications.

PubMed

Feng, Guo-Hua; Huang, Wei-Lun

2014-12-01

This paper presents a smart tuning-fork-shaped ionic polymer metal composite (IPMC) clamping actuator for biomedical applications. The two fingers of the actuator, which perform the clamping motion, can be electrically controlled through a unique electrode design on the IPMC material. The generated displacement or strain of the fingers can be sensed using an integrated soft strain-gage sensor. The IPMC actuator and associated soft strain gage were fabricated using a micromachining technique. A 13.5×4×2 mm(3) actuator was shaped from Nafion solution and a selectively grown metal electrode formed the active region. The strain gage consisted of patterned copper foil and polyethylene as a substrate. The relationship between the strain gage voltage output and the displacement at the front end of the actuator's fingers was characterized. The equivalent Young's modulus, 13.65 MPa, of the soft-strain-gage-integrated IPMC finger was analyzed. The produced clamping force exhibited a linear increasing rate of 1.07 mN/s, based on a dc driving voltage of 7 V. Using the developed actuator to clamp soft matter and simultaneously acquire its Young's modulus was achieved. This demonstrated the feasibility of the palpation function and the potential use of the actuator in minimally invasive surgery. Copyright © 2014 Elsevier B.V. All rights reserved.

Coarse-Grained Molecular Dynamics Simulation of Ionic Polymer Networks

DTIC Science & Technology

2008-07-01

AFRL-RX-WP-TP-2009-4198 COARSE-GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) T.E. Dirama, V. Varshney, K.L...GRAINED MOLECULAR DYNAMICS SIMULATION OF IONIC POLYMER NETWORKS (Postprint) 5a. CONTRACT NUMBER FA8650-05-D-5807-0052 5b. GRANT NUMBER 5c...We studied two types of networks which differ only by one containing ionic pairs that amount to 7% of the total number of bonds present. The stress

Surface-potential decay of biased-probe contact-charged amorphous polymer films

NASA Astrophysics Data System (ADS)

Knorr, Nikolaus; Rosselli, Silvia; Nelles, Gabriele

2010-03-01

We have investigated the decay of scanning Kelvin probe force microscopy (KPFM) and electric force microscopy (EFM) signals from biased-probe contact-charged films of three different amorphous polymers representing wide-ranging water absorption capabilities. The surface-potential decay (SPD) has been measured by repeatedly scanning the charge pattern as a function of dissipation time t while varying the relative humidity (RH), the film thickness d, the temperature, the charging voltage, and the load on the scanning probe. Whereas increases in KPFM and EFM peak widths are appreciable only in the long run, the decay in the peak heights is rapid at the beginning and then strongly slowing down with time. Peak heights can be approximated for t <1 hour by power laws of negative exponents (-β), with 0<β<0.5 in dry conditions. β increases for thinner films and when scanning with higher probe loads. Raising the humidity or heating to temperatures well below the glass transition temperature of the polymer considerably increases β, with much stronger impacts for polymers with a higher water uptake capability. From the findings, we conclude that ionic charge carriers are trapped by the charge injection process in the volume of the polymers at low depths. A main contribution to SPD is by drift of the ions in their own space-charge field, mutually repelling each other and being attracted by their mirror charge in the grounded back electrode. Lateral drifts for small t are not resolved, increases in peak widths for t ≫1 h are predominantly due to increased probe—charge carrier distances. We interpret the power law approximation in terms of dispersive transport theory. We approximate trap-controlled apparent mobilities μ from isothermal KPFM peak height data, taken within a few minutes after charging, by a linear and a hyperbolic SPD model. Both models yield μ ≈10-14 cm2/(V s) for thin films (d ≈50 nm) in dry conditions. For mobilities derived similarly from isohumid measurements series, we find an exponential increase as a function of RH%. We furthermore suggest that two more mechanisms contributing to SPD are: first, by potential shielding of charge carriers by water dipoles, and second, in an indirect manner, by diffusion of injected water.

In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

DOE PAGES

Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

2015-10-23

We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

A correlation between extensional displacement and architecture of ionic polymer transducers

NASA Astrophysics Data System (ADS)

Akle, Barbar J.; Duncan, Andrew; Leo, Donald J.

2008-03-01

Ionic polymer transducers (IPT), sometimes referred to as artificial muscles, are known to generate a large bending strain and a moderate stress at low applied voltages (<5V). Bending actuators have limited engineering applications due to the low forcing capabilities and the need for complicated external devices to convert the bending action into rotating or linear motion desired in most devices. Recently Akle and Leo reported extensional actuation in ionic polymer transducers. In this study, extensional IPTs are characterized as a function of transducer architecture. In this study 2 actuators are built and there extensional displacement response is characterized. The transducers have similar electrodes while the middle membrane in the first is a Nafion / ionic liquid and an aluminum oxide - ionic liquid in the second. The first transducer is characterized for constant current input, voltage step input, and sweep voltage input. The model prediction is in agreement in both shape and magnitude for the constant current experiment. The values of α and β used are within the range of values reported in Akle and Leo. Both experiments and model demonstrate that there is a preferred direction of applying the potential so that the transducer will exhibit large deformations. In step response the model well predicted the negative potential and the early part of the step in the positive potential and failed to predict the displacement after approximately 180s has elapsed. The model well predicted the sweep response, and the observed 1st harmonic in the displacement further confirmed the existence of a quadratic in the charge response. Finally the aluminum oxide based transducer is characterized for a step response and compared to the Nafion based transducer. The second actuator demonstrated electromechanical extensional response faster than that in the Nafion based transducer. The Aluminum oxide based transducer is expected to provide larger forces and hence larger energy density.

Structure and mechanisms underlying ion transport in ternary polymer electrolytes containing ionic liquids

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2017-02-01

We use all atom molecular dynamics simulations to investigate the influence of 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) ionic liquid on the structure and transport properties of poly(ethylene oxide) (PEO) polymer electrolytes doped with LiPF6 salt. We observe enhanced diffusivities of the Li+, PF6-, and BMIM+ ions with increasing loading of the ionic liquid. Interplay between the different ion-ion and ion-polymer interactions is seen to lead to a destabilization of the Li-PF6 coordination and increase in the strength of association between the Li+ cations and the polymer backbone. As a consequence, the polymer segmental relaxation times are shown to be only moderately affected by the addition of ionic liquids. The ionic-liquid induced changes in the mobilities of Li+ ions are seen to be correlated to polymer segmental relaxation times. However, the mobilities of BMIM+ ions are seen to be more strongly correlated to the BMIM-PF6 ion-pair relaxation times.

Ionic liquids as novel solvents for ionic polymer transducers

NASA Astrophysics Data System (ADS)

Bennett, Matthew D.; Leo, Donald J.

2004-07-01

The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

Advances in mucoadhesion and mucoadhesive polymers.

PubMed

Khutoryanskiy, Vitaliy V

2011-06-14

Mucoadhesion is the ability of materials to adhere to mucosal membranes in the human body and provide a temporary retention. This property has been widely used to develop polymeric dosage forms for buccal, oral, nasal, ocular and vaginal drug delivery. Excellent mucoadhesive properties are typical for hydrophilic polymers possessing charged groups and/or non-ionic functional groups capable of forming hydrogen bonds with mucosal surfaces. This feature article considers recent advances in the study of mucoadhesion and mucoadhesive polymers. It provides an overview on the structure of mucosal membranes, properties of mucus gels and the nature of mucoadhesion. It describes the most common methods to evaluate mucoadhesive properties of various dosage forms and discusses the main classes of mucoadhesives. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Revisiting structure-property relationship of pH-responsive polymers for drug delivery applications.

PubMed

Bazban-Shotorbani, Salime; Hasani-Sadrabadi, Mohammad Mahdi; Karkhaneh, Akbar; Serpooshan, Vahid; Jacob, Karl I; Moshaverinia, Alireza; Mahmoudi, Morteza

2017-05-10

pH-responsive polymers contain ionic functional groups as pendants in their structure. The total number of charged groups on polymer chains determines the overall response of the system to changes in the external pH. This article reviews various pH-responsive polymers classified as polyacids (e.g., carboxylic acid based polymers, sulfonamides, anionic polysaccharides, and anionic polypeptides) and polybases (e.g., polyamines, pyridine and imidazole containing polymers, cationic polysaccharides, and cationic polypeptides). We correlate the pH variations in the body at the organ level (e.g., gastrointestinal tract and vaginal environment), tissue level (e.g., cancerous and inflamed tissues), and cellular level (e.g., sub-cellular organelles), with the intrinsic properties of pH-responsive polymers. This knowledge could help to select more effective ('smart') polymeric systems based on the biological target. Considering the pH differences in the body, various drug delivery systems can be designed by utilizing smart biopolymeric compounds with the required pH-sensitivity. We also review the pharmaceutical application of pH-responsive polymeric carriers including hydrogels, polymer-drug conjugates, micelles, dendrimers, and polymersomes. © 2016.

Electromagnetic Interference Behavior of Multiwall Carbon Nanotubes and Carbon Nanofibers Composites Under Fatigue

DTIC Science & Technology

2012-03-01

introducing conductive metallic materials onto or into the polymer composite. The earlier process steps included metallic paint coating, insertion......onboard from critical data loss to permanent damage. The ionized radiation strips electrons from atoms in the space plasma, creating charged

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

Tandem SAM Domain Structure of Human Caskin1: A Presynaptic, Self-Assembling Scaffold for CASK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stafford, Ryan L.; Hinde, Elizabeth; Knight, Mary Jane

2012-02-07

The synaptic scaffolding proteins CASK and Caskin1 are part of the fibrous mesh of proteins that organize the active zones of neural synapses. CASK binds to a region of Caskin1 called the CASK interaction domain (CID). Adjacent to the CID, Caskin1 contains two tandem sterile a motif (SAM) domains. Many SAM domains form polymers so they are good candidates for forming the fibrous structures seen in the active zone. We show here that the SAM domains of Caskin1 form a new type of SAM helical polymer. The Caskin1 polymer interface exhibits a remarkable segregation of charged residues, resulting in amore » high sensitivity to ionic strength in vitro. The Caskin1 polymers can be decorated with CASK proteins, illustrating how these proteins may work together to organize the cytomatrix in active zones.« less

Beyond superquenching: Hyper-efficient energy transfer from conjugated polymers to gold nanoparticles

PubMed Central

Fan, Chunhai; Wang, Shu; Hong, Janice W.; Bazan, Guillermo C.; Plaxco, Kevin W.; Heeger, Alan J.

2003-01-01

Gold nanoparticles quench the fluorescence of cationic polyfluorene with Stern–Volmer constants (KSV) approaching 1011 M—1, several orders of magnitude larger than any previously reported conjugated polymer–quencher pair and 9–10 orders of magnitude larger than small molecule dye–quencher pairs. The dependence of KSV on ionic strength, charge and conjugation length of the polymer, and the dimensions (and thus optical properties) of the nanoparticles suggests that three factors account for this extraordinary efficiency: (i) amplification of the quenching via rapid internal energy or electron transfer, (ii) electrostatic interactions between the cationic polymer and anionic nanoparticles, and (iii) the ability of gold nanoparticles to quench via efficient energy transfer. As a result of this extraordinarily high KSV, quenching can be observed even at subpicomolar concentrations of nanoparticles, suggesting that the combination of conjugated polymers with these nanomaterials can potentially lead to improved sensitivity in optical biosensors. PMID:12750470

Structural rearrangement and dispersion of functionalized graphene sheets in aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Yun Jung; Huang, Liwei; Wang, Howard

2015-09-01

Surfactants are widely used for dispersing graphene and functionalized graphene sheets (FGS) in colloidal suspensions, but there have been few studies of the structure of the dispersed graphene-surfactant complexes in suspension and of their time evolution. Here, we combine experimental study of efficiencies of ionic surfactants/polymers in suspending FGS in water with characterization using atomic force microscopy, small angle neutron scattering, and molecular simulations to probe the detailed structures of FGSs. A systematic study of FGS dispersions using ionic surfactants with varying chain lengths revealed that the effective charge density of surfactant layer defines the concentration of dispersed FGS whilemore » the strength of interfacial binding defines the stability of graphene dispersion over long time aging. Ionic surfactants with strong interfacial binding and large molecular weight increase the dispersing power by over an order of magnitude.« less

Adsorption behavior of proteins on temperature-responsive resins.

PubMed

Poplewska, Izabela; Muca, Renata; Strachota, Adam; Piątkowski, Wojciech; Antos, Dorota

2014-01-10

The adsorption behavior of proteins on thermo-responsible resins based on poly(N-isopropylacrylamide) and its copolymer containing an anionic co-monomer has been investigated. The influence of the polymer composition, i.e., the content of the co-monomer and crosslinker on the thermo-sensitivity of the protein adsorption has been quantified. The properties of ungrafted polymer as well grafted onto the agarose matrix have been analyzed and compared. Batch and dynamic (column) experiments have been performed to measure the adsorption equilibrium of proteins and to quantify the phase transition process. As model proteins lysozyme, lactoferrin, α-chymotrypsinogen A and ovalbumin have been used. The adsorption process was found to be governed by ionic interactions between the negatively charged surface of resin and the protein, which enabled separation of proteins differing in electrostatic charge. The interactions enhanced with increase of temperature. Decrease of temperature facilitated desorption of proteins and reduced the salt usage in the desorption buffer. Grafted polymers exhibited markedly higher mechanical stability and, however, weaker temperature response compared to the ungrafted ones. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrode-Impregnable and Cross-Linkable Poly(ethylene oxide)-Poly(propylene oxide)-Poly(ethylene oxide) Triblock Polymer Electrolytes with High Ionic Conductivity and a Large Voltage Window for Flexible Solid-State Supercapacitors.

PubMed

Han, Jae Hee; Lee, Jang Yong; Suh, Dong Hack; Hong, Young Taik; Kim, Tae-Ho

2017-10-04

We present cross-linkable precursor-type gel polymer electrolytes (GPEs) that have large ionic liquid uptake capability, can easily penetrate electrodes, have high ion conductivity, and are mechanically strong as high-performance, flexible all-solid-state supercapacitors (SC). Our polymer precursors feature a hydrophilic-hydrophobic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock main-chain structure and trifunctional silane end groups that can be multi-cross-linked with each other through a sol-gel process. The cross-linked solid-state electrolyte film with moderate IL content (200 wt %) shows a well-balanced combination of excellent ionic conductivity (5.0 × 10 -3 S cm -1 ) and good mechanical stability (maximum strain = 194%). Moreover, our polymer electrolytes have various advantages including high thermal stability (decomposition temperature > 330 °C) and the capability to impregnate electrodes to form an excellent electrode-electrolyte interface due to the very low viscosity of the precursors. By assembling our GPE-impregnated electrodes and solid-state GPE film, we demonstrate an all-solid-state SC that can operate at 3 V and provides an improved specific capacitance (112.3 F g -1 at 0.1 A g -1 ), better rate capability (64% capacity retention until 20 A g -1 ), and excellent cycle stability (95% capacitance decay over 10 000 charge/discharge cycles) compared with those of a reference SC using a conventional PEO electrolyte. Finally, flexible SCs with a high energy density (22.6 W h kg -1 at 1 A g -1 ) and an excellent flexibility (>93% capacitance retention after 5000 bending cycles) can successfully be obtained.

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Influence of Ambient Humidity on the Voltage Response of Ionic Polymer-Metal Composite Sensor.

PubMed

Zhu, Zicai; Horiuchi, Tetsuya; Kruusamäe, Karl; Chang, Longfei; Asaka, Kinji

2016-03-31

Electrical potential based on ion migration exists not only in natural systems but also in ionic polymer materials. In order to investigate the influence of ambient humidity on voltage response, classical Au-Nafion IPMC was chosen as the reference sample. Voltage response under a bending deformation was measured in two ways: first, continuous measurement of voltage response in the process of absorption and desorption of water to study the tendency of voltage variation at all water states; second, measurements at multiple fixed ambient humidity levels to characterize the process of voltage response quantitatively. Ambient humidity influences the voltage response mainly by varying water content in ionic polymer. Under a step bending, the amplitude of initial voltage peak first increases and then decreases as the ambient humidity and the inherent water content decrease. This tendency is explained semiquantitatively by mass storage capacity related to the stretchable state of the Nafion polymer network. Following the initial peak, the voltage shows a slow decay to a steady state, which is first characterized in this paper. The relative voltage decay during the steady state always decreases as the ambient humidity is lowered. It is ascribed to progressive increase of the ratio between the water molecules in the cation hydration shell to the free water. Under sinusoidal mechanical bending excitation in the range of 0.1-10 Hz, the voltage magnitude increases with frequency at high ambient humidity but decreases with frequency at low ambient humidity. The relationship is mainly controlled by the voltage decay effect and the response speed.

Conjugated Polymer Zwitterions: Efficient Interlayer Materials in Organic Electronics.

PubMed

Liu, Yao; Duzhko, Volodimyr V; Page, Zachariah A; Emrick, Todd; Russell, Thomas P

2016-11-15

Conjugated polymer zwitterions (CPZs) are neutral, hydrophilic, polymer semiconductors. The pendent zwitterions, viewed as side chain dipoles, impart solubility in polar solvents for solution processing, and open opportunities as interfacial components of optoelectronic devices, for example, between metal electrodes and organic semiconductor active layers. Such interlayers are crucial for defining the performance of organic electronic devices, e.g., field-effect transistors (OFETs), light-emitting diodes (OLEDs), and photovoltaics (OPVs), all of which consist of multilayer structures. The interlayers reduce the Schottky barrier height and thus improve charge injection in OFETs and OLEDs. In OPVs, the interlayers serve to increase the built-in electric potential difference (V bi ) across the active layer, ensuring efficient extraction of photogenerated charge carriers. In general, polar and even charged electronically active polymers have gained recognition for their ability to modify metal/semiconductor interfaces to the benefit of organic electronics. While conjugated polyelectrolytes (CPEs) as interlayer materials are well-documented, open questions remain about the role of mobile counterions in CPE-containing devices. CPZs possess the processing advantages of CPEs, but as neutral molecules lack any potential complications associated with counterions. The electronic implications of CPZs on metal electrodes stem from the orientation of the zwitterion dipole moment in close proximity to the metal surface, and the resultant surface-induced polarization. This generates an interfacial dipole (Δ) at the CPZ/metal interface, altering the work function of the electrode, as confirmed by ultraviolet photoelectron spectroscopy (UPS), and improving device performance. An ideal cathode interlayer would reduce electrode work function, have orthogonal processability to the active layer, exhibit good film forming properties (i.e., wettability/uniformity), prevent exciton quenching, possess optimal electron affinity that neither limits the work function reduction nor impedes the charge extraction, transport electrons selectively, and exhibit long-term stability. Our recent discoveries show that CPZs achieve many of these attributes, and are poised for further expansion and development in the interfacial science of organic electronics. This Account reviews a recent collaboration that began with the synthesis of CPZs and a study of their structural and electronic properties on metals, then extended to their application as interlayer materials for OPVs. We discuss CPZ structure-property relationships based on several material platforms, ranging from homopolymers to copolymers, and from materials with intrinsic p-type conjugated backbones to those with intrinsic n-type conjugated backbones. We discuss key components of such interlayers, including (i) the origin of work function reduction of CPZ interlayers on metals; (ii) the role of the frontier molecular orbital energy levels and their trade-offs in optimizing electronic and device properties; and (iii) the role of polymer conductivity type and the magnitude of charge carrier mobility. Our motivation is to present our prior use and current understanding of CPZs as interlayer materials in organic electronics, and describe outstanding issues and future potential directions.

Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

NASA Astrophysics Data System (ADS)

Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

2015-07-01

Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

EDITORIAL: Artificial Muscles: Selected papers from the 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio (Osaka, Japan, 25-27 November 2009) Artificial Muscles: Selected papers from the 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio (Osaka, Japan, 25-27 November 2009)

NASA Astrophysics Data System (ADS)

Shahinpoor, Mohsen

2011-12-01

The 5th World Congress on Biomimetics, Artificial Muscles and Nano-Bio and the 4th International Conference on Artificial Muscles were held in Osaka, Japan, 23-27 November 2009. This special section of Smart Materials and Structures is devoted to a selected number of research papers presented at this international conference and congress. Of the 76 or so papers presented at the conference, only 10 papers were finally selected, reviewed and accepted for this special section, following the regular reviewing procedures of the journal. This special section is focused on polymeric artificial muscles, electroactive polymers, multifunctional nanocomposites and their applications. In particular, an electromechanical model for self-sensing ionic polymer-metal composite actuating devices with patterned surface electrodes is presented which discusses the concept of creating self-sensing ionic polymer-metal composite (IPMC) actuating devices with patterned surface electrodes where actuator and sensor elements are separated by a grounded shielding electrode. Eventually, an electromechanical model of the device is also proposed and validated. Following that, there is broad coverage of polytetrahydrofurane-polyethylene oxide-PEDOT conducting interpenetrating polymer networks (IPNs) for high speed actuators. The conducting polymer (poly(3,4-ethylenedioxythiophene)) is incorporated within the IPNs, which are synthesized from polyethylene oxide (PEO)/polytetrahydrofurane (PTHF) networks. PEO/PTHF IPNs are prepared using poly(ethylene glycol) methacrylate and dimethacrylate and hydroxythelechelic PTHF as starting materials. The conducting IPN actuators are prepared by oxidative polymerization of 3,4-ethylenedioxithiophene (EDOT) using FeCl3 as an oxidizing agent within the PEO/PTHF IPN host matrix. Subsequently, giant and reversible magnetorheology of carrageenan/iron oxide magnetic gels are discussed and the effect of magnetic fields on the viscoelastic properties, magnetorheological effect of carrageenan gel containing iron oxide particles are investigated using dynamic viscoelastic measurements under magnetic fields. Furthermore, the relationship between the magnetorheology and the elasticity of magnetic gel is discussed. This special section then covers the characteristics of ionic polymer-metal composite with chemically-doped TiO2 particles to improve the bending performance of ionic polymer-metal composite (IPMC) actuators. This study is mainly focused on the characterization of the physical, electrochemical, and electromechanical properties of TiO2-doped ionic polymer membranes, and IPMCs prepared by the sol-gel method, which results in a uniform distribution of the particles inside the polymer membrane. It was determined that the lifetime of IPMC is strongly dependent on the level of water uptake. This paper is then followed by a presentation on training and shape retention in conducting polymer artificial muscles. Electrochemomechanical deformation (ECMD) of the conducting polymer, polyaniline film, is studied to investigate the behavior of actuation under tensile loads. The ECMD is induced by strains due to insertion of ionic species (cyclic strain) and a creep due to applied loads during the redox cycle. The cyclic strain is enhanced by the experience of high tensile loads, indicating a training effect. The training effect is explained by the enhanced electrochemical activity of the film. The special section then presents a paper on the current status and future prospects of power generators using dielectric elastomers. Electroactive polymer artificial muscle (EPAM), known as 'dielectric elastomer', appears to offer unique capabilities as an actuator and electrical power generator. However, the power output levels of such generators are small and the efficiencies are rather high. For example, electrical energy conversion efficiency of over 70% has been achieved. The ability of EPAM to produce hydrogen fuel for energy storage was also demonstrated. Because the energy conversion principle of EPAM is capacitive in nature, the performance is largely size-independent. Formation of motile assembly of microtubules driven by kinesins is presented next. Microtubule (MT) and kinesin are rail and motor proteins that are involved in various moving events of eukaryotic cells in natural systems. In vitro, the sliding motion of microtubules (rail) can be reproduced on a kinesin (motor protein)-coated surface coupled with adenosine triphosphate (ATP) hydrolysis, which is called a 'motility assay'. Based on this technique, a method is reported for forming MT assemblies by an active self-assembly (AcSA) process, in which MTs are crosslinked during a sliding motion on a kinesin-coated surface. Streptavidin (ST) is employed as glue to crosslink biotin-labeled MTs. This discussion is then followed by a paper on the performances of fast-moving low-voltage electromechanical actuators based on single-walled carbon nanotubes and ionic liquids. Here the mechanical and electrical properties of the polymer-free single-walled carbon nanotube (SWNT) sheets containing different contents of ionic liquids (ILs) are reported. The polymer-free SWNT sheets are prepared with the knowledge that millimeter-long 'super growth' carbon nanotubes (SG-SWNTs), produced by a water-assisted modified CVD method, associate together tightly with ILs. The molecular mechanism of electroactive polymer actuators is then discussed in the next paper. Movement of ionic electroactive polymer actuators utilizes their anisotropic volume change, which is induced by the applied voltage. The mechanism of the volume change is, however, not well understood, especially at the molecular level. The current understanding of the mechanism of the volume change at the molecular level is reviewed, focusing on the actuators made with carbon materials. Then, the pressure generated in the actuators in response to the applied voltage based on the results of the Monte Carlo simulation is discussed. It is shown that the mechanism of the actuators can be analyzed at the molecular level in terms of the balance between the electrostatic and volume exclusion interactions that act among the electrode materials and the electrolyte ions. The special section then presents a master curve for analyzing the electrochemical aging and memory effects of poly(3,4-ethylenedioxythiophene). The memory effect of conducting polymers in an electrochemical environment is investigated. This memory effect is related to the electromechanical responses of the conducting polymer. Poly(3,4-ethylenedioxythiophene) is chosen because of its interesting properties—mainly its chemical and electrochemical stabilities. By means of cyclic voltammetry, the influence of the waiting time tw at a holding potential Ew in relation to the conformational relaxation process occurring in the conducting polymer is analyzed. The effect of electrochemical aging on the electrical properties is also explained from the viewpoint of the rearrangement of polymer chains. This completes a brief report on the content of the special section on artificial muscles. I would like to thank the contributing authors of this collection of papers on artificial muscles for their outstanding and unique contributions. I am also indebted to all of the reviewers, editors and editorial staff who handled the reviews of all the papers for their time and effort. I would like to express my sincere thanks and appreciation to Professor E Garcia, Editor-in-Chief, for his encouragement and support, and for providing the opportunity to publish this special section of Smart Materials and Structures. I am also grateful to the IOP Publishing team for their support. In particular, I am greatly indebted to publisher Natasha Leeper, for her help and excellent management in the preparation of this special section on artificial muscles.

Applying electric field to charged and polar particles between metallic plates: extension of the Ewald method.

PubMed

Takae, Kyohei; Onuki, Akira

2013-09-28

We develop an efficient Ewald method of molecular dynamics simulation for calculating the electrostatic interactions among charged and polar particles between parallel metallic plates, where we may apply an electric field with an arbitrary size. We use the fact that the potential from the surface charges is equivalent to the sum of those from image charges and dipoles located outside the cell. We present simulation results on boundary effects of charged and polar fluids, formation of ionic crystals, and formation of dipole chains, where the applied field and the image interaction are crucial. For polar fluids, we find a large deviation of the classical Lorentz-field relation between the local field and the applied field due to pair correlations along the applied field. As general aspects, we clarify the difference between the potential-fixed and the charge-fixed boundary conditions and examine the relationship between the discrete particle description and the continuum electrostatics.

Robust and versatile ionic liquid microarrays achieved by microcontact printing

NASA Astrophysics Data System (ADS)

Gunawan, Christian A.; Ge, Mengchen; Zhao, Chuan

2014-04-01

Lab-on-a-chip and miniaturized systems have gained significant popularity motivated by marked differences in material performance at the micro-to-nano-scale realm. However, to fully exploit micro-to-nano-scale chemistry, solvent volatility and lack of reproducibility need to be overcome. Here, we combine the non-volatile and versatile nature of ionic liquids with microcontact printing in an attempt to establish a facile protocol for high throughput fabrication of open microreactors and microfluidics. The micropatterned ionic liquid droplets have been demonstrated as electrochemical cells and reactors for microfabrication of metals and charge transfer complexes, substrates for immobilization of proteins and as membrane-free high-performance amperometric gas sensor arrays. The results suggest that miniaturized ionic liquid systems can be used to solve the problems of solvent volatility and slow mass transport in viscous ionic liquids in lab-on-a-chip devices, thus providing a versatile platform for a diverse number of applications.

Atomistic Molecular Dynamics Simulations of Charged Latex Particle Surfaces in Aqueous Solution.

PubMed

Li, Zifeng; Van Dyk, Antony K; Fitzwater, Susan J; Fichthorn, Kristen A; Milner, Scott T

2016-01-19

Charged particles in aqueous suspension form an electrical double layer at their surfaces, which plays a key role in suspension properties. For example, binder particles in latex paint remain suspended in the can because of repulsive forces between overlapping double layers. Existing models of the double layer assume sharp interfaces bearing fixed uniform charge, and so cannot describe aqueous binder particle surfaces, which are soft and diffuse, and bear mobile charge from ionic surfactants as well as grafted multivalent oligomers. To treat this industrially important system, we use atomistic molecular dynamics simulations to investigate a structurally realistic model of commercial binder particle surfaces, informed by extensive characterization of particle synthesis and surface properties. We determine the interfacial profiles of polymer, water, bound and free ions, from which the charge density and electrostatic potential can be calculated. We extend the traditional definitions of the inner and outer Helmholtz planes to our diffuse interfaces. Beyond the Stern layer, the simulated electrostatic potential is well described by the Poisson-Boltzmann equation. The potential at the outer Helmholtz plane compares well to the experimental zeta potential. We compare particle surfaces bearing two types of charge groups, ionic surfactant and multivalent oligomers, with and without added salt. Although the bare charge density of a surface bearing multivalent oligomers is much higher than that of a surfactant-bearing surface at realistic coverage, greater counterion condensation leads to similar zeta potentials for the two systems.

Driving mechanisms of ionic polymer actuators having electric double layer capacitor structures.

PubMed

Imaizumi, Satoru; Kato, Yuichi; Kokubo, Hisashi; Watanabe, Masayoshi

2012-04-26

Two solid polymer electrolytes, composed of a polyether-segmented polyurethaneurea (PEUU) and either a lithium salt (lithium bis(trifluoromethanesulfonyl)amide: Li[NTf2]) or a nonvolatile ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: [C2mim][NTf2]), were prepared in order to utilize them as ionic polymer actuators. These salts were preferentially dissolved in the polyether phases. The ionic transport mechanism of the polyethers was discussed in terms of the diffusion coefficients and ionic transference numbers of the incorporated ions, which were estimated by means of pulsed-field gradient spin-echo (PGSE) NMR. There was a distinct difference in the ionic transport properties of each polymer electrolyte owing to the difference in the magnitude of interactions between the cations and the polyether. The anionic diffusion coefficient was much faster than that of the cation in the polyether/Li[NTf2] electrolyte, whereas the cation diffused faster than the anion in the polyether/[C2mim][NTf2] electrolyte. Ionic polymer actuators, which have a solid-state electric-double-layer-capacitor (EDLC) structure, were prepared using these polymer electrolyte membranes and ubiquitous carbon materials such as activated carbon and acetylene black. On the basis of the difference in the motional direction of each actuator against applied voltages, a simple model of the actuation mechanisms was proposed by taking the difference in ionic transport properties into consideration. This model discriminated the behavior of the actuators in terms of the products of transference numbers and ionic volumes. The experimentally observed behavior of the actuators was successfully explained by this model.

Gel polymer electrolytes for batteries

DOEpatents

Balsara, Nitash Pervez; Eitouni, Hany Basam; Gur, Ilan; Singh, Mohit; Hudson, William

2014-11-18

Nanostructured gel polymer electrolytes that have both high ionic conductivity and high mechanical strength are disclosed. The electrolytes have at least two domains--one domain contains an ionically-conductive gel polymer and the other domain contains a rigid polymer that provides structure for the electrolyte. The domains are formed by block copolymers. The first block provides a polymer matrix that may or may not be conductive on by itself, but that can soak up a liquid electrolyte, thereby making a gel. An exemplary nanostructured gel polymer electrolyte has an ionic conductivity of at least 1.times.10.sup.-4 S cm.sup.-1 at 25.degree. C.

Efficient Energy Conversion by Grafting Nanochannels with End-charged Stimuli-responsive Polyelectrolyte Brush

NASA Astrophysics Data System (ADS)

Chen, Guang; Das, Siddhartha

2017-11-01

Polyelectrolyte (PE) brushes have aroused increasing attention in applications in energy conversion and chemical sensing due to the environmentally-responsive and designable nature. PE brushes are charged polymer chains densely grafted on solid-liquid interfaces. By designing copolymeric systems, one can localize the ionizable sites at the brush tip in order to get end-charged PE brushes. Such brushes demonstrate anomalous shrinking/swelling behaviors with tunable environmental parameters such as pH and salt concentration. In this study, we probe the conformation and electrostatics of such PE brush systems with various size, grafting density and charge distribution, and exploit the electrochemomechanical energy conversion capabilities of nanochannels grafted with such PE brush systems. Our results indicate that the presence of the end-charged PE brush layer can massively enhance the streaming potential mediated energy conversion efficiency, and the improvement is more significant in strongly ionic solution.

Active disturbance rejection control for output force creep characteristics of ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Xiong, Yan; Chen, Yang; Sun, Zhiyong; Hao, Lina; Dong, Jie

2014-07-01

Ionic polymer metal composites (IPMCs) are a type of electroactive polymer (EAP) that can be used as both sensors and actuators. An IPMC has enormous potential application in the field of biomimetic robotics, medical devices, and so on. However, an IPMC actuator has a great number of disadvantages, such as creep and time-variation, making it vulnerable to external disturbances. In addition, the complex actuation mechanism makes it difficult to model and the demand of the control algorithm is laborious to implement. In this paper, we obtain a creep model of the IPMC by means of model identification based on the method of creep operator linear superposition. Although the mathematical model is not approximate to the IPMC accurate model, it is accurate enough to be used in MATLAB to prove the control algorithm. A controller based on the active disturbance rejection control (ADRC) method is designed to solve the drawbacks previously given. Because the ADRC controller is separate from the mathematical model of the controlled plant, the control algorithm has the ability to complete disturbance estimation and compensation. Some factors, such as all external disturbances, uncertainty factors, the inaccuracy of the identification model and different kinds of IPMCs, have little effect on controlling the output block force of the IPMC. Furthermore, we use the particle swarm optimization algorithm to adjust ADRC parameters so that the IPMC actuator can approach the desired block force with unknown external disturbances. Simulations and experimental examples validate the effectiveness of the ADRC controller.

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

PubMed

Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

2017-04-10

A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO 2 /N 2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO 2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO 2 /epoxides cycloaddition and Nformylation of amines from CO 2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO 2 near the catalytic centers in the CO 2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lowering the operational temperature of all-solid-state lithium polymer cell with highly conductive and interfacially robust solid polymer electrolytes

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Martinez-Ibañez, Maria; Piszcz, Michal; Rodriguez-Martinez, Lide M.; Zhang, Heng; Armand, Michel

2018-04-01

Novel solid polymer electrolytes (SPEs), comprising of comb polymer matrix grafted with soft and disordered polyether moieties (Jeffamine®) and lithium bis(fluorosulfonyl)imide (LiFSI) are investigated in all-solid-state lithium metal (Li°) polymer cells. The LiFSI/Jeffamine-based SPEs are fully amorphous at room temperature with glass transitions as low as ca. -55 °C. They show higher ionic conductivities than conventional poly(ethylene oxide) (PEO)-based SPEs at ambient temperature region, and good electrochemical compatibility with Li° electrode. These exceptional properties enable the operational temperature of Li° | LiFePO4 cells to be decreased from an elevated temperature (70 °C) to room temperature. Those results suggest that LiFSI/Jeffamine-based SPEs can be promising electrolyte candidates for developing safe and high performance all-solid-state Li° batteries.

Fe3O4/cyclodextrin polymer nanocomposites for selective heavy metals removal from industrial wastewater.

PubMed

Badruddoza, Abu Zayed M; Shawon, Zayed Bin Zakir; Tay, Wei Jin Daniel; Hidajat, Kus; Uddin, Mohammad Shahab

2013-01-02

In this work, carboxymethyl-β-cyclodextrin (CM-β-CD) polymer modified Fe(3)O(4) nanoparticles (CDpoly-MNPs) was synthesized for selective removal of Pb(2+), Cd(2+), Ni(2+) ions from water. This magnetic adsorbent was characterized by TEM, FTIR, XPS and VSM. The adsorption of all studied metal ions onto CDpoly-MNPs was found to be dependent on pH, ionic strength, and temperature. Batch adsorption equilibrium was reached in 45 min and maximum uptakes for Pb(2+), Cd(2+) and Ni(2+) in non-competitive adsorption mode were 64.5, 27.7 and 13.2 mg g(-1), respectively at 25 °C. Adsorption data were fitted well to Langmuir isotherm and pseudo-second-order models for kinetic study. The polymer grafted on MNPs enhanced the adsorption capacity because of the complexing abilities of the multiple hydroxyl and carboxyl groups in polymer backbone with metal ions. In competitive adsorption experiments, CDpoly-MNPs could preferentially adsorb Pb(2+) ions with an affinity order of Pb(2+)>Cd(2+)>Ni(2+) which can be explained by hard and soft acids and bases (HASB) theory. Furthermore, we explored the recyclability of CDpoly-MNPs. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effects of anhydrous AlCl3 dopant on the structural, optical and electrical properties of PVA-PVP polymer composite films

NASA Astrophysics Data System (ADS)

Shanmugam, G.; Krishnakumar, V.

2018-05-01

Polymer composite films based on PVA-PVP with AlCl3 as the dopant at different concentrations were prepared using solution casting technique. XRD patterns reveal the increase in amorphousity of the films with AlCl3 doping. Optical absorption studies exhibit that the values of optical absorption coefficient, direct and indirect optical band gaps are found to decrease with increase in AlCl3 concentration. It confirms the charge transfer in complexes between the polymer and the dopant. The dielectric studies show the increase in dielectric constant at low frequency with increasing AlCl3 concentration and temperature. The ac conductivity and ionic conductivity increase with the AlCl3 content and the maximum value at room temperature is found to be 6.89 × 10-4 and 8.05 × 10-5 S/cm for higher AlCl3 doped PVA-PVP film. The estimated ionic conductivity value is three or four orders of magnitude greater than those obtained in the certain representative polymer-salt complexes as reported earlier. Electrical modulus plots confirm the removal of electrode polarization and the low conductivity relaxation time with Al doping. The activation energy estimated from the temperature dependent dc conductivity plot is agreed well with the migration energy calculated from the temperature dependent electric modulus plot.

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

PubMed Central

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

NASA Astrophysics Data System (ADS)

Porcarelli, Luca; Gerbaldi, Claudio; Bella, Federico; Nair, Jijeesh Ravi

2016-01-01

Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm-1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

Electric double-layer capacitor based on an ionic clathrate hydrate.

PubMed

Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

2013-07-01

Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me4NOH⋅5 H2O show a high specific capacitance, reversible charge-discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation of bipolar charge transport in nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Lean, Meng H.; Chu, Wei-Ping L.

2015-03-01

This paper describes 3D particle-in-cell simulation of bipolar charge injection and transport through nanocomposite film comprised of ferroelectric ceramic nanofillers in an amorphous polymer matrix. The classical electrical double layer (EDL) model for a monopolar core is extended (eEDL) to represent the nanofiller by replacing it with a dipolar core. Charge injection at the electrodes assumes metal-polymer Schottky emission at low to moderate fields and Fowler-Nordheim tunneling at high fields. Injected particles migrate via field-dependent Poole-Frenkel mobility and recombine with Monte Carlo selection. The simulation algorithm uses a boundary integral equation method for solution of the Poisson equation coupled with a second-order predictor-corrector scheme for robust time integration of the equations of motion. The stability criterion of the explicit algorithm conforms to the Courant-Friedrichs-Levy limit assuring robust and rapid convergence. The model is capable of simulating a wide dynamic range spanning leakage current to pre-breakdown. Simulation results for BaTiO3 nanofiller in amorphous polymer matrix indicate that charge transport behavior depend on nanoparticle polarization with anti-parallel orientation showing the highest leakage conduction and therefore lowest level of charge trapping in the interaction zone. Charge recombination is also highest, at the cost of reduced leakage conduction charge. The eEDL model predicts the meandering pathways of charge particle trajectories.

Membrane separation of ionic liquid solutions

DOEpatents

Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

2015-09-01

A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self‐Catalyzed Strategy toward Facile Synthesis

PubMed Central

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Feng, Jiwen

2017-01-01

Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

PubMed

Huang, Wei; Guo, Peijun; Zeng, Li; Li, Ran; Wang, Binghao; Wang, Gang; Zhang, Xinan; Chang, Robert P H; Yu, Junsheng; Bedzyk, Michael J; Marks, Tobin J; Facchetti, Antonio

2018-04-25

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In 2 O 3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In 2 O 3 , but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (μ peak ) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield μ peak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.

Electrochemical Behavior of PEDOT/Lignin in Ionic Liquid Electrolytes: Suitable Cathode/Electrolyte System for Sodium Batteries.

PubMed

Casado, Nerea; Hilder, Matthias; Pozo-Gonzalo, Cristina; Forsyth, Maria; Mecerreyes, David

2017-04-22

Biomass-derived polymers, such as lignin, contain quinone/ hydroquinone redox moieties that can be used to store charge. Composites based on the biopolymer lignin and several conjugated polymers have shown good charge-storage properties. However, their performance has been only studied in acidic aqueous media limiting their applications mainly to supercapacitors. Here, we show that PEDOT/lignin (PEDOT: poly(3,4-ethylenedioxythiophene)) biopolymers are electroactive in aprotic ionic liquids (ILs) and we move a step further by assembling sodium full cell batteries using PEDOT/lignin as electrode material and IL electrolytes. Thus, the electrochemical activity and cycling of PEDOT/lignin electrodes was investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (BMPyrFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) IL electrolytes. The effects of water and sodium salt addition to the ILs were investigated to obtain optimum electrolyte systems for sodium batteries. Finally, sodium batteries based on PEDOT/lignin cathode with imidazolium-based IL electrolyte showed higher capacity values than pyrrolidinium ones, reaching 70 mAhg -1 . Our results demonstrate that PEDOT/lignin composites can serve as low cost and sustainable cathode materials for sodium batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensorless position estimator applied to nonlinear IPMC model

NASA Astrophysics Data System (ADS)

Bernat, Jakub; Kolota, Jakub

2016-11-01

This paper addresses the issue of estimating position for an ionic polymer metal composite (IPMC) known as electro active polymer (EAP). The key step is the construction of a sensorless mode considering only current feedback. This work takes into account nonlinearities caused by electrochemical effects in the material. Owing to the recent observer design technique, the authors obtained both Lyapunov function based estimation law as well as sliding mode observer. To accomplish the observer design, the IPMC model was identified through a series of experiments. The research comprises time domain measurements. The identification process was completed by means of geometric scaling of three test samples. In the proposed design, the estimated position accurately tracks the polymer position, which is illustrated by the experiments.

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf2N ionic liquid

PubMed Central

Sandoval, Andrea P; Suárez-Herrera, Marco F

2015-01-01

Summary Thin films of PEDOT synthesized on platinum single electrodes in contact with the ionic liquid 1-ethyl-2,3-dimethylimidazolium triflimide ([EMMIM]Tf2N) were studied by cyclic voltammetry, chronoamperometry, infrared spectroscopy and atomic force microscopy. It was found that the polymer grows faster on Pt(111) than on Pt(110) or Pt(100) and that the redox reactions associated with the PEDOT p-doping process are much more reversible in [EMMIM]Tf2N than in acetonitrile. Finally, the ion exchange and charge carriers’ formation during the p-doping reaction of PEDOT were studied using in situ FTIR spectroscopy. PMID:25815089

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

Modeling back-relaxation in ionic polymer metal composites: The role of steric effects and composite layers

NASA Astrophysics Data System (ADS)

Porfiri, Maurizio; Sharghi, Hesam; Zhang, Peng

2018-01-01

Ionic polymer metal composites (IPMCs) are a new class of active materials that are gaining traction as soft actuators in medical and industrial applications. IPMCs can undergo large deformations under modest voltage inputs, in dry and wet environments. Past studies have demonstrated that physical and geometric properties of all the IPMC constituents (ionomer, electrodes, and counterions) may all influence the time scales of the transient response and severity of the back-relaxation. In this study, we present a detailed mathematical model to investigate how the finite size of the counterions and the presence of metal particles in the vicinity of the electrodes modulate IPMC actuation. We build on previous work by our group on thermodynamically consistent modeling of IPMC mechanics and electrochemistry, which attributes IPMC actuation to the interplay between Maxwell stress and osmotic forces. To gain insight into the role of physical and geometric parameters, the resulting nonlinear partial differential equations are solved semianalytically using the method of matched asymptotic expansions, for the initial transient and the steady-state. A numerical solution in COMSOL Multiphysics® is developed to verify semianalytical findings and further explore IPMC actuation. Our model can successfully predict the entire response of IPMCs, from the initial bending toward the anode to the steady-state toward the cathode. We find that the steric effect can abolish the back-relaxation of IPMCs by restraining the counterions' concentration near the electrodes. We also find that increasing the thickness of the ionomer-metal composite layers may enhance IPMC actuation through increased osmotic forces and Maxwell stress.

Powering up the future: radical polymers for battery applications.

PubMed

Janoschka, Tobias; Hager, Martin D; Schubert, Ulrich S

2012-12-18

Our society's dependency on portable electric energy, i.e., rechargeable batteries, which permit power consumption at any place and in any time, will eventually culminate in resource wars on limited commodities like lithium, cobalt, and rare earth metals. The substitution of conventional metals as means of electric charge storage by organic and polymeric materials, which may ultimately be derived from renewable resources, appears to be the only feasible way out. In this context, the novel class of organic radical batteries (ORBs) excelling in rate capability (i.e., charging speed) and cycling stability (>1000 cycles) sets new standards in battery research. This review examines stable nitroxide radical bearing polymers, their processing to battery systems, and their promising performance. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-consistent field theory of polymer-ionic molecule complexation.

PubMed

Nakamura, Issei; Shi, An-Chang

2010-05-21

A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

DOE PAGES

Webb, Michael A.; Jung, Yukyung; Pesko, Danielle M.; ...

2015-07-10

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds viamore » a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.« less

Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes

PubMed Central

2015-01-01

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials. PMID:27162971

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

Numerical modelling of electrochemical polarization around charged metallic particles

NASA Astrophysics Data System (ADS)

Bücker, Matthias; Undorf, Sabine; Flores Orozco, Adrián; Kemna, Andreas

2017-04-01

We extend an existing analytical model and carry out numerical simulations to study the polarization process around charged metallic particles immersed in an electrolyte solution. Electro-migration and diffusion processes in the electrolyte are described by the Poisson-Nernst-Planck system of partial differential equations. To model the surface charge density, we consider a time- and frequency-invariant electric potential at the particle surface, which leads to the build-up of a static electrical double layer (EDL). Upon excitation by an external electric field at low frequencies, we observe the superposition of two polarization processes. On the one hand, the induced dipole moment on the metallic particle leads to the accumulation of opposite charges in the electrolyte. This charge polarization corresponds to the long-known response of uncharged metallic particles. On the other hand, the unequal cation and anion concentrations in the EDL give rise to a salinity gradient between the two opposite sides of the metallic particle. The resulting concentration polarization enhances the magnitude of the overall polarization response. Furthermore, we use our numerical model to study the effect of relevant model parameters such as surface charge density and ionic strength of the electrolyte on the resulting spectra of the effective conductivity of the composite model system. Our results do not only give interesting new insight into the time-harmonic variation of electric potential and ion concentrations around charged metallic particle. They are also able to reduce incongruities between earlier model predictions and geophysical field and laboratory measurements. Our model thereby improves the general understanding of IP signatures of metallic particles and represents the next step towards a quantitative interpretation of IP imaging results. Part of this research is funded by the Austrian Federal Ministry of Science, Research and Economy under the Raw Materials Initiative.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES).

PubMed

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-05-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO 3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min -1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO 3 . The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L -1 , respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples.

Selective solid phase extraction of copper using a new Cu(II)-imprinted polymer and determination by inductively coupled plasma optical emission spectroscopy (ICP-OES)

PubMed Central

Yilmaz, Vedat; Arslan, Zikri; Hazer, Orhan; Yilmaz, Hayriye

2014-01-01

This work reports the preparation of a novel Cu(II)-ion imprinted polymer using 2-thiozylmethacrylamide (TMA) for on-line preconcentration of Cu(II) prior to its determination by inductively coupled optical emission spectroscopy (ICP-OES). Cu(II)-TMA monomer (complex) was synthesized and copolymerized via bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was washed with 5% (v/v) HNO3 to remove Cu(II) ions and then with water until a neutral pH. The ion imprinted polymer was characterized by FT-IR and scanning electron microscopy. The experimental conditions were optimized for on-line preconcentration of Cu(II) using a minicolumn of ion imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 6.0, whereas the recoveries for the non-imprinted polymer (NIP) were about 61%. The IIP showed about 30 times higher selectivity to Cu(II) in comparison to NIP. The IIP also exhibited excellent selectivity for Cu(II) against the competing transition and heavy metal ions, including Cd, Co, Cr, Fe, Mn, Ni, Pb and Zn. Computational calculations revealed that the selectivity of IIP was mediated by the stability of Cu(II)-TMA complex which was far more stable than those of Co(II), Ni(II) and Zn(II) that have similar charge and ionic radii to Cu(II). A volume of 10 mL sample solution was loaded onto the column at 4.0 mL min−1 by using a sequential injection system (FIALab 3200) followed by elution with 1.0 mL of 2% (v/v) HNO3. The relative standard deviation (RSD) and limit of detection (LOD, 3s) of the method were 3.2% and 0.4 μg L−1, respectively. The method was successfully applied to determination of Cu(II) in fish otoliths (CRM 22), bone ash (SRM 1400) and coastal seawater and estuarine water samples. PMID:24511158

Simulation of polymer translocation through protein channels

PubMed Central

Muthukumar, M.; Kong, C. Y.

2006-01-01

A modeling algorithm is presented to compute simultaneously polymer conformations and ionic current, as single polymer molecules undergo translocation through protein channels. The method is based on a combination of Langevin dynamics for coarse-grained models of polymers and the Poisson–Nernst–Planck formalism for ionic current. For the illustrative example of ssDNA passing through the α-hemolysin pore, vivid details of conformational fluctuations of the polymer inside the vestibule and β-barrel compartments of the protein pore, and their consequent effects on the translocation time and extent of blocked ionic current are presented. In addition to yielding insights into several experimentally reported puzzles, our simulations offer experimental strategies to sequence polymers more efficiently. PMID:16567657

Ambipolar transport in CVD grown MoSe2 monolayer using an ionic liquid gel gate dielectric

NASA Astrophysics Data System (ADS)

Ortiz, Deliris N.; Ramos, Idalia; Pinto, Nicholas J.; Zhao, Meng-Qiang; Kumar, Vinayak; Johnson, A. T. Charlie

2018-03-01

CVD grown MoSe2 monolayers were electrically characterized at room temperature in a field effect transistor (FET) configuration using an ionic liquid (IL) as the gate dielectric. During the growth, instead of using MoO3 powder, ammonium heptamolybdate was used for better Mo control of the source and sodium cholate added for lager MoSe2 growth areas. In addition, a high specific capacitance (˜7 μF/cm2) IL was used as the gate dielectric to significantly reduce the operating voltage. The device exhibited ambipolar charge transport at low voltages with enhanced parameters during n- and p-FET operation. IL gating thins the Schottky barrier at the metal/semiconductor interface permitting efficient charge injection into the channel and reduces the effects of contact resistance on device performance. The large specific capacitance of the IL was also responsible for a much higher induced charge density compared to the standard SiO2 dielectric. The device was successfully tested as an inverter with a gain of ˜2. Using a common metal for contacts simplifies fabrication of this ambipolar device, and the possibility of radiative recombination of holes and electrons could further extend its use in low power optoelectronic applications.

Anomalously large capacitance of an ionic liquid described by the restricted primitive model

NASA Astrophysics Data System (ADS)

Loth, M. S.; Skinner, Brian; Shklovskii, B. I.

2010-11-01

We use Monte Carlo simulations to examine the simplest model of a room-temperature ionic liquid (RTIL), called the “restricted primitive model,” at a metal surface. We find that at moderately low temperatures the capacitance of the metal-RTIL interface is so large that the effective thickness of the electrostatic double layer is up to three times smaller than the ion radius. To interpret these results we suggest an approach which is based on the interaction between discrete ions and their image charges in the metal surface and which therefore goes beyond the mean-field approximation. When a voltage is applied across the interface, the strong image attraction causes counterions to condense onto the metal surface to form compact ion-image dipoles. These dipoles repel each other to form a correlated liquid. When the surface density of these dipoles is low, the insertion of an additional dipole does not require much energy. This leads to a large capacitance C that decreases monotonically with voltage V , producing a “bell-shaped” curve C(V) . We also consider what happens when the electrode is made from a semimetal rather than a perfect metal. In this case, the finite screening radius of the electrode shifts the reflection plane for image charges to the interior of the electrode, and we arrive at a “camel-shaped” C(V) . These predictions seem to be in qualitative agreement with experiment.

Frequency-Stable Ionic-Type Hybrid Gate Dielectrics for High Mobility Solution-Processed Metal-Oxide Thin-Film Transistors

PubMed Central

Heo, Jae Sang; Choi, Seungbeom; Jo, Jeong-Wan; Kang, Jingu; Park, Ho-Hyun; Kim, Yong-Hoon; Park, Sung Kyu

2017-01-01

In this paper, we demonstrate high mobility solution-processed metal-oxide thin-film transistors (TFTs) by using a high-frequency-stable ionic-type hybrid gate dielectric (HGD). The HGD gate dielectric, a blend of sol-gel aluminum oxide (AlOx) and poly(4-vinylphenol) (PVP), exhibited high dielectric constant (ε~8.15) and high-frequency-stable characteristics (1 MHz). Using the ionic-type HGD as a gate dielectric layer, an minimal electron-double-layer (EDL) can be formed at the gate dielectric/InOx interface, enhancing the field-effect mobility of the TFTs. Particularly, using the ionic-type HGD gate dielectrics annealed at 350 °C, InOx TFTs having an average field-effect mobility of 16.1 cm2/Vs were achieved (maximum mobility of 24 cm2/Vs). Furthermore, the ionic-type HGD gate dielectrics can be processed at a low temperature of 150 °C, which may enable their applications in low-thermal-budget plastic and elastomeric substrates. In addition, we systematically studied the operational stability of the InOx TFTs using the HGD gate dielectric, and it was observed that the HGD gate dielectric effectively suppressed the negative threshold voltage shift during the negative-illumination-bias stress possibly owing to the recombination of hole carriers injected in the gate dielectric with the negatively charged ionic species in the HGD gate dielectric. PMID:28772972

Investigation of charge injection and transport behavior in multilayer structure consisted of ferromagnetic metal and organic polymer under external fields

NASA Astrophysics Data System (ADS)

Zhao, Hua; Meng, Wei-Feng

2017-10-01

In this paper a five layer organic electronic device with alternately placed ferromagnetic metals and organic polymers: ferromagnetic metal/organic layer/ferromagnetic metal/organic layer/ferromagnetic metal, which is injected a spin-polarized electron from outsides, is studied theoretically using one-dimensional tight binding model Hamiltonian. We calculated equilibrium state behavior after an electron with spin is injected into the organic layer of this structure, charge density distribution and spin polarization density distribution of this injected spin-polarized electron, and mainly studied possible transport behavior of the injected spin polarized electron in this multilayer structure under different external electric fields. We analyze the physical process of the injected electron in this multilayer system. It is found by our calculation that the injected spin polarized electron exists as an electron-polaron state with spin polarization in the organic layer and it can pass through the middle ferromagnetic layer from the right-hand organic layer to the left-hand organic layer by the action of increasing external electric fields, which indicates that this structure may be used as a possible spin-polarized charge electronic device and also may provide a theoretical base for the organic electronic devices and it is also found that in the boundaries between the ferromagnetic layer and the organic layer there exist induced interface local dipoles due to the external electric fields.

Flow measurement and thrust estimation of a vibrating ionic polymer metal composite

NASA Astrophysics Data System (ADS)

Chae, Woojin; Cha, Youngsu; Peterson, Sean D.; Porfiri, Maurizio

2015-09-01

Ionic polymer metal composites (IPMCs) are an emerging class of soft active materials that are finding growing application as underwater propulsors for miniature biomimetic swimmers. Understanding the hydrodynamics generated by an IPMC vibrating under water is central to the design of such biomimetic swimmers. In this paper, we propose the use of time-resolved particle image velocimetry to detail the fluid kinematics and kinetics in the vicinity of an IPMC vibrating along its fundamental structural mode. The reconstructed pressure field is ultimately used to estimate the thrust produced by the IPMC. The vibration frequency is systematically varied to elucidate the role of the Reynolds number on the flow physics and the thrust production. Experimental results indicate the formation and shedding of vortical structures from the IPMC tip during its vibration. Vorticity shedding is sustained by the pressure gradients along each side of the IPMC, which are most severe in the vicinity of the tip. The mean thrust is found to robustly increase with the Reynolds number, closely following a power law that has been derived from direct three-dimensional numerical simulations. A reduced order distributed model is proposed to describe IPMC underwater vibration and estimate thrust production, offering insight into the physics of underwater propulsion and aiding in the design of IPMC-based propulsors.

Comparative Experimental Study on Ionic Polymer Mental Composite based on Nafion and Aquivion Membrane as Actuators

NASA Astrophysics Data System (ADS)

Luo, B.; Chen, Z.

2017-11-01

Most ionic polymer mental composites employ Nafion as the polymer matrix, Aquivion can also manufactured as ionic polymer mental composite while research was little. This paper researched on two kinds of ionic polymer mental composite based on Aquivion and Nafion matrix with palladium electrode called Aquivion-IPMC and Nafion-IPMC. The samples were fabricated by the same preparation process. The current and deformation responses of the samples were measured at voltage to characterize the mechano-electrical properties. The experimental observations revealed that shorter flexible side chains in Aquivion-IPMC provide a larger force than Nafion-IPMC, while the displacement properties were similar in two different samples. The results also showed that Aquivion membrane can also replace Nafion to reproduce IPMC application in soft robots, MEMS, and so on.

Influence of polymeric electron injection layers on the electrical properties of solution-processed multilayered polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Itoh, Eiji; Kurami, Kazuhiko

2016-02-01

In this study, we fabricated multilayered polymer-based light-emitting diodes (pLEDs) with various solution-processed electron-injection layers (EILs), and investigated the influence of the EILs on the electrical properties of pLEDs in indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDOT:PSS)/poly[(9,9-dioctylfluorene-alt-(1,4-phenylene((4-sec-butylphenyl)amino)-1,4-phenylene))] (TFB) (HTL)/poly(9,9-dioctylfluorene-alt-1,4-benzothiadiazole) (F8BT) (EML)/EIL/Al structures. We have used the quaternized ammonium π-conjugated polyelectrolyte derivative (poly[(9,9-di(3,3‧-N,N‧-trimethylammonium)propylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]diiodide salt) (PF-PDTA), a mixture of PF-PDTA and CS2CO3, and the aliphatic-amine-based polymer poly(ethylene imine) (PEI) as solution-processed EILs, and compared them with LiF as a solvent-free EIL. The EILs enhanced the electron injection and improve the pLED performance. High external quantum efficiencies of nearly 4% were obtained in the pLEDs with the combination of a multilayered structure fabricated by a transfer printing technique and EILs of a PF-PDTA:CS2CO3 mixture and PEI. On the other hand, the device with PF-PDTA exhibited lower efficiency, higher driving voltage, and larger leakage current at lower voltage. The migration of ionic charges was suggested from the abnormal dielectric behaviors, and serious damage on the electrode material occurred when both an acid hole-injection layer (PEDOT:PSS) and PF-PDTA were used. On the other hand, the pLEDs with ultrathin PEI showed high performance and stable device operation in terms of the influence of ionic charges.

Factors affecting drug encapsulation and stability of lipid-polymer hybrid nanoparticles.

PubMed

Cheow, Wean Sin; Hadinoto, Kunn

2011-07-01

Lipid-polymer hybrid nanoparticles are polymeric nanoparticles enveloped by lipid layers that combine the highly biocompatible nature of lipids with the structural integrity afforded by polymeric nanoparticles. Recognizing them as attractive drug delivery vehicles, antibiotics are encapsulated in the present work into hybrid nanoparticles intended for lung biofilm infection therapy. Modified emulsification-solvent-evaporation methods using lipid as surfactant are employed to prepare the hybrid nanoparticles. Biodegradable poly (lactic-co-glycolic acid) and phosphatidylcholine are used as the polymer and lipid models, respectively. Three fluoroquinolone antibiotics (i.e. levofloxacin, ciprofloxacin, and ofloxacin), which vary in their ionicity, lipophilicity, and aqueous solubility, are used. The hybrid nanoparticles are examined in terms of their drug encapsulation efficiency, drug loading, stability, and in vitro drug release profile. Compared to polymeric nanoparticles prepared using non-lipid surfactants, hybrid nanoparticles in general are larger and exhibit higher drug loading, except for the ciprofloxacin-encapsulated nanoparticles. Hybrid nanoparticles, however, are unstable in salt solutions, but the stability can be conferred by adding TPGS into the formulation. Drug-lipid ionic interactions and drug lipophilicity play important roles in the hybrid nanoparticle preparation. First, interactions between oppositely charged lipid and antibiotic (i.e. ciprofloxacin) during preparation cause failed nanoparticle formation. Charge reversal of the lipid facilitated by adding counterionic surfactants (e.g. stearylamine) must be performed before drug encapsulation can take place. Second, drug loading and the release profile are strongly influenced by drug lipophilicity, where more lipophilic drug (i.e. levofloxacin) exhibit a higher drug loading and a sustained release profile attributed to the interaction with the lipid coat. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemical Impedance Analysis of a PEDOT:PSS-Based Textile Energy Storage Device

PubMed Central

Gokceoren, Argun Talat; Odhiambo, Sheilla Atieno; De Mey, Gilbert; Hertleer, Carla; Van Langenhove, Lieva

2017-01-01

A textile-based energy storage device with electroactive PEDOT:PSS (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)) polymer functioning as a solid-state polyelectrolyte has been developed. The device was fabricated on textile fabric with two plies of stainless-steel electroconductive yarn as the electrodes. In this study, cyclic voltammetry and electrochemical impedance analysis were used to investigate ionic and electronic activities in the bulk of PEDOT:PSS and at its interfaces with stainless steel yarn electrodes. The complex behavior of ionic and electronic origins was observed in the interfacial region between the conductive polymer and the electrodes. The migration and diffusion of the ions involved were confirmed by the presence of the Warburg element with a phase shift of 45° (n = 0.5). Two different equivalent circuit models were found by simulating the model with the experimental results: (QR)(QR)(QR) for uncharged and (QR)(QR)(Q(RW)) for charged samples. The analyses also showed that the further the distance between electrodes, the lower the capacitance of the cell. The distribution of polymer on the cell surface also played important role to change the capacitance of the device. The results of this work may lead to a better understanding of the mechanism and how to improve the performance of the device. PMID:29283427

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2007-10-28

Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF(6) and [1-butyl-3-methylimidazolium]PF(6) ([dmim]PF(6) and [bmim]PF(6)), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO[bmim]PF(6) is higher than in PEO[dmim]PF(6), so that the ionic conductivity kappa of the former is approximately ten times larger than the latter. The ratio between kappa and its estimate from the Nernst-Einstein equation kappa/kappa(NE), which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li(+) cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

Ionic Liquids as a Medium for Ionic Chain Polymerizations: An Environmentally Responsible Approach to Macromolecular Synthesis with Controlled Architecture

DTIC Science & Technology

2004-09-16

published in non peer-reviewed journals: 1. Gross, SM, Hamilton JL. "Polymer Gels for Use in Lithium Polymer Batteries", Nebraska Academy of Science...a process for the anionic polymerization of styrene and methyl methacrylate in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ...Current polymer electrolyte composites used for these applications typically comprise polyethers with ethylene carbonate solvents containing lithium

Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study

NASA Astrophysics Data System (ADS)

Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

Chain Conformation of Phosphorycholine-based Zwitterionic Polymer Brushes in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Mao, Jun; Yu, Jing; Lee, Sungsik; Yuan, Guangcui; Satija, Sushil; Chen, Wei; Tirrell, Matthew

Polyzwitterionic brushes are resistant to nonspecific accumulation of proteins and microorganisms, making them excellent candidates for antifouling applications. It is well-known that polyzwitterions exhibit the so-called antipolyelectrolyte effect: Polyzwitterionic brushes would adopt a collapsed conformation at a low ionic strength due to the electrostatic inter/intra-chain association; whereas at a high ionic strength, they would exhibit an extended conformation because the electrostatic inter/intra-chain dipole-dipole interaction is weakened. However, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a unique member in polyzwitterionic families. Its ultrahigh affinity to water leads to no detectable shrinks in aqueous solutions even at low ionic strengths. In this study, we synthesized highly dense PMPC brushes via surface initiated radical polymerization and systematically investigate their conformational behaviors at solid-liquid interfaces in the presence of multivalent counterions, combining X-ray and neutron scattering and force measurements. We have demonstrated that despite no obvious changes of the entire lengths of extended PMPC brushes in aqueous solutions, the chain conformations including, but not limited to, polyzwitterion distribution and charge correlation, varied, dependent on salt types, ionic strengths and ion valences.

Synthesis, Multinuclear NMR Characterization and Dynamic Property of Organic–Inorganic Hybrid Electrolyte Membrane Based on Alkoxysilane and Poly(oxyalkylene) Diamine

PubMed Central

Saikia, Diganta; Pan, Yu-Chi; Kao, Hsien-Ming

2012-01-01

Organic–inorganic hybrid electrolyte membranes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) complexed with LiClO4 via the co-condensation of tetraethoxysilane (TEOS) and 3-(triethoxysilyl)propyl isocyanate have been prepared and characterized. A variety of techniques such as differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, alternating current (AC) impedance and solid-state nuclear magnetic resonance (NMR) spectroscopy are performed to elucidate the relationship between the structural and dynamic properties of the hybrid electrolyte and the ion mobility. A VTF (Vogel-Tamman-Fulcher)-like temperature dependence of ionic conductivity is observed for all the compositions studied, implying that the diffusion of charge carriers is assisted by the segmental motions of the polymer chains. A maximum ionic conductivity value of 5.3 × 10−5 Scm−1 is obtained at 30 °C. Solid-state NMR results provide a microscopic view of the effects of salt concentrations on the dynamic behavior of the polymer chains. PMID:24958176

Boosting current generation in microbial fuel cells by an order of magnitude by coating an ionic liquid polymer on carbon anodes.

PubMed

Yang, Lu; Deng, Wenfang; Zhang, Youming; Tan, Yueming; Ma, Ming; Xie, Qingji

2017-05-15

Microbial fuel cells (MFCs) have attracted great attentions due to their great application potentials, but the relatively low power densities of MFCs still hinder their widespread practical applications. Herein, we report that the current generation in MFCs can be boosted by an order of magnitude, simply by coating a hydrophilic and positively charged ionic liquid polymer (ILP) on carbon cloth (CC) or carbon felt (CF). The ILP coating not only can increase the bacterial loading capacity due to the electrostatic interactions between ILP and bacterial cells, but also can improve the mediated extracellular electron transfer between the electrode and the cytochrome proteins on the outer membrane of Shewanella putrefaciens cells. As a result, the maximum power density of a MFC equipped with the CF-ILP bioanode is as high as 4400±170mWm -2 , which is amongst the highest values reported to date. This work demonstrates a new strategy for greatly boosting the current generation in MFCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Preserving Charge and Oxidation State of Au(III) Ions in an Agent-Functionalized Nanocrystal Model System

PubMed Central

2011-01-01

Supporting functional molecules on crystal facets is an established technique in nanotechnology. To preserve the original activity of ionic metallorganic agents on a supporting template, conservation of the charge and oxidation state of the active center is indispensable. We present a model system of a metallorganic agent that, indeed, fulfills this design criterion on a technologically relevant metal support with potential impact on Au(III)-porphyrin-functionalized nanoparticles for an improved anticancer-drug delivery. Employing scanning tunneling microscopy and -spectroscopy in combination with photoemission spectroscopy, we clarify at the single-molecule level the underlying mechanisms of this exceptional adsorption mode. It is based on the balance between a high-energy oxidation state and an electrostatic screening-response of the surface (image charge). Modeling with first principles methods reveals submolecular details of the metal–ligand bonding interaction and completes the study by providing an illustrative electrostatic model relevant for ionic metalorganic agent molecules, in general. PMID:21736315

Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

PubMed

Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

2015-04-20

Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of composite membranes using copper metal organic framework for energy application

NASA Astrophysics Data System (ADS)

Gahlot, Swati; Rajput, Abhishek; Kulshrestha, Vaibhav

2018-04-01

Present manuscript deals with the synthesis of nanocomposite polymer electrolyte membrane (PEM) based on copper based metal organic framework (Cu-MOF) and sulfonated poly ether sulfone (SPES) for fuel cell application. Prepared material and composite membrane has been analyzed through various techniques. Structural and thermal characterization of prepared material has been carried out through XRD, FTIR and TGA technique. Measurement shows the successful synthesis of MOF and also confirms the thermal stability. Prepared membranes shows good physicochemical properties and good ionic conductivity which can be utilized as PEM for fuel cell application.

Self-doped microphase separated block copolymer electrolyte

DOEpatents

Mayes, Anne M.; Sadoway, Donald R.; Banerjee, Pallab; Soo, Philip; Huang, Biying

2002-01-01

A polymer electrolyte includes a self-doped microphase separated block copolymer including at least one ionically conductive block and at least one second block that is immiscible in the ionically conductive block, an anion immobilized on the polymer electrolyte and a cationic species. The ionically conductive block provides a continuous ionically conductive pathway through the electrolyte. The electrolyte may be used as an electrolyte in an electrochemical cell.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

Covalently functionalized noble metal nanoparticles for molecular imprinted polymer biosensors: Synthesis, characterization, and SERS detection

NASA Astrophysics Data System (ADS)

Volkert, Anna Allyse

This dissertation evaluates how gold nanoparticle structure and local environment influence resulting sensor function when using these nanomaterials for complex sample analysis. Molecular imprinted polymers (MIPs), a class of plastic antibodies, are engineered and incorporated into these nanosensors thereby facilitating the quantitative detection of a variety of small molecules when Raman spectroscopy and surface enhanced Raman scattering (SERS) are used for detection. First, homogeneous seeded growth gold nanosphere synthesis is evaluated as a function of ionic double layer composition and thickness. Systematically increasing the citrate concentration during synthesis improves nanomaterial shape homogeneity; however, further elevations of citrate concentration increase the number of internal and/or external atomic defects in the nanomaterials which leads to decreasing solution-phase stability. Next, spherical gold nanoparticles are modified with self-assembled monolayer (SAM), modeled using interfacial energy calculations, and experimental characterized using transmission electron microscopy, NMR, extinction spectroscopy, zeta potential, X-ray photoelectron spectroscopy, and flocculation studies to assess the morphology, surface chemistry, optical properties, surface charge, SAM packing density, and nanoparticle stability, respectively. The number of molecules on the nanostructures increases with increasing ionic strength (by decreasing the electrostatic interfacial energy between assembled molecules) which subsequently promotes nanoparticle stability. Third, plastic antibodies that recognize three drugs commonly used to treat migraines are engineered. These methacrylate-based MIPs are synthesized, extracted, characterized, and used to quantitatively and directly detect over-the-counter drugs in complex samples using Raman microscopy. These results along with numerical approximation methods to estimate drug binding site densities and dissociation constants with the MIPs serve as a foundation for understanding how modest recognition selectivity of MIPs coupled with shifts in the vibrational energy modes from the drugs upon hydrogen binding to the polymer backbone promote sensitive and selective drug detection in complex samples. Finally, nanomaterial incorporation into MIPs for applications in SERS-based biosensors is evaluated. Importantly, gold nanorod concentration increases the detectability of the same drugs using MIPs as pre-concentration and recognition elements. This combination of materials, theory, and applications forms a solid foundation which should aid in the design and development of MIP nanobiosensors for specific and sensitive detection of small molecules in complex matrices.

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

NASA Astrophysics Data System (ADS)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

Thin Films from Solvated Metal Atoms and Metal-Metal Bonded Compounds

DTIC Science & Technology

1988-07-01

University 1596 Manhattan, Kansas 66506 1 1 . CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE July 1988 13. NUMBER OF PAGES 14. MONITORING AGENCY...these colloidal particles are of interest: ( 1 ) the particles appear to scavenge electrons to become negatively charged, and (2) strong salvation...of metal doped polymers. C. A Listing of Technical Reports Submitted 1 . S. T. Lin, M. T. Franklin, and K. J. Klabunde, "Non-Aqueous Colloidal Gold

Nanodisperse transition metal electrodes (NTME) for electrochemical cells

DOEpatents

Striebel, Kathryn A.; Wen, Shi-Jie

2000-01-01

Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Mohapatra, Saumya R.

2018-05-01

Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.

Preparation and properties of chitosan-metal complex: Some factors influencing the adsorption capacity for dyes in aqueous solution.

PubMed

Rashid, Sadia; Shen, Chensi; Yang, Jing; Liu, Jianshe; Li, Jing

2018-04-01

Chitosan-metal complexes have been widely studied in wastewater treatment, but there are still various factors in complex preparation which are collectively responsible for improving the adsorption capacity need to be further studied. Thus, this study investigates the factors affecting the adsorption ability of chitosan-metal complex adsorbents, including various kinds of metal centers, different metal salts and crosslinking degree. The results show that the chitosan-Fe(III) complex prepared by sulfate salts exhibited the best adsorption efficiency (100%) for various dyes in very short time duration (10min), and its maximum adsorption capacity achieved 349.22mg/g. The anion of the metal salt which was used in preparation played an important role to enhance the adsorption ability of chitosan-metal complex. SO 4 2- ions not only had the effect of crosslinking through electrostatic interaction with amine group of chitosan polymer, but also could facilitate the chelation of metal ions with chitosan polymer during the synthesis process. Additionally, the pH sensitivity and the sensitivity of ionic environment for chitosan-metal complex were analyzed. We hope that these factors affecting the adsorption of the chitosan-metal complex can help not only in optimizing its use but also in designing new chitosan-metal based complexes. Copyright © 2017. Published by Elsevier B.V.

Optimization of structural and dielectric properties of CdSe loaded poly(diallyl dimethyl ammonium chloride) polymer in a desired frequency and temperature window

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tyagi, Chetna, E-mail: ctyagi05@gmail.com; Sharma, Ambika, E-mail: ambikasharma2004@yahoo.com

2016-01-07

In the present paper, investigations of CdSe loaded poly(diallyl dimethyl ammonium chloride) (PDADMAC) nanocomposites and pure PDADMAC synthesized by wet chemical technique have been carried out. Fourier transform infrared and X-ray diffraction analysis have been performed to reveal the structural details of pure polymer and polymer nanocomposite (PNC). The dielectric behavior of pure polymer and PNC has been recorded, which results in higher value of the real and imaginary part of dielectric constant for PNC, as compared with pure PDADMAC. The increase is attributed to the addition of CdSe quantum dots to the pure polymer. The contribution of ionic andmore » electronic polarization has been observed at higher frequency. The theoretical fitting of Cole-Cole function to the experimental data of dielectric constant of PNC and pure PDADMAC results in the determination of relaxation time and conductivity of space charge carriers. The CdSe loaded polymer nanocomposite has been used as an electrolyte in the battery fabrication with configuration Al/PNC/Ag{sub 2}O. The ac conductivity measurements have been carried out for both samples in a frequency window of 1 kHz–5 MHz and at different temperatures varying from 298 K to 523 K. Activation energy (E{sub a}) has been determined for pure polymer as well as PNC and is found to be less for PNC, as compared with pure polymer. Further, impedance measurement at different temperatures results in two frequency ranges corresponding to ionic conduction and blocking electrode effect. The value of bulk resistance for pure polymer and PNC has been found to be 3660 Ω and 442 Ω, respectively, at 298 K temperature. Electric modulus has been determined and is observed to support the dielectric constant data; it further reveals the deviation from Debye behavior at a higher frequency.« less

Biomimetic heterogeneous multiple ion channels: a honeycomb structure composite film generated by breath figures

NASA Astrophysics Data System (ADS)

Han, Keyu; Heng, Liping; Wen, Liping; Jiang, Lei

2016-06-01

We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields.We design a novel type of artificial multiple nanochannel system with remarkable ion rectification behavior via a facile breath figure (BF) method. Notably, even though the charge polarity in the channel wall reverses under different pH values, this nanofluidic device displays the same ionic rectification direction. Compared with traditional nanochannels, this composite multiple ion channel device can be more easily obtained and has directional ionic rectification advantages, which can be applied in many fields. Electronic supplementary information (ESI) available: Pore size distribution histograms of the AAO substrates; SEM images of the side view of pure AAO membranes and top view of the flat PI/AAO composite film; the current-time curves of the flat composite film; the current-voltage characteristics curves of pure AAO nanochannels with different mean pore diameters; CA of the two surfaces of the composite PI/AAO film, the structural formula of the polymer polyimide resin (PI), and solid surface zeta potential. See DOI: 10.1039/c6nr02506d

Capillary Thinning and Pinch-off Dynamics and Printability of Polyelectrolyte Solutions

NASA Astrophysics Data System (ADS)

Sharma, Vivek; Jimenez, Leidy N.; Dinic, Jelena; Parsi, Nikila

Biological macromolecules like proteins, DNA and polysaccharides, and many industrial polymers, are classified together as polyelectrolytes for in solution, the repeat units in their backbone are decorated with disassociated, charge-bearing ionic groups, surrounded by counter-ions. In diverse applications like inkjet printing, sprayable cosmetics and insecticides, paints and coatings that involve formation of fluid columns or sheets that undergo progressive thinning and pinch-off into drops, the dominant flow within the necking filament is extensional in nature. The extensional rheology response of the charged macromolecular solutions is not as well understood as that of their uncharged counterparts. Here focus on the characterization of capillary thinning and pinch-off dynamics, extensional rheology and printability of two model systems: sodium (polystyrene sulfonate) and poly(acrylic acid) by using dripping-onto-substrate (DoS) rheometry technique. Both the measured extensional relaxation times and the extensional viscosity values show salt- and polymer concentration-dependent behavior that is not expected or anticipated from the typical shear rheology response.

MIPs and Aptamers for Recognition of Proteins in Biomimetic Sensing.

PubMed

Menger, Marcus; Yarman, Aysu; Erdőssy, Júlia; Yildiz, Huseyin Bekir; Gyurcsányi, Róbert E; Scheller, Frieder W

2016-07-18

Biomimetic binders and catalysts have been generated in order to substitute the biological pendants in separation techniques and bioanalysis. The two major approaches use either "evolution in the test tube" of nucleotides for the preparation of aptamers or total chemical synthesis for molecularly imprinted polymers (MIPs). The reproducible production of aptamers is a clear advantage, whilst the preparation of MIPs typically leads to a population of polymers with different binding sites. The realization of binding sites in the total bulk of the MIPs results in a higher binding capacity, however, on the expense of the accessibility and exchange rate. Furthermore, the readout of the bound analyte is easier for aptamers since the integration of signal generating labels is well established. On the other hand, the overall negative charge of the nucleotides makes aptamers prone to non-specific adsorption of positively charged constituents of the sample and the "biological" degradation of non-modified aptamers and ionic strength-dependent changes of conformation may be challenging in some application.

Effects of anthropogenic surfactants on the conversion of marine dissolved organic carbon and microgels.

PubMed

Shiu, Ruei-Feng; Lee, Chon-Lin

2017-04-15

The possible impact of three types of anthropogenic surfactants on the ability of marine dissolved organic carbon (DOC) to form self-assembled microgels was evaluated. The behavior of existing native microgels was also examined in the presence of surfactants. These results reveal that the release of surfactants even at low concentrations into the aquatic environment could effectively hinder the self-assembly of DOC polymers. The extent of the size reduction had the following order: anionic, cationic, and non-ionic. Furthermore, charged surfactants can disrupt existing native microgels, converting large assemblies into smaller particles. One possible mechanisms is that surfactants are able to enhance the stability of DOC polymers and disrupt aggregates due to their surface charges and protein-denaturing activities. These findings suggest that the ecological system is altered by anthropogenic surfactants, and provide useful information for ecological assessments of different types of surfactants and raise warnings about surfactant applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reactions between NO/+/ and metal atoms using magnetically confined afterglows

NASA Technical Reports Server (NTRS)

Lo, H. H.; Clendenning, L. M.; Fite, W. L.

1977-01-01

A new method of studying thermal energy ion-neutral collision processes involving nongaseous neutral atoms is described. A long magnetic field produced by a solenoid in a vacuum chamber confines a thermal-energy plasma generated by photoionization of gas at very low pressure. As the plasma moves toward the end of the field, it is crossed by a metal atom beam. Ionic products of ion-atom reactions are trapped by the field and both the reactant and product ions move to the end of the magnetic field where they are detected by a quadrupole mass filter. The cross sections for charge transfer between NO(+) and Na, Mg, Ca, and Sr and that for rearrangement between NO(+) and Ca have been obtained. The charge-transfer reaction is found strongly dominant over the rearrangement reaction that forms metallic oxide ions.

Nanostructured pseudocapacitive materials decorated 3D graphene foam electrodes for next generation supercapacitors.

PubMed

Patil, Umakant; Lee, Su Chan; Kulkarni, Sachin; Sohn, Ji Soo; Nam, Min Sik; Han, Suhyun; Jun, Seong Chan

2015-04-28

Nowadays, advancement in performance of proficient multifarious electrode materials lies conclusively at the core of research concerning energy storage devices. To accomplish superior capacitance performance the requirements of high capacity, better cyclic stability and good rate capability can be expected from integration of electrochemical double layer capacitor based carbonaceous materials (high power density) and pseudocapacitive based metal hydroxides/oxides or conducting polymers (high energy density). The envisioned three dimensional (3D) graphene foams are predominantly advantageous to extend potential applicability by offering a large active surface area and a highly conductive continuous porous network for fast charge transfer with decoration of nanosized pseudocapacitive materials. In this article, we review the latest methodologies and performance evaluation for several 3D graphene based metal oxides/hydroxides and conducting polymer electrodes with improved electrochemical properties for next-generation supercapacitors. The most recent research advancements of our and other groups in the field of 3D graphene based electrode materials for supercapacitors are discussed. To assess the studied materials fully, a careful interpretation and rigorous scrutiny of their electrochemical characteristics is essential. Auspiciously, both nano-structuration as well as confinement of metal hydroxides/oxides and conducting polymers onto a conducting porous 3D graphene matrix play a great role in improving the performance of electrodes mainly due to: (i) active material access over large surface area with fast charge transportation; (ii) synergetic effect of electric double layer and pseudocapacitive based charge storing.

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains.

PubMed

Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R

2017-09-27

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.

Ion-Containing Polymers: Ionomers.

ERIC Educational Resources Information Center

Bazuin, C. G.; Eisenberg, A.

1981-01-01

Demonstrates how the incorporation of relatively low amounts of ionic material into nonionic polymers affects the structure and properties of these polymers. The extent to which properties are altered depends on dielectric constant of the backbone, position and type of ionic group, counterion type, ion concentration, and degree of neutralization.…

MIS capacitor studies on silicon carbide single crystals

NASA Technical Reports Server (NTRS)

Kopanski, J. J.

1990-01-01

Cubic SIC metal-insulator-semiconductor (MIS) capacitors with thermally grown or chemical-vapor-deposited (CVD) insulators were characterized by capacitance-voltage (C-V), conductance-voltage (G-V), and current-voltage (I-V) measurements. The purpose of these measurements was to determine the four charge densities commonly present in an MIS capacitor (oxide fixed charge, N(f); interface trap level density, D(it); oxide trapped charge, N(ot); and mobile ionic charge, N(m)) and to determine the stability of the device properties with electric-field stress and temperature. The section headings in the report include the following: Capacitance-voltage and conductance-voltage measurements; Current-voltage measurements; Deep-level transient spectroscopy; and Conclusions (Electrical characteristics of SiC MIS capacitors).

Characterization of Highly Sulfonated SIBS Polymer Partially Neutralized With Mg(+2) Cations

DTIC Science & Technology

2008-08-01

protective clothing, block copolymer ionomer membranes emerge. They are highly ordered sequence of both ionic and nonionic blocks, in which the ionic ...incorporated into the ionic polymer. Fourier-transform infrared spectroscopy results revealed that a significant amount of ordering occurred as a result on...increasing Mg content. This band indicates Mg complexation formed when two or more sulfonate groups ionically bonded to the Mg+2 cation

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Thermodynamic model for polyelectrolyte hydrogels.

PubMed

Arndt, Markus C; Sadowski, Gabriele

2014-09-04

The composition and swelling behavior of hydrogels may be dramatically influenced by external stimuli. Polyelectrolyte hydrogels consisting of charged polymers are particularly well-known for a high sensitivity to the presence of ionic species. For a thermodynamic description of such systems, the polyelectrolyte Perturbed-Chain Statistical Association Fluid Theory (pePC-SAFT) equation of state was augmented and merged with an extension of the modeling of hydrogels. This combined approach allowed for two effects to be taken into account: first, charges along the polymer chain and their interaction with mobile ions of the same or opposite charge in aqueous solutions and, second, the elastic interactions of swellable networks and their effect on Helmholtz energy and pressure. Thus, predictions of the degree of counterion condensation on the polymer chains could be made both for vapor-liquid equilibria of aqueous polyelectrolyte solutions and for polyelectrolyte hydrogels in aqueous salt solutions. The influence of temperature and molecular weight thereon was predicted successfully, and the impact of the degree of neutralization and the effect of additional salts were examined in comparison to literature data. With the inclusion of the influence of the Donnan potential, our model gave good predictions of swellable polyelectrolyte hydrogel systems in salt solutions. Poly(acrylic acid) and poly(methacrylic acid) gels were studied along with their corresponding sodium salts. Their swelling behavior in aqueous NaCl and NaNO3 solutions was examined.

The Role of Polymer Electrolytes in Drug Delivery

NASA Astrophysics Data System (ADS)

Latham, R. J.; Linford, R. G.; Schlindwein, W. S.

2002-12-01

30 years ago Michel Armand, who was working on intercalation cathode materials in high energy power sources, identified the need to develop flexible, ionically conducting, electronically insulating electrolyte materials to accommodate the gross dimensional changes that occur on charge and discharge. In 1973, Peter Wright produced the first such materials designed for this purpose. His "polymer electrolytes" consisted of thin films of sodium or potassium salts dissolved in poly (ethylene oxide) PEO. Many polymer electrolytes had been developed in the ensuing years. Those for power source use have focussed on Lithium as the conducting species whereas complementary materials have been utilised for sensor and other applications. It is well known that the flexible matrix, a heteropolymer usually modified by additives such as plasticisers and/or inert fillers, provides a facile conducting pathway for ions. It is a significant disadvantage of many early polymer electrolytes that both the electrochemically active cations and the charge-compensating anions were mobile. Classic methods of drug delivery have embraced a number of routes into the site of pharmacological action, including ingestion into the lung, the digestive tract or the colon; injection into muscle tissue; and intravenous delivery through a catheter (a "drip"). Modern preference, wherever possible, is for a non-invasive route to minimise the chance of cross infection, especially of the AIDS virus. The skin, which is the largest organ in the human body, is a particularly appealing route as, in the absence of wounds and blemishes, it offers a natural, high-integrity, barrier to the outside world. Skin patches containing active drug that is allowed to diffuse across the external skin barrier into the bloodstream now enjoy wide application but a problem is that the rate of egress is often slow. Transport can be enhanced by artificially dilating the skin pores and/or by opening up additional pores by the application of voltage pulses (electroporation). For certain ionic drugs, including local anaesthetics such as Novacaine and, more recently peptides and gene-based, biotechnological engineered pharmaceuticals, it is possible substantially to enhance transdermal transport by iontophoresis. Key issues affecting iontophoretic delivery are reviewed in this paper and the potential role of polymer electrolyte materials in iontophoretic devices will be described.

Characterization and modeling of ionic polymeric smart materials as artificial muscles and robotic swimming structures

NASA Astrophysics Data System (ADS)

Mojarrad, Mehran

2001-07-01

In this dissertation document, a thorough review and investigation of works in connection with the ionic polymeric gels as artificial muscles and electrically controllable polymeric network structures were performed. Where possible, comparisons were made with biological muscles and applications in marine propulsion using such polymeric materials were investigated. Furthermore, methods of fabrication of several chemically active ionic polymeric gel muscles such as PolyAcryloNitrile (PAN), Poly(2-Acrylamido-2-Methyl-1-PropaneSulfonic) acid (PAMPS), and PolyAcrylic-acid-bis-AcrylaMide (PAAM) as well as a new class of electrically active composite muscle such as Ion-Exchange-Metal-Composites (IEMC) or Ionic Polymer Metal Composites (IPMC) materials are introduced and investigated that resulted in two US patents regarding their fabrication and application capabilities as actuators and sensors. In this research, various forms of the IPMC fabrication were explored and reported. In addition, characterization of PAN muscles, bundling and encapsulation were investigated. Conversion of chemical to electrical artificial muscles were also investigated using chemical plating techniques as well as physical vapor deposition methods of the pH-activated muscles like PAN fibers. Experimental methods were devised to characterize contraction, expansion, and bending of various actuators using isometric, isoionic, and isotonic characterization methods. Several apparatuses for modeling and testing of the various artificial muscles were built to show the viability of the application of both chemoactive and electroactive muscles. Furthermore PAN fiber muscles in different configurations such as spring-loaded fiber bundles, biceps, triceps, ribbon type muscles, and segmented fiber bundles were fabricated to make a variety of actuators. Additionally, swimming robotic structures and associated hardware were built to incorporate IPMC as biomimetic propulsion fin actuators. In addition, various configuration of IPMC such as linear actuators and multiplayer actuators were fabricated and evaluated for load and sensing capability. Theories associated with ionic polymer gels electrodynamics and chemodynamics were proposed, analyzed and modeled for the manufactured material. Futhermore, theoretical models of swimming structures were developed and compared with biological fish propulsion models and dynamically evaluated for robotic applications.

Fullerene reinforced ionic polymer transducer

NASA Astrophysics Data System (ADS)

Jung, J. H.; Cheng, T. H.; Oh, I. K.

2009-07-01

Novel fullerene reinforced nano-composite transducers based on nafion were developed inorder to improve the ionic polymer metal composite transducer. The fullerene reinforced nano-composite membranes were fabricated by recasting method with 0.1 and 0.5 weight percentage of a Fullerenes. Stress-Strain tests showed tremendous increase in stiffness and modulus of the nano-composite membranes even at these minute concentrations of Fullerenes. Ionic exchange capacity analysis and proton conductivity test were performed to calculate the electrical property of the composite films. Water uptake was measured to understand the liquid adsorbing characteristics of the membranes. Also, tip displacement of the nano-composite membrane transducer was investigated under AC excitations with various magnitudes and frequencies. Furthermore, the generated energy was measured from external sinusoidal physical input vibration with several displacements and frequencies by using a mechanical shaker. As a result, the fullerene reinforced nanocomposite membrane based on nafion shows higher stiffness and Young's modulus than that of pure nafion membrane. Also, the nano-composite membrane had better water uptake and proton conductivity than the pure membrane. Fullerene reinforced nano-composite membrane transducer actuates to a much larger deformations than pure nafion membrane transducer. The developed membrane transducer dissipates more energy from the physical input vibration than that of unfilled(or virgin) Nafion membrane transducer.

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

PubMed Central

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

Lithium salts based on a series of new anilinyl-perfluorosulfonamide salts and their polymer electrolytes

NASA Astrophysics Data System (ADS)

Thiam, A.; Iojoiu, C.; Leprêtre, J.-C.; Sanchez, J.-Y.

2017-10-01

Polymer electrolytes based on a series of new lithium anilinyl-perfluorosulfonamide exhibit conductivities close to LiTFSI ones and higher cationic transference numbers. Taking advantage of an extended delocalization on the negative charge, the anodic stability of the salts was found to range between 4.2 and 4.9 V vs Li/Li+, according to the electron-withdrawing group EWG located in para/ortho position. The simplicity of the synthesis process of the new salts, with lower fluorine content than LiPF6 and LiTFSI, paves the way for a further semi-pilot scale-up. Moreover, Linear Free Energy Relationships, LFER, were established for the first time, for both ionic conductivity and anodic stability. These LFER demonstrate unambiguously and quantitatively the conductivity dependence on anion basicity. Polymer electrolytes were soundly investigated through a variety of physicochemical and electrochemical characterizations.

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

NASA Astrophysics Data System (ADS)

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm-1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

Polymer-based chromophore-catalyst assemblies for solar energy conversion

NASA Astrophysics Data System (ADS)

Leem, Gyu; Sherman, Benjamin D.; Schanze, Kirk S.

2017-12-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

Polymer-based chromophore-catalyst assemblies for solar energy conversion.

PubMed

Leem, Gyu; Sherman, Benjamin D; Schanze, Kirk S

2017-01-01

The synthesis of polymer-based assemblies for light harvesting has been motivated by the multi-chromophore antennas that play a role in natural photosynthesis for the potential use in solar conversion technologies. This review describes a general strategy for using polymer-based chromophore-catalyst assemblies for solar-driven water oxidation at a photoanode in a dye-sensitized photoelectrochemical cell (DSPEC). This report begins with a summary of the synthetic methods and fundamental photophysical studies of light harvesting polychormophores in solution which show these materials can transport excited state energy to an acceptor where charge-separation can occur. In addition, studies describing light harvesting polychromophores containing an anchoring moiety (ionic carboxylate) for covalent bounding to wide band gap mesoporous semiconductor surfaces are summarized to understand the photophysical mechanisms of directional energy flow at the interface. Finally, the performance of polychromophore/catalyst assembly-based photoanodes capable of light-driven water splitting to oxygen and hydrogen in a DSPEC are summarized.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards an all-copper redox flow battery based on a copper-containing ionic liquid.

PubMed

Schaltin, Stijn; Li, Yun; Brooks, Neil R; Sniekers, Jeroen; Vankelecom, Ivo F J; Binnemans, Koen; Fransaer, Jan

2016-01-07

The first redox flow battery (RFB), based on the all-copper liquid metal salt [Cu(MeCN)4][Tf2N], is presented. Liquid metal salts (LMS) are a new type of ionic liquid that functions both as solvent and electrolyte. Non-aqueous electrolytes have advantages over water-based solutions, such as a larger electrochemical window and large thermal stability. The proof-of-concept is given that LMSs can be used as the electrolyte in RFBs. The main advantage of [Cu(MeCN)4][Tf2N] is the high copper concentration, and thus high charge and energy densities of 300 kC l(-1) and 75 W h l(-1) respectively, since the copper(i) ions form an integral part of the electrolyte. A Coulombic efficiency up to 85% could be reached.

An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes.

PubMed

Fattah, N F A; Ng, H M; Mahipal, Y K; Numan, Arshid; Ramesh, S; Ramesh, K

2016-06-06

Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge-discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g -1 , which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

Multispectral Visible/Infrared Sensors Based on Polymer-Metal Nanocomposites

DTIC Science & Technology

2010-01-06

transport in the dielectric zone is governed by an activated tunneling process, while the electron transport in the metallic zone can be described by...electrical pathway has formed at this stage, and thermally activated tunneling dominates the charge transport. At very high metal concentration, metallic...25 -20 -15 -10 -5 0 5 10 Cu rre nt , m A Bias Voltage, V Dark Bright Bright >850 nm Figure 12a. Optical absorption spectrum of Blackberry dye

Soft- and reactive landing of ions onto surfaces: Concepts and applications: CONCEPTS AND APPLICATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Gunaratne, Don; Laskin, Julia

2015-04-16

Soft- and reactive landing of mass-selected ions is gaining attention as a promising approach for the precisely-controlled preparation of materials on surfaces that are not amenable to deposition using conventional methods. A broad range of ionization sources and mass-filters are available that make ion soft-landing a versatile tool for surface modification using beams of hyperthermal (< 100 eV) ions. The ability to select the mass-to-charge ratio of the ion, its kinetic energy and charge state, along with precise control of the size, shape, and position of the ion beam on the deposition target distinguishes ion soft landing from other surfacemore » modification techniques. Soft- and reactive landing have been used to prepare interfaces for practical applications as well as precisely-defined model surfaces for fundamental investigations in chemistry, physics, and materials science. For instance, soft- and reactive landing have been applied to study the surface chemistry of ions isolated in the gas-phase, prepare arrays of proteins for high-throughput biological screening, produce novel carbon-based and polymer materials, enrich the secondary structure of peptides and the chirality of organic molecules, immobilize electrochemically-active proteins and organometallics on electrodes, create thin films of complex molecules, and immobilize catalytically active organometallics as well as ligated metal clusters. In addition, soft landing has enabled investigation of the size-dependent behavior of bare metal clusters in the critical subnanometer size regime where chemical and physical properties do not scale predictably with size. The morphology, aggregation, and immobilization of larger bare metal nanoparticles, which are directly relevant to the design of catalysts as well as improved memory and electronic devices, have also been studied using ion soft landing. This review article begins in section 1 with a brief introduction to the existing applications of ion soft- and reactive landing. Section 2 provides an overview of the ionization sources and mass filters that have been used to date for soft landing of mass-selected ions. A discussion of the competing processes that occur during ion deposition as well as the types of ions and surfaces that have been investigated follows in section 3. Section 4 discusses the physical phenomena that occur during and after ion soft landing including retention and reduction of ionic charge along with factors that impact the efficiency of ion deposition. The influence of soft landing on the secondary structure and biological activity of complex ions is addressed in section 5. Lastly, an overview of the structure and mobility as well as the catalytic, optical, magnetic, and redox properties of bare ionic clusters and nanoparticles deposited onto surfaces is presented in section 6.« less

Probing of barrier induced deviations in current-voltage characteristics of polymer devices by impedance spectroscopy

NASA Astrophysics Data System (ADS)

Khan, Motiur Rahman; Rao, K. S. R. Koteswara; Menon, R.

2017-05-01

Temperature dependent current-voltage measurements have been performed on poly(3-methylthiophene) based devices in metal/polymer/metal geometry in temperature range 90-300 K. Space charge limited current (SCLC) controlled by exponentially distributed traps is observed at all the measured temperatures at intermediate voltage range. At higher voltages, trap-free SCLC is observed at 90 K only while slope less than 2 is observed at higher temperatures which is quiet unusual in polymer devices. Impedance measurements were performed at different bias voltages. The unusual behavior observed in current-voltage characteristics is explained by Cole-Cole plot which gives the signature of interface dipole on electrode/polymer interface. Two relaxation mechanisms are obtained from the real part of impedance vs frequency spectra which confirms the interface related phenomena in the device

Synthesis of electroactive ionic liquids for flow battery applications

DOEpatents

Anderson, Travis Mark; Ingersoll, David; Staiger, Chad; Pratt, Harry

2015-09-01

The present disclosure is directed to synthesizing metal ionic liquids with transition metal coordination cations, where such metal ionic liquids can be used in a flow battery. A cation of a metal ionic liquid includes a transition metal and a ligand coordinated to the transition metal.

Characterization of Intermediate Oxidation States in CO2 Activation

NASA Astrophysics Data System (ADS)

Dodson, Leah G.; Thompson, Michael C.; Weber, J. Mathias

2018-04-01

Redox chemistry during the activation of carbon dioxide involves changing the charge state in a CO2 molecular unit. However, such changes are usually not well described by integer formal charges, and one can think of COO functional units as being in intermediate oxidation states. In this article, we discuss the properties of CO2 and CO2-based functional units in various charge states. Besides covering isolated CO2 and its ions, we describe the CO2-based ionic species formate, oxalate, and carbonate. Finally, we provide an overview of CO2-based functional groups and ligands in clusters and metal-organic complexes.

Metal cation controls phosphate release in the myosin ATPase.

PubMed

Ge, Jinghua; Huang, Furong; Nesmelov, Yuri E

2017-11-01

Myosin is an enzyme that utilizes ATP to produce a conformational change generating a force. The kinetics of the myosin reverse recovery stroke depends on the metal cation complexed with ATP. The reverse recovery stroke is slow for MgATP and fast for MnATP. The metal ion coordinates the γ phosphate of ATP in the myosin active site. It is accepted that the reverse recovery stroke is correlated with the phosphate release; therefore, magnesium "holds" phosphate tighter than manganese. Magnesium and manganese are similar ions in terms of their chemical properties and the shell complexation; hence, we propose to use these ions to study the mechanism of the phosphate release. Analysis of octahedral complexes of magnesium and manganese show that the partial charge of magnesium is higher than that of manganese and the slightly larger size of manganese ion makes its ionic potential smaller. We hypothesize that electrostatics play a role in keeping and releasing the abstracted γ phosphate in the active site, and the stronger electric charge of magnesium ion holds γ phosphate tighter. We used stable myosin-nucleotide analog complex and Raman spectroscopy to examine the effect of the metal cation on the relative position of γ phosphate analog in the active site. We found that in the manganese complex, the γ phosphate analog is 0.01 nm further away from ADP than in the magnesium complex. We conclude that the ionic potential of the metal cation plays a role in the retention of the abstracted phosphate. © 2017 The Protein Society.

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

A sealed optical cell for the study of lithium-electrode|electrolyte interfaces

NASA Astrophysics Data System (ADS)

Howlett, P. C.; MacFarlane, D. R.; Hollenkamp, A. F.

A sealed, symmetrical, lithium optical cell, which enables optical images of lithium surface deposits and in situ Raman spectra to be obtained simply and conveniently during charge-discharge cycling of lithium metal electrodes, has been designed and tested. A conventional aprotic liquid, 1 M lithium hexafluorophosphate in propylene carbonate, and an experimental ionic liquid, 20 mol% lithium bis(trifluoromethanesulfonyl)amide in 1-ethyl 3-methyl imidazolium bis(trifluoromethanesulfonyl)amide, are investigated as electrolyte solutions. Images obtained from the cell with the former electrolyte solution demonstrate the problems associated with cycling lithium metal electrodes. Images obtained with the latter electrolyte solution provide clear evidence that continued investigation of ionic liquids for use with lithium metal electrodes is warranted. Operation of the cell with the conventional electrolyte yields Raman spectra of good quality. The spectra display vibrational modes which arise from the electrolyte, as well as several additional modes which are associated with the deposits formed during cycling.

Tuning of electrostatic vs. depletion interaction in deciding the phase behavior of nanoparticle-polymer system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sugam, E-mail: sugam@barc.gov.in; Aswal, V. K.; Kohlbrecher, J.

2015-06-24

Nanoparticle-polymer system interestingly show a re-entrant phase behavior where charge stabilized silica nanoparticles (phase I) undergo particle clustering (phase II) and then back to individual particles (phase I) as a function of polymer concentration. Such phase behavior arises as a result of dominance of various interactions (i) nanoparticle-nanoparticle electrostatic repulsion (ii) polymer induced attractive depletion between nanoparticles and (iii) polymer-polymer repulsion, at different concentration regimes. Small-angle neutron scattering (SANS) has been used to study the evolution of interaction during this re-entrant phase behavior of nanoparticles by contrast-marching the polymer. The SANS data have been modeled using a two-Yukawa potential accountingmore » for both attractive and repulsive parts of the interaction between nanoparticles. The degree of both of these parts has been separately tuned by varying the polymer concentration and ionic strength of the solution. Both of these parts are found to have long-range nature. At low polymer concentrations, the electrostatic repulsion dominates over the depletion attraction. The magnitude and the range of the depletion interaction increase with the polymer concentration leading to nanoparticle clustering. At higher polymer concentrations, the increased polymer-polymer repulsion reduces the strength of depletion leading to re-entrant phase behavior. The clusters formed under depletion attraction are found to have surface fractal morphology.« less

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

Recent experimental studies measured the ionic conductivities of a series of poly(glycidyl ether)s with varying neat dielectric constants (ɛ), viscosities (η), and glass transition temperatures (Tg), as hosts for lithium bistrifluoromethanesulfonimide (LiTFSI) salt. In such a context, it was demonstrated that the ionic conductivity of these polymer electrolytes was a function of ɛ rather than Tg or η, suggesting that there may exist regimes in which ionic conductivity is not limited by slow segmental dynamics but rather by low ionic dissociation. Motivated by such results, we used atomistic molecular dynamics to study the structure and transport characteristics of the same set of host polymers. We found that the coordination number of TFSI- about Li+ in the first solvation shell and the total fraction of free ions increased as a function of ɛ, implying the polymer hosts enhanced ion dissociation. In addition, we found that increasing the dielectric constant of the host polymer enhanced self-correlated ion transport, as evidenced by an increase in the diffusion coefficients of each ion species. Overall, we confirmed that limited ion dissociation in low- ɛ polymer electrolyte hosts hampers ionic conductivity. We would like to thank the National Science Foundation Graduate Research Fellowship Program for funding this research endeavor.

Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

PubMed

Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

2017-05-24

Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

Metal/Ion Interactions Induced p–i–n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals

DOE PAGES

Wu, Ting; Mukherjee, Rupam; Ovchinnikova, Olga S.; ...

2017-11-17

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. Here, we report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI 3 single crystals with Au/MAPbI 3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA +) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI 3 interface, whereas iodine anions (I –) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI 3 interface due to the formation of MA +more » vacancies, and an n-doped region near the Ag/MAPbI 3 interface due to formation of I – vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI 3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.« less

Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

NASA Astrophysics Data System (ADS)

Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

2017-02-01

In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

Polarized emission from light-emitting electrochemical cells using uniaxially oriented polymer thin films of poly(9,9-dioctylfluorene-co-bithiophene)

NASA Astrophysics Data System (ADS)

Miyazaki, Masumi; Sakanoue, Tomo; Takenobu, Taishi

2018-03-01

Uniaxially oriented poly(9,9-dioctylfluorene-co-bithiophene) (F8T2) films were prepared on rubbed polyimide substrates and applied to emitting layers of light-emitting electrochemical cells (LECs). The layered structure of the uniaxially oriented F8T2 film and ionic liquid electrolytes enabled us to demonstrate LEC operations with high anisotropic characteristics both in emission and charge transport. Polarized electroluminescence (EL) from electrochemically induced p-n junctions in the uniaxially oriented F8T2 was obtained. The dichroic ratios of EL were the same as those of photoluminescence, suggesting that the doping process into the oriented F8T2 did not interrupt the polymer ordering. This indicates the usefulness of the layered structure of the polymer/electrolyte for the fabrication of LECs based on highly oriented polymer films. In addition, uniaxially oriented F8T2 was found to show reduced threshold energy in optically pumped amplified spontaneous emission. These demonstrations suggest the advantage of uniaxially oriented polymer-based LECs for potential application in future electrically pumped lasers.

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

PubMed

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Lithium metal protection enabled by in-situ olefin polymerization for high-performance secondary lithium sulfur batteries

NASA Astrophysics Data System (ADS)

An, Yongling; Zhang, Zhen; Fei, Huifang; Xu, Xiaoyan; Xiong, Shenglin; Feng, Jinkui; Ci, Lijie

2017-09-01

Lithium metal is considered to be the optimal choice of next-generation anode materials due to its ultrahigh theoretical capacity and the lowest redox potential. However, the growth of dendritic and mossy lithium for rechargeable Li metal batteries lead to the possible short circuiting and subsequently serious safety issues during charge/discharge cycles. For the further practical applications of Li anode, here we report a facile method for fabricating robust interfacial layer via in-situ olefin polymerization. The resulting polymer layer effectively suppresses the formation of Li dendrites and enables the long-term operation of Li metal batteries. Using Li-S cells as a test system, we also demonstrate an improved capacity retention with the protection of tetramethylethylene-polymer. Our results indicate that this method could be a promising strategy to tackle the intrinsic problems of lithium metal anodes and promote the development of Li metal batteries.

FROM THE HISTORY OF PHYSICS: Electrolysis and surface phenomena. To the bicentenary of Volta's publication on the first direct-current source

NASA Astrophysics Data System (ADS)

Gokhshtein, Aleksandr Ya

2000-07-01

The development of knowledge about electric current, potential, and the conversion of energy at the interface between electronic- and ionic-conductivity phases is briefly reviewed. Although soon after its discovery it was realized that electric current is the motion of charged particles, the double-layer field promoting charge transfer through the interface was considered for a long time to be as uniform as in a capacitor. One-dimensional ion discharge theory failed to explain the observed dependence of the current on the potential jump across the interface. The spatial segmentation of energy in the double layer due to the quantum evolution of the layer's periphery puts a limit on the charge transfer work the field may perform locally, and creates conditions for the ionic atmosphere being spontaneously compressed after the critical potential jump has been reached. A discrete interchange of states also occurs due to the adsorption of discharged particles and corresponds to the consecutive exclusion of the d-wave function nodes of metal surface atoms, the exclusion manifesting itself in the larger longitudinal and smaller lateral sizes of the atomic orbital. The elastic extension of the metal surface reduces the d-function overlap thus intensifying adsorption. Advances in experimentation, in particular new techniques capable of detecting alternating surface tension of solids, enabled these and some other phenomena to be observed.

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices

DOE PAGES

Black, Jennifer M.; Come, Jeremy; Bi, Sheng; ...

2017-10-24

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal–insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment andmore » theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.« less

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Black, Jennifer M.; Come, Jeremy; Bi, Sheng

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal–insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment andmore » theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.« less

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Transport and spectroscopic studies of liquid and polymer electrolytes

NASA Astrophysics Data System (ADS)

Bopege, Dharshani Nimali

Liquid and polymer electrolytes are interesting and important materials to study as they are used in Li rechargeable batteries and other electrochemical devices. It is essential to investigate the fundamental properties of electrolytes such as ionic conductivity, diffusion, and ionic association to enhance battery performance in different battery markets. This dissertation mainly focuses on the temperature-dependent charge and mass transport processes and ionic association of different electrolyte systems. Impedance spectroscopy and pulsed field gradient nuclear magnetic resonance spectroscopy were used to measure the ionic conductivity and diffusion coefficients of ketone and acetate based liquid electrolytes. In this study, charge and mass transport in non-aqueous liquid electrolytes have been viewed from an entirely different perspective by introducing the compensated Arrhenius formalism. Here, the conductivity and diffusion coefficient are written as an Arrhenius-like expression with a temperature-dependent static dielectric constant dependence in the exponential prefactor. The compensated Arrhenius formalism reported in this dissertation very accurately describes temperature-dependent conductivity data for acetate and ketone-based electrolytes as well as temperature-dependent diffusion data of pure solvents. We found that calculated average activation energies of ketone-based electrolytes are close to each other for both conductivity and diffusion data (in the range 24-26 kJ/mol). Also, this study shows that average activation energies of acetate-based electrolytes are higher than those for the ketone systems (in the range 33-37 kJ/mol). Further, we observed higher dielectric constants and ionic conductivities for both dilute and concentrated ketone solutions with temperature. Vibrational spectroscopy (Infrared and Raman) was used to probe intermolecular interactions in both polymer and liquid electrolytes, particularly those which contain lithium trifluoromethanesulfonate, LiCF3SO3, abbreviated here as lithium triflate(LiTf). The molar absorption coefficients of nus(SO3), deltas(CF3), and deltas(SO3) vibrational modes of triflate anion in the LiTf-2-pentanone system were found to be 6708+/-89, 5182+/-62, and 189+/-2 kg mol-1 cm-1, respectively using Beer-Lambert law. Our results show that there is strong absorption by nu s(SO3) mode and weak absorption by deltas(CF 3) mode. Also, the absorptivity of each mode is independent of the ionic association with Li ions. This work allows for the direct quantitative comparison of calculated concentrations in different samples and different experimental conditions. In addition, this dissertation reports the temperature-dependent vibrational spectroscopic studies of pure poly(ethylene oxide) and LiTf-poly(ethylene oxide) complexes. A significant portion of this dissertation focuses on crystallographic studies of ketone-salt (LiTf:2-pentanone and NaTf:2-hexanone) and amine-acid (diethyleneamine: H3PO4, N,N'-dimethylethylenediamine:H 3PO4, and piperazine:H3PO4) systems. Here, sodium trifluoromethanesulfonate, NaCF3SO3 is abbreviated as NaTf. As model compounds, these systems provide valuable information about ion-ion interactions, which are helpful for understanding complex polymer systems. During this study, five crystal structures were solved using single X-ray diffractometry, and their vibrational modes were studied in the mid-infrared region. In the secondary amine/phosphoric acid systems, the nature of hydrogen-bonding network was examined.

Transport of ARS-labeled hydroxyapatite nanoparticles in saturated granular media is influenced by surface charge variability even in the presence of humic acid

USDA-ARS?s Scientific Manuscript database

Hydroxyapatite nanoparticles (nHAP) are increasingly being used to remediate soils and water polluted by metals and radionuclides. The transport and retention of Alizarin red S (ARS)-labeled nHAP in water-saturated granular media were investigated. Experiments were conducted over a range of ionic ...

Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan

2015-09-25

Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increasemore » with the ionic liquid ratio.« less

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Ionic liquids screening for desulfurization of natural gasoline by liquid-liquid extraction.

PubMed

Likhanova, Natalya V; Guzmán-Lucero, Diego; Flores, Eugenio A; García, Paloma; Domínguez-Aguilar, Marco A; Palomeque, Jorge; Martínez-Palou, Rafael

2010-11-01

Seventy five ionic liquids (ILs) were tested as a sequestering agent of sulfured compounds in natural gasoline (NG). Desulphurization of NG was performed by means of liquid-liquid extraction method at room temperature and atmospheric pressure. Experimental ILs containing imidazolium, pyridinium, and ammonium cations along with organic and inorganic anions were synthesized conventionally and under microwave and sonochemical conditions. The effect of the molecular structure of ILs on the desulfurization efficiency of NG with high sulfur content was evaluated. Analysis indicated that the anion type played a more important role than the cation on the desulphurization process. ILs based on halogen-ferrates and halogen-aluminates exhibited the highest efficiency in sulfur removal, and their efficiency is further improved when there is an excess of metallic salt in a ratio of at least 1:1.3 during the synthesis of the corresponding IL. An explanation for the ability of metallic ILs to remove sulfur-containing compounds from natural gasoline based on the ratio of the ionic charge to the atomic radius is proposed. Furthermore, a method to recover and reuse water-sensitive to halogenated precursors is described.

Suppression of protein adsorption on a charged phospholipid polymer interface.

PubMed

Xu, Yan; Takai, Madoka; Ishihara, Kazuhiko

2009-02-09

High capability of a charged interface to suppress adsorption of both anionic and cationic proteins was reported. The interface was covalently constructed on quartz by modifying with an anionic phospholipid copolymer, poly(2-methacryloyloxyethyl phosphorylcholine (MPC)-co-n-butyl methacrylate (BMA)-co-potassium 3-methacryloyloxypropyl sulfonate (PMPS)-co-3-methacryloxypropyl trimethoxysilane (MPTMSi)) (PMBSSi). The PMBSSi interfaces were very hydrophilic and homogeneous and could function effectively for a long time even under long-term fluidic working conditions. The PMBSSi density on the interface, which was controllable by adjusting the PMBSSi concentration of the modification solution, affected the surface properties, including the surface contact angle, the surface roughness, and the surface zeta-potential. When a PMBSSi modification was applied, the adsorption of various proteins (isoelectric point varying from 1.0 to 11.0) on quartz was reduced to at least 87% in amount, despite the various electrical natures these proteins have. The protein adsorption behavior on the PMBSSi interface depended more on the PMBSSi density than on the surface charge. The PMBSSi modification had a stable impact on the surface, not only at the physiologic ionic strength, but also over a range of the ionic strength, suggesting that electrostatic interactions do not dominate the behavior of protein adsorption to the PMBSSi surface.

Modelling compression sensing in ionic polymer metal composites

NASA Astrophysics Data System (ADS)

Volpini, Valentina; Bardella, Lorenzo; Rodella, Andrea; Cha, Youngsu; Porfiri, Maurizio

2017-03-01

Ionic polymer metal composites (IPMCs) consist of an ionomeric membrane, including mobile counterions, sandwiched between two thin noble metal electrodes. IPMCs find application as sensors and actuators, where an imposed mechanical loading generates a voltage across the electrodes, and, vice versa, an imposed electric field causes deformation. Here, we present a predictive modelling approach to elucidate the dynamic sensing response of IPMCs subject to a time-varying through-the-thickness compression (‘compression sensing’). The model relies on the continuum theory recently developed by Porfiri and co-workers, which couples finite deformations to the modified Poisson-Nernst-Planck (PNP) system governing the IPMC electrochemistry. For the ‘compression sensing’ problem we establish a perturbative closed-form solution along with a finite element (FE) solution. The systematic comparison between these two solutions is a central contribution of this study, offering insight on accuracy and mathematical complexity. The method of matched asymptotic expansions is employed to find the analytical solution. To this end, we uncouple the force balance from the modified PNP system and separately linearise the PNP equations in the ionomer bulk and in the boundary layers at the ionomer-electrode interfaces. Comparison with FE results for the fully coupled nonlinear system demonstrates the accuracy of the analytical solution to describe IPMC sensing for moderate deformation levels. We finally demonstrate the potential of the modelling scheme to accurately reproduce experimental results from the literature. The proposed model is expected to aid in the design of IPMC sensors, contribute to an improved understanding of IPMC electrochemomechanical response, and offer insight into the role of nonlinear phenomena across mechanics and electrochemistry.

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy.

PubMed

Schäfer, Thomas; Di Paolo, Roberto E; Franco, Ricardo; Crespo, João G

2005-05-28

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.

Dynamic curvature sensing employing ionic-polymer-metal composite sensors

NASA Astrophysics Data System (ADS)

Bahramzadeh, Yousef; Shahinpoor, Mohsen

2011-09-01

A dynamic curvature sensor is presented based on ionic-polymer-metal composite (IPMC) for curvature monitoring of deployable/inflatable dynamic space structures. Monitoring the curvature variation is of high importance in various engineering structures including shape monitoring of deployable/inflatable space structures in which the structural boundaries undergo a dynamic deployment process. The high sensitivity of IPMCs to the applied deformations as well as its flexibility make IPMCs a promising candidate for sensing of dynamic curvature changes. Herein, we explore the dynamic response of an IPMC sensor strip with respect to controlled curvature deformations subjected to different forms of input functions. Using a specially designed experimental setup, the voltage recovery effect, phase delay, and rate dependency of the output voltage signal of an IPMC curvature sensor are analyzed. Experimental results show that the IPMC sensor maintains the linearity, sensitivity, and repeatability required for curvature sensing. Besides, in order to describe the dynamic phenomena such as the rate dependency of the IPMC sensor, a chemo-electro-mechanical model based on the Poisson-Nernst-Planck (PNP) equation for the kinetics of ion diffusion is presented. By solving the governing partial differential equations the frequency response of the IPMC sensor is derived. The physical model is able to describe the dynamic properties of the IPMC sensor and the dependency of the signal on rate of excitations.

Conducting polymer electrodes for visual prostheses.

PubMed

Green, R A; Devillaine, F; Dodds, C; Matteucci, P; Chen, S; Byrnes-Preston, P; Poole-Warren, L A; Lovell, N H; Suaning, G J

2010-01-01

Conducting polymers (CPs) have the potential to provide superior neural interfaces to conventional metal electrodes by introducing more efficient charge transfer across the same geometric area. In this study the conducting polymer poly(ethylene dioxythiophene) (PEDOT) was coated on platinum (Pt) microelectrode arrays. The in vitro electrical characteristics were assessed during biphasic stimulation regimes applied between electrode pairs. It was demonstrated that PEDOT could reduce the potential excursion at a Pt electrode interface by an order of magnitude. The charge injection limit of PEDOT was found to be 15 x larger than Pt. Additionally, PEDOT coated electrodes were acutely implanted in the suprachoroidal space of a cat retina. It was demonstrated that PEDOT coated electrodes also had lower potential excursions in vivo and electrically evoked potentials (EEPs) could be detected within the vision cortex.

Undoped polythiophene field-effect transistors with mobility of 1 cm2 V-1 s-1

NASA Astrophysics Data System (ADS)

Hamadani, B. H.; Gundlach, D. J.; McCulloch, I.; Heeney, M.

2007-12-01

We report on charge transport in organic field-effect transistors based on poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) as the active polymer layer with saturation field-effect mobilities as large as 1cm2V-1s-1. This is achieved by employing Pt instead of the commonly used Au as the contacting electrode and allows for a significant reduction in the metal/polymer contact resistance. The mobility increases as a function of decreasing channel length, consistent with a Poole-Frenkel model of charge transport, and reaches record mobilities of 1cm2V-1s-1 or more at channel lengths on the order of few microns in an undoped solution-processed polymer cast on an oxide gate dielectric.

Multi-Scale Structure of Coacervates formed by Oppositely Charged Polyelectrolytes

NASA Astrophysics Data System (ADS)

Rubinstein, Michael

We develop a scaling model of coacervates formed by oppositely charged polyelectrolytes and demonstrate that they self-organize into multi-scale structures. The intramolecular electrostatic interactions in dilute polyanion or polycation solutions are characterized by the electrostatic blobs with size D- and D+ respectively, that repel neighboring blobs on the same chains with electrostatic energy on the order of thermal energy kT . After mixing, electrostatic intramolecular repulsion of polyelectrolytes with higher charged density, say polyanions, keeps these polyanions in coacervates aligned into stretched arrays of electrostatic blobs of size D-

Impedance analysis on PVA/PVP: GO blend nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Rao, M. C.; Basha, S. K. Shahenoor; Kumar, B. Ranjit

2018-05-01

Nanocomposite polymer films have been prepared by doping Graphene oxide (GO) in PVA/PVP blend polymers by solution cast technique. AC conductivity studies were performed on to the prepared nanocomposite films and the maximum ionic conductivity is found to be 6.13x10-4 Scm-1 for (0.30:0.3) wt% of nanocomposite polymer film at room temperature. The maximum ionic conductivity of nanocomposite polymer films of PVA/PVP: GO holds great promise in potential applications.

Effect of nanochitosan and succinonitrile on the AC ionic conductivity of plasticized nanocomposite solid polymer electrolytes (PNCSPE)

NASA Astrophysics Data System (ADS)

Karuppasamy, K.; Vani, C. Vijil; Nichelson, A.; Balakumar, S.; Shajan, X. Sahaya

2013-06-01

In the present study, the filler chitosan was converted into nanochitosan by ionotropic gelation method. Plasticized nanocomposite solid polymer electrolytes (PNCSPE) composed of poly ethylene oxide as host polymer, LiBOB (lithium bis(oxalatoborate)) as salt, SN as plasticizer and nanochitosan as filler were prepared by membrane hot-press technique. Succinonitrile and nanochitosan incorporation in PEO-LiBOB matrix enhanced the room temperature ionic conductivity. The highest ionic conductivities were found to be in the order of 10-3.2 S/cm.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C.A.; Xu, K.; Liu, C.

1996-01-16

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C. Austen; Xu, Kang; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

Ion-ion correlations across and between electrified graphene layers

NASA Astrophysics Data System (ADS)

Mendez-Morales, Trinidad; Burbano, Mario; Haefele, Matthieu; Rotenberg, Benjamin; Salanne, Mathieu

2018-05-01

When an ionic liquid adsorbs onto a porous electrode, its ionic arrangement is deeply modified due to a screening of the Coulombic interactions by the metallic surface and by the confinement imposed upon it by the electrode's morphology. In particular, ions of the same charge can approach at close contact, leading to the formation of a superionic state. The impact of an electrified surface placed between two liquid phases is much less understood. Here we simulate a full supercapacitor made of the 1-butyl-3-methylimidazolium hexafluorophosphate and nanoporous graphene electrodes, with varying distances between the graphene sheets. The electrodes are held at constant potential by allowing the carbon charges to fluctuate. Under strong confinement conditions, we show that ions of the same charge tend to adsorb in front of each other across the graphene plane. These correlations are allowed by the formation of a highly localized image charge on the carbon atoms between the ions. They are suppressed in larger pores, when the liquid adopts a bilayer structure between the graphene sheets. These effects are qualitatively similar to the recent templating effects which have been reported during the growth of nanocrystals on a graphene substrate.

Response surface method (RSM) for optimization of ionic conductivity of membranes polymer electrolyte poly (vinylidene fluoride) (PVDF) with polyvinyl pyrrolidone (PVP) as pore forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, E. R.; Susanto, H.; Widiasa, I. N.; Purwanto, A.

2017-06-01

The Membranes Polymer Gel Electrolyte (MPGEs) based poly (vinylidene fluoride) (PVDF) was prepared by a phase inversion method using polyvinyl pyrrolidone (PVP) as a pore-forming agent and N, N-dimethyl acetamide (DMAc) as a solvent and water as non solvet. The membranes were then soaked in 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC) / dimethyl carbonate (DMC) / Diethyl carbonate (DEC) (4:2:4 %vol) solution in order to prepare polymer electrolyte membranes. The MPEGs PVDF/PVP/Nanoclay was applied using central composite design (CCD) experimental design to obtain a quantitative relationship between selected membranes prepared parameters namely (PVDF, PVP as pore forming agent and nanoclay filler concentration) and Ionic conductivity MPEGs. The model was used to find the optimum ionic conductivity from polymer electrolyte membranes. The polymer electrolyte membranes show good ionic conductivity on the order of 6.3 - 8.7 x 10-3 S cm-1 at the ambient temperatures. The ionic conductivity tended to increase with PVP and nanoclay concentration and decrease with PVDF composition. The model predicted the maximum ionic conductivity of 8.47 x 10-3 S cm-1 when the PVDF, PVP and nanoclay concentration were set at 8.01 %, 8.04 % and 10.12%, respectively. The first section in your paper.

Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes.

PubMed

Hou, Ye; Cheng, Yingwen; Hobson, Tyler; Liu, Jie

2010-07-14

For efficient use of metal oxides, such as MnO(2) and RuO(2), in pseudocapacitors and other electrochemical applications, the poor conductivity of the metal oxide is a major problem. To tackle the problem, we have designed a ternary nanocomposite film composed of metal oxide (MnO(2)), carbon nanotube (CNT), and conducting polymer (CP). Each component in the MnO(2)/CNT/CP film provides unique and critical function to achieve optimized electrochemical properties. The electrochemical performance of the film is evaluated by cyclic voltammetry, and constant-current charge/discharge cycling techniques. Specific capacitance (SC) of the ternary composite electrode can reach 427 F/g. Even at high mass loading and high concentration of MnO(2) (60%), the film still showed SC value as high as 200 F/g. The electrode also exhibited excellent charge/discharge rate and good cycling stability, retaining over 99% of its initial charge after 1000 cycles. The results demonstrated that MnO(2) is effectively utilized with assistance of other components (fFWNTs and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) in the electrode. Such ternary composite is very promising for the next generation high performance electrochemical supercapacitors.

Efficient charge injection in p-type polymer field-effect transistors with low-cost molybdenum electrodes through V2O5 interlayer.

PubMed

Baeg, Kang-Jun; Bae, Gwang-Tae; Noh, Yong-Young

2013-06-26

Here we report high-performance polymer OFETs with a low-cost Mo source/drain electrode by efficient charge injection through the formation of a thermally deposited V2O5 thin film interlayer. A thermally deposited V2O5 interlayer is formed between a regioregular poly(3-hexylthiophene) (rr-P3HT) or a p-type polymer semiconductor containing dodecyl-substituted thienylenevinylene (TV) and dodecylthiophene (PC12TV12T) and the Mo source/drain electrode. The P3HT or PC12TV12T OFETs with the bare Mo electrode exhibited lower charge carrier mobility than those with Au owing to a large barrier height for hole injection (0.5-1.0 eV). By forming the V2O5 layer, the P3HT or PC12TV12T OFETs with V2O5 on the Mo electrode exhibited charge carrier mobility comparable to that of a pristine Au electrode. Best P3HT or PC12TV12T OFETs with 5 nm thick V2O5 on Mo electrode show the charge carrier mobility of 0.12 and 0.38 cm(2)/(V s), respectively. Ultraviolet photoelectron spectroscopy results exhibited the work-function of the Mo electrode progressively changed from 4.3 to 4.9 eV with an increase in V2O5 thickness from 0 to 5 nm, respectively. Interestingly, the V2O5-deposited Mo exhibits comparable Rc to Au, which mainly results from the decreased barrier height for hole carrier injection from the low-cost metal electrode to the frontier molecular orbital of the p-type polymer semiconductor after the incorporation of the transition metal oxide hole injection layer, such as V2O5. This enables the development of large-area, low-cost electronics with the Mo electrodes and V2O5 interlayer.

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains

PubMed Central

2017-01-01

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937

Removal of toxic metal ions from landfill leachate by complementary sorption and transport across polymer inclusion membranes.

PubMed

Zawierucha, Iwona; Kozlowski, Cezary; Malina, Grzegorz

2013-10-01

In this study, performance of a lab-scale two-step treatment system was evaluated for removal of toxic metal ions from landfill leachate. The technology of polymer inclusion membranes (PIMs) was the first step, while the second step of the treatment system was based on sorption on impregnated resin. The PIMs were synthesized from cellulose triacetate as a support, macrocyclic compound i.e. alkyl derivative of resorcinarene as a ionic carrier and o-nitrophenyl pentyl ether as a plasticizer. The transport experiments through PIM were carried out in a permeation cell, in which the membrane film was tightly clamped between two cell compartments. The sorption tests were carried out using a column filled with a resin impregnated with resorcinarene derivative. The obtained results show the good performance with respect to the removal of heavy metals from landfill leachate with the overall removal efficiency of 99%, 88% and 55% for Pb(II), Cd(II) and Zn(II) ions, respectively. Moreover the contents of metal ions in the leachate sample after treatment system were below permissible limit for wastewater according to the Polish Standards. Copyright © 2012 Elsevier Ltd. All rights reserved.

Noncovalent Pi-Pi Stacking at the Carbon-Electrolyte Interface: Controlling the Voltage Window of Electrochemical Supercapacitors.

PubMed

Li, Mengya; Westover, Andrew S; Carter, Rachel; Oakes, Landon; Muralidharan, Nitin; Boire, Timothy C; Sung, Hak-Joon; Pint, Cary L

2016-08-03

A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π-π stacking at a carbon-ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode-electrolyte interface introduced by poly(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π-π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode-electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon-ionic liquid electrode-electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability.

EDITORIAL: Charge transport in non-metallic solids

NASA Astrophysics Data System (ADS)

Youngs, Ian J.; Almond, Darryl P.

2009-03-01

Workers engaged in a wide range of investigations of charge transport in non-metallic solids came together at a meeting of the Institute of Physics Dielectric Group, held in London on 2 April 2008. Topics included both ionic and electronic conduction, investigations of the fundamental mechanisms of charge transport, percolation, modelling the conduction process in both natural and man-made composite electrical and electromagnetic materials, the design and development of solids with specified conduction properties and the ac characteristics of non-metallic solids. In the first session, the long-standing problem of the anomalous power law increase in ac conductivity with frequency was addressed by a set of four presentations. Jeppe Dyre, an invited speaker from Roskilde University, Denmark, introduced the problem and stressed the universality of the frequency dependence observed in the ac conductivities of disordered non-metallic materials. He showed that it could be obtained from a simple random barrier model, independent of the barrier distribution. Darryl Almond, University of Bath, showed that the electrical responses of large networks of randomly positioned resistors and capacitors, simulating the microstructures of disordered two-phase (conductor insulator) materials, exhibit the same frequency dependence. He demonstrated their robustness to component value and distribution and suggested that it was an emergent property of these networks and of two-phase materials. Klaus Funke, an invited speaker from the University of Munster, Germany, presented a detailed model of ion motion in disordered ionic materials. He stressed the need to account for the concerted many-particle processes that occur whilst ions hop from site to site in response to an applied electric field. The conductivity spectra obtained from this work reproduce the same frequency dispersion and have the additional feature of conductivity saturation at high frequencies. Tony West, University of Sheffield, UK, discussed the analysis of the ac electrical response data of ionically or electrically conducting ceramics, using constant phase elements to deal with power law dispersions. He presented strategies for dealing with data made complex by the overlapping, in the frequency domain, of different materials response components: bulk, grain boundary, electrode, etc. The final morning paper concerning space charge measurement was given by Kaori Fukunagwa, NICT, Japan. The closely linked but diverse nature of the morning papers stimulated healthy debate between the presentations and during the lunch break and poster session, during which the Mansel Davies prize was awarded to Dr Shahid Hussain from QinetiQ for his poster entitled Dielectric relaxation of glass particles with nanoscale metallic coatings. In the second session, again through a set of four presentations, the electrical and electromagnetic properties of composite materials were more broadly considered. Isaac Balberg, an invited speaker from The Hebrew University in Jerusalem, gave a detailed and in many ways philosophical review of critical behaviour in composites near the percolation threshold. He focused on the validity of using critical response developed from the classic Scher and Zallen model of a regular lattice when considering the more realistic situation of composites in which hopping and tunnelling are prevalent, the key to observing universal or non-universal critical behaviour being the significance of nearest neighbour versus non-nearest neighbour conducting paths and the distribution of resistances in the composite. Ian Youngs, from Dstl, described the microwave response of conductor--insulator percolating composites and especially the observation of novel plasma-like response under certain circumstances. It was shown that the standard low frequency approximation of the dielectric function of the metallic phase impedes modelling of this response. Christian Brosseau, Université de Bretagne Occidentale, France, presented an invited paper discussing electromagneto-mechanical coupling in ferrite-filled plastics. A model for the changes to the electromagnetic properties of the composite as a function of applied mechanical stress was presented and linked to the elastic network response of the composite. The work is relevant to flexible materials such as circuits and for smart sensor applications. Rolf Pelster, Universität des Saarlandes, Germany, concluded the meeting with a comparison of micro- and nano-composites of magnetic particles dispersed in polymer. Broadband dielectric spectroscopy was used to highlight the particle-size differences and the likely modification of the host polymer when nano-sized filler particles were used. The dielectric data was used to infer the microstructural contribution to the effective properties of each composite and this information was used to extract an estimate of the intrinsic magnetic properties of the filler particles, again showing a difference between micro- and nano-sized particles. This cluster issue of Journal of Physics D: Applied Physics contains four of the above-mentioned papers presented at the meeting. We would like to thank those authors for preparing their contributions to this special cluster. Their papers provide a cross section of the topics presented at the meeting and we hope you enjoy reading them.

Hindered Diffusion in Polymeric Solutions Studied by Fluorescence Correlation Spectroscopy

PubMed Central

Zustiak, Silviya P.; Nossal, Ralph; Sackett, Dan L.

2011-01-01

Diffusion of molecules in the crowded and charged interior of the cell has long been of interest for understanding cellular processes. Here, we introduce a model system of hindered diffusion that includes both crowding and binding. In particular, we obtained the diffusivity of the positively charged protein, ribonuclease A (RNase), in solutions of dextrans of various charges (binding) and concentrations (crowding), as well as combinations of both, in a buffer of physiological ionic strength. Using fluorescence correlation spectroscopy, we observed that the diffusivity of RNase was unaffected by the presence of positively charged or neutral dextrans in the dilute regime but was affected by crowding at higher polymer concentrations. Conversely, protein diffusivity was significantly reduced by negatively charged dextrans, even at 0.4 μM (0.02% w/v) dextran. The diffusivity of RNase decreased with increasing concentrations of negative dextran, and the amount of bound RNase increased until it reached a plateau of ∼80% bound RNase. High salt concentrations were used to establish the electrostatic nature of the binding. Binding of RNase to the negatively charged dextrans was further confirmed by ultrafiltration. PMID:21723836

Modification of the Tunneling Barrier in Polymer Light-Emitting Diodes Through Doping

NASA Astrophysics Data System (ADS)

Romero, Danilo

1996-03-01

Improvement in the performance of polymer light-emitting diodes (LEDs) is achieved upon light doping of the organic layer. The LEDs betrayed symmetrical electrical and light-emission characteristics. Their turn-on voltage is lower and their external quantum and power conversion efficiencies are higher by nearly an order of magnitude when compared with devices that utilized a nominally undoped organic layer. We attributed these results to the modification of the tunneling barrier in metal-polymer-metal junctions due to the presence of an induced polarization electric field associated with the ionized dopant counterions and charged polymer chains. Acknowledgement: I would like to thank my collaborators in this work: B. Cesar and B. François at the Institut Charles Sadron in Strasbourg, France and M. Schaer and especially Professor Libero Zuppiroli who has been the main driving force for the direction of the polymer LED project in Lausanne. I would like to acknowledge the financial support of the Optics Priority Program in Switzerland.

Highly Selective Ionic Block Copolymer Membranes

DTIC Science & Technology

2010-11-10

Multicomponent Diffusion and Sorption in an Ionic Polymer Membrane We recently measured the diffusion and sorption of methanol/water mixtures in Nafion (most...methanol feed concentration (17 M). Figure 1 shows one experiment where hydrated Nafion was exposed to a 2 M methanol/water liquid mixture resulting...copolymer membranes revealed several surprising results. Contrary to what has been observed in most ionic polymer membranes (e.g., Nafion ), the proton

Modeling the formation of ordered nano-assemblies comprised by dendrimers and linear polyelectrolytes: The role of Coulombic interactions

NASA Astrophysics Data System (ADS)

Eleftheriou, E.; Karatasos, K.

2012-10-01

Models of mixtures of peripherally charged dendrimers with oppositely charged linear polyelectrolytes in the presence of explicit solvent are studied by means of molecular dynamics simulations. Under the influence of varying strength of electrostatic interactions, these systems appear to form dynamically arrested film-like interconnected structures in the polymer-rich phase. Acting like a pseudo-thermodynamic inverse temperature, the increase of the strength of the Coulombic interactions drive the polymeric constituents of the mixture to a gradual dynamic freezing-in. The timescale of the average density fluctuations of the formed complexes initially increases in the weak electrostatic regime reaching a finite limit as the strength of electrostatic interactions grow. Although the models are overall electrically neutral, during this process the dendrimer/linear complexes develop a polar character with an excess charge mainly close to the periphery of the dendrimers. The morphological characteristics of the resulted pattern are found to depend on the size of the polymer chains on account of the distinct conformational features assumed by the complexed linear polyelectrolytes of different length. In addition, the length of the polymer chain appears to affect the dynamics of the counterions, thus affecting the ionic transport properties of the system. It appears, therefore, that the strength of electrostatic interactions together with the length of the linear polyelectrolytes are parameters to which these systems are particularly responsive, offering thus the possibility for a better control of the resulted structure and the electric properties of these soft-colloidal systems.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Energy harvesting efficiency of piezoelectric polymer film with graphene and metal electrodes.

PubMed

Park, Sanghoon; Kim, Yura; Jung, Hyosub; Park, Jun-Young; Lee, Naesung; Seo, Yongho

2017-12-11

In this study, we investigated an energy harvesting effect of tensile stress using piezoelectric polymers and flexible electrodes. A chemical-vapor-deposition grown graphene film was transferred onto both sides of the PVDF and P(VDF-TrFE) films simultaneously by means of a conventional wet chemical method. Output voltage induced by sound waves was measured and analyzed when a mechanical tension was applied to the device. Another energy harvester was made with a metallic electrode, where Al and Ag were deposited by using an electron-beam evaporator. When acoustic vibrations (105 dB) were applied to the graphene/PVDF/graphene device, an induced voltage of 7.6 V pp was measured with a tensile stress of 1.75 MPa, and this was increased up to 9.1 V pp with a stress of 2.18 MPa for the metal/P(VDF-TrFE)/metal device. The 9 metal/PVDF/metal layers were stacked as an energy harvester, and tension was applied by using springs. Also, we fabricated a full-wave rectifying circuit to store the electrical energy in a 100 μF capacitor, and external vibration generated the electrical charges. As a result, the stored voltage at the capacitor, obtained from the harvester via a bridge diode rectifier, was saturated to ~7.04 V after 180 s charging time.

Application of the solubility parameter concept to the design of chemiresistor arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hughes, R.C.; Yelton, W.G.; Ricco, A.J.

1998-04-01

Arrays of unheated chemically sensitive resistors (chemiresistors) can serve as extremely small, low power consumption sensors with simple read out electronics. Most work has focused on the exotic polymeric organic metals, but here the authors report new results on carbon loaded polymer composites, as well as polymeric ionic conductors. They use the solubility parameter concept to understand and categorize the chemiresistor responses and, in particular, they compare chemiresistors fabricated from polyisobutylene (PIB) to results from PIB coated acoustic wave sensors.

Field enhanced charge carrier reconfiguration in electronic and ionic coupled dynamic polymer resistive memory.

PubMed

Zhao, Jun Hui; Thomson, Douglas J; Pilapil, Matt; Pillai, Rajesh G; Rahman, G M Aminur; Freund, Michael S

2010-04-02

Dynamic resistive memory devices based on a conjugated polymer composite (PPy(0)DBS(-)Li(+) (PPy: polypyrrole; DBS(-): dodecylbenzenesulfonate)), with field-driven ion migration, have been demonstrated. In this work the dynamics of these systems has been investigated and it has been concluded that increasing the applied field can dramatically increase the rate at which information can be 'written' into these devices. A conductance model using space charge limited current coupled with an electric field induced ion reconfiguration has been successfully utilized to interpret the experimentally observed transient conducting behaviors. The memory devices use the rising and falling transient current states for the storage of digital states. The magnitude of these transient currents is controlled by the magnitude and width of the write/read pulse. For the 500 nm length devices used in this work an increase in 'write' potential from 2.5 to 5.5 V decreased the time required to create a transient conductance state that can be converted into the digital signal by 50 times. This work suggests that the scaling of these devices will be favorable and that 'write' times for the conjugated polymer composite memory devices will decrease rapidly as ion driving fields increase with decreasing device size.

Rapid adsorption of Pb, Cu and Cd from aqueous solutions by β-cyclodextrin polymers

NASA Astrophysics Data System (ADS)

He, Junyong; Li, Yulian; Wang, Chengming; Zhang, Kaisheng; Lin, Dongyue; Kong, Lingtao; Liu, Jinhuai

2017-12-01

Removing heavy metals from aqueous solutions has drawn more and more attentions these years because of their serious global health challenge to human society. To develop an adsorbent with low-cost and high-efficiency for removal of heavy metals (HMs), β-cyclodextrin (β-CD) polymers crosslinked with rigid aromatic groups were prepared and used for lead (Pb), copper (Cu) and cadmium (Cd) removal for the first time. The negatively charged β-CD polymers with large BET surface area were suitable to be used in HMs adsorption. The adsorption process completed in 5 min was well fit by Freundlich isotherm model and pseudo-second-order model. The intraparticle diffusion model was also appropriate to describe the adsorption of Pb, Cu and Cd on β-CD polymer. The maximum of adsorption capacities at 25 °C for Pb, Cu and Cd were 196.42, 164.43 and 136.43 mg/g when the initial concentration was 200 mg/L. The HMs adsorption process on the surface of β-CD polymer was an endothermic and spontaneous process. Both of the electrostatic interaction and distribution of Pb, Cu and Cd species influenced the adsorption process at different pH values. The order of removal efficiencies in multi-component adsorption for the three metal ions were Pb > Cu > Cd. The adsorption mechanisms were H+ ions on hydroxyl groups exchanged with heavy metal ions and electrostatic interactions. This study indicated that β-CD polymers could be developed into effective adsorbents for rapid removal of heavy metals.