Polymer Physics Prize Talk

NASA Astrophysics Data System (ADS)

Olvera de La Cruz, Monica

Polymer electrolytes have been particularly difficult to describe theoretically given the large number of disparate length scales involved in determining their physical properties. The Debye length, the Bjerrum length, the ion size, the chain length, and the distance between the charges along their backbones determine their structure and their response to external fields. We have developed an approach that uses multi-scale calculations with the capability of demonstrating the phase behavior of polymer electrolytes and of providing a conceptual understanding of how charge dictates nano-scale structure formation. Moreover, our molecular dynamics simulations have provided an understanding of the coupling of their conformation to their dynamics, which is crucial to design self-assembling materials, as well as to explore the dynamics of complex electrolytes for energy storage and conversion applications.

Application of Organic Solid Electrolytes

NASA Technical Reports Server (NTRS)

Sekido, S.

1982-01-01

If ions are considered to be solid material which transport electric charges, polymer materials can then be considered as organic solid electrolytes. The role of these electrolytes is discussed for (1) ion concentration sensors; (2) batteries using lithium as the cathode and a charge complex of organic material and iodine in the anode; and (3) elements applying electrical double layer capability.

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

Rechargeable solid polymer electrolyte battery cell

DOEpatents

Skotheim, Terji

1985-01-01

A rechargeable battery cell comprising first and second electrodes sandwiching a solid polymer electrolyte comprising a layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte adjacent said polymer blend and a layer of dry solid polymer electrolyte adjacent said layer of polymer blend and said second electrode.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, Kenneth Orville

1998-01-01

A polymer bonded sheet product suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance.

Chemical modification of electrolytes for lithium batteries

NASA Astrophysics Data System (ADS)

Afanas'ev, Vladimir N.; Grechin, Aleksandr G.

2002-09-01

Modern approaches to modifying chemically electrolytes for lithium batteries are analysed with the aim of optimising the charge-transfer processes in liquid-phase and solid (polymeric) media. The main regularities of transport properties of lithium electrolyte solutions containing complex (encapsulated) ions in aprotic solvents and polymers are discussed. The prospects for the development of electrolytic solvosystems with the chain (ionotropic) mechanism of conduction with respect to lithium ions are outlined. The bibliography includes 126 references.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, K.O.

1998-06-30

A polymer bonded sheet product is described suitable for use as an electrode in a non-aqueous battery system. A porous electrode sheet is impregnated with a solid polymer electrolyte, so as to diffuse into the pores of the electrode. The composite is allowed to cool, and the electrolyte is entrapped in the porous electrode. The sheet products composed have the solid polymer electrolyte composition diffused into the active electrode material by melt-application of the solid polymer electrolyte composition into the porous electrode material sheet. The solid polymer electrolyte is maintained at a temperature that allows for rapid diffusion into the pores of the electrode. The composite electrolyte-electrode sheets are formed on current collectors and can be coated with solid polymer electrolyte prior to battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte coating has low resistance. 1 fig.

Nanoporous polymer electrolyte

DOEpatents

Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

2012-04-24

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

Synthesis and characterization of nanocomposite polymer blend electrolyte thin films by spin-coating method

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

Chapi, Sharanappa; Niranjana, M.; Devendrappa, H., E-mail: dehu2010@gmail.com

2016-05-23

Solid Polymer blend electrolytes based on Polyethylene oxide (PEO) and poly vinyl pyrrolidone (PVP) complexed with zinc oxide nanoparticles (ZnO NPs; Synthesized by Co-precipitation method) thin films have prepared at a different weight percent using the spin-coating method. The complexation of the NPs with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR). The variation in film morphology was examined by polarized optical micrographs (POMs). The thermal behavior of blends was investigated under non-isothermal conditions by differential thermal analyses (DTA). A single glass transition temperature for each blend was observed, which supports the existence ofmore » compatibility of such system. The obtained results represent that the ternary based thin films are prominent materials for battery and optoelectronic device applications.« less

Electrical study on Carboxymethyl Cellulose-Polyvinyl alcohol based bio-polymer blend electrolytes

NASA Astrophysics Data System (ADS)

Saadiah, M. A.; Samsudin, A. S.

2018-04-01

The present work deals with the formulation of bio-materials namely carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) for bio-polymer blend electrolytes (BBEs) system which was successfully carried out with different ratio of polymer blend. The biopolymer blend was prepared via economical & classical technique that is solution casting technique and was characterized by using impedance spectroscopy (EIS). The ionic conductivity was achieved to optimum value 9.12 x 10-6 S/cm at room temperature for sample containing ratio 80:20 of CMC:PVA. The highest conducting sample was found to obey the Arrhenius behaviour with a function of temperature. The electrical properties were analyzed using complex permittivity ε* and complex electrical modulus M* for BBEs system and it shows the non-Debye characteristics where no single relaxation time has observed.

Multilayered composite proton exchange membrane and a process for manufacturing the same

DOEpatents

Santurri, Pasco R; Duvall, James H; Katona, Denise M; Mausar, Joseph T; Decker, Berryinne

2015-05-05

A multilayered membrane for use with fuel cells and related applications. The multilayered membrane includes a carrier film, at least one layer of an undoped conductive polymer electrolyte material applied onto the carrier film, and at least one layer of a conductive polymer electrolyte material applied onto the adjacent layer of polymer electrolyte material. Each layer of conductive polymer electrolyte material is doped with a plurality of nanoparticles. Each layer of undoped electrolyte material and doped electrolyte material may be applied in an alternating configuration, or alternatively, adjacent layers of doped conductive polymer electrolyte material is employed. The process for producing a multilayered composite membrane includes providing a carrier substrate and solution casting a layer of undoped conductive polymer electrolyte material and a layer of conductive polymer electrolyte material doped with nanoparticles in an alternating arrangement or in an arrangement where doped layers are adjacent to one another.

Polymer Electrolytes for Lithium/Sulfur Batteries

PubMed Central

Zhao, Yan; Zhang, Yongguang; Gosselink, Denise; Doan, The Nam Long; Sadhu, Mikhail; Cheang, Ho-Jae; Chen, Pu

2012-01-01

This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S) batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes. PMID:24958296

Assimilation of NH₄Br in Polyvinyl Alcohol/Poly(N-vinyl pyrrolidone) Polymer Blend-Based Electrolyte and Its Effect on Ionic Conductivity.

PubMed

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

2018-06-01

Biodegradable polymer blend electrolyte based on ammonium based salt in variation composition consisting of PVA:PVP were prepared by using solution casting technique. The obtained films have been analyzed by various technical methods like as XRD, FT-IR, TG-DSC, SEM analysis and impedance spectroscopy. The XRD and FT-IR analysis exposed the amorphous nature and structural properties of the complex formation between PVA/PVP/NH4Br. Impedance spectroscopy analysis revealed the ionic conductivity and the dielectric properties of PVA/PVP/NH4Br polymer blend electrolyte films. The maximum ionic conductivity was determined to be 6.14 × 10-5 Scm-1 for the composition of 50%PVA: 50%PVP: 10% NH4Br with low activation energy 0.3457 eV at room temperature. Solid state battery is fabricated using highest ionic conducting polymer blend as electrolyte with the configuration Zn/ZnSO4 · 7H2O (anode) ∥ 50%PVA: 50%PVP: 10% NH4Br ∥ Mn2O3 (cathode). The observed open circuit voltage is 1.2 V and its performance has been studied.

Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, Terry Song-Hsing; Keller, David Gerard; MacFadden, Kenneth Orville

1998-01-01

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte-electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be overcoated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance.

Proton conduction of polyAMPS brushes on titanate nanotubes

PubMed Central

Feng, Jun; Huang, Yaqin; Tu, Zhengkai; Zhang, Haining; Pan, Mu; Tang, Haolin

2014-01-01

Proton conducting materials having reasonable proton conductivity at low humidification conditions are critical for decrease in system complexity and improvement of power density for polymer electrolyte membrane fuel cells. This study shows that polyelectrolyte brushes on titanate nanotubes formed through surface-initiated free radical polymerization exhibit less humidity-dependent proton conduction because of the high grafting density of polymer electrolyte chains and well-distribution of ionic groups. The results described in this study provide an idea for design of new proton conductors with effective ion transport served at relatively low humidification levels. PMID:25169431

Ionic conductivity and dielectric permittivity of polymer electrolyte plasticized with polyethylene glycol

NASA Astrophysics Data System (ADS)

Das, S.; Ghosh, A.

2016-05-01

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolyte plasticized with polyethylene glycol (PEG). The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. The maximum dielectric constant is observed for 30 wt. % of PEG content. To get further insights into the ion dynamics, the complex dielectric permittivity has been studied with Havriliak-Negami function. The variation of relaxation time with inverse temperature obtained from HN formalism follows VTF nature.

Composite polymer electrolyte based on PEO/Pvdf-HFP with MWCNT for lithium battery applications

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

Pradeepa, P.; Edwinraj, S.; Sowmya, G.

In the present study PEO and PVdF-HFP blend based composite polymer electrolytes (CPEs) has been prepared by using Multi Walled Carbon Nanotube (MWCNT), in order to examine the filler addition effect on the electrochemical properties. The complexed nanocomposite polymer electrolytes were obtained in the form of dimensionally stable and free standing films by using solution casting technique. The electrochemical properties of CPEs were measured by the AC impedance method. From the ionic conductivity results, the CPE containing MWCNT 2wt% showed the highest ionic conductivity with an excellent thermal stability at room temperature. The dielectric loss curve s for the samplemore » 6.25wt% PEO: 18.75 wt% PVdF-HFP: 2wt% MWCNT reveal the low frequency β relaxation peak pronounced at high temperature, and it may caused by side group dipoles.« less

Continuous process to produce lithium-polymer batteries

DOEpatents

Chern, T.S.H.; Keller, D.G.; MacFadden, K.O.

1998-05-12

Solid polymer electrolytes are extruded with active electrode material in a continuous, one-step process to form composite electrolyte-electrodes ready for assembly into battery cells. The composite electrolyte electrode sheets are extruded onto current collectors to form electrodes. The composite electrodes, as extruded, are electronically and ionically conductive. The composite electrodes can be over coated with a solid polymer electrolyte, which acts as a separator upon battery assembly. The interface between the solid polymer electrolyte composite electrodes and the solid polymer electrolyte separator has low resistance. 1 fig.

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.

Synthesis, Characterization and Conductivity Study of Poly(vinyl 4-HYDROXY-3-METHOXY Benzal) and its Sodio Salt in Solid State

NASA Astrophysics Data System (ADS)

Borah, P.; Hussain, S.; Dutta, A.

Among the various ion-conducting materials, polymer salt complexes are of current interest due to their possible application as solid electrolyte as well as their physical nature in advanced high-energy electrochemical devices such as batteries, fuel cells, electrochromic display devices, photo electro-chemical solar cells52-55 etc. The main advantages of polymeric electrolytes are their mechanical properties, ease of fabrication of thin films of desired sizes and their ability to form proper electrode-electrolyte contact. Polymer electrolyte usually consists of a polymer and a salt and is considered to be solid solutions in which the polymer functions as solvent. In the present paper the synthesis, characterization and the conductivity study of the polymer poly (vinyl 4-hydroxy-3-methoxy benzal) (PV-HMB) and its sodio salt (PV-HMB-Na) have been reported. The polymer was prepared by carrying out homogenous acetalization between the prepolymer poly vinylalcohol (PVA) and 4-hydroxy-3-methoxy benzaldehyde (vanilline). PVA was dissolved in dimethyl formamide (DMF) and lithium chloride (LiCl) system i.e., in non-aqueous medium. The sodio salt was prepared by alkalization. The polymer and its salt were characterized by IR, 1H NMR and DSC. Frequency and temperature dependence of ac conductivity has been studied to learn about the electrical conduction behaviour in this material. The electrical conductivity of the new polymeric salt was found to be in the range 10-4 to 10-6 Scm-1. There is about 103 to 104 fold increase in the conductivity of the new polymer salt. Apparent activation energy of the polymer and its salt were found to be 0.139 and 0.08998 ev respectively.

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.

Structure, dielectric, thermal and I-V studies of electron beam irradiated PVDF-HFP/LiClO4 electrolyte film

NASA Astrophysics Data System (ADS)

Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Basappa, M.; Ganesh, S.; Devendrappa, H.

2018-05-01

The effect of electron beam (EB) irradiation on polymer electrolyte (PVDF-HFP: LiClO4=90:10, PHL10) films prepared by solution casting method. FT-IR confirms the complexation between salt and polymer upon EB dose. Degradation of polymer and decrease in % of crystallinity from 50.10 to 40.96 at 2θ=19.90° at 120 kGy dose indicates increased amorphousity confirmed by XRD. The TGA result show decrease in Tm from 460 °C to 418 °C is leads to degradation of polymer chain at higher dosage. The dielectric parameters have been determined and observed decreasing trend with increased frequency as well as temperature due to increase the mobility of charge carrier confirms the capacitive nature. I-V plots exhibit an ohmic behavior with applied voltage and irradiation dose. The results notice the change in polymer properties upon irradiation.

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.

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.

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.

Small-Angle Neutron Scattering Study of Interplay of Attractive and Repulsive Interactions in Nanoparticle-Polymer System.

PubMed

Kumar, Sugam; Aswal, Vinod K; Kohlbrecher, Joachim

2016-02-16

The phase behavior of nanoparticle (silica)-polymer (polyethylene glycol) system without and with an electrolyte (NaCl) has been studied. It is observed that nanoparticle-polymer system behaves very differently in the presence of electrolyte. In the absence of electrolyte, the nanoparticle-polymer system remains in one-phase even at very high polymer concentrations. On the other hand, a re-entrant phase behavior is found in the presence of electrolyte, where one-phase (individual) system undergoes two-phase (nanoparticle aggregation) and then back to one-phase with increasing polymer concentration. The regime of two-phase system has been tuned by varying the electrolyte concentration. The polymer concentration range over which the two-phase system exists is significantly enhanced with the increase in the electrolyte concentration. These systems have been characterized by small-angle neutron scattering (SANS) experiments of contrast-marching the polymer to the solvent. The data are modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The phase behavior of nanoparticle-polymer system is explained by interplay of attractive (polymer-induced attractive depletion between nanoparticles) and repulsive (nanoparticle-nanoparticle electrostatic repulsion and polymer-polymer repulsion) interactions present in the system. In the absence of electrolyte, the strong electrostatic repulsion between nanoparticles dominates over the polymer-induced depletion attraction and the nanoparticle system remains in one-phase. With addition of electrolyte, depletion attraction overcomes electrostatic repulsion at some polymer concentration, resulting into nanoparticle aggregation and two-phase system. Further addition of polymer increases the polymer-polymer repulsion which eventually reduces the strength of depletion and hence re-entrant phase behavior. The effects of varying electrolyte concentration on the phase behavior of nanoparticle-polymer system are understood in terms of modifications in nanoparticle-nanoparticle and polymer-polymer interactions. The nanoparticle aggregates in two-phase systems are found to have surface fractal morphology.

Preliminary Evaluations of Polymer-based Lithium Battery Electrolytes Under Development for the Polymer Electrolyte Rechargeable Systems Program

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.; Bennett, William R.

2003-01-01

A component screening facility has been established at The NASA Glenn Research Center (GRC) to evaluate candidate materials for next generation, lithium-based, polymer electrolyte batteries for aerospace applications. Procedures have been implemented to provide standardized measurements of critical electrolyte properties. These include ionic conductivity, electronic resistivity, electrochemical stability window, cation transference number, salt diffusion coefficient and lithium plating efficiency. Preliminary results for poly(ethy1ene oxide)-based polymer electrolyte and commercial liquid electrolyte are presented.

Fuel cells with solid polymer electrolyte and their application on vehicles

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

Fateev, V.

1996-04-01

In Russia, solid polymer electrolyte MF-4-SK has been developed for fuel cells. This electrolyte is based on perfluorinated polymer with functional sulfogroups. Investigations on electrolyte properties and electrocatalysts have been carried out.

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.

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.

Synthesis and ion transport characterization of hot-pressed Ag+ ion conducting glass-polymer electrolytes

NASA Astrophysics Data System (ADS)

Chandra, A.

2013-07-01

Synthesis and ion transport characterization of a new Ag+ ion conducting glass-polymer electrolyte (GPE) films: (1- x) PEO: x [0.8(0.75AgI:0.25AgCl):0.2(Ag2O:V2O5)], where 0 < x < 50 wt%, are reported. The composition: 70PEO: 30[0.8(0.75AgI:0.25AgCl):0.2(Ag2O:V2O5)] with conductivity ( σ) 7.7 × 10-7 Ω-1 cm-1 is identified as highest conducting composition referred to as the optimum conducting composition (OCC). Approximately two and half orders of conductivity enhancement have been achieved in OCC from that of the pure polymer poly(ethylene oxide). The glass-polymer complexation is confirmed by the XRD, FTIR, DSC and TGA techniques. The ion transport behavior has been reported on the basis of experimental measurements on some basic ionic parameters. A solid state polymeric battery has been fabricated by using GPE OCC as an electrolyte and their important cell parameters have been also calculated from the discharge profiles.

Electrical and structural studies of polymer electrolyte based on chitosan/methyl cellulose blend doped with BMIMTFSI

NASA Astrophysics Data System (ADS)

Misenan, M. S. M.; Isa, M. I. N.; Khiar, A. S. A.

2018-05-01

In this study, blended polymer electrolyte of methylcellulose (MC)/chitosan (CS) was prepared with different weight percentage of 1-butyl-3-methylimidazolium bis(trifluoromethyl sulfonyl) imide (BMIMTFSI) which acts as ion donor. This polymer blend was prepared by solution casting technique. The micro structure was observed by Field Emission Scanning Electron Microscopy (FESEM) where the multilayer could possibly be ascribed to the limited chain mobility. Sample having 60 wt% CS: 40 wt% MC was determined to have the most amorphous morphology extracted using deconvoluted data from x-ray Diffractography (XRD). Fourier Transform Infrared Spectroscopy (FTIR) peaks analysis shows the significant shift indicates complexation between ionic liquid and polymer backbone. The film was also characterized by impedance spectroscopy to measure its ionic conductivity. Samples with 45% of BMITFSI exhibit the highest conductivity of (1.51 ± 0.13) × 10‑6 S cm‑1 at ambient. Conductivity at elevated temperature was also studied, and the electrolytes obeys the Arrhenius behaviour. The conduction mechanism was best presented by small polaron hopping model.

Study on characteristics of PVDF/nano-clay composite polymer electrolyte using PVP as pore-forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, Endah R.; Purwanto, Agus; Widiasa, I. Nyoman; Susanto, Heru

2016-02-01

Polyvinylidene fluoride (PVDF) based polymer electrolytes have a high dielectric constant, which can assist in greater ionization of lithium salts. The main advantages of PVDF are its durability in long battery operation and its ability to be a good ion conductor. However, the limitation of this polymer is its crystalline molecular structure. Dispersing nano-particles in the polymer matrix may improve the characteristics of the PVDF polymer. This paper aims to investigate the impact of nano-clay addition on the characteristics of PVDF polymer to be used as a polymer electrolyte membrane. In addition, the effect of poly(vinyl pyrrolidone) (PVP) is also investigated. The membrane was prepared by phase separation method whereas the polymer electrolyte membranes was prepared by immersing into 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC) electrolytes for 1 h. The membranes were characterized by scanning electron microscope (SEM), porosity and electrolyte uptake and performance in battery cell. The results showed that both nano-clay and PVP have significant impacts on the improvement of PVDF membranes to be used as polymer electrolyte.

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.

Charge-discharge characteristics of nickel/zinc battery with polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Iwakura, Chiaki; Murakami, Hiroki; Nohara, Shinji; Furukawa, Naoji; Inoue, Hiroshi

A new nickel/zinc (Ni/Zn) battery was assembled by using polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) and KOH aqueous solution, and its charge-discharge characteristics were investigated. The experimental Ni/Zn cell with the polymer hydrogel electrolyte exhibited well-defined charge-discharge curves and remarkably improved charge-discharge cycle performance, compared to that with a KOH aqueous solution. Moreover, it was found that dendritic growth hardly occurred on the zinc electrode surface during charge-discharge cycles in the polymer hydrogel electrolyte. These results indicate that the polymer hydrogel electrolyte can successfully be used in Ni/Zn batteries as an electrolyte with excellent performance.

Methods of enhancing conductivity of a polymer-ceramic composite electrolyte

DOEpatents

Kumar, Binod

2003-12-02

Methods for enhancing conductivity of polymer-ceramic composite electrolytes are provided which include forming a polymer-ceramic composite electrolyte film by a melt casting technique and uniaxially stretching the film from about 5 to 15% in length. The polymer-ceramic composite electrolyte is also preferably annealed after stretching such that it has a room temperature conductivity of from 10.sup.-4 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1. The polymer-ceramic composite electrolyte formed by the methods of the present invention may be used in lithium rechargeable batteries.

Solid polymer electrolyte composite membrane comprising a porous support and a solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide

DOEpatents

Liu, Han; Mittelsteadt, Cortney K; Norman, Timothy J; Griffith, Arthur E; LaConti, Anthony B

2015-02-24

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a thin, rigid, dimensionally-stable, non-electrically-conducting support, the support having a plurality of cylindrical, straight-through pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores are unevenly distributed, with some or no pores located along the periphery and more pores located centrally. The pores are completely filled with a solid polymer electrolyte, the solid polymer electrolyte including a dispersed reduced noble metal or noble metal oxide. The solid polymer electrolyte may also be deposited over the top and/or bottom surfaces of the support.

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, Terje

1986-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, T.

1984-09-28

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Gel polymer electrolyte for lithium-ion batteries comprising cyclic carbonate moieties

NASA Astrophysics Data System (ADS)

Tillmann, S. D.; Isken, P.; Lex-Balducci, A.

2014-12-01

A polymer system based on oligo (ethylene glycol) methyl ether methacrylate (OEGMA) and cyclic carbonate methacrylate (CCMA) was chosen as matrix to realize high-performance gel polymer electrolytes due to the fact that both monomers are able to interact with the liquid electrolyte, thus, retaining it inside the matrix. Additionally, OEGMA enables high flexibility, while CCMA provides mechanical stability. The polymer displays a high thermal stability up to 200 °C and a glass transition temperature below room temperature (5 °C) allowing an easy handling of the obtained films. By immobilizing the liquid electrolyte 1 M LiPF6 in EC:DMC 1:1 w:w in the polymer host a gel polymer electrolyte with a high conductivity of 2.3 mS cm-1 at 25 °C and a stable cycling behavior with high capacities and efficiencies in Li(Ni1/3Co1/3Mn1/3)O2 (NCM)/graphite full cells is obtained. The investigated gel polymer electrolyte is identified as promising electrolyte for lithium-ion batteries, because it combines good electrochemical properties comparable to that of liquid electrolytes with the safety advantage that no leakage of the flammable electrolyte solvents can occur.

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.

Electrolyte materials containing highly dissociated metal ion salts

DOEpatents

Lee, H.S.; Geng, L.; Skotheim, T.A.

1996-07-23

The present invention relates to metal ion salts which can be used in electrolytes for producing electrochemical devices, including both primary and secondary batteries, photoelectrochemical cells and electrochromic displays. The salts have a low energy of dissociation and may be dissolved in a suitable polymer to produce a polymer solid electrolyte or in a polar aprotic liquid solvent to produce a liquid electrolyte. The anion of the salts may be covalently attached to polymer backbones to produce polymer solid electrolytes with exclusive cation conductivity. 2 figs.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Study on characteristics of PVDF/nano-clay composite polymer electrolyte using PVP as pore-forming agent

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

Dyartanti, Endah R., E-mail: heru.susanto@undip.ac.id, E-mail: endah-rd@uns.ac.id; Department of Chemical Engineering, Diponegoro University, Semarang; Purwanto, Agus

2016-02-08

Polyvinylidene fluoride (PVDF) based polymer electrolytes have a high dielectric constant, which can assist in greater ionization of lithium salts. The main advantages of PVDF are its durability in long battery operation and its ability to be a good ion conductor. However, the limitation of this polymer is its crystalline molecular structure. Dispersing nano-particles in the polymer matrix may improve the characteristics of the PVDF polymer. This paper aims to investigate the impact of nano-clay addition on the characteristics of PVDF polymer to be used as a polymer electrolyte membrane. In addition, the effect of poly(vinyl pyrrolidone) (PVP) is alsomore » investigated. The membrane was prepared by phase separation method whereas the polymer electrolyte membranes was prepared by immersing into 1 M lithium hexafluorophosphate (LiPF{sub 6}) in ethylene carbonate/dimethyl carbonate (EC/DMC) electrolytes for 1 h. The membranes were characterized by scanning electron microscope (SEM), porosity and electrolyte uptake and performance in battery cell. The results showed that both nano-clay and PVP have significant impacts on the improvement of PVDF membranes to be used as polymer electrolyte.« less

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, T.

A polymer blend is disclosed of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Charge carrier dynamics in PMMA-LiClO4 based polymer electrolytes plasticized with different plasticizers

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2017-07-01

We have studied the charge carrier dynamics in poly(methylmethacrylate)-LiClO4 polymer electrolytes plasticized with different plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), polyethylene glycol (PEG), and dimethyl carbonate (DMC). We have measured the broadband complex conductivity spectra of these electrolytes in the frequency range of 0.01 Hz-3 GHz and in the temperature range of 203 K-363 K and analyzed the conductivity spectra in the framework of the random barrier model by taking into account the contribution of the electrode polarization observed at low frequencies and/or at high temperatures. It is observed that the temperature dependences of the ionic conductivity and relaxation time follow the Vogel-Tammann-Fulcher relation for all plasticized electrolytes. We have also performed the scaling of the conductivity spectra, which indicates that the charge carrier dynamics is almost independent of temperature and plasticizers in a limited frequency range. The existence of nearly constant loss in these electrolytes has been observed at low temperatures and/or high frequencies. We have studied the dielectric relaxation in these electrolytes using electric modulus formalism and obtained the stretched exponent and the decay function. We have observed less cooperative ion dynamics in electrolytes plasticized with DMC compared to electrolytes plasticized with EC, PC, and PEG.

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.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, Terje

1984-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Thiourea incorporated poly(ethylene oxide) as transparent gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Pavithra, Nagaraj; Velayutham, David; Sorrentino, Andrea; Anandan, Sambandam

2017-06-01

A new series of transparent gel polymer electrolytes are prepared by adding various weight percent of thiourea coupled with poly(ethylene oxide) for the application of dye-sensitized solar cells. Coupling of thiourea in the presence of iodine undergoes dimerization reaction to produce formamidine disulfide. Fourier Transform Infrared spectroscopy shows that the interactions of thiourea and formamidine disulfide with electronegative ether linkage of poly(ethylene oxide) results in conformational changes of gel polymer electrolytes. Electrochemical impedance spectroscopy and linear sweep voltammetry experiments reveal an increment in ionic conductivity and tri-iodide diffusion coefficient, for thiourea modified gel polymer electrolytes. Finally, the prepared electrolytes are used as a redox mediator in dye-sensitized solar cells and the photovoltaic properties were studied. Apart from transparency, the gel polymer electrolytes with thiorurea show higher photovoltaic properties compared to bare gel polymer electrolyte and a maximum photocurrent efficiency of 7.17% is achieved for gel polymer electrolyte containing 1 wt% of thiourea with a short circuit current of 11.79 mA cm-2 and open circuit voltage of 834 mV. Finally, under rear illumination, almost 90% efficiency is retained upon compared to front illumination.

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

PubMed Central

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Preparation and electrochemical characterization of gel polymer electrolyte based on electrospun polyacrylonitrile nonwoven membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Manuel, James; Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Jou-Hyeon; Nah, Changwoon

Electrospun membranes of polyacrylonitrile are prepared, and the electrospinning parameters are optimized to get fibrous membranes with uniform bead-free morphology. The polymer solution of 16 wt.% in N, N-dimethylformamide at an applied voltage of 20 kV results in the nanofibrous membrane with average fiber diameter of 350 nm and narrow fiber diameter distribution. Gel polymer electrolytes are prepared by activating the nonwoven membranes with different liquid electrolytes. The nanometer level fiber diameter and fully interconnected pore structure of the host polymer membranes facilitate easy penetration of the liquid electrolyte. The gel polymer electrolytes show high electrolyte uptake (>390%) and high ionic conductivity (>2 × 10 -3 S cm -1). The cell fabricated with the gel polymer electrolytes shows good interfacial stability and oxidation stability >4.7 V. Prototype coin cells with gel polymer electrolytes based on a membrane activated with 1 M LiPF 6 in ethylene carbonate/dimethyl carbonate or propylene carbonate are evaluated for discharge capacity and cycle property in Li/LiFePO 4 cells at room temperature. The cells show remarkably good cycle performance with high initial discharge properties and low capacity fade under continuous cycling.

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

NASA Astrophysics Data System (ADS)

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham; Yahya, Muhd Zu Azhan; Ali, Ab Malik Marwan

2015-08-01

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance (1HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in 1HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF3SO3 show the highest conductivity. The complexation between EMG30 and LiCF3SO3 were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR).

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.

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.

Effect of methyl red dye on dielectric and conductivity properties of PEO/CdCl{sub 2} electrolytes

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

Kamath, Archana; Devendrappa, H., E-mail: dehu2010@gmail.com

2016-05-06

In this report the conductivity and dielectric properties of polyethylene oxide-cadmium chloride (PEO/CdCl{sub 2}) polymer electrolyte films doped with an azo dye methyl red (MR) are discussed. The films were prepared by solution casting technique at different concentrations of the dye in PEO/CdCl{sub 2} electrolyte. The thermal behavior, chemical interaction of the dye with the electrolyte and surface morphology were studied by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) respectively. The conductivity and dielectric properties were measured as a function of composition and temperature using complex impedance spectroscopy. The temperature dependent electrical conductivitymore » of the films exhibited Arrhenius type behavior. Conductivity and dielectric results also signify the enhancement in the amorphous phase of the polymer electrolyte dye systems. The value of highest conductivity observed is 1.21x10{sup −4} at 343K and the conductivity of the film was enhanced by a three orders of magnitude.« less

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

Smyrl, William H.; Owens, Boone B.; Mann, Kent; Pappenfus, T.; Henderson, W.

2004-01-01

PAPERS PUBLISHED: 1. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Complexes of Lithium Imide Salts with Tetraglyme and Their Polyelectrolyte Composite Materials. Journal of the Electrochemical Society (2004), 15 1 (2), A209-A2 15. 2. Pappenfus, Ted M.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; Smyrl, William H. Ionic-liquidlpolymer electrolyte composite materials for electrochemical device applications. Polymeric Materials Science and Engineering (2003), 88 302. 3. Pappenfus, Ted R.; Henderson, Wesley A.; Owens, Boone B.; Mann, Kent R.; and Smyrl, William H. Ionic Conductivity of a poly(vinylpyridinium)/Silver Iodide Solid Polymer Electrolyte System. Solid State Ionics (in press 2004). 4. Pappenfus Ted M.; Mann, Kent R; Smyrl, William H. Polyelectrolyte Composite Materials with LiPFs and Tetraglyme. Electrochemical and Solid State Letters, (2004), 7(8), A254.

Solid polymer electrolyte composite membrane comprising laser micromachined porous support

DOEpatents

Liu, Han [Waltham, MA; LaConti, Anthony B [Lynnfield, MA; Mittelsteadt, Cortney K [Natick, MA; McCallum, Thomas J [Ashland, MA

2011-01-11

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 5 microns, are made by laser micromachining and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

Solid polymer electrolyte composite membrane comprising plasma etched porous support

DOEpatents

Liu, Han; LaConti, Anthony B.

2010-10-05

A solid polymer electrolyte composite membrane and method of manufacturing the same. According to one embodiment, the composite membrane comprises a rigid, non-electrically-conducting support, the support preferably being a sheet of polyimide having a thickness of about 7.5 to 15 microns. The support has a plurality of cylindrical pores extending perpendicularly between opposing top and bottom surfaces of the support. The pores, which preferably have a diameter of about 0.1 to 5 microns, are made by plasma etching and preferably are arranged in a defined pattern, for example, with fewer pores located in areas of high membrane stress and more pores located in areas of low membrane stress. The pores are filled with a first solid polymer electrolyte, such as a perfluorosulfonic acid (PFSA) polymer. A second solid polymer electrolyte, which may be the same as or different than the first solid polymer electrolyte, may be deposited over the top and/or bottom of the first solid polymer electrolyte.

Development of dye-sensitized solar cells composed of liquid crystal embedded, electrospun poly(vinylidene fluoride-co-hexafluoropropylene) nanofibers as polymer gel electrolytes.

PubMed

Ahn, Sung Kwang; Ban, Taewon; Sakthivel, P; Lee, Jae Wook; Gal, Yeong-Soon; Lee, Jin-Kook; Kim, Mi-Ra; Jin, Sung-Ho

2012-04-01

In order to overcome the problems associated with the use of liquid electrolytes in dye-sensitized solar cells (DSSCs), a new system composed of liquid crystal embedded, polymer electrolytes has been developed. For this purpose, three types of DSSCs have been fabricated. The cells contain electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (e-PVdF-co-HFP) polymer gel electrolyte, with and without doping with the liquid crystal E7 and with a liquid electrolyte. The morphologies of the newly prepared DSSCs were explored using field emission scanning electron microscopy (FE-SEM). Analysis of the FE-SEM images indicate that the DSSC composed of E7 embedded on e-PVdF-co-HFP polymer gel electrolyte has a greatly regular morphology with an average diameter. The ionic conductivity of E7 embedded on e-PVdF-co-HFP polymer gel electrolyte was found to be 2.9 × 10(-3) S/cm at room temperature, a value that is 37% higher than that of e-PVdF-co-HFP polymer gel electrolyte. The DCCS containing the E7 embedded, e-PVdF-co-HFP polymer gel electrolyte was observed to possess a much higher power conversion efficiency (PCE = 6.82%) than that of an e-PVdF-co-HFP nanofiber (6.35%). In addition, DSSCs parameters of the E7 embedded, e-PVdF-co-HFP polymer gel electrolyte (V(oc) = 0.72 V, J(sc) = 14.62 mA/cm(2), FF = 64.8%, and PCE = 6.82% at 1 sun intensity) are comparable to those of a liquid electrolyte (V(oc) = 0.75 V, J(sc) = 14.71 mA/cm(2), FF = 64.9%, and PCE = 7.17%, both at a 1 sun intensity).

NREL, Giner Evaluated Polymer Electrolyte Membrane for Maximizing Renewable

Science.gov Websites

Energy on Grid | Energy Systems Integration Facility | NREL Giner NREL, Giner Evaluated Polymer -scale polymer electrolyte membrane (PEM) stack designed to maximize renewable energy on the grid by converting it to hydrogen when supply exceeds demand. Photo of a polymer electrolyte membrane stack in a

Reciprocated suppression of polymer crystallization toward improved solid polymer electrolytes: Higher ion conductivity and tunable mechanical properties

DOE PAGES

Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; ...

2015-08-06

Solid polymer electrolytes based on lithium bis(trifluoromethanesulfonyl) imide and polymer matrix were extensively studied in the past due to their excellent potential in a broad range of energy related applications. Poly(vinylidene fluoride) (PVDF) and polyethylene oxide (PEO) are among the most examined polymer candidates as solid polymer electrolyte matrix. In this paper, we study the effect of reciprocated suppression of polymer crystallization in PVDF/PEO binary matrix on ion transport and mechanical properties of the resultant solid polymer electrolytes. With electron and X-ray diffractions as well as energy filtered transmission electron microscopy, we identify and examine the appropriate blending composition thatmore » is responsible for the diminishment of both PVDF and PEO crystallites. Laslty, a three-fold conductivity enhancement is achieved along with a highly tunable elastic modulus ranging from 20 to 200 MPa, which is expected to contribute toward future designs of solid polymer electrolytes with high room-temperature ion conductivities and mechanical flexibility.« less

Facile control of nanoporosity in Cellulose Acetate using Nickel(II) nitrate additive and water pressure treatment for highly efficient battery gel separators.

PubMed

Lee, Woong Gi; Kim, Do Hyeong; Jeon, Woo Cheol; Kwak, Sang Kyu; Kang, Seok Ju; Kang, Sang Wook

2017-04-28

We succeed in fabricating nearly straight nanopores in cellulose acetate (CA) polymers for use as battery gel separators by utilizing an inorganic hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) complex and isostatic water pressure treatment. The continuous nanopores are generated when the polymer film is exposed to isostatic water pressure after complexing the nickel(II) nitrate hexahydrate (Ni(NO 3 ) 2 ·6H 2 O) with the CA. These results can be attributed to the manner in which the polymer chains are weakened because of the plasticization effect of the Ni(NO 3 ) 2 ·6H 2 O that is incorporated into the CA. Furthermore, we performed extensive molecular dynamics simulation for confirming the interaction between electrolyte and CA separator. The well controlled CA membrane after water pressure treatment enables fabrication of highly reliable cell by utilizing 2032-type coin cell structure. The resulting cell performance exhibits not only the effect of the physical morphology of CA separator, but also the chemical interaction of electrolyte with CA polymer which facilitates the Li-ion in the cell.

Insights into the use of polyethylene oxide in energy storage/conversion devices: a critical review

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2017-11-01

In this review, the latest updates in poly (ethylene oxide) based electrolytes are summarized. The ultimate goal of researchers globally is towards the development of free-standing solid polymeric separators for energy storage devices. This single free-standing solid polymeric separator may replace the liquid and separator (organic/inorganic) used in existing efficient/smart energy technology. As an example, polyethylene oxide (PEO) consists of an electron donor-rich group which provides coordinating sites to the cation for migration. Owing to this exclusive structure, PEO exhibits some remarkable properties, such as a low glass transition temperature, excellent flexibility, and the ability to make complexation with various metal salts which are unattainable by another polymer host. Hence, the PEO is an emerging candidate that has been most examined or is currently under consideration for application in energy storage devices. This review article first provides a detailed study of the PEO properties, characteristics of the constituents of the polymer electrolyte, and suitable approaches for the modification of polymer electrolytes. Then, the synthesization and characterizations techniques are outlined. The structures, characteristics, and performance during charge-discharge of four types of electrolyte/separators (liquid, plasticized, and dispersed and intercalated electrolyte) are highlighted. The suitable ion transport mechanism proposed by researchers in different renowned groups have been discussed for the better understanding of the ion dynamics in such systems.

Preliminary study of application of Moringa oleifera resin as polymer electrolyte in DSSC solar cells

NASA Astrophysics Data System (ADS)

Saehana, Sahrul; Darsikin, Muslimin

2016-04-01

This study reports the preliminary study of application of Moringa oleifera resin as polymer electrolyte in dye-sensitized solar cell (DSSC). We found that polymer electrolyte membrane was formed by using solution casting methods. It is observed that polymer electrolyte was in elastic form and it is very potential to application as DSSC component. Performance of DSSC which employing Moringa oleifera resin was also observed and photovoltaic effect was found.

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.

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

Padmaraj, O.; Satyanarayana, N., E-mail: nallanis2011@gmail.com; Venkateswarlu, M.

A novel fibrous polymer blend [(100-x) % P(VdF-co-HFP)/x % PMMA, x = 10, 20, 30, 40, 50] electrolyte membranes were prepared by electrospinning technique. Structural, thermal and surface morphology of all the compositions of electrospun polymer blend membranes were studied by using XRD, DSC & SEM. The newly developed five different compositions of polymer blend fibrous electrolyte membranes were obtained by soaking in an electrolyte solution contains 1M LiPF{sub 6} in EC: DEC (1:1,v/v). The wet-ability and conductivity of all the compositions of polymer blend electrolyte membranes are evaluated through electrolyte uptake and impedance measurements. The polymer blend [90% P(VdF-co-HFP)/10%more » PMMA] electrolyte membrane showed good wet-ability and high conductivity (1.788 × 10{sup −3} Scm{sup −1}) at room temperature.« less

Conductivity studies of PEG based polymer electrolyte for applications as electrolyte in ion batteries

NASA Astrophysics Data System (ADS)

Patil, Ravikumar V.; Praveen, D.; Damle, R.

2018-05-01

Development of lithium ion batteries employing solid polymer electrolytes as electrolyte material has led to efficient energy storage and usage in many portable devices. However, due to a few drawbacks like lower ionic conductivity of solid polymer electrolytes (SPEs), studies on SPEs for improvement in conductivity still have a good scope. In the present paper, we report the conductivity studies of a new SPE with low molecular weight poly ethylene glycol (PEG) as host polymer in which a salt with larger anion Lithium trifluro methane sulphonate (LTMS). XRD studies have revealed that the salt completely dissociates in the polymer giving a good stable electrolyte at lower salt concentration. Conductivity of the SPEs has been studied as a function of temperature and we reiterate that the conductivity is a thermally activated process and follows Arrhenius type behavior.

Polymeric electrolytes based on hydrosilyation reactions

DOEpatents

Kerr, John Borland [Oakland, CA; Wang, Shanger [Fairfield, CA; Hou, Jun [Painted Post, NY; Sloop, Steven Edward [Berkeley, CA; Han, Yong Bong [Berkeley, CA; Liu, Gao [Oakland, CA

2006-09-05

New polymer electrolytes were prepared by in situ cross-linking of allyl functional polymers based on hydrosilation reaction using a multifunctional silane cross-linker and an organoplatinum catalyst. The new cross-linked electrolytes are insoluble in organic solvent and show much better mechanical strength. In addition, the processability of the polymer electrolyte is maintained since the casting is finished well before the gel formation.

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

Das, S.; Ghosh, A., E-mail: sspag@iacs.res.in

We have studied ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate. Differential scanning calorimetry and X-ray diffraction studies confirm minimum volume fraction of crystalline phase for the polymer electrolyte with 40 wt. % propylene carbonate. The ionic conductivity exhibits a maximum for the same composition. The temperature dependence of the ionic conductivity has been well interpreted using Vogel-Tamman-Fulcher equation. Ion-ion interactions in the polymer electrolytes have been studied using Raman spectra and the concentrations of free ions, ion-pairs and ion-aggregates have been determined. The ionic conductivity increases due to the increase of freemore » ions with the increase of propylene carbonate content. But for higher content of propylene carbonate, the ionic conductivity decreases due to the increase of concentrations of ion-pairs and ion-aggregates. To get further insights into the ion dynamics, the experimental data for the complex dielectric permittivity have been studied using Havriliak–Negami function. The variation of relaxation time with temperature obtained from this formalism follows Vogel-Tamman-Fulcher equation similar to the ionic conductivity.« less

Dynamic and Structure of Polymer-Cellulose Composite Electrolyte for Li-ion Battery

NASA Astrophysics Data System (ADS)

Zhan, Pengfei; Maranas, Janna

Crystalline PEO6LiX complex is a tunnel-like polymer/salt structure that promotes fast Li motion. The application is limited because high ion conductivity is only observed with short molecular weight PEO, as the molecular weight increase, tunnels are misaligned and the conductivity is decreased. High aspect ratio nanofillers based on cellulose nanowhiskers are hypothesized to promote the formation of tunnel structures. Compared with unfilled electrolyte, the room temperature ion conductivity increased as much as 1100% in filled electrolyte. With wide angle x-ray scattering (WAXS), we observe that the structure transitions from amorphous phase to crystalline phase as we add cellulose nanowhiskers and this is because the interaction between cellulose surface and polymer chain enhances the crystallization. From the temperature dependence of conductivity, the calculated Li+ hopping activation energy is shown to be lower in acidic cellulose nanowhisker filled samples. Our quasi-elastic neutron scattering (QENS) indicates with acidic surface, the rotation of PEO6 channels are more stabilized and this could be the origin of the low activation energy and high conductivity

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, M.; Abraham, K.M.

1993-10-12

This invention pertains to Lithium batteries using Li ion (Li[sup +]) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride). 3 figures.

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, Mohamed; Abraham, Kuzhikalail M.

1993-01-01

This invention pertains to Lithium batteries using Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized in a solid organic polymer matrix. In particular, this invention relates to Li batteries using solid polymer electrolytes derived by immobilizing solvates formed between a Li salt and an aprotic organic solvent (or mixture of such solvents) in poly(vinyl chloride).

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety.

PubMed

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-08-29

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm(-1) at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350 °C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance.

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

NASA Astrophysics Data System (ADS)

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-08-01

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm-1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance.

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

PubMed Central

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-01-01

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm−1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance. PMID:25168687

Effect of Al2O3 nanoparticles in plasticized PMMA-LiClO4 based solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2017-05-01

We have studied the broadband complex conductivity spectra covering a 0.01 Hz-3 GHz frequency range for plasticized PMMA-LiClO4 based solid polymer electrolyte embedded with Al2O3 nanoparticle. We have analyzed the conductivity spectra using the random free-energy barrier model (RBM) coupled with electrode polarization contribution in the low frequency region and at high temperatures. The temperature dependence of the ionic conductivity obtained from the analysis has been analyzed using Vogel-Tammann-Fulcher equation. The maximum ionic conductivity ˜ 1.93×10-4 S/cm has been obtained for 1 wt% Al2O3 nanoparticle.

Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries.

PubMed

Kil, Eun-Hye; Choi, Keun-Ho; Ha, Hyo-Jeong; Xu, Sheng; Rogers, John A; Kim, Mi Ri; Lee, Young-Gi; Kim, Kwang Man; Cho, Kuk Young; Lee, Sang-Young

2013-03-13

A class of imprintable, bendable, and shape-conformable polymer electrolyte with excellent electrochemical performance in a lithium battery system is reported. The material consists of a UV-cured polymer matrix, high-boiling point liquid electrolyte, and Al2 O3 nanoparticles, formulated for use in lithium-ion batteries with 3D-structured electrodes or flexible characteristics. The unique structural design and well-tuned rheological characteristics of the UV-curable electrolyte mixture, in combination with direct UV-assisted nanoimprint lithography, allow the successful fabrication of polymer electrolytes in geometries not accessible with conventional materials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries

DOEpatents

Mullin, Scott; Panday, Ashoutosh; Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

2014-04-22

A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics. In another aspect, the electrolyte exhibits a conductivity drop when the temperature of electrolyte increases over a threshold temperature, thereby providing a shutoff mechanism for preventing thermal runaway in lithium battery cells.

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.

Investigating catalyst coated membrane equilibration time for polymer electrolyte membrane fuel cell manufacturing

NASA Astrophysics Data System (ADS)

Cote, Philippe

Mercedes-Benz Canada Inc., Fuel Cell Division, manufactures polymer electrolyte membrane fuel cell stacks for use in vehicles. The manufacturing line is being optimized for efficiency and quality control, in order to uphold the high standards of Mercedes-Benz Inc. vehicles. In an operating polymer electrolyte membrane fuel cell, the catalyst coated membrane facilitates the electrochemical reaction that generates electricity. This research examines the equilibration of catalyst coated membrane rolls to controlled temperature and humidity conditions, before they are used in the manufacturing of polymer electrolyte membrane fuel cells. Equilibration involves allowing the water content in the catalyst coated membrane to stabilize at the controlled conditions, in order to reduce mechanical stress in the material for better manufacturability. Initial equilibration measurements were conducted on discrete catalyst coated membrane samples using novel electronic conductivity measurements of the catalyst layer, and compared to ionic conductivity measurements of the membrane. Electronic conductivity measurements are easier to implement in the manufacturing environment than the more complex ionic conductivity measurements. When testing discrete catalyst coated membrane samples in an environmental chamber, the equilibration trends for the measured ionic and electronic conductivity signals were similar enough to permit us to adapt the electronic conductivity measurements for catalyst coated membrane in roll form. Equilibration measurements of catalyst coated membrane rolls were optimized to achieve a robust and repeatable procedure which could be used in the manufacturing environment at Mercedes-Benz Canada Inc., Fuel Cell Division.

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.

Novel Stable Gel Polymer Electrolyte: Toward a High Safety and Long Life Li-Air Battery.

PubMed

Yi, Jin; Liu, Xizheng; Guo, Shaohua; Zhu, Kai; Xue, Hailong; Zhou, Haoshen

2015-10-28

Nonaqueous Li-air battery, as a promising electrochemical energy storage device, has attracted substantial interest, while the safety issues derived from the intrinsic instability of organic liquid electrolytes may become a possible bottleneck for the future application of Li-air battery. Herein, through elaborate design, a novel stable composite gel polymer electrolyte is first proposed and explored for Li-air battery. By use of the composite gel polymer electrolyte, the Li-air polymer batteries composed of a lithium foil anode and Super P cathode are assembled and operated in ambient air and their cycling performance is evaluated. The batteries exhibit enhanced cycling stability and safety, where 100 cycles are achieved in ambient air at room temperature. The feasibility study demonstrates that the gel polymer electrolyte-based polymer Li-air battery is highly advantageous and could be used as a useful alternative strategy for the development of Li-air battery upon further application.

Electrochemical characteristics of Li/LiMn 2O 4 cells using gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Ko, Jang-Myoun; Chun, Jong-Han

Gel polymer electrolytes composed of acrylonitrile-methylmethacrylate (AM) copolymer and 1 M LiClO 4-ethylene carbonate (EC)/propylene carbonate (PC) are prepared. The ionic conductivity reaches 1.9×10 -3 S cm -1 in a gel polymer electrolyte with 20 wt.% of AM copolymer and 80 wt.% of LiClO 4-EC/PC at room temperature. These systems showed no solvent exudation from the matrix polymer due to enhanced compatibility between AM copolymer and organic liquid electrolyte. A Li/gel polymer electrolyte/LiMn 2O 4 cell has a reversible capacity of 132 mAh g -1 in the voltage range of 3.0-4.3 V at the C/5 rate and shows good cycling performance with a coulombic efficiency >99%.

Photoelectrochemical cells for conversion of solar energy to electricity and methods of their manufacture

DOEpatents

Skotheim, Terje

1984-04-10

A photoelectric device is disclosed which comprises first and second layers of semiconductive material, each of a different bandgap, with a layer of dry solid polymer electrolyte disposed between the two semiconductor layers. A layer of a polymer blend of a highly conductive polymer and a solid polymer electrolyte is further interposed between the dry solid polymer electrolyte and the first semiconductor layer. A method of manufacturing such devices is also disclosed.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

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

Solid electrolyte material manufacturable by polymer processing methods

DOEpatents

Singh, Mohit; Gur, Ilan; Eitouni, Hany Basam; Balsara, Nitash Pervez

2012-09-18

The present invention relates generally to electrolyte materials. According to an embodiment, the present invention provides for a solid polymer electrolyte material that is ionically conductive, mechanically robust, and can be formed into desirable shapes using conventional polymer processing methods. An exemplary polymer electrolyte material has an elastic modulus in excess of 1.times.10.sup.6 Pa at 90 degrees C. and is characterized by an ionic conductivity of at least 1.times.10.sup.-5 Scm-1 at 90 degrees C. An exemplary material can be characterized by a two domain or three domain material system. An exemplary material can include material components made of diblock polymers or triblock polymers. Many uses are contemplated for the solid polymer electrolyte materials. For example, the present invention can be applied to improve Li-based batteries by means of enabling higher energy density, better thermal and environmental stability, lower rates of self-discharge, enhanced safety, lower manufacturing costs, and novel form factors.

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.

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.

Dynamics of Lithium Polymer Electrolytes using X-ray Photon Correlation Spectroscopy and Rheology

NASA Astrophysics Data System (ADS)

Oparaji, Onyekachi; Narayanan, Suresh; Sandy, Alec; Hallinan, Daniel, Jr.

Polymer electrolytes are promising materials for high energy density rechargeable batteries. Battery fade can be caused by structural evolution in the battery electrode and loss of electrode/electrolyte adhesion during cycling. Both of these effects are dependent on polymer mechanical properties. In addition, cycling rate is dictated by the ion mobility of the polymer electrolyte. Lithium ion mobility is expected to be strongly coupled to polymer dynamics. Therefore, we investigate polymer dynamics as a function of salt concentration using X-ray Photon Correlation Spectroscopy (XPCS) and rheology. We report the influence of lithium salt concentration on the structural relaxation time (XPCS) and stress relaxation time (rheology) of high molecular weight poly(styrene - ethylene oxide) block copolymer membranes.

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.

Preparation and characterization of hydrophobic P(TFE) blend electrospun gel polymer electrolyte fibrous membranes for Li-O2 battery

NASA Astrophysics Data System (ADS)

Padmaraj, O.; Suthanthiraraj, S. Austin

2018-04-01

A novel stable electrospun gel polymer electrolyte [(100-x)% P(VdF-co-HFP)+(x)% P(TFE), (x = 5, 10, 15, 20, 25 & 30)/1 M Li(CF3SO2)2N-] fibrous membranes with an addition of various concentrations of hydrophobic P(TFE) polymer were prepared by an electrospinning technique. All the prepared electrospun polymer blend fibrous membranes were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, high resolution scanning electron microscopy techniques and water contact angle measurements. The newly developed electrospun pure and hydrophobic P(TFE) blend fibrous membranes were activated into separator-cum gel polymer electrolyte fibrous membranes by soaking in an electrolyte solution contains 1 M Li(CF3SO2)2N- in EC: PC (1:1, v/v) in an argon filled glove box. Among the various concentrations of hydrophobic P(TFE) blend polymer fibrous membranes, the electrospun gel polymer blend electrolyte with 5% P(TFE) showed low crystallinity, high thermal stability, high electrolyte uptake, good hydrophobicity and high ionic conductivity (2.680×10-2 S cm-1) at room temperature.

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.

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.

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.

A High-Energy-Density Potassium Battery with a Polymer-Gel Electrolyte and a Polyaniline Cathode.

PubMed

Gao, Hongcai; Xue, Leigang; Xin, Sen; Goodenough, John B

2018-05-04

A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K + ion of the KPF 6 salt is plated/stripped on the potassium-metal anode. The use of a p-type polymer cathode increases the cell voltage. By replacing the organic-liquid electrolyte in a glass-fiber separator with a polymer-gel electrolyte of cross-linked poly(methyl methacrylate), a dendrite-free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross-linked architecture provides small pores of adjustable sizes to stabilize a solid-electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low-cost potassium batteries for the stationary storage of electric power. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Effect of epoxidation on 30% poly(methyl methacrylate)-grafted natural rubber polymer electrolytes

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

Nazir, Khuzaimah; Aziz, Ahmad Fairoz; Adam, Nurul Ilham

Epoxidized 30% poly(methyl methacrylate)-grafted natural rubber (EMG 30) as a polymer host in solid polymer electrolytes (SPEs) has been investigated. EMG30 was synthesized via performicepoxidation method onto 30% poly(methyl methacrylate)-grafted natural rubber (MG30) and the formations of epoxy group were discussed. The EMG30 were characterized by proton nuclear magnetic resonance ({sup 1}HNMR) to investigate their chemical structure and differential scanning calorimeter to determine their crystallinity. A new peak in {sup 1}HNMR spectra (2.71 ppm) confirmed the appearance of epoxy group. SPE based on EMG30 doped with 40 wt% LiCF{sub 3}SO{sub 3} show the highest conductivity. The complexation between EMG30 and LiCF{submore » 3}SO{sub 3} were confirmed by attenuated total reflection Fourier transform infrared (ATR-FTIR)« less

iCVD Cyclic Polysiloxane and Polysilazane as Nanoscale Thin-Film Electrolyte: Synthesis and Properties.

PubMed

Chen, Nan; Reeja-Jayan, B; Liu, Andong; Lau, Jonathan; Dunn, Bruce; Gleason, Karen K

2016-03-01

A group of crosslinked cyclic siloxane (Si-O) and silazane (Si-N) polymers are synthesized via solvent-free initiated chemical vapor deposition (iCVD). Notably, this is the first report of cyclic polysilazanes synthesized via the gas-phase iCVD method. The deposited nanoscale thin films are thermally stable and chemically inert. By iCVD, they can uniformly and conformally cover nonplanar surfaces having complex geometry. Although polysiloxanes are traditionally utilized as dielectric materials and insulators, our research shows these cyclic organosilicon polymers can conduct lithium ions (Li(+) ) at room temperature. The conformal coating and the room temperature ionic conductivity make these cyclic organosilicon polymers attractive for use as thin-film electrolytes in solid-state batteries. Also, their synthesis process and properties have been systemically studied and discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance improvement of gel- and solid-state dye-sensitized solar cells by utilization the blending effect of poly (vinylidene fluoride-co-hexafluropropylene) and poly (acrylonitrile-co-vinyl acetate) co-polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Shanmugam; Obadja, Nesia; Chang, Ting-Wei; Chen, Li-Tung; Lee, Yuh-Lang

2014-12-01

Poly (vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) and poly (acrylonitrile-co-vinyl acetate) (PAN-VA) are used as gelator to prepare gel- and solid-state polymer electrolytes for dye sensitized solar cells (DSSCs) applications. The electrolytes prepared using PVDF-HFP have higher conductivities than those prepared using PAN-VA. In blended polymers, the conductivities of the electrolytes increase with increasing composition of PVDF-HFP; at 75% PVDF-HFP, conductivity of the blended polymer surpassed that of pure polymers. It is also found that the viscosity of the electrolyte prepared by PAN-VA (1.2 kPaS) is much lower than that by PVDF-HFP (11 kPaS). Therefore, increasing PAN-VA composition can decrease the viscosity of the electrolyte, improving the penetration of electrolytes in the TiO2 matrix. By controlling the ratio of PVDF-HFP/PAN-VA, the conductivity and viscosity of the electrolyte can be regulated and an optimal ratio based on the conversion efficiency of the gel- and solid state DSSCs is obtained at the ratio of 3/1. The highest efficiency achieved by the gel- and solid-state cells using the blending polymers are 6.3% and 4.88%, respectively, which are higher than those prepared using pure polymers (5.53% and 4.56%, respectively). The introduction of TiO2 fillers to the solid electrolyte can further increase the cell efficiency to 5.34%.

Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

NASA Astrophysics Data System (ADS)

Pandey, G. P.; Hashmi, S. A.

2013-12-01

Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

High elastic modulus polymer electrolytes

DOEpatents

Balsara, Nitash Pervez; Singh, Mohit; Eitouni, Hany Basam; Gomez, Enrique Daniel

2013-10-22

A polymer that combines high ionic conductivity with the structural properties required for Li electrode stability is useful as a solid phase electrolyte for high energy density, high cycle life batteries that do not suffer from failures due to side reactions and dendrite growth on the Li electrodes, and other potential applications. The polymer electrolyte includes a linear block copolymer having a conductive linear polymer block with a molecular weight of at least 5000 Daltons, a structural linear polymer block with an elastic modulus in excess of 1.times.10.sup.7 Pa and an ionic conductivity of at least 1.times.10.sup.-5 Scm.sup.-1. The electrolyte is made under dry conditions to achieve the noted characteristics.

Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Gao, Han

Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms. The optimized polymer electrolyte demonstrated even higher proton conductivity than pure HPAs and the enabled electrochemical capacitors have demonstrated an exceptionally high rate capability of 50 Vs-1 in cyclic voltammograms and a 10 ms time constant in impedance analyses.

Oxygen reduction reaction catalyzed by nickel complexes based on thiophosphorylated calix[4]resorcinols and immobilized in the membrane electrode assembly of fuel cells.

PubMed

Kadirov, M K; Knyazeva, I R; Nizameev, I R; Safiullin, R A; Matveeva, V I; Kholin, K V; Khrizanforova, V V; Ismaev, T I; Burilov, A R; Budnikova, Yu H; Sinyashin, O G

2016-10-18

The catalytic activity of the nickel complexes of thiophosphorylated calix[4]resorcinols for oxygen reduction in a polymer electrolyte membrane fuel cell (PEMFC) has been studied. The conformation of the macrocyclic ligand determines the morphology and catalytic properties of the resulting organometallic species.

Effect of Al2O3 in poly(methyl methacrylate) composite polymer electrolytes

NASA Astrophysics Data System (ADS)

Sun, C. C.; You, A. H.; Teo, L. L.; Thong, L. W.

2018-05-01

In this work, the effect of inert fillers on poly(methyl methacrylate) (PMMA) composite polymer electrolytes (CPEs) are investigated. The PMMA-LiCF3SO3-EC-Al2O3 composite polymer electrolytes were prepared using solution casting method at room temperature. Lithium trifluoromethanesulfonate (LiCF3SO3) is used as the electrolyte salt which plays an important role in Li ion transfer. In order to soften the polymer matrix, ethylene carbonate (EC) is introduced into the CPEs to help in the disassociation of lithium salt ion pairs. Nano sized aluminium oxide (Al2O3) is then incorporated to enhance mechanical strength and ionic conductivity of the polymer electrolyte. The optimum of 2 wt.% 50 nm Al2O3 was added into the PMMA polymer electrolyte sample. Through Electrochemical Impedance Spectroscopy (EIS) measurements, the highest ionic conductivity at room temperature is determined as 1.52×10-4 S/cm. FTIR spectra analysis showed CH2 twisting mode at 1383.43 cm-1, C=O stretching mode at 1721.56 cm-1 which proven the interaction between host polymer and lithium salt and CH3 stretching mode at 2981.34 cm-1. XRD analysis had also been performed to study the structural behaviour of the PMMA polymer electrolyte. The intense peak at position 2θ angle of 15.04°, 30.92° and 45.58° occur upon interaction with Al2O3. Lastly, the surface morphology is studied through SEM+EDX analysis.

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

Fauzi, Iqbal, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: arcana@chem.itb.ac.id

Recently, the need of secondary battery application continues to increase. The secondary battery which using a liquid electrolyte was indicated had some weakness. A solid polymer electrolyte is an alternative electrolytes membrane which developed in order to replace the liquid electrolyte type. In the present study, the effect of phosphorylation on to polymer electrolyte membrane which synthesized from chitosan and lithium perchlorate salts was investigated. The effect of the component’s composition respectively on the properties of polymer electrolyte, was carried out by analyzed of it’s characterization such as functional groups, ion conductivity, and thermal properties. The mechanical properties i.e tensilemore » resistance and the morphology structure of membrane surface were determined. The phosphorylation processing of polymer electrolyte membrane of chitosan and lithium perchlorate was conducted by immersing with phosphoric acid for 2 hours, and then irradiated on a microwave for 60 seconds. The degree of deacetylation of chitosan derived from shrimp shells was obtained around 75.4%. Relative molecular mass of chitosan was obtained by viscometry method is 796,792 g/mol. The ionic conductivity of chitosan membrane was increase from 6.33 × 10{sup −6} S/cm up to 6.01 × 10{sup −4} S/cm after adding by 15 % solution of lithium perchlorate. After phosphorylation, the ionic conductivity of phosphorylated lithium chitosan membrane was observed 1.37 × 10{sup −3} S/cm, while the tensile resistance of 40.2 MPa with a better thermal resistance. On the strength of electrolyte membrane properties, this polymer electrolyte membrane was suggested had one potential used for polymer electrolyte in field of lithium battery applications.« less

Frequency-dependent learning achieved using semiconducting polymer/electrolyte composite cells

NASA Astrophysics Data System (ADS)

Dong, W. S.; Zeng, F.; Lu, S. H.; Liu, A.; Li, X. J.; Pan, F.

2015-10-01

Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP.Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02891d

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

Present status of solid state photoelectrochemical solar cells and dye sensitized solar cells using PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Singh, Pramod Kumar; Nagarale, R. K.; Pandey, S. P.; Rhee, H. W.; Bhattacharya, Bhaskar

2011-06-01

Due to energy crises in the future, much effort is being directed towards alternate sources. Solar energy is accepted as a novel substitute for conventional sources of energy. Out of the long list of various types of solar cells available on the market, solid state photoelectrochemical solar cells (SSPECs) and dye sensitized solar cells (DSSCs) are proposed as an alternative to costly crystalline solar cell. This review provides a common platform for SSPECs and DSSCs using polymer electrolyte, particularly on polyethylene oxide (PEO)-based polymer electrolytes. Due to numerous advantageous properties of PEO, it is frequently used as an electrolyte in both SSPECs as well as DSSCs. In DSSCs, so far high efficiency (more than 11%) has been obtained only by using volatile liquid electrolyte, which suffers many disadvantages, such as corrosion, leakage and evaporation. The PEO-based solid polymer proves its importance and could be used to solve the problems stated above. The recent developments in SSPECs and DSSCs using modified PEO electrolytes by adding nano size inorganic fillers, blending with low molecular weight polymers and ionic liquid (IL) are discussed in detail. The role of ionic liquid in modifying the electrical, structural and photoelectrochemical properties of PEO polymer electrolytes is also described.

Role of salt concentration in blend polymer for energy storage conversion devices

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

Arya, Anil; Sharma, A. L., E-mail: alsharmaiitkgp@gmail.com; Sadiq, M.

2016-05-06

Solid Polymer Electrolytes (SPE) are materials of considerable interest worldwide, which serves dual purpose of electrolyte and separator between electrode compartments in renewable energy conversion/storage devices such as; high energy density batteries, electrochromic display devices, and supercapacitors. Polymer blend electrolytes are prepared for various concentration of salt (Ö/Li) with the constant ratio (0.5 gm) of each PEO and PAN polymers (blend polymer) using solution casting technique. Solid polymeric ionic conductor as a separator is the ultimate substitute to eliminate the drawback related to liquid and gel polymer ionic conductors. In the present work, solid polymer electrolyte film consisting of PEO,more » PAN and LiPF{sub 6} are examined for various concentration of lithium salt by keeping PEO/PAN blend ratio as a constant with a view to optimize the dominant salt concentration which could give the maximum conductivity at ambient temperature.« less

Computer Simulations of Ion Transport in Polymer Electrolyte Membranes.

PubMed

Mogurampelly, Santosh; Borodin, Oleg; Ganesan, Venkat

2016-06-07

Understanding the mechanisms and optimizing ion transport in polymer membranes have been the subject of active research for more than three decades. We present an overview of the progress and challenges involved with the modeling and simulation aspects of the ion transport properties of polymer membranes. We are concerned mainly with atomistic and coarser level simulation studies and discuss some salient work in the context of pure binary and single ion conducting polymer electrolytes, polymer nanocomposites, block copolymers, and ionic liquid-based hybrid electrolytes. We conclude with an outlook highlighting future directions.

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

Impedance studies of a green blend polymer electrolyte based on PVA and Aloe-vera

NASA Astrophysics Data System (ADS)

Selvalakshmi, S.; Mathavan, T.; Vijaya, N.; Selvasekarapandian, Premalatha, M.; Monisha, S.

2016-05-01

The development of polymer electrolyte materials for energy generating and energy storage devices is a challenge today. A new type of blended green electrolyte based on Poly-vinyl alcohol (PVA) and Aloe-vera has been prepared by solution casting technique. The blending of polymers may lead to the increase in stability due to one polymer portraying itself as a mechanical stiffener and the other as a gelled matrix supported by the other. The prepared blend electrolytes were subjected to Ac impedance studies. It has been found out that the polymer film in which 1 gm of PVA was dissolved in 40 ml of Aloe-vera extract exhibits highest conductivity and its value is 3.08 × 10-4 S cm-1.

Electrochemical performance of a solvent-free hybrid ceramic-polymer electrolyte based on Li7La3Zr2O12 in P(EO)15LiTFSI

NASA Astrophysics Data System (ADS)

Keller, Marlou; Appetecchi, Giovanni Battista; Kim, Guk-Tae; Sharova, Varvara; Schneider, Meike; Schuhmacher, Jörg; Roters, Andreas; Passerini, Stefano

2017-06-01

The preparation of hybrid ceramic-polymer electrolytes, consisting of 70 wt% of Li+ cation conducting Li7La3Zr2O12 (LLZO) and 30 wt% of P(EO)15LiTFSI polymer electrolyte, through a solvent-free procedure is reported. The LLZO-P(EO)15LiTFSI hybrid electrolytes exhibit remarkable improvement in terms of flexibility and processability with respect to pure LLZO ceramic electrolytes. The physicochemical and electrochemical investigation shows the effect of LLZO annealing, resulting in ion conduction gain. However, slow charge transfer at the ceramic-polymer interface is also observed especially at higher temperatures. Nevertheless, improved compatibility with lithium metal anodes and good Li stripping/plating behavior are exhibited by the LLZO-P(EO)15LiTFSI hybrid electrolytes with respect to P(EO)15LiTFSI.

Submicroporous/microporous and compatible/incompatible multi-functional dual-layer polymer electrolytes and their interfacial characteristics with lithium metal anode

NASA Astrophysics Data System (ADS)

Lee, Young-Gi; Kyhm, Kwangseuk; Choi, Nam-Soon; Ryu, Kwang Sun

A novel multi-functional dual-layer polymer electrolyte was prepared by impregnating the interconnected pores with an ethylene carbonate (EC)/dimethyl carbonate (DMC)/lithium hexafluorophosphate (LiPF 6) solution. An incompatible layer is based on a microporous polyethylene (PE) and a compatible layer, based on a poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) is sub-microporous and compatible with an electrolyte solution. The Li electrode/the dual-layer polymer electrolyte/Li[Ni 0.15Li 0.23M n0.62]O 2 cell showed stable cycle performance under prolonged cycle number. This behavior is due to the enhanced compatibility between the matrix polymer and the liquid electrolytes within the submicroporous compatible layer, which could lead to a controlled Li + deposition on the Li anode surface by forming homegeneous electrolyte zone near the anode.

Cured composite materials for reactive metal battery electrolytes

DOEpatents

Harrup, Mason K.; Stewart, Frederick F.; Peterson, Eric S.

2006-03-07

A solid molecular composite polymer-based electrolyte is made for batteries, wherein silicate compositing produces a electrolytic polymer with a semi-rigid silicate condensate framework, and then mechanical-stabilization by radiation of the outer surface of the composited material is done to form a durable and non-tacky texture on the electrolyte. The preferred ultraviolet radiation produces this desirable outer surface by creating a thin, shallow skin of crosslinked polymer on the composite material. Preferably, a short-duration of low-medium range ultraviolet radiation is used to crosslink the polymers only a short distance into the polymer, so that the properties of the bulk of the polymer and the bulk of the molecular composite material remain unchanged, but the tough and stable skin formed on the outer surface lends durability and processability to the entire composite material product.

Taichi-inspired rigid-flexible coupling cellulose-supported solid polymer electrolyte for high-performance lithium batteries

PubMed Central

Zhang, Jianjun; Yue, Liping; Hu, Pu; Liu, Zhihong; Qin, Bingsheng; Zhang, Bo; Wang, Qingfu; Ding, Guoliang; Zhang, Chuanjian; Zhou, Xinhong; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

2014-01-01

Inspired by Taichi, we proposed rigid-flexible coupling concept and herein developed a highly promising solid polymer electrolyte comprised of poly (ethylene oxide), poly (cyano acrylate), lithium bis(oxalate)borate and robust cellulose nonwoven. Our investigation revealed that this new class solid polymer electrolyte possessed comprehensive properties in high mechanical integrity strength, sufficient ionic conductivity (3 × 10−4 S cm−1) at 60°C and improved dimensional thermostability (up to 160°C). In addition, the lithium iron phosphate (LiFePO4)/lithium (Li) cell using such solid polymer electrolyte displayed superior rate capacity (up to 6 C) and stable cycle performance at 80°C. Furthermore, the LiFePO4/Li battery could also operate very well even at an elevated temperature of 160°C, thus improving enhanced safety performance of lithium batteries. The use of this solid polymer electrolyte mitigates the safety risk and widens the operation temperature range of lithium batteries. Thus, this fascinating study demonstrates a proof of concept of the use of rigid-flexible coupling solid polymer electrolyte toward practical lithium battery applications with improved reliability and safety. PMID:25183416

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PVA:LiClO4: a robust, high Tg polymer electrolyte for adjustable ion gating of 2D materials

NASA Astrophysics Data System (ADS)

Kinder, Erich; Fullerton, Susan; CenterLow Energy Systems Technology Team

2015-03-01

Polymer electrolytes are an effective way to gate organic semiconductors and nanomaterials, such as nanotubes and 2D materials, by establishing an electrostatic double layer with large capacitance. Widely used solid electrolytes, such as those based on polyethylene oxide, have a glass transition temperature below room temperature. This permits relatively fast ion mobility at T = 23 °C, but requires a constant applied field to maintain a doping profile. Moreover, PEO-based electrolytes cannot withstand a variety of solvents, limiting its use. Here, we demonstrate a polymer electrolyte using polyvinyl alcohol (PVA) with Tg >23 °C, through which a doping profile can be defined by a potential applied when the polymer is heated above Tg, then ``locked-in'' by cooling the electrolyte to room temperature (

In Situ Formation of Polysulfonamide Supported Poly(ethylene glycol) Divinyl Ether Based Polymer Electrolyte toward Monolithic Sodium Ion Batteries.

PubMed

Zhang, Jianjun; Wen, Huijie; Yue, Liping; Chai, Jingchao; Ma, Jun; Hu, Pu; Ding, Guoliang; Wang, Qingfu; Liu, Zhihong; Cui, Guanglei; Chen, Liquan

2017-01-01

Sodium ion battery is one of the promising rechargeable batteries due to the low-cost and abundant sodium sources. In this work, a monolithic sodium ion battery based on a Na 3 V 2 (PO 4 ) 3 cathode, MoS 2 layered anode, and polyether-based polymer electrolyte is reported. In addition, a new kind of polysulfonamide-supported poly(ethylene glycol) divinyl ether based polymer electrolyte is also demonstrated for monolithic sodium ion battery via in situ preparation. The resultant polymer electrolyte exhibits relatively high ionic conductivity (1.2 mS cm -1 ) at ambient temperature, wide electrochemical window (4.7 V), and favorable mechanical strength (25 MPa). Moreover, such a monolithic Na 3 V 2 (PO 4 ) 3 /MoS 2 sodium ion battery using this polymer electrolyte delivers outstanding rate capability (up to 10 C) and superior cyclic stability (84%) after 1000 cycles at 0.5 C. What is more essential, such a polymer electrolyte based soft-package monolithic sodium ion cell can still power a red light emitting diode lamp and run finite times without suffering from any internal short-circuit failures, even in the case of a bended and wrinkled state. Considering these aspects, this work no doubt provides a new approach for the design of a high-performance polymer electrolyte toward monolithic sodium ion battery with exceptional rate capability and high safety. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2001-06-19

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

Composite solid polymer electrolyte membranes

DOEpatents

Formato, Richard M.; Kovar, Robert F.; Osenar, Paul; Landrau, Nelson; Rubin, Leslie S.

2006-05-30

The present invention relates to composite solid polymer electrolyte membranes (SPEMs) which include a porous polymer substrate interpenetrated with an ion-conducting material. SPEMs of the present invention are useful in electrochemical applications, including fuel cells and electrodialysis.

Polymer Electrolyte Through Enzyme Catalysis for High Performance Lithium-Ion Batteries

DTIC Science & Technology

1998-10-16

by block number) FIELD GROUP SUB-GROUP Polymer Electrolyte, Solid State, Enzyme Catalysis, Lithium - Ion Battery , Sol Gel, High Conductivity 19...excellent candidates for lithium - ion battery development. Furthermore, the processes used to achieve the final product yield very good mechanical properties...Objectives This research was initiated to investigate synthesis of improved polymer electrolytes for lithium - ion battery applications. The overall

Selection of new Kynar-based electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Christie, Alasdair M.; Christie, Lynn; Vincent, Colin A.

New electrolyte solution compositions have been identified for use in lithium-ion batteries after gelling with an appropriate quantity of Kynar polymer. Since the Li + conducting medium is largely the liquid electrolyte component, the assessment of these solutions as suitable lithium-ion cell candidates were investigated before adding the polymer. Selected electrolyte solutions were then used in the preparation of polymer gels. The specific conductivities of Kynar-based gels were determined as a function of salt concentration and polymer concentration. Optimised self-supporting polymer films, based on mixtures of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and lithium hexafluorophosphate (LiPF 6) or lithium tetrafluoroborate (LiBF 4), showed good high current density cycling performance when used as separators in coke and Li 1- xMn 2O 4 (spinel) half-cells.

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2002-01-01

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

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.

Composite Solid Electrolyte For Lithium Cells

NASA Technical Reports Server (NTRS)

Peled, Emmanuel; Nagasubramanian, Ganesan; Halpert, Gerald; Attia, Alan I.

1994-01-01

Composite solid electrolyte material consists of very small particles, each coated with thin layer of Lil, bonded together with polymer electrolyte or other organic binder. Material offers significant advantages over other solid electrolytes in lithium cells and batteries. Features include high ionic conductivity and strength. Composite solid electrolyte expected to exhibit flexibility of polymeric electrolytes. Polymer in composite solid electrolyte serves two purposes: used as binder alone, conduction taking place only in AI2O3 particles coated with solid Lil; or used as both binder and polymeric electrolyte, providing ionic conductivity between solid particles that it binds together.

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 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.

Influence of nanoparticle-ion and nanoparticle-polymer interactions on ion transport and viscoelastic properties of polymer electrolytes

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

Mogurampelly, Santosh; Sethuraman, Vaidyanathan; Pryamitsyn, Victor

We use atomistic simulations to probe the ion conductivities and mechanical properties of polyethylene oxide electrolytes containing Al{sub 2}O{sub 3} nanoparticles. We specifically study the influence of repulsive polymer-nanoparticle and ion-nanoparticle interactions and compare the results with those reported for electrolytes containing the polymorph β-Al{sub 2}O{sub 3} nanoparticles. We observe that incorporating repulsive nanoparticle interactions generally results in increased ionic mobilities and decreased elastic moduli for the electrolyte. Our results indicate that both ion transport and mechanical properties are influenced by the polymer segmental dynamics in the interfacial zones of the nanoparticle in the ion-doped systems. Such effects were seenmore » to be determined by an interplay between the nanoparticle-polymer, nanoparticle-ion, and ion-polymer interactions. In addition, such interactions were also observed to influence the number of dissociated ions and the resulting conductivities. Within the perspective of the influence of nanoparticles on the polymer relaxation times in ion-doped systems, our results in the context of viscoelastic properties were consistent with the ionic mobilities. Overall, our results serve to highlight some issues that confront the efforts to use nanoparticle dispersions to simultaneously enhance the conductivity and the mechanical strength of polymer electrolyte.« less

Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries

DOE PAGES

Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; ...

2016-03-31

Fluorinated carbonate solvents are pursued as liquid electrolytes for high-voltage Li-ion batteries. We report aggregation of [Li +(FEC) 3] n polymer species from fluoroethylene carbonate containing electrolytes and scrutinized the causes for this behavior.

Cationic Polymers Developed for Alkaline Fuel Cell Applications

DTIC Science & Technology

2015-01-20

into five categories: proton exchange membrane fuel cell ( PEMFC ), alkaline fuel cell (AFC), molten carbonate fuel cell (MCFC), solid oxide fuel...SOFC and PAFC belong to high temperature fuel cell, which can be applied in stationary power generation. PEMFC and AFC belong to low temperature fuel...function of the polymer electrolyte is to serve as electrolyte to transport ions between electrodes. PEMFC uses a polymer as electrolyte and works

High cation transport polymer electrolyte

DOEpatents

Gerald, II, Rex E.; Rathke, Jerome W [Homer Glen, IL; Klingler, Robert J [Westmont, IL

2007-06-05

A solid state ion conducting electrolyte and a battery incorporating same. The electrolyte includes a polymer matrix with an alkali metal salt dissolved therein, the salt having an anion with a long or branched chain having not less than 5 carbon or silicon atoms therein. The polymer is preferably a polyether and the salt anion is preferably an alkyl or silyl moiety of from 5 to about 150 carbon/silicon atoms.

Multifunctional Sandwich‐Structured Electrolyte for High‐Performance Lithium–Sulfur Batteries

PubMed Central

Qu, Hongtao; Zhang, Jianjun; Du, Aobing; Chen, Bingbing; Chai, Jingchao; Xue, Nan; Wang, Longlong; Qiao, Lixin; Wang, Chen; Zang, Xiao; Yang, Jinfeng; Wang, Xiaogang

2018-01-01

Abstract Due to its high theoretical energy density (2600 Wh kg−1), low cost, and environmental benignity, the lithium–sulfur (Li‐S) battery is attracting strong interest among the various electrochemical energy storage systems. However, its practical application is seriously hampered by the so‐called shuttle effect of the highly soluble polysulfides. Herein, a novel design of multifunctional sandwich‐structured polymer electrolyte (polymer/cellulose nonwoven/nanocarbon) for high‐performance Li‐S batteries is demonstrated. It is verified that Li‐S battery with this sandwich‐structured polymer electrolyte delivers excellent cycling stability (only 0.039% capacity decay cycle−1 on average exceeding 1500 cycles at 0.5 C) and rate capability (with a reversible capacity of 594 mA h g−1 at 4 C). These electrochemical performances are attributed to the synergistic effect of each layer in this unique sandwich‐structured polymer electrolyte including steady lithium stripping/plating, strong polysulfide absorption ability, and increased redox reaction sites. More importantly, even with high sulfur loading of 4.9 mg cm−2, Li‐S battery with this sandwich‐structured polymer electrolyte can deliver high initial areal capacity of 5.1 mA h cm−2. This demonstrated strategy here may open up a new era of designing hierarchical structured polymer electrolytes for high‐performance Li‐S batteries. PMID:29593953

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.

Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

PubMed

Pandey, Gaind P; Klankowski, Steven A; Li, Yonghui; Sun, Xiuzhi Susan; Wu, Judy; Rojeski, Ronald A; Li, Jun

2015-09-23

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Lithium-Ion Battery Program Status

NASA Technical Reports Server (NTRS)

Surampudi, S.; Huang, C. K.; Smart, M.; Davies, E.; Perrone, D.; Distefano, S.; Halpert, G.

1996-01-01

The objective of this program is to develop rechargeable Li-ion cells for future NASA missions. Applications that would benefit from this project are: new millenium spacecraft; rovers; landers; astronaut equipment; and planetary orbiters. The approach of this program is: select electrode materials and electrolytes; identify failure modes and mechanisms and enhance cycle life; demonstrate Li-ion cell technology with liquid electrolyte; select candidate polymer electrolytes for Li-ion polymer cells; and develop Li-ion polymer cell technology.

Advances in the high performance polymer electrolyte membranes for fuel cells.

PubMed

Zhang, Hongwei; Shen, Pei Kang

2012-03-21

This critical review tersely and concisely reviews the recent development of the polymer electrolyte membranes and the relationship between their properties and affecting factors like operation temperature. In the first section, the advantages and shortcomings of the corresponding polymer electrolyte membrane fuel cells are analyzed. Then, the limitations of Nafion membranes and their alternatives to large-scale commercial applications are discussed. Secondly, the concepts and approaches of the alternative proton exchange membranes for low temperature and high temperature fuel cells are described. The highlights of the current scientific achievements are given for various aspects of approaches. Thirdly, the progress of anion exchange membranes is presented. Finally, the perspectives of future trends on polymer electrolyte membranes for different applications are commented on (400 references).

High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature

NASA Astrophysics Data System (ADS)

Mindemark, Jonas; Sun, Bing; Törmä, Erik; Brandell, Daniel

2015-12-01

Incorporation of carbonate repeating units in a poly(ε-caprolactone) (PCL) backbone used as a host material in solid polymer electrolytes is found to not only suppress crystallinity in the polyester material, but also give higher ionic conductivity in a wide temperature range exceeding the melting point of PCL crystallites. Combined with high cation transference numbers, this electrolyte material has sufficient lithium transport properties to be used in battery cells that are operational at temperatures down to below 23 °C, thus clearly demonstrating the potential of using non-polyether electrolytes in high-performance all-solid lithium polymer batteries.

Carboxymethylcellulose adsorption on molybdenite: the effect of electrolyte composition on adsorption, bubble-surface collisions, and flotation.

PubMed

Kor, Mohammad; Korczyk, Piotr M; Addai-Mensah, Jonas; Krasowska, Marta; Beattie, David A

2014-10-14

The adsorption of carboxymethylcellulose polymers on molybdenite was studied using spectroscopic ellipsometry and atomic force microscopy imaging with two polymers of differing degrees of carboxyl group substitution and at three different electrolyte conditions: 1 × 10(-2) M KCl, 2.76 × 10(-2) M KCl, and simulated flotation process water of multicomponent electrolyte content, with an ionic strength close to 2.76 × 10(-2) M. A higher degree of carboxyl substitution in the adsorbing polymer resulted in adsorbed layers that were thinner and with more patchy coverage; increasing the ionic strength of the electrolyte resulted in increased polymer layer thickness and coverage. The use of simulated process water resulted in the largest layer thickness and coverage for both polymers. The effect of the adsorbed polymer layer on bubble-particle attachment was studied with single bubble-surface collision experiments recorded with high-speed video capture and image processing and also with single mineral molybdenite flotation tests. The carboxymethylcellulose polymer with a lower degree of substitution resulted in almost complete prevention of wetting film rupture at the molybdenite surface under all electrolyte conditions. The polymer with a higher degree of substitution prevented rupture only when adsorbed from simulated process water. Molecular kinetic theory was used to quantify the effect of the polymer on the dewetting dynamics for collisions that resulted in wetting film rupture. Flotation experiments confirmed that adsorbed polymer layer properties, through their effect on the dynamics of bubble-particle attachment, are critical to predicting the effectiveness of polymers used to prevent mineral recovery in flotation.

Optimized performance of quasi-solid-state DSSC with PEO-bismaleimide polymer blend electrolytes filled with a novel procedure.

PubMed

Lee, Dong Ha; Sun, Kyung Chul; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2014-12-01

Dye-sensitized solar cell (DSSC) is an attractive renewable energy technology currently under intense investigation. Electrolyte plays an important role in the photovoltaic performance of the DSSCs and many efforts have been contributed to study different kinds of electrolytes with various characteristics such as liquid electrolytes, polymer electrolytes and so on. In this study, DSSC is developed by using quasi-solid electrolyte and a novel procedure is adopted for filling this electrolyte. The quasi-solid-state electrolyte was prepared by mixing Poly ethylene oxide (PEO) and bismaleimide together and constitution was taken as PEO (15 wt%) at various bismaleimide concentrations (1, 3, 5 wt%). The novel procedure of filling electrolyte consists of three major steps (first step: filling liquid electrolyte, second step: vaporization of liquid electrolyte, third step: refilling quasi-solid-state electrolyte). The electrochemical and photovoltaic performances of DSSCs with these electrolytes were also investigated. The electrochemical impedance spectroscopy (EIS) indicated that TiO2/Dye/electrolyte impedance is reduced and electron lifetime is increased, and consequently efficiency of cell has been improved after using this novel procedure. The photovoltaic power conversion efficiency of 6.39% has been achieved under AM 1.5 simulated sunlight (100 W/cm2) through this novel procedure and by using specified blend of polymers.

Incorporating allylated lignin-derivatives in thiol-ene gel-polymer electrolytes.

PubMed

Baroncini, Elyse A; Stanzione, Joseph F

2018-07-01

Growing environmental and economic concerns as well as the uncertainty that accompanies finite petrochemical resources contributes to the increase in research and development of bio-based, renewable polymers. Concurrently, industrial and consumer demand for smaller, safer, and more flexible technologies motivates a global research effort to improve electrolytic polymer separators in lithium-ion batteries. To incorporate the aromatic structural advantages of lignin, a highly abundant and renewable resource, into gel-polymer electrolytes, lignin-derived molecules, vanillyl alcohol and gastrodigenin are functionalized and UV-polymerized with multi-functional thiol monomers. The resulting thin, flexible, polymer films possess glass transition temperatures ranging from -42.1°C to 0.3°C and storage moduli at 25°C ranging from 1.90MPa to 10.08MPa. The crosslinked polymer films swollen with electrolyte solution impart conductivities in the range of 7.04×10 -7 to 102.73×10 -7 Scm -1 . Thiol molecular weight has the most impact on the thermo-mechanical properties of the resulting films while polymer crosslink density has the largest effect on conductivity. The conducting abilities of the bio-based gel-polymer electrolytes in this study prove the viability of lignin-derived feedstock for use in lithium-ion battery applications and reveal structurally and thermally desirable traits for future work. Copyright © 2018 Elsevier B.V. All rights reserved.

Tuning filler shape, surface chemistry and ion content in nanofilled polymer electrolytes

NASA Astrophysics Data System (ADS)

Ganapatibhotla, Lalitha V. N. R.

We investigate how nanofiller surface chemistry and aspect ratio affect the performance of nanofilled solid polymer electrolytes. Polymer-based electrolytes are an attractive alternative to the organic electrolytes currently used in lithium ion batteries. We characterize acidic nanoparticle filled electrolytes and compare them to neutral particle-filled electrolytes previously measured in our lab. Dielectric spectroscopy measurements indicate that the highest increase in conductivity occurs at the eutectic composition (EO/Li=10) and is independent of filler surface chemistry. We measure PEO dynamics using quasi-elastic neutron scattering and do not observe any change in polymer dynamics with particle surface chemistry. When we examine the elastic incoherent structure factor associated with the rotational process, fillers are found to restrict the rotation of the highly conducting PEO6:LiClO4 tunnels. At the eutectic composition, these tunnels are stabilized at the filler surface even above PEO melting temperature. Marginal stability theory predicts formation of alternating layers of coexisting phases at the eutectic composition. We propose a new mechanism, via stabilization of alternating layers of PEO and highly conducting PEO 6:LiClO4 tunnels at the filler surface. When compared to spherical particles, more such structures would be stabilized at a filler surface with high aspect ratio. Consistent with this hypothesis, neutral gamma-Al2O3 nanowhiskers (2-4 nm in diameter and 200-400 nm in length) intensify the effect of neutral gamma-Al 2O3 nanoparticles. The diameters of the two fillers are similar, but the change in aspect ratio (1 to 100) improves conductivity by a factor of 5. This enhancement occurs at battery operation temperatures! Although the change in aspect ratio does not affect thermal transitions and segmental dynamics at optimal whisker loading, the rotation of PEO6 remnants is distinct at the eutectic composition. Because the mechanism by which nanofillers enhance conductivity is related to stabilization of conducting structures at the filler-electrolyte interface, we determine the interface morphology using neutron reflectometry. For this, we spin-coat the unfilled electrolytes EO/Li = 8, 10 on sapphire substrate, which has the same surface chemistry as alpha-Al2O3. When freshly-spin coated on sapphire substrate, the non-eutectic sample does not exhibit any segregation of layers. The freshly spin-coated eutectic sample forms layers with alternating high and low salt concentrations, very similar to the eutectic lamellae predicted by the marginal stability theory for eutectic solidification. Such lamellae do not develop further when the sample is annealed at eutectic temperature and the salt concentration in the polymer decreases gradually away from the surface of sapphire. To take fullest advantage of the surface mechanism and obtain larger increases in conductivity we tailor the aspect ratio of high aspect ratio fillers. Commercial availability of alumina nanowhiskers is limited to neutral surface chemistry and aspect ratio of 100, cellulose nanowhiskers provide a model system where a wide range of surface chemistries may be accessed with variable aspect ratio. We synthesized cellulose whiskers of two different aspect ratios [cotton whiskers: aspect ratio ˜ 10, acetobacter whiskers: aspect ratio ˜ 200] and tested their influence on conductivity and morphology of polymer electrolytes. Similar to all fillers studied in this work, both types of cellulose whiskers provide highest increase in conductivity at the eutectic composition, with the longer acetobacter whiskers providing a marginally higher increase than the cotton whiskers. Although both cellulose whiskers do not alter the crystallinity or glass transition temperature at the optimal 1 wt% loading, they amplify the faint cold crystallization behavior observed in the unfilled eutectic electrolyte without changing the overall crystallinity. At the non-eutectic compositions, cellulose whiskers behave similar to the acidic nanoparticles. To determine the function of nanofillers in entire composition range of the phase diagram, we extend the range of measurements on the nanofilled PEO+LiClO4 electrolyte to EO/Li = 4 to 100. Because PEO+LiAsF 6 electrolytes have similar phase diagram as the PEO+LiClO4 electrolytes, we augment the study of nanofilled PEO+LiAsF6 complexes to the PEO+LiClO4 electrolytes. At compositions near the high and low ends of the phase diagram, the effect of nanofillers on conductivity is governed by reduction in crystallinity of PEO and PEO-salt complexes. In the absence of PEO6, fillers interact directly with PEO and suppress crystallization. This is consistent with the reflectometry experiment where sapphire surface prefers to interact with the salt-rich layers. Around the eutectic composition fillers restrict the highly conducting PEO6 complex at their surface and any increase in conductivity is due to stabilization of these conducting tunnels. For room temperature applications, lithium hexafluoroarsenate seems to be the better salt than lithium perchlorate. At temperatures higher than the eutectic temperature (50°C), conductivity levels off at the value set by the eutectic composition. (Abstract shortened by ProQuest.).

The influence of TiO2 composition in LiBOB electrolyte polymer composite membrane characteristics for lithium ion batteries applications

NASA Astrophysics Data System (ADS)

Lestariningsih, T.; Sabrina, Q.; Wigayati, E. M.

2018-03-01

Characterization of the composite membrane of LiBOB electrolyte polymers made from poly (vinylidene fluoride co-hexafluororopylene) (PVdF-HFP) as the polymer, LiBOB or LiB(C2O4)2 as electrolyte salt and titanium dioxide (TiO2) as ceramic filler of three different concentrations have been done. Sample of membrane was prepared using solution casting technique. Microstructural study by SEM shows non-uniform distribution of pore over the surface of the sample. X-ray structural analysis, impedance spectroscopy, and cyclic voltammetry (CV) studies were carried out. Membrane composite polymer of LiBOB electrolyte without additional ceramic filler with composition of 70% polymer, 30% LiBOB, and 0% TiO2 has the greatest conductivity for forming amorphous phase and is compatible with material membrane composite. Meanwhile, sample with 70% polymer composition, 28% LiBOB and 2% TiO2 shows oxidation reaction at the most perfect discharge despite very slow current speed.

Transparent, flexible supercapacitors from nano-engineered carbon films.

PubMed

Jung, Hyun Young; Karimi, Majid B; Hahm, Myung Gwan; Ajayan, Pulickel M; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Transparent, flexible supercapacitors from nano-engineered carbon films

PubMed Central

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications. PMID:23105970

Transparent, flexible supercapacitors from nano-engineered carbon films

NASA Astrophysics Data System (ADS)

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-10-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Broadband Dielectric Spectroscopy and Quasi-Elastic Neutron Scattering on Single-Ion Polymer Conductors

NASA Astrophysics Data System (ADS)

Soles, Christopher; Peng, Hua-Gen; Page, Kirt; Snyder, Chad; Pandy, Ashoutosh; Jeong, Youmi; Runt, James; NIST Collaboration; Pennsylvania Collaboration

2011-03-01

The application of solid polymer electrolytes in rechargeable batteries has not been fully realized after decades of research due to its low conductivity. Dramatic increases of the ion conductivity are needed and this progress requires the understanding of conduction mechanism. We address this topic in two fronts, namely, the effect of plasticizer additives and geometric confinement on the charge transfer mechanism. To this end, we combine broadband dielectric spectroscopy (BDS) to characterize the ion mobility and quasi-elastic neutron scattering (QENS) to quantify segmental motion on a single-ion model polymer electrolyte. Deuterated small molecules were used as plasticizers so that the segmental motion of the polymer electrolyte could be monitored by QENS to understand the mechanism behind the increased conductivity. Anodic aluminum oxide (AAO) membranes with well defined channel sizes are used as the matrix to study the transport of ions solvated in a 1D polymer 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

A plasticized polymer-electrolyte-based photoelectrochemical solar cell

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

Mao, D.; Ibrahim, M.A.; Frank, A.J.

1998-01-01

A photoelectrochemical solar cell based on an n-GaAs/polymer-redox-electrolyte junction is reported. Di(ethylene glycol) ethyl ether acrylate containing ferrocene as a redox species and benzoin methyl ether as a photoinitiator is polymerized in situ. Propylene carbonate is used as a plasticizer to improve the conductivity of the polymer redox electrolyte. For thin (1 {micro}m) polymer electrolytes, the series resistance of the cell is negligible. However, the short-circuit photocurrent density of the cell at light intensities above 10 mW/cm{sup 2} is limited by mass transport of redox species within the polymer matrix. At a light intensity of 70 mW/cm{sup 2}, a moderatemore » light-to-electrical energy conversion efficiency (3.1%) is obtained. The interfacial charge-transfer properties of the cell in the dark and under illumination are studied.« less

Impact of electrostatics on the chemodynamics of highly charged metal-polymer nanoparticle complexes.

PubMed

Duval, Jérôme F L; Farinha, José Paulo S; Pinheiro, José P

2013-11-12

In this work, the impact of electrostatics on the stability constant, the rate of association/dissociation, and the lability of complexes formed between Cd(II), Pb(II), and carboxyl-modified polymer nanoparticles (also known as latex particles) of radius ∼ 50 nm is systematically investigated via electroanalytical measurements over a wide range of pHs and NaNO3 electrolyte concentrations. The corresponding interfacial structure and key electrostatic properties of the particles are independently derived from their electrokinetic response, successfully interpreted using soft particle electrohydrodynamic formalism, and complemented by Förster resonance energy transfer (FRET) analysis. The results underpin the presence of an ∼0.7-1 nm thick permeable and highly charged shell layer at the surface of the polymer nanoparticles. Their electrophoretic mobility further exhibits a minimum versus NaNO3 concentration due to strong polarization of the electric double layer. Integrating these structural and electrostatic particle features with recent theory on chemodynamics of particulate metal complexes yields a remarkable recovery of the measured increase in complex stability with increasing pH and/or decreasing solution salinity. In the case of the strongly binding Pb(II), the discrepancy at pH > 5.5 is unambiguously assigned to the formation of multidendate complexes with carboxylate groups located in the particle shell. With increasing pH and/or decreasing electrolyte concentration, the theory further predicts a kinetically controlled formation of metal complexes and a dramatic loss of their lability (especially for lead) on the time-scale of diffusion toward a macroscopic reactive electrode surface. These theoretical findings are again shown to be in agreement with experimental evidence.

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.

Effect of polymer electrolyte on the performance of natural dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Adel, R.; Abdallah, T.; Moustafa, Y. M.; Al-sabagh, A. M.; Talaat, H.

2015-10-01

Polymer electrolyte based on polyacrylonitrile (PAN), Ethylene Carbonate (EC) and Acetonitrile (ACN) mixed with Potassium Iodide and Iodine in liquid and thin film forms were employed in natural dye sensitized solar cells (NDSSCs). Three natural dyes; black berry, hibiscus and rose are used as the sensitizing dye. The NDSSCs used, follow the configuration: FTO/TiO2/Natural Dye/Electrolyte/ Carbon/FTO. The liquid form polymer electrolyte with black berry natural dye gives an increase of 111% in short circuit photocurrent density (Jsc), 17.5% to open circuit voltage (Voc), fill factor of 0.57 ± 0.05 and three times increase in the conversion efficiency of 0.242 ± 0.012% compared to the iodine electrolyte.

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.

DNA Based Electrolyte/Separator for Lithium Battery Application (Postprint)

DTIC Science & Technology

2015-10-07

Lithium - ion or sodium- ion ) batteries and the second are the gel polymer electrolyte (GPE) metal- ion batteries also known as metal- ion polymer...AFRL-RX-WP-JA-2016-0302 DNA BASED ELECTROLYTE/SEPARATOR FOR LITHIUM BATTERY APPLICATION (POSTPRINT) Jitendra Kumar1, Fahima...BASED ELECTROLYTE/SEPARATOR FOR LITHIUM BATTERY APPLICATION (POSTPRINT) 5a. CONTRACT NUMBER FA8650-15-D-5405-0001 5b. GRANT NUMBER 5c. PROGRAM

Fuel cell electrolyte membrane with basic polymer

DOEpatents

Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

2012-12-04

The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

Fuel cell electrolyte membrane with basic polymer

DOEpatents

Larson, James M.; Pham, Phat T.; Frey, Matthew H.; Hamrock, Steven J.; Haugen, Gregory M.; Lamanna, William M.

2010-11-23

The present invention is an electrolyte membrane comprising an acid and a basic polymer, where the acid is a low-volatile acid that is fluorinated and is either oligomeric or non-polymeric, and where the basic polymer is protonated by the acid and is stable to hydrolysis.

A comparative study of nano-SiO2 and nano-TiO2 fillers on proton conductivity and dielectric response of a silicotungstic acid-H3PO4-poly(vinyl alcohol) polymer electrolyte.

PubMed

Gao, Han; Lian, Keryn

2014-01-08

The effects of nano-SiO2 and nano-TiO2 fillers on a thin film silicotungstic acid (SiWA)-H3PO4-poly(vinyl alcohol) (PVA) proton conducting polymer electrolyte were studied and compared with respect to their proton conductivity, environmental stability, and dielectric properties, across a temperature range from 243 to 323 K. Three major effects of these fillers have been identified: (a) barrier effect; (b) intrinsic dielectric constant effect; and (c) water retention effect. Dielectric analyses were used to differentiate these effects on polymer electrolyte-enabled capacitors. Capacitor performance was correlated to electrolyte properties through dielectric constant and dielectric loss spectra. Using a single-ion approach, proton density and proton mobility of each polymer electrolyte were derived as a function of temperature. The results allow us to deconvolute the different contributions to proton conductivity in SiWA-H3PO4-PVA-based electrolytes, especially in terms of the effects of fillers on the dynamic equilibrium of free protons and protonated water in the electrolytes.

Ohm's Law, Batteries, and the Clean Energy Landscape

NASA Astrophysics Data System (ADS)

Balsara, Nitash

The need for creating safe electrolytes for lithium batteries is significant given the continued safety problems associated with current lithium-ion batteries. Nonflammable polymer electrolytes offer a possible solution but the rate of lithium ion transport is too low for practical applications. In this talk, I will discuss some of the fundamental factors that limit ion transport in polymers. Polymer electrolytes obey Ohm's Law, i.e. in the limit of small applied potentials, the current generated at steady state is proportional to the applied potential. Factors that determine the current generated will be determined using the continuum theory of Newman. Independent measurements of ion diffusion by pulsed-field gradient NMR will also be presented. The talk will end with a discussion of the possibility of commercializing all-solid batteries with polymer electrolytes.

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.

Negative Transference Numbers in Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Timachova, Ksenia; Balsara, Nitash

Energy density and safety of conventional lithium-ion batteries is limited by the use of flammable organic liquids as a solvent for lithium salts. Polymer electrolytes have the potential to address both limitations. The poor performance of batteries with polymer electrolytes is generally attributed to low ionic conductivity. The purpose of our work is to show that another transport property, the cation transference number, t +, of polymer electrolytes is fundamentally different from that of conventional electrolytes. Our experimental approach, based on concentrated solution theory, indicates that t + of mixtures of poly(ethylene oxide) and LiTFSI salt are negative over most of the accessible concentration window. In contrast, approaches based on dilute solution theory suggest that t + in the same system is positive. In addition to presenting a new approach for determining t +, we also present data obtained from the steady-state current method, pulsed-field-gradient NMR, and the current-interrupt method. Discrepancies between different approaches are resolved. Our work implies that in the absence of concentration gradients, the net fluxes of both cations and anions are directed toward the positive electrode. Conventional liquid electrolytes do not suffer from this constraint.

Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

McIntosh, Lucas D.

Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the disordered structure observed in diblock polymer melts near the order-disorder transition. In the resulting solid PEMs, the conductivity and modulus are both high, exceeding the 1 mS/cm and approaching the 1 GPa metrics, respectively, often cited for lithium-metal batteries. In the final chapter, an alternative synthetic route to generate nanostructured PEMs is presented. This strategy relies on the formation of a thermodynamically stable network morphology exhibited by a triblock terpolymer prepared with crosslinking moieties along the backbone. Although the mechanical properties of the resulting PEM are excellent, the conductivity is found to be somewhat limited by network defects that result from the solvent-casting procedure.

Liquid-free rechargeable Li polymer battery

NASA Astrophysics Data System (ADS)

Matsui, S.; Muranaga, T.; Higobashi, H.; Inoue, S.; Sakai, T.

Safety is a key concern for high-power energy storage systems such as will be required for electric vehicles. Present lithium ion batteries, which use a flammable organic liquid electrolyte, lack inherent safety. Our approach in solving this problem is to replace the liquid electrolyte with a liquid-free polymer electrolyte. Data of the composition of the positive electrode, charge-discharge and cycle-life capability are presented. The cell using metallic lithium anode and crosslinked polymer electrolyte P(EO/MEEGE/AGE)-LiTFSI showed a discharge capacity of 134 mAh g -1 of LiCoO 2 at 60°C and 140 mAh g -1 at 140°C.

Electrodeposition of polymer electrolyte in nanostructured electrodes for enhanced electrochemical performance of thin-film Li-ion microbatteries

NASA Astrophysics Data System (ADS)

Salian, Girish D.; Lebouin, Chrystelle; Demoulin, A.; Lepihin, M. S.; Maria, S.; Galeyeva, A. K.; Kurbatov, A. P.; Djenizian, Thierry

2017-02-01

We report that electrodeposition of polymer electrolyte in nanostructured electrodes has a strong influence on the electrochemical properties of thin-film Li-ion microbatteries. Electropolymerization of PMMA-PEG (polymethyl methacrylate-polyethylene glycol) was carried out on both the anode (self-supported titania nanotubes) and the cathode (porous LiNi0.5Mn1.5O4) by cyclic voltammetry and the resulting electrode-electrolyte interface was examined by scanning electron microscopy. The electrochemical characterizations performed by galvanostatic experiments reveal that the capacity values obtained at different C-rates are doubled when the electrodes are completely filled by the polymer electrolyte.

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

NASA Technical Reports Server (NTRS)

Subbarao, S. (Editor); Koch, V. R. (Editor); Owens, B. B. (Editor); Smyrl, W. H. (Editor)

1990-01-01

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

Performance assessment of polymer based electrodes for in vitro electrophysiological sensing: the role of the electrode impedance

NASA Astrophysics Data System (ADS)

Medeiros, Maria C. R.; Mestre, Ana L. G.; Inácio, Pedro M. C.; Santos, José M. L.; Araujo, Inês M.; Bragança, José; Biscarini, Fabio; Gomes, Henrique L.

2016-09-01

Conducting polymer electrodes based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) are used to record extracellular signals from autonomous cardiac contractile cells and glioma cell cultures. The performance of these conducting polymer electrodes is compared with Au electrodes. A small-signal impedance analysis shows that in the presence of an electrolyte, both Au and polymer electrodes establish high capacitive double-layers. However, the polymer/electrolyte interfacial resistance is 3 orders of magnitude lower than the resistance of the metal/electrolyte interface. The polymer low interfacial resistance minimizes the intrinsic thermal noise and increases the system sensitivity. However, when measurements are carried out in current mode a low interfacial resistance partially acts as a short circuit of the interfacial capacitance, this affects the signal shape.

Solid Polymer Electrolyte (SPE) fuel cell technology program

NASA Technical Reports Server (NTRS)

1979-01-01

The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

Alkaline polymer electrolyte membranes for fuel cell applications.

PubMed

Wang, Yan-Jie; Qiao, Jinli; Baker, Ryan; Zhang, Jiujun

2013-07-07

In this review, we examine the most recent progress and research trends in the area of alkaline polymer electrolyte membrane (PEM) development in terms of material selection, synthesis, characterization, and theoretical approach, as well as their fabrication into alkaline PEM-based membrane electrode assemblies (MEAs) and the corresponding performance/durability in alkaline polymer electrolyte membrane fuel cells (PEMFCs). Respective advantages and challenges are also reviewed. To overcome challenges hindering alkaline PEM technology advancement and commercialization, several research directions are then proposed.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

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

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

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.

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

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.

Micellar Electrolytes in Organic Electrochemical Transistors

NASA Astrophysics Data System (ADS)

Cicoira, Fabio; Giuseppe, Tarabella; Nanda, Gaurav; Iannotta, Salvatore; Santato, Clara

2012-02-01

Organic electrochemical transistors (OECTs) are promising for applications in sensing and bioelectronics. OECTs consist of a conducting polymer film (transistor channel) in contact with an electrolyte. A gate electrode immersed in the electrolyte controls the doping/dedoping level of the conducting polymer. OECTs can be operated in aqueous electrolytes, making possible the implementation of organic electronic materials at the interface with biology. The inherent signal amplification of OECTs has the potential to yield sensors with low detection limits and high sensitivity. In this talk we will present recent studies on OECTs using ionic surfactants (such as hexadecyl-trimethyl-ammonium bromide) as electrolytes. As the conducting polymer we used PEDOT:PSS, i.e. (Poly,3-4 ethylenedioxythiopene) doped with Poly(styrene sulphonate). Interestingly, ionic surfactant electrolytes result in large transistor current modulation, especially beyond the critical micellar concentration (CMC). Since micelles play a primary role in biological processes and drug-delivery systems, the use for micellar electrolytes opens new exciting opportunities for the use of OECTs in bioelectronics.

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.

Studies on the effect of dispersoid(ZrO2) in PVdF-co-HFP based gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Sivakumar, M.; Subadevi, R.; Muthupradeepa, R.

2013-06-01

Gel polymer electrolytes containing poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) / Lithium bis(trifluoromethane sulfon)imide (LiTFSI) / mixture of ethylene carbonate and propylene carbonate (EC+PC) with different concendration of ZrO2 has been prepared using the solution casting technique. The conductivity of the prepared electrolyte sample has been determined by AC impedance technique in the range 303-353K. The temperature dependent ionic conductivity plot seems to obey VTF relation. The maximum ionic conductivity value of 4.46 × 10-3S/cm has been obtained for PVdF-co-HFP(32%) - LiTFSI(8%) - EC+PC (60%) + ZrO2(6wt%) based polymer electrolyte. The surface morphology of the prepared electrolyte sample has been studied using SEM.

A Polymer Electrolyte for Dye-Sensitized Solar Cells Based on a Poly(Polyvinylidenefluoride-Co-Hexafluoropropylene)/Hydroxypropyl Methyl Cellulose Blend

NASA Astrophysics Data System (ADS)

Won, Lee Ji; Kim, Jae Hong; Thogiti, Suresh

2018-05-01

A novel polymer blend electrolyte for dye-sensitized solar cells (DSSCs) was synthesized by quasi-solidifying a liquid-based electrolyte containing an iodide/triiodide redox couple and supporting salts with a mixture of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and indigenous hydroxypropyl methyl cellulose (HPMC). A high ionic conductivity of 8.8 × 10-4 S cm-1 was achieved after introducing 5 wt% of HPMC with respect to the weight of PVDH-HFP. DSSCs were fabricated using gel polymer blend electrolytes, and the J-V characteristics of the fabricated devices were analyzed. Under optimal conditions, the photovoltaic conversion efficiency of cells with the novel HPMC-blended gel electrolyte (5.34%) was significantly greater than that of cells without HPMC (3.97%).

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.

The interplay of ion crosslinking, free ion content, and polymer mobility in PEO-based single-ion conductors

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2010-03-01

We use molecular dynamics simulation to study ion clustering and dynamics in ion containing polymers. This PEO based single-ion conducting ionomer serves as a model system for understanding cation transport in solid state polymer electrolytes (SPEs). Although small-angle x-ray scattering does not show an ionomer peak, we observer various cation-anion complexes in the simulation, suggesting ionomer backbones are crosslinked through ion complexes. These crosslinks reduce the adjacent PEO mobility resulting in a symmetric mobility gradient along the PEO chain. We vary the cation-anion interaction in the simulation to observe the interplay of cation-anion association, polymer mobility and cation motion. Cation-anion association controls the number of free ions, which is important in ionic conductivity when these materials are used as SPEs. Polymer mobility controls how fast the free ions are able to move through the SPE. High conductivity requires both a high free ion content and fast polymer motion. To understand the connection between the two, we ``tune'' the force field in order to manipulate the free ion content and observe the influence on PEO dynamics.

Solid polymer battery electrolyte and reactive metal-water battery

DOEpatents

Harrup, Mason K.; Peterson, Eric S.; Stewart, Frederick F.

2000-01-01

In one implementation, a reactive metal-water battery includes an anode comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

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.

Status and applicability of solid polymer electrolyte technology to electrolytic hydrogen and oxygen production

NASA Technical Reports Server (NTRS)

Titterington, W. A.

1973-01-01

The solid polymer electrolyte (SPE) water electrolysis technology is presented as a potential energy conversion method for wind driven generator systems. Electrolysis life and performance data are presented from laboratory sized single cells (7.2 sq in active area) with high cell current density selected (1000 ASF) for normal operation.

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.

Poly(arylene)-based anion exchange polymer electrolytes

DOEpatents

Kim, Yu Seung; Bae, Chulsung

2015-06-09

Poly(arylene) electrolytes including copolymers lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte

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

Vassal, N.; Salmon, E.; Fauvarque, J.F.

1999-01-01

Sealed alkaline solid polymer electrolyte nickel/metal hydride laboratory cells have been constructed and tested to evaluate their properties. Studies of the cycle life, self-discharge, and behavior of cells at different temperatures were carried out. The first results on the electrochemical behavior of an alkaline solid polymer electrolyte [based on poly(ethylene oxide), potassium hydroxide, and water] medium are presented here and show good reversibility of this all-solid-state system for more than 500 cycles, without significant loss of capacity and with a reasonable average discharge efficiency (close to 80%). The temperature-dependence study allowed the determination of optimum operating conditions between 0 andmore » 40 C. Characteristics of the solid polymer electrolyte based Ni/MH cells are compared to those of several other rechargeable battery systems.« less

Novel electrolyte chemistries for Mg-Ni rechargeable batteries.

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

Garcia-Diaz, Brenda; Kane, Marie; Au, Ming

2010-10-01

Commercial hybrid electric vehicles (HEV) and battery electric vehicles (BEV) serve as means to reduce the nation's dependence on oil. Current electric vehicles use relatively heavy nickel metal hydride (Ni-MH) rechargeable batteries. Li-ion rechargeable batteries have been developed extensively as the replacement; however, the high cost and safety concerns are still issues to be resolved before large-scale production. In this study, we propose a new highly conductive solid polymer electrolyte for Mg-Ni high electrochemical capacity batteries. The traditional corrosive alkaline aqueous electrolyte (KOH) is replaced with a dry polymer with conductivity on the order of 10{sup -2} S/cm, as measuredmore » by impedance spectroscopy. Several potential novel polymer and polymer composite candidates are presented with the best-performing electrolyte results for full cell testing and cycling.« less

Micromold methods for fabricating perforated substrates and for preparing solid polymer electrolyte composite membranes

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

Mittelsteadt, Cortney; Argun, Avni; Laicer, Castro

In polymer electrolyte membrane (PEM) fuel cells and electrolyzes, attaining and maintaining high membrane conductivity and durability is crucial for performance and efficiency. The use of low equivalent weight (EW) perfluorinated ionomers is one of the few options available to improve membrane conductivity. However, excessive dimensional changes of low EW ionomers upon application of wet/dry or freeze/thaw cycles yield catastrophic losses in membrane integrity. Incorporation of ionomers within porous, dimensionally-stable perforated polymer electrolyte membrane substrates provides improved PEM performance and longevity. The present invention provides novel methods using micromolds to fabricate the perforated polymer electrolyte membrane substrates. These novel methodsmore » using micromolds create uniform and well-defined pore structures. In addition, these novel methods using micromolds described herein may be used in batch or continuous processing.« less

Electrolyte-gated transistors based on conducting polymer nanowire junction arrays.

PubMed

Alam, Maksudul M; Wang, Jun; Guo, Yaoyao; Lee, Stephanie P; Tseng, Hsian-Rong

2005-07-07

In this study, we describe the electrolyte gating and doping effects of transistors based on conducting polymer nanowire electrode junction arrays in buffered aqueous media. Conducting polymer nanowires including polyaniline, polypyrrole, and poly(ethylenedioxythiophene) were investigated. In the presence of a positive gate bias, the device exhibits a large on/off current ratio of 978 for polyaniline nanowire-based transistors; these values vary according to the acidity of the gate medium. We attribute these efficient electrolyte gating and doping effects to the electrochemically fabricated nanostructures of conducting polymer nanowires. This study demonstrates that two-terminal devices can be easily converted into three-terminal transistors by simply immersing the device into an electrolyte solution along with a gate electrode. Here, the field-induced modulation can be applied for signal amplification to enhance the device performance.

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.

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.

Lithium Polymer Electrolytes and Solid State NMR

NASA Technical Reports Server (NTRS)

Berkeley, Emily R.

2004-01-01

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Polymer-electrolyte-gated nanowire synaptic transistors for neuromorphic applications

NASA Astrophysics Data System (ADS)

Zou, Can; Sun, Jia; Gou, Guangyang; Kong, Ling-An; Qian, Chuan; Dai, Guozhang; Yang, Junliang; Guo, Guang-hua

2017-09-01

Polymer-electrolytes are formed by dissolving a salt in polymer instead of water, the conducting mechanism involves the segmental motion-assisted diffusion of ion in the polymer matrix. Here, we report on the fabrication of tin oxide (SnO2) nanowire synaptic transistors using polymer-electrolyte gating. A thin layer of poly(ethylene oxide) and lithium perchlorate (PEO/LiClO4) was deposited on top of the devices, which was used to boost device performances. A voltage spike applied on the in-plane gate attracts ions toward the polymer-electrolyte/SnO2 nanowire interface and the ions are gradually returned after the pulse is removed, which can induce a dynamic excitatory postsynaptic current in the nanowire channel. The SnO2 synaptic transistors exhibit the behavior of short-term plasticity like the paired-pulse facilitation and self-adaptation, which is related to the electric double-effect regulation. In addition, the synaptic logic functions and the logical function transformation are also discussed. Such single SnO2 nanowire-based synaptic transistors are of great importance for future neuromorphic devices.

Preparation of the polyelectrolyte complex hydrogel of biopolymers via a semi-dissolution acidification sol-gel transition method and its application in solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Zhao, Jian; Chen, Yu; Yao, Ying; Tong, Zong-Rui; Li, Pu-Wang; Yang, Zi-Ming; Jin, Shao-Hua

2018-02-01

Hydrogels have drawn many attentions as the solid-state electrolytes in flexible solid-state supercapacitors (SCs) recently. Among them, the polyelectrolyte complex hydrogel (PECH) electrolytes of natural polymers are more competitive because of their environmentally friendly property and low cost. However, while mixing two biopolymer solutions with opposite charges, the strong electrostatic interactions between the cationic and anionic biopolymers may result in precipitates instead of hydrogels. Here we report a novel method, semi-dissolution acidification sol-gel transition (SD-A-SGT), for the preparation of the PECH of chitosan (CTS) and sodium alginate (SA), with the controllable sol-gel transition and uniform composition and successfully apply it as the hydrogel electrolyte of solid-state supercapacitors (SCs). The CTS-SA PECH exhibits an extremely high ionic conductivity of 0.051 S·cm-1 and reasonable mechanical properties with a tensile strength of 0.29 MPa and elongation at break of 109.5%. The solid-state SC fabricated with the CTS-SA PECH and conventional polyaniline (PANI) nanowire electrodes provided a high specific capacitance of 234.6 F·g-1 at 5 mV·s-1 and exhibited excellent cycling stability with 95.3% capacitance retention after 1000 cycles. Our work may pave a novel avenue to the preparation of biodegradable PECHs of full natural polymers, and promote the development of environmentally friendly electronic devices.

The electrical conductivities of polyimide and polyimide/Li triflate composites: An a.c. impedance study

NASA Astrophysics Data System (ADS)

Aziz, Nor Diyana Abdul; Kamarulzaman, Norlida; Subban, Ri Hanum Yahaya; Hamzah, Ahmad Sazali; Ahmed, Azni Zain; Osman, Zurina; Rusdi, Roshidah; Kamarudin, Norashikin; Mohalid, Norhanim; Romli, Ahmad Zafir; Shaameri, Zurina

2017-09-01

Polymer electrolytes have been an essential area of research for many decades. One of the reasons was the need to find new electrolyte materials suitable for device applications like solid-state batteries, supercapacitors, fuel cells, etc. with enhanced characteristics. For more than 40 years, polyimide has been known as a super-engineering plastic due to its excellent thermal stability (Tg > 250 °C) and mechanical properties. Therefore, in an effort to develop new polymer electrolytes, polyimide as a polymer matrix was chosen. Composite films of the polymer doped with lithium salt, LiCF3SO3 was prepared. These PI based polymer electrolyte films were investigated by the alternating current (a.c.) impedance spectroscopy method in the temperature range from 300 K to 373 K. It was observed that conductivity increased with the increase of temperature and amount of doping salt. Alternatively, the activation energy (Ea) of the composite films decreased with the increase of the doping salt, LiCF3SO3.

The electrolyte challenge for a direct methanol-air polymer electrolyte fuel cell operating at temperatures up to 200 C

NASA Technical Reports Server (NTRS)

Savinell, Robert; Yeager, Ernest; Tryk, Donald; Landau, Uziel; Wainright, Jesse; Gervasio, Dominic; Cahan, Boris; Litt, Morton; Rogers, Charles; Scherson, Daniel

1993-01-01

Novel polymer electrolytes are being evaluated for use in a direct methanol-air fuel cell operating at temperatures in excess of 100 C. The evaluation includes tests of thermal stability, ionic conductivity, and vapor transport characteristics. The preliminary results obtained to date indicate that a high temperature polymer electrolyte fuel cell is feasible. For example, Nafion 117 when equilibrated with phosphoric acid has a conductivity of at least 0.4 Omega(exp -1)cm(exp -1) at temperatures up to 200 C in the presence of 400 torr of water vapor and methanol vapor cross over equivalent to 1 mA/cm(exp 2) under a one atmosphere methanol pressure differential at 135 C. Novel polymers are also showing similar encouraging results. The flexibility to modify and optimize the properties by custom synthesis of these novel polymers presents an exciting opportunity to develop an efficient and compact methanol fuel cell.

Multifunctional structural lithium ion batteries for electrical energy storage applications

NASA Astrophysics Data System (ADS)

Javaid, Atif; Zeshan Ali, Muhammad

2018-05-01

Multifunctional structural batteries based on carbon fiber-reinforced polymer composites are fabricated that can bear mechanical loads and act as electrochemical energy storage devices simultaneously. Structural batteries, containing woven carbon fabric anode; lithium cobalt oxide/graphene nanoplatelets coated aluminum cathode; filter paper separator and cross-linked polymer electrolyte, were fabricated through resin infusion under flexible tooling (RIFT) technique. Compression tests, dynamic mechanical thermal analysis, thermogravimetric analysis and impedance spectroscopy were done on the cross-linked polymer electrolytes while cyclic voltammetry, impedance spectroscopy, dynamic mechanical thermal analysis and in-plane shear tests were conducted on the fabricated structural batteries. A range of solid polymer electrolytes with increasing concentrations of lithium perchlorate salt in crosslinked polymer epoxies were formulated. Increased concentrations of electrolyte salt in cross-linked epoxy increased the ionic conductivity, although the compressive properties were compromised. A structural battery, exhibiting simultaneously a capacity of 0.16 mAh L‑1, an energy density of 0.32 Wh L‑1 and a shear modulus of 0.75 GPa have been reported.

Renewable Fuels-to-Grid Integration | Energy Systems Integration Facility |

Science.gov Websites

hydrogen, other than electrolysis. Read more about this research. Partnerships Photo of a polymer electrolyte membrane stack in a laboratory Giner NREL helped evaluate a large-scale polymer electrolyte

Low Permeable Hydrocarbon Polymer Electrolyte Membrane for Vanadium Redox Flow Battery.

PubMed

Jung, Ho-Young; Moon, Geon-O; Jung, Seunghun; Kim, Hee Tak; Kim, Sang-Chai; Roh, Sung-Hee

2017-04-01

Polymer electrolyte membrane (PEM) confirms the life span of vanadium redox flow battery (VRFB). Products from Dupont, Nafion membrane, is mainly used for PEM in VRFB. However, permeation of vanadium ion occurs because of Nafion’s high permeability. Therefore, the efficiency of VRFB decreases and the prices becomes higher, which hinders VRFB’s commercialization. In order to solve this problem, poly(phenylene oxide) (PPO) is sulfonated for the preparation of low-priced hydrocarbon polymer electrolyte membrane. sPPO membrane is characterized by fundamental properties and VRFB cell test.

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…

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.

Effect of dopant on electrical properties of PVA doped NaF polymer electrolyte films

NASA Astrophysics Data System (ADS)

Irfan, Mohammed; Razikha Banu, S.; Manjunath, A.; Mahesh, S. S.

2018-05-01

Polymer electrolyte films of Poly (vinyl alcohol) (PVA) doped with Sodium fluoride (NaF) of different weight ratios (6, 8 and 10 wt %) were prepared by solution casting method. We observed that AC conductivity was found to increase with rise in temperature and frequency with slope S ranging from 0.7 to 0.9. The Correlated Barrier Hopping (CBH) model is used because the value of S is temperature dependent and its value decreases by increasing temperature. The dielectric constant has high values in the low frequency region; this is due to the existence of various types of polarization mechanisms. The X-ray diffraction (XRD) diagram of pure PVA shows a characteristic peak at 2θ=19.490 indicating its semi-crystalline nature. On the incorporation of NaF salt into the polymer, the intensity of peak decreases gradually, suggesting a decrease in the degree of crystallinity of the complex. The CBH model is used to calculate the polaron binding energy (WM), the Hoping distance (R), the minimum hoping distance (Rmin) and the activation energy (Ea) results are discussed.

High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

PubMed

Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

2016-01-20

Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc.

Theoretical voltammetric response of electrodes coated by solid polymer electrolyte membranes.

PubMed

Gómez-Marín, Ana M; Hernández-Ortíz, Juan P

2014-09-24

A model for the differential capacitance of metal electrodes coated by solid polymer electrolyte membranes, with acid/base groups attached to the membrane backbone, and in contact with an electrolyte solution is developed. With proper model parameters, the model is able to predict a limit response, given by Mott-Schottky or Gouy-Chapman-Stern theories depending on the dissociation degree and the density of ionizable acid/base groups. The model is also valid for other ionic membranes with proton donor/acceptor molecules as membrane counterions. Results are discussed in light of the electron transfer rate at membrane-coated electrodes for electrochemical reactions that strongly depend on the double layer structure. In this sense, the model provides a tool towards the understanding of the electro-catalytic activity on modified electrodes. It is shown that local maxima and minima in the differential capacitance as a function of the electrode potential may occur as consequence of the dissociation of acid/base molecular species, in absence of specific adsorption of immobile polymer anions on the electrode surface. Although the model extends the conceptual framework for the interpretation of cyclic voltammograms for these systems and the general theory about electrified interfaces, structural features of real systems are more complex and so, presented results only are qualitatively compared with experiments. Copyright © 2014 Elsevier B.V. All rights reserved.

Fuel cell membranes and crossover prevention

DOEpatents

Masel, Richard I [Champaign, IL; York, Cynthia A [Newington, CT; Waszczuk, Piotr [White Bear Lake, MN; Wieckowski, Andrzej [Champaign, IL

2009-08-04

A membrane electrode assembly for use with a direct organic fuel cell containing a formic acid fuel includes a solid polymer electrolyte having first and second surfaces, an anode on the first surface and a cathode on the second surface and electrically linked to the anode. The solid polymer electrolyte has a thickness t:.gtoreq..times..times..times..times. ##EQU00001## where C.sub.f is the formic acid fuel concentration over the anode, D.sub.f is the effective diffusivity of the fuel in the solid polymer electrolyte, K.sub.f is the equilibrium constant for partition coefficient for the fuel into the solid polymer electrolyte membrane, I is Faraday's constant n.sub.f is the number of electrons released when 1 molecule of the fuel is oxidized, and j.sub.f.sup.c is an empirically determined crossover rate of fuel above which the fuel cell does not operate.

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

1989-01-01

Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

Conductivity and properties of polysiloxane-polyether cluster-LiTFSI networks as hybrid polymer electrolytes

NASA Astrophysics Data System (ADS)

Boaretto, Nicola; Joost, Christine; Seyfried, Mona; Vezzù, Keti; Di Noto, Vito

2016-09-01

This report describes the synthesis and the properties of a series of polymer electrolytes, composed of a hybrid inorganic-organic matrix doped with LiTFSI. The matrix is based on ring-like oligo-siloxane clusters, bearing pendant, partially cross-linked, polyether chains. The dependency of the thermo-mechanic and of the transport properties on several structural parameters, such as polyether chains' length, cross-linkers' concentration, and salt concentration is studied. Altogether, the materials show good thermo-mechanical and electrochemical stabilities, with conductivities reaching, at best, 8·10-5 S cm-1 at 30 °C. In conclusion, the cell performances of one representative sample are shown. The scope of this report is to analyze the correlations between structure and properties in networked and hybrid polymer electrolytes. This could help the design of optimized polymer electrolytes for application in lithium metal batteries.

Simultaneous improvement in ionic conductivity and flexibility of solid polymer electrolytes for thin film lithium ion batteries

NASA Astrophysics Data System (ADS)

Ji, Jianying

Solid polymer electrolytes (SPEs) provide advantages over liquid electrolytes in terms of safety, reliability, less temperature sensitive, and simplicity of design. With the use of a SPE in lithium batteries, high specific energy and specific power, safe operation, flexibility in packaging, and low cost of fabrication can be expected. However, after 30 years, SPEs have rarely found commercial success due to the low ionic conductivity and/or insufficient mechanical properties, both of which are related to the movement of the polymer chains. Many physical/chemical methods have been exploited to simultaneously create enhancement in ionic conductivity and mechanical properties, and some suggested ways have shown promise. However, the complex strategies have always introduced other challenge issues and incurred extra costs for manufacturing. In such a context, the development of dry solid state electrolytes is the central challenge to be faced worldwide. This thesis deals with the approaches to improving ionic conductivity and mechanical properties simultaneously. The method is to apply two kinds of controllable organic fillers: copolymer and protein. Our work revealed that the commercial available copolymer, poly (ethylene oxide)- block-polyethylene (PEO-b-PE), possesses a capability for enhancing the multiple performances of poly(ethylene oxide)(PEO)-based polymer electrolyte. And the effects of composition and molecular weight of the copolymers on performance of the resulting SPEs were examined. It was found that increasing the PE block percentage in the copolymer resulted in a significant increase in both ionic conductivity and mechanical properties, while increasing the molecular weight of the copolymer resulted in better mechanical properties, and an identical ionic conductivity. A rubber-like, soy protein-based SPE (s-SPE)was obtained by employing soy protein isolate (SPI), a soy product usually used as rigid fillers for enhancing mechanical properties of polymers, blended with poly(ethylene oxide)(PEO). The results indicated that the s-SPE with 55 wt% of SPI possesses a fully amorphous uniform structure having low Tg, in contrast with crystalline PEO-based SPE having discernable Tg and Tm. The conductivity and elasticity are both significantly improved with SPI involvement. Remarkably, this film has been elongated up to 100% without loss of ionic conductivity and 700% without mechanical damage.

Conductive polymeric compositions for lithium batteries

DOEpatents

Angell, Charles A [Mesa, AZ; Xu, Wu [Tempe, AZ

2009-03-17

Novel chain polymers comprising weakly basic anionic moieties chemically bound into a polyether backbone at controllable anionic separations are presented. Preferred polymers comprise orthoborate anions capped with dibasic acid residues, preferably oxalato or malonato acid residues. The conductivity of these polymers is found to be high relative to that of most conventional salt-in-polymer electrolytes. The conductivity at high temperatures and wide electrochemical window make these materials especially suitable as electrolytes for rechargeable lithium batteries.

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.

Dual phase polymer gel electrolyte based on non-woven poly(vinylidenefluoride-co-hexafluoropropylene)–layered clay nanocomposite fibrous membranes for lithium ion batteries

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

Shubha, Nageswaran; Prasanth, Raghavan; Energy Research Institute - NTU

2013-02-15

Graphical abstract: Display Omitted Highlights: ► P(VdF-co-HFP)–clay nanocomposite based electrospun membranes are prepared. ► The membranes are used as polymer gel electrolyte (PGE) in lithium ion batteries. ► The composite PGE shows ionic conductivity of 5.5 mS cm{sup −1} at room temperature. ► Li/PGE/LiFePO{sub 4} cell delivers initial discharge capacity of 160 mAh g{sup −1}. ► The use of prepared electrolyte significantly improved the cell performance. -- Abstract: A new approach for fabricating polymer gel electrolytes (PGEs) based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) incorporated with layered nanoclay has been employed to enhance the ionic conductivity and electrochemical properties of P(VdF-co-HFP) withoutmore » compromising its mechanical strength. The effect of layered nanoclay on properties of membranes has been evaluated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Surface morphology of the membranes has been studied using field-emission scanning electron microscopy (FE-SEM). Polymer gel electrolytes are prepared by soaking the fibrous membrane into 1 M LiPF{sub 6} in EC/DEC. The electrochemical studies show that incorporation of layered nanoclay into the polymer matrix greatly enhanced the ionic conductivity and compatibility with lithium electrodes. The charge–discharge properties and cycling performance of Li/LiFePO{sub 4} cells comprising nanocomposite polymer gel electrolytes have been evaluated at room temperature.« less

Visual Observation of Dissolution of Copper Ions from a Copper Electrode

ERIC Educational Resources Information Center

Ikemoto, Isao; Saitou, Kouichi

2013-01-01

During electrolysis, to visually observe the conversion of a metal to its cation, either the cation or its complex ion should have a distinct color while the electrolyte solution must be colorless and transparent. A demonstration is described in which copper is used as the electrodes and sodium polyacrylate (a superabsorbent polymer) solution is…

Polymers for new battery technologies.

NASA Astrophysics Data System (ADS)

Singh, Mohit

2009-03-01

The chemical and electrochemical reactivity of the components comprising today's lithium batteries has severely limited their lifetime and stability, and attempts to push the limits on energy density have exacerbated these stability issues. The weakest link in terms of safety and stability of Li ion systems is the organic liquid electrolyte that facilitates the Li^+ ion transport between the electrodes. The electrolyte is flammable and electrochemically unstable against the graphitic anode. It is the continuous electrochemical degradation of the electrolyte at the electrodes that leads to poor cycle life of the batteries, and in some cases runaway reactions that lead to explosions. Dry polymer electrolytes alleviate the electrochemical stability problem by offering a stable electrode-electrolyte interface. The absence of flammable liquids prevents runaway reactions. The main hurdle that has prevented dry polymer electrolytes from being commercialized is low ionic conductivity, and challenges in interfacing with the electrode materials. We demonstrate a novel approach towards addressing these challenges that renders batteries with excellent cycle lives, and thermal stability.

Electrical conductivity studies on (1-x)[PVA/PVP]: x[MgCl2{6H2O}] blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Basha, S. K. Shahenoor; Reddy, K. Veera Bhadra; Rao, M. C.

2018-05-01

Blend polymer electrolytes of polyvinyl alcohol and polyvinyl pyrrolidone were prepared with different molecular wt% ratios of MgCl2.6H2O by solution cast technique. Electrical conductivity measurements for the prepared films were performed using Keithley electrometer model 6514 and the maximum ionic conductivity was found to be 1.01x10-3 S/cm at 373 K for the prepared composition of 35PVA/35PVP:30MgCl2.6H2O. The maximum ionic conductivity of polymer electrolyte has been used in fabrication of electrochemical cell with the configuration of Mg+/(PVA/PVP+MgCl2.6H2O)/(I2+C+electrolyte).

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.

Tailor-Made Electrospun Multilayer Composite Polymer Electrolytes for High-Performance Lithium Polymer Batteries.

PubMed

Lim, Du-Hyun; Haridas, Anupriya K; Figerez, Stelbin Peter; Raghavan, Prasanth; Matic, Aleksandar; Ahn, Jou-Hyeon

2018-09-01

A novel tailor-made multilayer composite polymer electrolyte, consisting of two outer layers of electrospun polyacrylonitrile (PAN) and one inner layer of poly(vinyl acetate) (PVAc)/poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) fibrous membrane, was prepared using continuous electrospinning. These membranes, which are made up of fibers with diameters in the nanometer range, were stacked in layers to produce interconnected pores that result in a high porosity. Gel polymer electrolytes (GPEs) were prepared by entrapping a liquid electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate) in the membranes. The composite membranes exhibited a high electrolyte uptake of 450-510%, coupled with an improved room temperature ionic conductivity of up to 4.72 mS cm-1 and a high electrochemical stability of 4.6 V versus Li/Li+. Electrochemical investigations of a composite membrane of PAN-PVAc-PAN, with a LiFePO4 cathode synthesized in-house, showed a high initial discharge capacity of 145 mAh g-1, which corresponds to 85% utilization of the active material, and displayed stable cycle performance.

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

Phosphazenes for energy production and storage: Applied and exploratory synthesis

NASA Astrophysics Data System (ADS)

Hess, Andrew R.

This dissertation involves progress toward phosphazene-based ion conducting materials with a focus on structure-property relationships to improve these materials. This dissertation also includes some more fundamental exploratory syntheses to probe the limits of phosphazene chemistry and discover structure-property relationships that may be useful in designing compounds to fulfill important technical requirements. Chapter 1 provides a brief introduction to polymers and polyphosphazenes as well as ion-conducting materials and the contribution of polyphosphazene chemistry to that field. Chapter 1 also provides a brief introduction to some analytical techniques. Chapter 2 begins with the use of organophosphates as stand-alone non-volatile and fire-retardant liquid electrolyte media for dye sensitized solar cells (DSSCs) as well as their use as plasticizer in polymer gel electrolytes intended for application in lithium batteries. These organophosphates are the smallest phosphorus containing model molecules investigated in this dissertation. A homologous series of oligoalkyleneoxy substituted phosphates was synthesized and the effect of the substituent chain length on viscosity and conductivity was investigated. Small, test-scale DSSCs were constructed and showed promising results with overall cell efficiencies of up to 3.6% under un-optimized conditions. Conductivity measurements were performed on polymer gel-electrolytes based on poly[bis(2-(2-methoxyethoxy)ethoxy)phosphazene] (MEEP) plasticized with the phosphate with the best combination of properties, using a system loaded with lithium trifluoromethanesulfonate as the charge carrier. In chapter 3 the effect of the cation of the charge carrier species on the anionic conductivity of DSSC type electrolytes is evaluated using hexakis(2-(2-methoxyethoxy)ethoxy)cyclotriphosphazene (MEE-trimer) as a small molecule model for MEEP. The iodides of lithium, sodium, and ammonium as well as the ionic liquid, 1-propyl-3-methylimidazolium iodide (PMII) were tested in various electrolyte concentrations. After identifying PMII as the most efficient salt additive for promoting anion conduction in the MEE-trimer systems, it was tested in MEEP-based DSSC polymer-gel electrolytes plasticized with propylene carbonate (PC). The MEEP/PMII type electrolytes were compared against and outperformed similar formulations based on poly(ethylene oxide). Chapter 4 extends the concept of poly[(oligoethyleneoxy)phosphazene] electrolytes by the synthesis of MEEP-analogues with various ammonium ions covalently bound to the polymer side chains in order to create a single-ion conducting polyelectrolyte. In this case iodide is the only ion that is free to move and carry charge since the cation is bound to the polymer. Two candidates from the series of polyelectrolytes were selected for extensive study, one in which the ammonium ion has a hexyl group, and another in which the ammonium ion has an MEE-group. The polymers were characterized by dielectric spectroscopy, X-ray scattering, and density functional theory calculations. In chapter 5 the concept of polyphosphazene based polyelectrolytes is extended further by quaternization of nitrogen atoms that are a part of the polymer backbone rather than a pendent group. The feasibility of the concept is first explored using cyclic-trimeric phosphazenes as small molecule models and is then extended to high polymeric systems. Chapter 6 begins a new section of exploratory synthesis meant to probe the limits of phosphazene chemistry and discover useful structure-property relationships as well as to improve on the synthetic procedures of the past. Thus, in chapter 6 a series of cyclotriphosphazenes is synthesized for evaluation as compounds with the ability to complex to metal surfaces or to form ceramic materials after pyrolysis. Several known compounds are resynthesized, many with improvements over previously published procedures either in yield or simplicity of reaction conditions. Also, two new cyclotriphosphazenes were synthesized in an attempt to produce a catechol-like side group that could mimic the metal complexation and adhesive abilities of mussel adhesive proteins which take advantage of similar catecholic moieties. Chapter 7 presents the synthesis of fluorine-bearing aryloxy phosphazenes in an attempt to overcome the deficiencies of some of the classical fluorinated organic polymers. Poly(fluoroaryloxy)phosphazenes can offer many of the same advantages without the deficiencies of some of the more classical organic fluorinated polymers. The materials synthesized are excellent candidates for dielectric film materials in capacitors. In chapter 8 new ground is broken in phosphazene chemistry, wherein cycloalkanoxy groups, a type of side-group for phosphazenes that has been neglected in the past, are attached to the phosphazene skeleton. First, a single previous report of the synthesis of hexakis(cyclohexanoxy)cyclotriphosphazene was reproduced as a model system. Then a series of single substituent polyphosphazenes was synthesized in order to determine how large a saturated cyclic ring can be attached to the polymer backbone while still completing the replacement of the chlorine atoms attached to the backbone. Subsequently, a series of mixed substituent polymers containing both cycloalkanoxy groups (from cyclopentoxy to cyclooctanoxy) and the well-studied trifluoroethoxy group was synthesized and characterized in order to study larger saturated cyclic rings as polyphosphazene side-groups. Chapter 9 contains the author's recommendations. (Abstract shortened by UMI.).

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

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.

Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

NASA Astrophysics Data System (ADS)

Li, Qin; Ardebili, Haleh

2016-01-01

The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

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

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.

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

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Extrusion of electrode material by liquid injection into extruder barrel

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

Keller, David Gerard; Giovannoni, Richard Thomas; MacFadden, Kenneth Orville

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells.

Ionic Salt Effect on the Phase Transition of PS-b-P2VP Copolymers

NASA Astrophysics Data System (ADS)

Kim, Bokyung; An, Hyungju; Ryu, Du Yeol; Kim, Jehan

2009-03-01

Solid-state electrolytes have long been considered as suitable candidates owing to the simple and easy processes for rechargeable battery manufactures, compared to conventional liquid electrolyte counterparts. Especially, polymer/salt systems involving PMMA and PVP complex forms have been studied since they provide stable electrochemical characteristics as well as mechanical properties. We studied the phase behavior of PS-b-P2VP upon the salt addition by small angle x-ray scattering (SAXS) and depolarized light scattering. Transition temperatures of block copolymer were significantly influenced by the salt addition in addition to the changes of d-spacings, which is caused by the effective coordinative interaction between P2VP block and salt. This study suggests a simple approach to solid-state block copolymer electrolytes.

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.

Systematic Experimental and Computational Investigation of Ion Transport in Novel Polyether Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Webb, Michael; Jung, Yukyung; Zheng, Qi; Miller, Thomas, III; Coates, Geoffrey; Balsara, Nitash

Polyethers, such as poly(ethylene oxide) (PEO), are considered to be the most promising polymer electrolyte materials due to their high ionic conductivity and electrochemical stability, both essential for battery applications. To gain a fundamental understanding of the transport properties of polyether systems, we design a systematic set of linear PEO-like polymers to explore the effect of adding carbon spacers to the backbone of the chain. Ac impedance spectroscopy is employed to measure the ionic conductivity of polyether/lithium salt electrolytes; the results elucidate tradeoffs between lowering the glass transition temperature and diluting the polar groups on the polymer chain. Molecular-level insight is provided by molecular dynamics simulations of the polyether electrolytes. We define the useful and intuitive metric of ``connectivity'', a parameter calculated from simulations which describes the physical arrangements of solvation sites in a polymer melt. Direct comparison of experiment and theory allows us to determine the relationship between connectivity and conductivity. The comparison provides insight regarding the factors that control conductivity, and highlights considerations that must be taken when designing new ion-conducting polymers.

Aggregate-mediated charge transport in ionomeric electrolytes

NASA Astrophysics Data System (ADS)

Lu, Keran; Maranas, Janna; Milner, Scott

Polymers such PEO can conduct ions, and have been studied as possible replacements for organic liquid electrolytes in rechargeable metal-ion batteries. More generally, fast room-temperature ionic conduction has been reported for a variety of materials, from liquids to crystalline solids. Unfortunately, polymer electrolytes generally have limited conductivity; these polymers are too viscous to have fast ion diffusion like liquids, and too unstructured to promote cooperative transport like crystalline solids. Ionomers are polymer electrolytes in which ionic groups are covalently bound to the polymer backbone, neutralized by free counterions. These materials also conduct ions, and can exhibit strong ionic aggregation. Using coarse-grained molecular dynamics, we explore the forces driving ionic aggregation, and describe the role ion aggregates have in mediating charge transport. The aggregates are string-like such that ions typically have two neighbors. We find ion aggregates self-assemble like worm-like micelles. Excess charge, or free ions, occasionally coordinate with aggregates and are transported along the chain in a Grotthuss-like mechanism. We propose that controlling ionomer aggregate structure through materials design can enhance cooperative ion transport.

Vibrational studies of flexible solid polymer electrolyte based on PCL-EC incorporated with proton conducting NH4SCN

NASA Astrophysics Data System (ADS)

Woo, H. J.; Arof, A. K.

2016-05-01

A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50 wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94 × 10- 7 Scm- 1 to 3.82 × 10- 5 Scm- 1. Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN- stretching mode (2030-2090 cm- 1). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4+ complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.

Electrodeposition of Polymer Nanostructures using Three Diffuse Double Layers: Polymerization beyond the Liquid/Liquid Interfaces

NASA Astrophysics Data System (ADS)

Divya, Velpula; Sangaranarayanan, M. V.

2018-04-01

Nanostructured conducting polymers have received immense attention during the past few decades on account of their phenomenal usefulness in diverse contexts, while the interface between two immiscible liquids is of great interest in chemical and biological applications. Here we propose a novel Electrode(solid)/Electrolyte(aqueous)/Electrolyte(organic) Interfacial assembly for the synthesis of polymeric nanostructures using a novel concept of three diffuse double layers. There exist remarkable differences between the morphologies of the polymers synthesized using the conventional electrode/electrolyte method and that of the new approach. In contrast to the commonly employed electrodeposition at liquid/liquid interfaces, these polymer modified electrodes can be directly employed in diverse applications such as sensors, supercapacitors etc.

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.

Preparation and Characterization of PVA Alkaline Solid Polymer Electrolyte with Addition of Bamboo Charcoal.

PubMed

Fan, Lidan; Wang, Mengyue; Zhang, Zhen; Qin, Gang; Hu, Xiaoyi; Chen, Qiang

2018-04-26

Natural bamboo charcoal (BC) powder has been developed as a novel filler in order to further improve performances of the polyvinyl alcohol (PVA)-based alkaline solid polymer electrolyte (ASPE) by solution casting method. X-ray diffraction patterns of composite polymer electrolyte with BC revealed the decrease in the degree of crystallinity with increasing content of BC. Scanning electron microscopy images showed pores on a micrometer scale (average diameter about 2 μm) distributed inside and on the surface of the membranes, indicating a three-dimension network formed in the polymer framework. The ionic conductivity was measured by the alternating-current (AC) impedance method, and the highest conductivity value of 6.63 × 10 −2 S·cm −1 was obtained with 16 wt % of BC content and m KOH : m PVA = 2:1.5 at 30 °C. The contents of BC and KOH could significantly influence the conductivity. The temperature dependence of the bulk electrical conductivity displayed a combination of Arrhenius nature, and the activation energy for the ion in polymer electrolyte has been calculated. The electrochemical stability window of the electrolyte membrane was over 1.6 V. The thermogravimetric analysis curves showed that the degradation temperatures of PVA-BC-KOH ASPE membranes shifted toward higher with adding BC. A simple nickel-hydrogen battery containing PVA-BC-KOH electrolyte membrane was assembled with a maximum discharge capacity of 193 mAh·g −1 .

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Simple One-Pot Syntheses and Characterizations of Free Fluoride- and Bifluoride-Containing Polymers Soluble in Non-Aqueous Solvents

PubMed Central

Steinle, Dominik; Friedrich, Laura; Bevilacqua, Nico; von Hauff, Elizabeth; Gschwind, Fabienne

2016-01-01

One of the problems that arise with bifluoride- or fluoride-containing compounds is their poor solubility in non-aqueous solvents. We report herein a facile one-pot synthesis and the chemical analysis of fluoride/bifluoride-containing polymers, which are soluble in MeCN. Different polymers, such as Polyvinylacetate or Polyethylene imine and saccharides, such as maltodextrin, were complexed with ammonium (bi)fluoride using hydrogen bonds to form the desired (bi)fluoride-containing compounds. The newly formed hydrogen bonding (bi)fluoride-doped polymer matrices were analyzed using infrared and nuclear magnetic resonance spectroscopies, and X-ray diffraction. The promising materials also underwent impedance spectroscopy, conductivity measurements and preliminary tests as electrolytes for room temperature fluoride ion batteries along with an analysis of their performance. PMID:28774092

Solid State Ionics Advanced Materials for Emerging Technologies

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.

2006-06-01

Keynote lecture. Challenges and opportunities of solid state ionic devices / W. Weppner -- pt. I. Ionically conducting inorganic solids. Invited papers. Multinuclear NMR studies of mass transport of phosphoric acid in water / J. R. P. Jayakody ... [et al.]. Crystalline glassy and polymeric electrolytes: similarities and differences in ionic transport mechanisms / J.-L. Souquet. 30 years of NMR/NQR experiments in solid electrolytes / D. Brinkmann. Analysis of conductivity and NMR measurements in Li[symbol]La[symbol]TiO[symbol] fast Li[symbol] ionic conductor: evidence for correlated Li[symbol] motion / O. Bohnké ... [et al.]. Transport pathways for ions in disordered solids from bond valence mismatch landscapes / S. Adams. Proton conductivity in condensed phases of water: implications on linear and ball lightning / K. Tennakone -- Contributed papers. Proton transport in nanocrystalline bioceramic materials: an investigative study of synthetic bone with that of natural bone / H. Jena, B. Rambabu. Synthesis and properties of the nanostructured fast ionic conductor Li[symbol]La[symbol]TiO[symbol] / Q. N. Pham ... [et al.]. Hydrogen production: ceramic materials for high temperature water electrolysis / A. Hammou. Influence of the sintering temperature on pH sensor ability of Li[symbol]La[symbol]TiO[symbol]. Relationship between potentiometric and impedance spectroscopy measurements / Q. N. Pham ... [et al.]. Microstructure chracterization and ionic conductivity of nano-sized CeO[symbol]-Sm[symbol]O[symbol] system (x=0.05 - 0.2) prepared by combustion route / K. Singh, S. A. Acharya, S. S. Bhoga. Red soil in Northern Sri Lanka is a natural magnetic ceramic / K. Ahilan ... [et al.]. Neutron scattering of LiNiO[symbol] / K. Basar ... [et al.]. Preparation and properties of LiFePO[symbol] nanorods / L. Q. Mai ... [et al.]. Structural and electrochemical properties of monoclinic and othorhombic MoO[symbol] phases / O. M. Hussain ... [et al.]. Preparation of Zircon (ZrSiO[symbol]) ceramics via solid state sintering of Zr)[symbol] and SiO[symbol] and the effect of dopants on the zircon yield / U. Dhanayake, B. S. B. Karunaratne. Preparation and properties of vanadium doped ZnTe cermet thin films / M. S. Hossain, R. Islam, K. A. Khan. Dynamical properties and electronic structure of lithium-ion conductor / M. Kobayashi ... [et al.]. Cuprous ion conducting Montmorillonite-Polypyrrole nanocomposites / D. M. M. Krishantha ... [et al.]. Frequency dependence of conductivity studies on a newly synthesized superionic solid solution/mixed system: [0.75AgI: 0.25AgCl] / R. K. Nagarch, R. Kumar. Diffuse X-ray and neutron scattering from Powder PbS / X. Lian ... [et al.]. Electron affinity and work function of Pyrolytic MnO[symbol] thin films prepared from Mn(C[symbol]H[symbol]O[symbol])[symbol].4H[symbol]) / A. K. M. Farid Ul Islam, R. Islam, K. A. Khan. Crystal structure and heat capacity of Ba[symbol]Ca[symbol]Nb[symbol]O[symbol] / T. Shimoyama ... [et al.]. XPS and impedance investigations on amorphous vanadium oxide thin films / M. Kamalanathan ... [et al.]. Sintering and mixed electronic-ionic conducting properties of La[symbol]Sr[symbol]NiO[symbol] derived from a polyaminocarboxylate complex precursor / D.-P. Huang ... [et al.]. Preparation and characteristics of ball milled MgH[symbol] + M (M= Fe, VF[symbol] and FeF[symbol]) nanocomposites for hydrogen storage / N. W. B. Balasooriya, Ch. Poinsignon. Structural studies of oxysulfide glasses by X-ray diffraction and molecular dynamics simulation / R. Prasada Rao, M. Seshasayee, J. Dheepa. Synthesis, sintering and oxygen ionic conducting properties of Bi[symbol]V[symbol]Cu[symbol]O[symbol] / F. Zhang ... [et al.]. Synthesis and transport characteristics of PbI[symbol]-Ag[symbol]O-Cr[symbol]O[symbol] superioninc system / S. A. Suthanthiraraj, V. Mathew. Electronic conductivity of La[symbol]Sr[symbol]Ga[symbol]Mg[symbol]Co[symbol]O[symbol] electrolytes / K. Yamaji ... [et al.] -- pt. II. Electrode materials. Invited papers. Cathodic properties of Al-doped LiCoO[symbol] prepared by molten salt method Li-Ion batteries / M. V. Reddy, G. V. Subba Rao, B. V. R. Chowdari. Layered ion-electron conducting materials / M. A. Santa Ana, E. Benavente, G. González. LiNi[symbol]Co[symbol]O[symbol] cathode thin-film prepared by RF sputtering for all-solid-state rechargeable microbatteries / X. J. Zhu ... [et al.] -- Contributed papers. Contributed papers. Nanocomposite cathode for SOFCs prepared by electrostatic spray deposition / A. Princivalle, E. Djurado. Effect of the addition of nanoporous carbon black on the cycling characteristics of Li[symbol]Co[symbol](MoO[symbol])[symbol] for lithium batteries / K. M. Begam, S. R. S. Prabaharan. Protonic conduction in TiP[symbol]O[symbol] / V. Nalini, T. Norby, A. M. Anuradha. Preparation and electrochemical LiMn[symbol]O[symbol] thin film by a solution deposition method / X. Y. Gan ... [et al.]. Synthesis and characterization LiMPO[symbol] (M = Ni, Co) / T. Savitha, S. Selvasekarapandian, C. S. Ramya. Synthesis and electrical characterization of LiCoO[symbol] LiFeO[symbol] and NiO compositions / A. Wijayasinghe, B. Bergman. Natural Sri Lanka graphite as conducting enhancer in manganese dioxide (Emd type) cathode of alkaline batteries / N. W. B. Balasooriya ... [et al.]. Electrochemical properties of LiNi[symbol]Al[symbol]Zn[symbol]O[symbol] cathode material synthesized by emulsion method / B.-H. Kim ... [et al.]. LiNi[symbol]Co[symbol]O[symbol] cathode materials synthesized by particulate sol-gel method for lithium ion batteries / X. J. Zhu ... [et al.]. Pulsed laser deposition of highly oriented LiCoO[symbol] and LiMn[symbol]O[symbol] thin films for microbattery applications / O. M. Hussain ... [et al.]. Preparation of LiNi[symbol]Co[symbol]O[symbol] thin films by a sol-gel method / X. J. Zhu ... [et al.]. Electrochemical lithium insertion into a manganese dioxide electrode in aqueous solutions / M. Minakshi ... [et al.]. AC impedance spectroscopic analysis of thin film LiNiVO[symbol] prepared by pulsed laser deposition technique / S. Selvasekarapandian ... [et al.]. Synthesis and characterization of LiFePO[symbol] cathode materials by microwave processing / J. Zhou ... [et al.]. Characterization of Nd[symbol]Sr[symbol]CoO[symbol] including Pt second phase as the cathode material for low-temperature SOFCs / J. W. Choi ... [et al.]. Thermodynamic behavior of lithium intercalation into natural vein and synthetic graphite / N. W. B. Balasooriya, P. W. S. K. Bandaranayake, Ph. Touzain -- pt. III. Electroactive polymers. Invited papers. Organised or disorganised? looking at polymer electrolytes from both points of view / Y.-P. Liao ... [et al.]. Polymer electrolytes - simple low permittivity solutions? / I. Albinsson, B.-E. Mellander. Dependence of conductivity enhancement on the dielectric constant of the dispersoid in polymer-ferroelectric composite electrolytes / A. Chandra, P. K. Singh, S. Chandra. Design and application of boron compounds for high-performance polymer electrolytes / T. Fujinami. Structural, vibrational and AC impedance analysis of nano composite polymer electrolytes based on PVAC / S. Selvasekarapandian ... [et al.]. Absorption intensity variation with ion association in PEO based electrolytes / J. E. Furneaux ... [et al.]. Study of ion-polymer interactions in cationic and anionic ionomers from the dependence of conductivity on pressure and temperature / M. Duclot ... [et al.]. Triol based polyurethane gel electrolytes for electrochemical devices / A. R. Kulkarni. Contributed papers. Accurate conductivity measurements to solvation energies in nafion / M. Maréchal, J.-L Souquet. Ion conducting behaviour of composite polymer gel electrolyte: PEG-PVA-(NH[symbol]CH[symbol]CO[symbol])[symbol] system / S. L. Agrawal, A. Awadhia, S. K. Patel. Impedance spectroscopy and DSC studies of poly(vinylalcohol)/ silicotungstic acid crosslinked composite membranes / A. Anis, A. K. Banthia. (PEO)[symbol]:Na[symbol]P[symbol]O[symbol]: a report on complex formation / A. Bhide, K. Hariharan. Experimental studies on (PVC+LiClO[symbol]+DMP) polymer electrolyte systems for lithium battery / Ch. V. S. Reddy. Stability of the gel electrolyte, PAN: EC: PC: LiCF[symbol]SO[symbol] towards lithium / K. Perera ... [et al.]. Montmorillonite as a conductivity enhancer in (PEO)[symbol]LiCF[symbol]SO[symbol] polymer electrolyte / C. H. Manoratne ... [et al.]. Polymeric gel electrolytes for electrochemical capacitors / M. Morita ... [et al.]. Electrical conductivity studies on proton conducting polymer electrolytes based on poly (viniyl acetate) / D. Arun Kumar ... [et al.]. Conductivity and thermal studies on plasticized PEO:LiTf-Al[symbol]O[symbol] composite polymer electrolyte / H. M. J. C. Pitawala, M. A. K. L. Dissanayake, V. A. Seneviratne. Investigation of transport properties of a new biomaterials - gum mangosteen / S. S. Pradhan, A. Sarkar. Investigation of ionic conductivity of PEO-MgCl[symbol] based solid polymer electrolyte / M. Sundar ... [et al.]. [symbol]H NMR and Raman analysis of proton conducting polymer electrolytes based on partially hydrolyzed poly (vinyl alcohol) / G. Hirankumar ... [et al.]. Influence of Al[symbol]O[symbol] nanoparticles on the phase matrix of polyethylene oxide-silver triflate polymer electrolytes / S. Austin Suthanthiraraj, D. Joice Sheeba. Effect of different types of ceramic fillers on thermal, dielectric and transport properties of PEO[symbol]LiTf solid polymer electrolyte / K. Vignarooban ... [et al.]. Characterization of PVP based solid polymer electrolytes using spectroscopic techniques / C. S. Ramya ... [et al.]. Electrochemical and structural properties of poly vinylidene fluoride - silver triflate solid polymer electrolyte system / S. Austin Suthanthiraraj, B. Joseph Paul. Micro Raman, Li NMR and AC impedance analysis of PVAC:LiClO[symbol] solid polymer eectrolytes / R. Baskaran ... [et al.].Study of Na+ ion conduction in PVA-NaSCN solid polymer electrolytes / G. M. Brahmanandhan ... [et al.]. Effect of filler addition on plasticized polymer electrolyte systems / M. Sundar, S. Selladurai. Ionic motion in PEDOT and PPy conducting polymer bilayers / U. L. Zainudeen, S. Skaarup, M. A. Careem. Film formation mechanism and electrochemical characterization of V[symbol]O[symbol] xerogel intercalated by polyaniniline / Q. Zhu ... [et al.]. Effect of NH[symbol]NO[symbol] concentration on the conductivity of PVA based solid polymer electrolyte / M. Hema ... [et al.]. Dielectric and conductivity studies of PVA-KSCN based solid polymer electrolytes / J. Malathi ... [et al.] -- pt. IV. Emerging applications. Invited papers. The use of solid state ionic materials and devices in medical applications / R. Linford. Development of all-solid-state lithium batteries / V. Thangadurai, J. Schwenzei, W. Weppner. Reversible intermediate temperature solid oxide fuel cells / B.-E. Mellander, I. Albinsson. Nano-size effects in lithium batteries / P. Balaya, Y. Hu, J. Maier. Electrochromics: fundamentals and applications / C. G. Granqvist. Electrochemical CO[symbol] gas sensor / K. Singh. Polypyrrole for artificial muscles: ionic mechanisms / S. Skaarup. Development and characterization of polyfluorene based light emitting diodes and their colour tuning using Forster resonance energy transfer / P. C. Mattur ... [et al.]. Mesoporous and nanoparticulate metal oxides: applications in new photocatalysis / C. Boxall. Proton Conducting (PC) perovskite membranes for hydrogen separation and PC-SOFC electrodes and electrolytes / H. Jena, B. Rambabu. Contributed papers. Electroceramic materials for the development of natural gas fuelled SOFC/GT plant in developing country (Trinidad and Tobogo (T&T)) / R. Saunders, H. Jena, B. Rambabu. Thin film SOFC supported on nano-porous substrate / J. Hoon Joo, G. M. Choi. Characterization and fabrication of silver solid state battery Ag/AGI-AgPO[symbol]/I[symbol], C / E. Kartini ... [et al.]. Performance of lithium polymer cells with polyacrylonitrile based electrolyte / K. Perera ... [et al.]. Hydrothermal synthesis and electrochemical behavior of MoO[symbol] nanobelts for lithium batteries / Y. Qi ... [et al.]. Electrochemical behaviour of a PPy (DBS)/polyacrylonitrile: LiTF:EC:PC/Li cell / K. Vidanapathirana ... [et al.]. Characteristics of thick film CO[symbol] sensors based on NASICON using Li[symbol]CO[symbol]-CaCO[symbol] auxiliary phases / H. J. Kim ... [et al.]. Solid state battery discharge characteristic study on fast silver ion conducting composite system: 0.9[0.75AgI:0.25AgCl]: 0.1TiO[symbol] / R. K. Nagarch, R. Kumar, P. Rawat. Intercalating protonic solid-state batteries with series and parallel combination / K. Singh, S. S. Bhoga, S. M. Bansod. Synthesis and characterization of ZnO fiber by microwave processing / Lin Wang ... [et al.]. Preparation of Sn-Ge alloy coated Ge nanoparticles and Sn-Si alloy coated Si nanoparticles by ball-milling / J. K. D. S. Jayanett, S. M. Heald. Synthesis of ultrafine and crystallized TiO[symbol] by alalkoxied free polymerizable precursor method / M. Vijayakumar ... [et al.]. Development and characterization of polythiophene/fullerene composite solar cells and their degradation studies / P. K. Bhatnagar ... [et al.].

Solid polymeric electrolytes for lithium batteries

DOEpatents

Angell, Charles A.; Xu, Wu; Sun, Xiaoguang

2006-03-14

Novel conductive polyanionic polymers and methods for their preparion are provided. The polyanionic polymers comprise repeating units of weakly-coordinating anionic groups chemically linked to polymer chains. The polymer chains in turn comprise repeating spacer groups. Spacer groups can be chosen to be of length and structure to impart desired electrochemical and physical properties to the polymers. Preferred embodiments are prepared from precursor polymers comprising the Lewis acid borate tri-coordinated to a selected ligand and repeating spacer groups to form repeating polymer chain units. These precursor polymers are reacted with a chosen Lewis base to form a polyanionic polymer comprising weakly coordinating anionic groups spaced at chosen intervals along the polymer chain. The polyanionic polymers exhibit high conductivity and physical properties which make them suitable as solid polymeric electrolytes in lithium batteries, especially secondary lithium batteries.

U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications.

PubMed

Houchins, Cassidy; Kleen, Greg J; Spendelow, Jacob S; Kopasz, John; Peterson, David; Garland, Nancy L; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C

2012-12-18

Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed.

A simple polymer electrolyte membrane system for enrichment of low-level tritium (3H) in environmental water samples.

PubMed

Wassenaar, Leonard I; Han, Liang-Feng; Schiefer, Thomas; Kainz, Gustav; Araguas-Araguas, Luis; Aggarwal, Pradeep K

2018-06-01

Tritium ( 3 H) is an essential tracer of the Earth's water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of 3 H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich 3 H in 250-3000 mL environmental water samples to a 10-mL final volume. The IAEA PEM- 3 H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional 3 H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show 3 H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ∼4.5 %. Further work is needed to quantify inter-sample memory and to establish lower 3 H detection limits. The IAEA PEM- 3 H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others.

Characterization of conducting cellulose acetate based polymer electrolytes doped with "green" ionic mixture.

PubMed

Ramesh, S; Shanti, R; Morris, Ezra

2013-01-02

Polymer electrolytes were developed by solution casting technique utilizing the materials of cellulose acetate (CA), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and deep eutectic solvent (DES). The DES is synthesized from the mixture of choline chloride and urea of 1:2 ratios. The increasing DES content well plasticizes the CA:LiTFSI:DES matrix and gradually improves the ionic conductivity and chemical integrity. The highest conducting sample was identified for the composition of CA:LiTFSI:DES (28 wt.%:12 wt.%:60 wt.%), which has the greatest ability to retain the room temperature ionic conductivity over the entire 30 days of storage time. The changes in FTIR cage peaks upon varying the DES content in CA:LiTFSI:DES prove the complexation. This complexation results in the collapse of CA matrix crystallinity, observed from the reduced intensity of XRD diffraction peaks. The DES-plasticized sample is found to be more heat-stable compared to pure CA. Nevertheless, the addition of DES diminishes the CA:LiTFSI matrix's heat-resistivity but at the minimum addition the thermal stability is enhanced. Copyright © 2012 Elsevier Ltd. All rights reserved.

Heat transfer and thermal management studies of lithium polymer batteries for electric vehicle applications

NASA Astrophysics Data System (ADS)

Song, Li

The thermal conductivities of the polymer electrolyte and composite cathode are important parameters characterizing heat transport in lithium polymer batteries. The thermal conductivities of lithium polymer electrolytes, including poly-ethylene oxide (PEO), PEO-LiClO4, PEO-LiCF3SO 3, PEO-LiN(CF3SO2)2, PEO-LiC(CF 3SO2)3, and the thermal conductivities of TiS 2 and V6O13 composite cathodes, were measured over the temperature range from 25°C to 150°C by a guarded heat flow meter. The thermal conductivities of the electrolytes were found to be relatively constant for the temperature and for electrolytes with various concentrations of the lithium salt. The thermal conductivities of the composite cathodes were found to increase with the temperature below the melting temperature of the polymer electrolyte and only slightly increase above the melting temperature. Three different lithium polymer cells, including Li/PEO-LiCF3 S O3/TiS2, Li/PEO-LiC(CF3 S O2)3/V6 O13, and Li/PEO-LiN(CF3 S O2)2/ Li1+x Mn2 O4 were prepared and their discharge curves, along with heat generation rates, were measured at various galvanostatic discharge current densities, and at different temperature (70°C, 80°C and 90°C), by a potentiostat/galvanostat and an isothermal microcalorimeter. The thermal stability of a lithium polymer battery was examined by a linear perturbation analysis. In contrast to the thermal conductivity, the ionic conductivity of polymer electrolytes for lithium-polymer cell increases greatly with increasing temperature, an instability could arise from this temperature dependence. The numerical calculations, using a two dimensional thermal model, were carried out for constant potential drop across the electrolyte, for constant mean current density and for constant mean cell output power. The numerical calculations were approximately in agreement with the linear perturbation analysis. A coupled mathematical model, including electrochemical and thermal components, was developed to study the heat transfer and thermal management of lithium polymer batteries. The results calculated from the model, including temperature distributions, and temperatures at different stages of discharge are significantly different from those calculated from the thermal model. The discharge curves and heat generation rates calculated by the electrochemical-thermal model were in agreement with the experimental results. Different thermal management approaches, including a variable conductance insulation enclosure were studied.

A Long-Life Lithium-Air Battery in Ambient Air with a Polymer Electrolyte Containing a Redox Mediator.

PubMed

Guo, Ziyang; Li, Chao; Liu, Jingyuan; Wang, Yonggang; Xia, Yongyao

2017-06-19

Lithium-air batteries when operated in ambient air generally exhibit poor reversibility and cyclability, because of the Li passivation and Li 2 O 2 /LiOH/Li 2 CO 3 accumulation in the air electrode. Herein, we present a Li-air battery supported by a polymer electrolyte containing 0.05 m LiI, in which the polymer electrolyte efficiently alleviates the Li passivation induced by attacking air. Furthermore, it is demonstrated that I - /I 2 conversion in polymer electrolyte acts as a redox mediator that facilitates electrochemical decomposition of the discharge products during recharge process. As a result, the Li-air battery can be stably cycled 400 times in ambient air (relative humidity of 15 %), which is much better than previous reports. The achievement offers a hope to develop the Li-air battery that can be operated in ambient air. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

PubMed

Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

2009-12-01

Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable.

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.

Novel Elastomeric Membranes Developed for Polymer Electrolytes in Lithium Batteries

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Maryann B.; Kinder, James D.; Bennett, William R.

2005-01-01

Lithium-based polymer batteries for aerospace applications need to be highly conductive from -70 to 70 C. State-of-the-art polymer electrolytes are based on polyethylene oxide (PEO) because of the ability of its ether linkages to solvate lithium ions. Unfortunately, PEO has a tendency to form crystalline regions below 60 C, dramatically lowering conductivity below this temperature. PEO has acceptable ionic conductivities (10(exp -4) to 10(exp -3) S/cm) above 60 C, but it is not mechanically strong. The room-temperature conductivity of PEO can be increased by adding solvent or plasticizers, but this comes at the expense of thermal and mechanical stability. One of NASA Glenn Research Center s objectives in the Polymer Rechargeable System program (PERS) is to develop novel polymer electrolytes that are highly conductive at and below room temperature without added solvents or plasticizers.

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.

The Electrolyte Factor in O2 Reduction Electrocatalysis

DTIC Science & Technology

1993-04-23

molecule thick and does not seem to interfere with 02 and water/proton transport at this interface. This layer resembles a self-ordered Langmuir - Blodgett ... liquid electrolyte from within the polymer is in contact with the catalyst and completes the ionic circuit between the ionic conducting polymer and the...the free energy of adsorption of H2 0 and ionic components because of the lower effective dielectric constant in the electrolyte phase immediately

A stable perovskite electrolyte in moist air for Li-ion batteries.

PubMed

Li, Yutao; Xu, Henghui; Chien, Po-Hsiu; Wu, Nan; Xin, Sen; Xue, Leigang; Park, Kyusung; Hu, Yan-Yan; Goodenough, John B

2018-05-07

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air, H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell having a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, having a Li-ion conductivity σLi = 4.8×10-4 S cm-1 at 25 oC that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+-conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable on contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

PubMed

Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

2017-07-19

We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10 -3 S cm -1 at room temperature and >10 -4 S cm -1 at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g -1 at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g -1 ). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

Extrusion of electrode material by liquid injection into extruder barrel

DOEpatents

Keller, D.G.; Giovannoni, R.T.; MacFadden, K.O.

1998-03-10

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells. 1 fig.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Liu, Xiaoteng; Christensen, Paul A.; Kelly, Stephen M.; Rocher, Vincent; Scott, Keith

2013-01-01

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved. PMID:24957065

Extrusion of electrode material by liquid injection into extruder barrel

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

Keller, D.G.; Giovannoni, R.T.; MacFadden, K.O.

An electrode sheet product is formed using an extruder having a feed throat and a downstream section by separately mixing an active electrode material and a solid polymer electrolyte composition that contains lithium salt. The active electrode material is fed into the feed throat of the extruder, while a portion of at least one fluid component of the solid polymer electrolyte composition is introduced to the downstream section. The active electrode material and the solid polymer electrolyte composition are compounded in a downstream end of the extruder. The extruded sheets, adhered to current collectors, can be formed into battery cells.more » 1 fig.« 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.

High temperature lithium cells with solid polymer electrolytes

DOEpatents

Yang, Jin; Eitouni, Hany Basam; Singh, Mohit

2017-03-07

Electrochemical cells that use electrolytes made from new polymer compositions based on poly(2,6-dimethyl-1,4-phenylene oxide) and other high-softening-temperature polymers are disclosed. These materials have a microphase domain structure that has an ionically-conductive phase and a phase with good mechanical strength and a high softening temperature. In one arrangement, the structural block has a softening temperature of about 210.degree. C. These materials can be made with either homopolymers or with block copolymers. Such electrochemical cells can operate safely at higher temperatures than have been possible before, especially in lithium cells. The ionic conductivity of the electrolytes increases with increasing temperature.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells.

PubMed

Liu, Xiaoteng; Christensen, Paul A; Kelly, Stephen M; Rocher, Vincent; Scott, Keith

2013-12-05

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved.

On direct and indirect methanol fuel cells for transportation applications

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

Gottesfield, S.

1996-04-01

Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

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.

A Gel-Polymer Sn-C/LiMn0.5Fe0.5PO4 Battery Using a Fluorine-Free Salt.

PubMed

Di Lecce, Daniele; Fasciani, Chiara; Scrosati, Bruno; Hassoun, Jusef

2015-09-30

Safety and environmental issues, because of the contemporary use of common liquid electrolytes, fluorinated salts, and LiCoO2-based cathodes in commercial Li-ion batteries, might be efficiently mitigated by employing alternative gel-polymer battery configurations and new electrode materials. Herein we study a lithium-ion polymer cell formed by combining a LiMn0.5Fe0.5PO4 olivine cathode, prepared by simple solvothermal pathway, a nanostructured Sn-C anode, and a LiBOB-containing PVdF-based gel electrolyte. The polymer electrolyte, here analyzed in terms of electrochemical stability by impedance spectroscopy (EIS) and voltammetry, reveals full compatibility for cell application. The LiBOB electrolyte salt and the electrochemically delithiaded Mn0.5Fe0.5PO4 have a higher thermal stability compared to conventional LiPF6 and Li0.5CoO2, as confirmed by thermogravimetric analysis (TGA) and by galvanostatic cycling at high temperature. LiMn0.5Fe0.5PO4 and Sn-C, showing in lithium half-cell a capacity of about 120 and 350 mAh g(-1), respectively, within the gelled electrolyte configuration are combined in a full Li-ion polymer battery delivering a stable capacity of about 110 mAh g(-1), with working voltage ranging from 2.8 to 3.6 V.

High conductivity electrolyte solutions and rechargeable cells incorporating such solutions

DOEpatents

Angell, C.A.; Zhang, S.S.; Xu, K.

1998-10-20

This invention relates generally to electrolyte solvents for use in liquid or rubbery polymer electrolyte solutions as are used, for example, in electrochemical devices. More specifically, this invention relates to sulfonyl/phospho-compound electrolyte solvents and sulfonyl/phospho-compound electrolyte solutions incorporating such solvents. 9 figs.

Effect of conductive additives to gel electrolytes on activated carbon-based supercapacitors

NASA Astrophysics Data System (ADS)

Barzegar, Farshad; Dangbegnon, Julien K.; Bello, Abdulhakeem; Momodu, Damilola Y.; Johnson, A. T. Charlie; Manyala, Ncholu

2015-09-01

This article is focused on polymer based gel electrolyte due to the fact that polymers are cheap and can be used to achieve extended potential window for improved energy density of the supercapacitor devices when compared to aqueous electrolytes. Electrochemical characterization of a symmetric supercapacitor devices based on activated carbon in different polyvinyl alcohol (PVA) based gel electrolytes was carried out. The device exhibited a maximum energy density of 24 Wh kg-1 when carbon black was added to the gel electrolyte as conductive additive. The good energy density was correlated with the improved conductivity of the electrolyte medium which is favorable for fast ion transport in this relatively viscous environment. Most importantly, the device remained stable with no capacitance lost after 10,000 cycles.

Sodium ion conducting polymer electrolyte membrane prepared by phase inversion technique

NASA Astrophysics Data System (ADS)

Harshlata, Mishra, Kuldeep; Rai, D. K.

2018-04-01

A mechanically stable porous polymer membrane of Poly(vinylidene fluoride-hexafluoropropylene) has been prepared by phase inversion technique using steam as a non-solvent. The membrane possesses semicrystalline network with enhanced amorphicity as observed by X-ray diffraction. The membrane has been soaked in an electrolyte solution of 0.5M NaPF6 in Ethylene Carbonate/Propylene Carbonate (1:1) to obtain the gel polymer electrolyte. The porosity and electrolyte uptake of the membrane have been found to be 67% and 220% respectively. The room temperature ionic conductivity of the membrane has been obtained as ˜ 0.3 mS cm-1. The conductivity follows Arrhenius behavior with temperature and gives activation energy as 0.8 eV. The membrane has been found to possess significantly large electrochemical stability window of 5.0 V.

Composite Solid Electrolyte Containing Li+- Conducting Fibers

NASA Technical Reports Server (NTRS)

Appleby, A. John; Wang, Chunsheng; Zhang, Xiangwu

2006-01-01

Improved composite solid polymer electrolytes (CSPEs) are being developed for use in lithium-ion power cells. The matrix components of these composites, like those of some prior CSPEs, are high-molecular-weight dielectric polymers [generally based on polyethylene oxide (PEO)]. The filler components of these composites are continuous, highly-Li(+)-conductive, inorganic fibers. PEO-based polymers alone would be suitable for use as solid electrolytes, were it not for the fact that their room-temperature Li(+)-ion conductivities lie in the range between 10(exp -6) and 10(exp -8) S/cm, too low for practical applications. In a prior approach to formulating a CSPE, one utilizes nonconductive nanoscale inorganic filler particles to increase the interfacial stability of the conductive phase. The filler particles also trap some electrolyte impurities. The achievable increase in conductivity is limited by the nonconductive nature of the filler particles.

'All-solid-state' electrochemistry of a protein-confined polymer electrolyte film

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

Parthasarathy, Meera; Pillai, Vijayamohanan K.; Mulla, Imtiaz S.

2007-12-07

Interfacial redox behavior of a heme protein (hemoglobin) confined in a solid polymer electrolyte membrane, Nafion (a perfluoro sulfonic acid ionomer) is investigated using a unique 'all-solid-state' electrochemical methodology. The supple phase-separated structure of the polymer electrolyte membrane, with hydrophilic pools containing solvated protons and water molecules, is found to preserve the incorporated protein in its active form even in the solid-state, using UV-visible, Fluorescence (of Tryptophan and Tyrosine residues) and DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy. More specifically, solid-state cyclic voltammetry and electrochemical impedance of the protein-incorporated polymer films reveal that the Fe{sup 2+}-form of the entrapped proteinmore » is found to bind molecular oxygen more strongly than the native protein. In the 'all-solid-state' methodology, as there is no need to dip the protein-modified electrode in a liquid electrolyte (like the conventional electrochemical methods), it offers an easier means to study a number of proteins in a variety of polymer matrices (even biomimetic assemblies). In addition, the results of the present investigation could find interesting application in a variety of research disciplines, in addition to its fundamental scientific interest, including protein biotechnology, pharmaceutical and biomimetic chemistry.« less

Light-cured polymer electrolytes for safe, low-cost and sustainable sodium-ion batteries

NASA Astrophysics Data System (ADS)

Colò, Francesca; Bella, Federico; Nair, Jijeesh R.; Gerbaldi, Claudio

2017-10-01

In this work we present a very simple preparation procedure of a poly(ethylene oxide) (PEO)-based crosslinked polymer electrolyte (XPE) for application in sodium-ion batteries (NIBs). The polymer electrolyte, containing NaClO4 as Na+ source, is prepared by rapid, energy saving, solvent-free photopolymerization technique, in a single step. Thermal, mechanical, morphological and electrochemical properties of the resulting XPE are thoroughly investigated. The highly ionic conducting (>1 mS cm-1 at 25 °C) polymer electrolyte is used in a lab-scale sodium cell with nanostructured TiO2 working electrode. The obtained results in terms of ambient temperature cycling behaviour (stable specific capacity of about 250 mAh g-1 at 0.1 mA cm-2 and overall remarkable stability, for a quasi-solid state Na polymer cell, upon very long term cycling exceeding 1000 reversible cycles at 0.5 mA cm-2 corresponding to > 5000 h of continuous operation) demonstrate the promising prospects of this novel XPE to be implemented in the next-generation NIBs conceived for large-scale energy storage systems, such as those connected to photovoltaic and wind factories.

Preparation and characterization of plasticized palm-based polyurethane solid polymer electrolyte

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

Daud, Farah Nadia; Ahmad, Azizan; Badri, Khairiah Haji

2013-11-27

Palm-based polyurethane solid polymer electrolyte was prepared via prepolymerization method between palm kernel oil based polyols (PKO-p) and 2,4’-diphenylmethane diisocyanate (2,4’-MDI) in acetone at room temperature with the vary amount of lithium trifuoromethanesulfonate (LiCF{sub 3}SO{sub 3}) salt and polyethylene glycol (PEG). The film was analyzed using attenuated total reflection infrared (ATR-IR) spectroscopy, electrochemical impedance spectroscopy (EIS) and X-ray diffractometry (XRD). EIS result indicated ionic conductivity obtained with 30 wt% LiCF3SO3 increased to 6.55 × 10{sup −6} S cm{sup −1} when 10 wt.% of plasticizer was added into the system. FTIR analysis showed the interaction between lithium ions and amine (-N-H)more » at 3600–3100 cm{sup −1}, carbonyl (-C=O) at 1750–1650 cm{sup −1} and ether (-C-O-C-) at 1150–1000 cm{sup −1} of the polyurethane forming polymer-salt complexes. The XRD result confirmed that LiCF{sub 3}SO{sub 3} salt completely dissociated within the polyurethane film with the absence of crystalline peaks of LiCF{sub 3}SO{sub 3}.« less

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.

Investigation of bio polymer electrolyte based on cellulose acetate-ammonium nitrate for potential use in electrochemical devices.

PubMed

Monisha, S; Mathavan, T; Selvasekarapandian, S; Milton Franklin Benial, A; Aristatil, G; Mani, N; Premalatha, M; Vinoth Pandi, D

2017-02-10

Proton conducting materials create prime interest in electro chemical device development. Present work has been carried out to design environment friendly new biopolymer electrolytes (BPEs) using cellulose acetate (CA) complex with different concentrations of ammonium nitrate (NH 4 NO 3 ), which have been prepared as film and characterized. The 50mol% CA and 50mol% NH 4 NO 3 complex has highest ionic conductivity (1.02×10 -3 Scm -1 ). Differential scanning calorimetry shows the changes in glass transition temperature depends on salt concentration. Structural analysis indicates that the highest ionic conductivity complex exhibits more amorphous nature. Vibrational analysis confirms the complex formation, which has been validated theoretically by Gaussian 09 software. Conducting element in the BPEs has been predicted. Primary proton battery and proton exchange membrane fuel cell have been developed for highest ionic conductivity complex. Output voltage and power performance has been compared for single fuel cell application, which manifests the present BPE holds promise application in electrochemical devices. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of chitosan-starch blend based biopolymer electrolyte doped with ammonium nitrate

NASA Astrophysics Data System (ADS)

Shaffie, Ahmad Hakimi; Khiar, Azwani Sofia Ahmad

2018-06-01

Polymer electrolyte is an ionic conductor formed by dissolving salt in polymer host. In this work, starch/chitosan blend based polymer electrolyte was prepared with different weight percentage of Ammonium Nitrate (NH4NO3) via solution casting technique. The film was characterized by impedance spectroscopy HIOKI 3531- 01 LCR Hi-Tester to measure its ionic conductivity over a wide range of frequency between 50Hz-5MHz and at ambient temperature. Sample with 35 wt% of NH4NO3 shows the highest conductivity of (6.34 ± 1.52) = 10-7 Scm-1. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to correlate the ionic conductivity results.

Polymer Coatings Reduce Electro-osmosis

NASA Technical Reports Server (NTRS)

Herren, Blair J.; Snyder, Robert; Shafer, Steven G.; Harris, J. Milton; Van Alstine, James M.

1989-01-01

Poly(ethylene glycol) film controls electrostatic potential. Electro-osmosis in quartz or glass chambers reduced or reversed by coating inside surface of chambers with monomacromolecular layers of poly(ethylene glycol). Stable over long times. Electrostatic potential across surface of untreated glass or plastic chamber used in electro-phoresis is negative and attracts cations in aqueous electrolyte. Cations solvated, entrains flow of electrolyte migrating toward cathode. Electro-osmotic flow interferes with desired electrophoresis of particles suspended in electrolyte. Polymer coats nontoxic, transparent, and neutral, advantageous for use in electrophoresis.

Gel electrolytes and electrodes

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

Fleischmann, Sven; Bunte, Christine; Mikhaylik, Yuriy V.

Gel electrolytes, especially gel electrolytes for electrochemical cells, are generally described. In some embodiments, the gel electrolyte layers comprise components a) to c). Component a) may be at least one layer of at least one polymer comprising polymerized units of: a1) at least one monomer containing an ethylenically unsaturated unit and an amido group and a2) at least one crosslinker. Component b) may be at least one conducting salt and component c) may be at least one solvent. Electrodes may comprise the components a), d) and e), wherein component a) may be at least one layer of at least onemore » polymer as described herein. Component d) may be at least one electroactive layer and component e) may be at least one ceramic layer. Furthermore, electrochemical cells comprising component a) which may be at least one layer of at least one polymer as described herein, are also provided.« less

Na3.4Zr1.8Mg0.2Si2PO12 filled poly(ethylene oxide)/Na(CF3SO2)2N as flexible composite polymer electrolyte for solid-state sodium batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhizhen; Xu, Kaiqi; Rong, Xiaohui; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan

2017-12-01

Solid electrolytes with high ionic conductivity and excellent electrochemical stability are of prime significance to enable the application of solid-state batteries in energy storage and conversion. In this study, solid composite polymer electrolytes (CPEs) based on sodium bis(trifluorosulfonyl) imide (NaTFSI) and poly (ethylene oxide) (PEO) incorporated with active ceramic filler (NASICON) are reported for the first time. With the addition of NASICON fillers, the thermal stability and electrochemical stability of the CPEs are improved. A high conductivity of 2.8 mS/cm (at 80 °C) is readily achieved when the content of the NASICON filler in the composite polymer reaches 50 wt%. Furthermore, Na3V2(PO4)3/CPE/Na solid-state batteries using this composite electrolyte display good rate and excellent cycle performance.

Influence of confinement on polymer-electrolyte relaxational dynamics.

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

Zanotti, J.-M.; Smith, L. J.; Price, D. L.

2004-01-01

Conception and industrial production of viable high specific energy/power batteries is a central issue for the development of non-polluting vehicles. In terms of stored energy and safety, solid-state devices using polymer electrolytes are highly desirable. One of the most studied systems is PEO (polyethylene oxide) complexed by Li salts. Polymer segmental motions and ionic conductivity are closely related. Bulk PEO is actually a biphasic system where an amorphous and a crystalline state (Tm 335 K) coexist. To improve ionic conduction in those systems requires a significant increase of the amorphous phase fraction where lithium conduction is known to mainly takemore » place. Confinement strongly affects properties of condensed matter and in particular the collective phenomena inducing crystallization. Confinement of the polymer matrix is therefore a possible alternative route to the unpractical use of high temperature. Results of a quasi-elastic incoherent neutron scattering study of the influence of confinement on polyethylene oxide (PEO) and (PEO)8Li+[(CF3SO2)2N]- (or (POE)8LiTFSI) dynamics are presented. The nano-confining media is Vycor, a silica based hydrophilic porous glass (characteristic size of the 3D pore network 50 {angstrom}). As expected, the presence of Li salt slows down the bulk polymer dynamics. The confinement also affects dramatically the apparent mean-square displacement of the polymer. Local relaxational PEO dynamics is described KWW model. We also present an alternate model and show how the detailed polymer dynamics (correlation times and local geometry of the motions) can be described without the use of such stretched exponentials so as to access a rheology-related meaningful physical quantity: the monomeric friction coefficient.« less

Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

NASA Technical Reports Server (NTRS)

Bronstein, Lyudmila M.; Karlinsey, Robert L.; Ritter, Kyle; Joo, Chan Gyu; Stein, Barry; Zwanziger, Josef W.

2003-01-01

This paper reports synthesis, structure, and properties of novel hybrid solid polymer electrolytes (SPE's) consisting of organically modified aluminosilica (OM-ALSi), formed within a poly(ethylene oxide)-in-salt (Li triflate) phase. To alter the structure and properties we fused functionalized silanes containing poly(ethylene oxide) (PEO) tails or CN groups.

Quaternary Polymer Electrolytes Containing an Ionic Liquid and a Ceramic Filler.

PubMed

Sharova, Varvara; Kim, Guk-Tae; Giffin, Guinevere A; Lex-Balducci, Alexandra; Passerini, Stefano

2016-07-01

In this work, the individual and combined effects of an ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ceramic filler silicon dioxide on the thermal and electrochemical properties of poly(ethylene oxide) electrolytes have been investigated. The electrolyte containing both components has the lowest glass transition (-60 °C) and melting temperatures (27 °C), the highest conductivity at any investigated temperature, and the highest limiting current density (at 40 °C). This solid polymer electrolyte also exhibits the best long-term cycling performance in Li/LiFePO4 cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Simulation study of the lithium ion transport mechanism in ternary polymer electrolytes: the critical role of the segmental mobility.

PubMed

Diddens, Diddo; Heuer, Andreas

2014-01-30

We present an extensive molecular dynamics (MD) simulation study of the lithium ion transport in ternary polymer electrolytes consisting of poly(ethylene oxide) (PEO), lithium-bis(trifluoromethane)sulfonimide (LiTFSI), and the ionic liquid N-methyl-N-propylpyrrolidinium bis(trifluoromethane)sulfonimide (PYR13TFSI). In particular, we focus on two different strategies by which the ternary electrolytes can be devised, namely by (a) adding the ionic liquid to PEO20LiTFSI and (b) substituting the PEO chains in PEO20LiTFSI by the ionic liquid. To grasp the changes of the overall lithium transport mechanism, we employ an analytical, Rouse-based cation transport model (Maitra et al. Phys. Rev. Lett. 2007, 98, 227802), which has originally been devised for binary PEO-based electrolytes. This model distinguishes three different microscopic transport mechanisms, each quantified by an individual time scale. In the course of our analysis, we extend this mathematical description to account for an entirely new transport mechanism, namely, the TFSI-supported diffusion of lithium ions decoupled from the PEO chains, which emerges for certain stoichiometries. We find that the segmental mobility plays a decisive role in PEO-based polymer electrolytes. That is, whereas the addition of the ionic liquid to PEO20LiTFSI plasticizes the polymer network and thus also increases the lithium diffusion, the amount of free, mobile ether oxygens reduces when substituting the PEO chains by the ionic liquid, which compensates the plasticizing effect. In total, our observations allow us to formulate some general principles about the lithium ion transport mechanism in ternary polymer electrolytes. Moreover, our insights also shed light on recent experimental observations (Joost et al. Electrochim. Acta 2012, 86, 330).

Effect of Dispersoid on Sulfonium Ionic Liquid Based Gel Polymer Electrolyte for Lithium Secondary Battery.

PubMed

Muthupradeepa, R; Sivakumar, M; Subadevi, R; Suryanarayanan, V; Liu, Wei-Ren

2018-01-01

The present study emphases on the effect of toting of TiO2 filler on the electrochemical enactment of polymer electrolyte containing PVdF-co-HFP(30) + SEt3TFSI(10) + EC/PC(60) + TiO2(x) wt% (Poly (vinylidene fluoride-co-hexafluoropropylene + Triethylsulfoniumbis(trifluoromethylsulfonyl)imide + Ethylene carbonate/Propylene carbonate (1:1 ratio) + Titanium dioxide) for lithium battery applications. Composite electrolytes with different weight percentages of TiO2 were prepared and characterized by different surface analytical, thermal and electrochemical techniques. With gradual increase of the amount of TiO2 upto 6 wt%, broadening of the prominent peak has been noted, suggesting a decrease in the degree of crystallinity upon the addition of TiO2, as revealed by X-ray diffraction (XRD). Raman and FT-IR studies confirm the presence of various functional groups, present in the matrix. The electrolyte with TiO2 (6 wt%) has maximum stability of 460 °C, as confirmed by thermal analysis. Conductivity of the composite polymer electrolytes increases upto 6 wt% of TiO2 (3.42 × 10-3 S/cm at 303 K) and further addition, causes a dip down in conductivity, indicating an improvement in the ionic conductivity and thermal stability with the incorporation of TiO2 filler. Surface morphologic images show the presence of surface and cavity in the polymer matrix, filled with the filler uniformly. Voltammetric studies confirm the electrochemical stability of films upto 4.62 V. Coin cell containing Li anode and LiFePO4 cathode along with polymer electrolyte/6 wt% TiO2 filler, delivers a first discharge capacity of 145 mAh/g with the working voltage of 3.4 V.

Electrochemical device for converting carbon dioxide to a reaction product

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

Masel, Richard I.; Chen, Qingmei; Liu, Zengcai

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potentialmore » of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.« less

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

Single lithium-ion conducting solid polymer electrolytes: advances and perspectives.

PubMed

Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M; Armand, Michel; Zhou, Zhibin

2017-02-06

Electrochemical energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aqueous liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues, and the energy density of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theoretical capacity of lithium metal and its low negative potential. However, the progress in the field of non-aqueous liquid electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect solution to these safety concerns and to the enhancement of energy density. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concentration polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorganic backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference number (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on organic polymers, organic-inorganic hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental physical and electrochemical properties of SLIC-SPEs prepared by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic conductivity and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.

U.S. DOE Progress Towards Developing Low-Cost, High Performance, Durable Polymer Electrolyte Membranes for Fuel Cell Applications

PubMed Central

Houchins, Cassidy; Kleen, Greg J.; Spendelow, Jacob S.; Kopasz, John; Peterson, David; Garland, Nancy L.; Ho, Donna Lee; Marcinkoski, Jason; Martin, Kathi Epping; Tyler, Reginald; Papageorgopoulos, Dimitrios C.

2012-01-01

Low cost, durable, and selective membranes with high ionic conductivity are a priority need for wide-spread adoption of polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). Electrolyte membranes are a major cost component of PEMFC stacks at low production volumes. PEMFC membranes also impose limitations on fuel cell system operating conditions that add system complexity and cost. Reactant gas and fuel permeation through the membrane leads to decreased fuel cell performance, loss of efficiency, and reduced durability in both PEMFCs and DMFCs. To address these challenges, the U.S. Department of Energy (DOE) Fuel Cell Technologies Program, in the Office of Energy Efficiency and Renewable Energy, supports research and development aimed at improving ion exchange membranes for fuel cells. For PEMFCs, efforts are primarily focused on developing materials for higher temperature operation (up to 120 °C) in automotive applications. For DMFCs, efforts are focused on developing membranes with reduced methanol permeability. In this paper, the recently revised DOE membrane targets, strategies, and highlights of DOE-funded projects to develop new, inexpensive membranes that have good performance in hot and dry conditions (PEMFC) and that reduce methanol crossover (DMFC) will be discussed. PMID:24958432

Optimizing photovoltaic performance in CuInS 2 and CdS quantum dot-sensitized solar cells by using an agar-based gel polymer electrolyte

DOE PAGES

Raphael, E.; Jara, D. H.; Schiavon, M. A.

2017-01-19

Quantum dot-sensitized solar cells (QDSSCs) offer new opportunities to address the clean energy challenge, being one of the top candidates for third generation photovoltaics. Like dye-sensitized solar cells (DSSCs), QDSSCs normally use liquid electrolytes that suffer from issues such as evaporation or leakage. In this study a gel polysulfide electrolyte was prepared containing a natural polymer, agar, and was used as a quasi-solid-state electrolyte in solar cells to replace the conventional liquid electrolytes. This gel electrolyte shows almost the same conductivity as the liquid one. The solar cells were fabricated using CuInS 2 quantum dots (QDs), previously synthesized, deposited onmore » TiO 2 photoanodes by electrophoretic deposition (EPD). CdS was deposited on TiO 2 by successive ionic layer adsorption and reaction (SILAR). Reduced graphene oxide (RGO)–Cu 2S, brass, and thin film CuxS were used as counter electrodes. Compared to a liquid polysulfide water based electrolyte, solar cells based on CuInS 2 and CdS using gel polymer electrolyte (GPE) exhibit greater incident photon to current conversion efficiency (IPCE = 51.7% at 520 nm and 72.7% at 440 nm), photocurrent density (J sc = 10.75 and 13.51 mA cm -2), and power conversion efficiency (η = 2.97 and 2.98%) while exhibiting significantly enhanced stability. The solar cells employing the agar-based gel polymeric electrolyte are about a factor of 0.20 more stable than using a liquid electrolyte. The higher photovoltaic performance is due to the good conductivity and high wettability as well as the superior permeation capability of the gel electrolyte into the mesoporous matrix of a TiO 2 film« less

Optimizing photovoltaic performance in CuInS 2 and CdS quantum dot-sensitized solar cells by using an agar-based gel polymer electrolyte

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

Raphael, E.; Jara, D. H.; Schiavon, M. A.

Quantum dot-sensitized solar cells (QDSSCs) offer new opportunities to address the clean energy challenge, being one of the top candidates for third generation photovoltaics. Like dye-sensitized solar cells (DSSCs), QDSSCs normally use liquid electrolytes that suffer from issues such as evaporation or leakage. In this study a gel polysulfide electrolyte was prepared containing a natural polymer, agar, and was used as a quasi-solid-state electrolyte in solar cells to replace the conventional liquid electrolytes. This gel electrolyte shows almost the same conductivity as the liquid one. The solar cells were fabricated using CuInS 2 quantum dots (QDs), previously synthesized, deposited onmore » TiO 2 photoanodes by electrophoretic deposition (EPD). CdS was deposited on TiO 2 by successive ionic layer adsorption and reaction (SILAR). Reduced graphene oxide (RGO)–Cu 2S, brass, and thin film CuxS were used as counter electrodes. Compared to a liquid polysulfide water based electrolyte, solar cells based on CuInS 2 and CdS using gel polymer electrolyte (GPE) exhibit greater incident photon to current conversion efficiency (IPCE = 51.7% at 520 nm and 72.7% at 440 nm), photocurrent density (J sc = 10.75 and 13.51 mA cm -2), and power conversion efficiency (η = 2.97 and 2.98%) while exhibiting significantly enhanced stability. The solar cells employing the agar-based gel polymeric electrolyte are about a factor of 0.20 more stable than using a liquid electrolyte. The higher photovoltaic performance is due to the good conductivity and high wettability as well as the superior permeation capability of the gel electrolyte into the mesoporous matrix of a TiO 2 film« less

Dependence of Ion Dynamics on the Polymer Chain Length in Poly(ethylene oxide)-Based Polymer Electrolytes.

PubMed

Chattoraj, Joyjit; Knappe, Marisa; Heuer, Andreas

2015-06-04

It is known from experiments that in the polymer electrolyte system, which contains poly(ethylene oxide) chains (PEO), lithium-cations (Li(+)), and bis(trifluoromethanesulfonyl)imide-anions (TFSI(-)), the cation and the anion diffusion and the ionic conductivity exhibit a similar chain-length dependence: with increasing chain length, they start dropping steadily, and later, they saturate to constant values. These results are surprising because Li-cations are strongly correlated with the polymer chains, whereas TFSI-anions do not have such bonding. To understand this phenomenon, we perform molecular dynamics simulations of this system for four different polymer chain lengths. The diffusion results obtained from our simulations display excellent agreement with the experimental data. The cation transport model based on the Rouse dynamics can successfully quantify the Li-diffusion results, which correlates Li diffusion with the polymer center-of-mass motion and the polymer segmental motion. The ionic conductivity as a function of the chain length is then estimated based on the chain-length-dependent ion diffusion, which shows a temperature-dependent deviation for short chain lengths. We argue that in the first regime, counterion correlations modify the conductivity, whereas for the long chains, the system behaves as a strong electrolyte.

In-situ preparation of poly(ethylene oxide)/Li3PS4 hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Chen, Shaojie; Wang, Junye; Zhang, Zhihua; Wu, Linbin; Yao, Lili; Wei, Zhenyao; Deng, Yonghong; Xie, Dongjiu; Yao, Xiayin; Xu, Xiaoxiong

2018-05-01

Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10-4 S cm-1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g-1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.

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.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Nagasubramanian, Ganesan (Inventor)

1997-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

1994-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Nanomaterials for Polymer Electrolyte Membrane Fuel Cells; Materials Challenges Facing Electrical Energy Storate

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

Gopal Rao, MRS Web-Editor; Yury Gogotsi, Drexel University; Karen Swider-Lyons, Naval Research Laboratory

Symposium T: Nanomaterials for Polymer Electrolyte Membrane Fuel Cells Polymer electrolyte membrane (PEM) fuel cells are under intense investigation worldwide for applications ranging from transportation to portable power. The purpose of this seminar is to focus on the nanomaterials and nanostructures inherent to polymer fuel cells. Symposium topics will range from high-activity cathode and anode catalysts, to theory and new analytical methods. Symposium U: Materials Challenges Facing Electrical Energy Storage Electricity, which can be generated in a variety of ways, offers a great potential for meeting future energy demands as a clean and efficient energy source. However, the use ofmore » electricity generated from renewable sources, such as wind or sunlight, requires efficient electrical energy storage. This symposium will cover the latest material developments for batteries, advanced capacitors, and related technologies, with a focus on new or emerging materials science challenges.« less

A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

NASA Astrophysics Data System (ADS)

Rao, B. Narasimha; Suvarna, R. Padma

2016-05-01

Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

Solid polymer electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed; Choe, Hyoun S.

1995-01-01

This invention relates to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF.sub.3 SO.sub.2).sub.2, LiAsF.sub.6, and LiClO.sub.4.

Characterization of plasticized PEO-PAM blend polymer electrolyte system

NASA Astrophysics Data System (ADS)

Dave, Gargi; Kanchan, Dinesh

2017-05-01

Present study reports characterization studies of NaCF3SO3 based PEO-PAM Blend Polymer Electrolyte (BPE) system with varying amount of EC+PC as plasticizer prepared by solution cast technique. Structural analysis and surface topography have been performed using FTIR and SEM studies. To understand, thermal properties, DSC studies have been undertaken in the present paper

Development of a solid polymer electrolyte electrolysis cell module and ancillary components for a breadboard water electrolysis system

NASA Technical Reports Server (NTRS)

Porter, F. J., Jr.

1972-01-01

Solid polymer electrolyte technology in a water electrolysis system along with ancillary components to generate oxygen and hydrogen for a manned space station application are considered. Standard commercial components are utilized wherever possible. Presented are the results of investigations, surveys, tests, conclusions and recommendations for future development efforts.

The JPL Direct Methanol Liquid-feed PEM Fuel Cell

NASA Technical Reports Server (NTRS)

Halpert, G.; Surampudi, S.

1994-01-01

Recently, there has been a breakthrough in fuel cell technology in the Energy Storage Systems Group at the Jet Propulsion Laboratory with the develpment of a direct methanol, liquid-feed, solid polymer electrolyte membrane (PEM) fuel cell... The methanol liquid-feed, solid polymer electrolyte (PEM) design has numerous system level advantages over the gas-feed design. These include:...

Electrical and dielectric properties of PVdF-HFP - PMMA - (PC + DEC)- LiClO4 based gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Gohel, Khushbu; Kanchan, D. K.; Maheshwaran, C.

2018-04-01

In the present paper, AC impedance studies have been measured to evaluate ion conduction behavior of (PVdF-HFP - PMMA) + (PC-DEC) + LiClO4 gel polymer electrolyte system prepared by solution casting method. Structural characterization and morphology has been carried out using XRD and SEM respectively. The AC conductivity and dielectric permittivity, electric modulus and relaxation mechanism have been studied. The variation of ac conductivity with frequency obeys Jonscher power law. Maximum value of dielectric constant ɛ' in the lower frequency region has been observed for the gel polymer electrolyte containing 7.5 wt% LiClO4. The highest conducting sample shows the shortest relaxation time.

Development and Application of a Sample Holder for In Situ Gaseous TEM Studies of Membrane Electrode Assemblies for Polymer Electrolyte Fuel Cells.

PubMed

Kamino, Takeo; Yaguchi, Toshie; Shimizu, Takahiro

2017-10-01

Polymer electrolyte fuel cells hold great potential for stationary and mobile applications due to high power density and low operating temperature. However, the structural changes during electrochemical reactions are not well understood. In this article, we detail the development of the sample holder equipped with gas injectors and electric conductors and its application to a membrane electrode assembly of a polymer electrolyte fuel cell. Hydrogen and oxygen gases were simultaneously sprayed on the surfaces of the anode and cathode catalysts of the membrane electrode assembly sample, respectively, and observation of the structural changes in the catalysts were simultaneously carried out along with measurement of the generated voltages.

Performance Characteristics of Lithium Ion Polymeric Electrolyte Cells

NASA Technical Reports Server (NTRS)

Shen, D.; Nagasubramanian, G.; Huang, C-K.; Surampudi, S.; Halpert, G.

1994-01-01

A series of polyacrylonitrile-based (PAN) electrolytes containing LiAsF6 and a number of solvent mixtures including ethylene carbonate (EC) + propylene carbonate (PC) were prepared, electrochemically evaluated and used as electrolyte in the polymer cells.

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

Novel synthesis of highly durable and active Pt catalyst encapsulated in nitrogen containing carbon for polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Lee, Hyunjoon; Sung, Yung-Eun; Choi, Insoo; Lim, Taeho; Kwon, Oh Joong

2017-09-01

Novel synthesis of a Pt catalyst encapsulated in a N-containing carbon layer for use in a polymer electrolyte membrane fuel cell is described in this study. A Pt-aniline complex, formed by mixing Pt precursor and aniline monomer, was used as the source of Pt, C, and N. Heat treatment of the Pt-aniline complex with carbon black yielded 5 nm Pt nanoparticles encapsulated by a N-containing carbon layer originating from aniline carbonization. The synthesized Pt catalyst exhibited higher mass specific activity to oxygen reduction reaction than that shown by conventional Pt/C catalyst because pyridinic N with graphitic carbon in the carbon layer provided active sites for oxygen reduction reaction in addition to those provided by Pt. In single cell testing, initial performance of the synthesized catalyst was limited because the thick catalyst layer increased resistance related to mass transfer. However, it was observed that the carbon layer successfully prevented Pt nanoparticles from growing via agglomeration and Ostwald ripening under fuel cell operation, thereby improving durability. Furthermore, a mass specific performance of the synthesized catalyst higher than that of a conventional Pt/C catalyst was achieved by modifying the synthesized catalyst's layer thickness.

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Stabilizing electrochemical interfaces in viscoelastic liquid electrolytes

PubMed Central

2018-01-01

Electrodeposition is a widely practiced method for creating metal, colloidal, and polymer coatings on conductive substrates. In the Newtonian liquid electrolytes typically used, the process is fundamentally unstable. The underlying instabilities have been linked to failure of microcircuits, dendrite formation on battery electrodes, and overlimiting conductance in ion-selective membranes. We report that viscoelastic electrolytes composed of semidilute solutions of very high–molecular weight neutral polymers suppress these instabilities by multiple mechanisms. The voltage window ΔV in which a liquid electrolyte can operate free of electroconvective instabilities is shown to be markedly extended in viscoelastic electrolytes and is a power-law function, ΔV : η1/4, of electrolyte viscosity, η. This power-law relation is replicated in the resistance to ion transport at liquid/solid interfaces. We discuss consequences of our observations and show that viscoelastic electrolytes enable stable electrodeposition of many metals, with the most profound effects observed for reactive metals, such as sodium and lithium. This finding is of contemporary interest for high-energy electrochemical energy storage. PMID:29582017

Polymer complexes. LVII. Supramolecular assemblies of novel polymer complexes of dioxouranium(VI) with some substituted allyl azo dye compounds

NASA Astrophysics Data System (ADS)

Diab, M. A.; El-Sonbati, A. Z.; El-Bindary, A. A.; Balboula, M. Z.

2013-05-01

A novel method to synthesize some dioxouranium(VI) polymer complexes of the general formula [UO2(Ln)2(OAc)2] (where HLn = azo allyl rhodanine). The structure of the novel mononuclear dioxoutranium(VI) polymer complexes was characterized using elemental analysis, spectral (electronic, infrared, 1H &13C NMR) studies, magnetic susceptibility measurements and thermal analysis. The molar conductivities show that all the polymer complexes are non-electrolytes. The IR showed that the ligand HLn act as bidentate neutral through carbonyl group and imine group nitrogen atom forming thereby a six-membered chelating ring and concomitant formation of an intramolecular hydrogen bond. The υ3 frequency of UO2+2 has been shown to be an excellent molecular probe for studying the coordinating power of the ligands. The values of υ3 of the prepared complexes containing UO2+2 were successfully used to calculate the force constant, FUO (10-8 N/Å) and the bond length RUO (Å) of the Usbnd O bond. A strategy based upon both theoretical and experimental investigations has been adopted. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the Usbnd O bond distances from the values of the stretching and interaction force constants. The most probable correlation between Usbnd O force constant to Usbnd O bond distance were satisfactorily discussed in term of Badger's rule and the equations suggested by Jones and El-Sonbati. The effect of Hammet constant is also discussed.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

A Silica-Aerogel-Reinforced Composite Polymer Electrolyte with High Ionic Conductivity and High Modulus.

PubMed

Lin, Dingchang; Yuen, Pak Yan; Liu, Yayuan; Liu, Wei; Liu, Nian; Dauskardt, Reinhold H; Cui, Yi

2018-06-25

High-energy all-solid-state lithium (Li) batteries have great potential as next-generation energy-storage devices. Among all choices of electrolytes, polymer-based systems have attracted widespread attention due to their low density, low cost, and excellent processability. However, they are generally mechanically too weak to effectively suppress Li dendrites and have lower ionic conductivity for reasonable kinetics at ambient temperature. Herein, an ultrastrong reinforced composite polymer electrolyte (CPE) is successfully designed and fabricated by introducing a stiff mesoporous SiO 2 aerogel as the backbone for a polymer-based electrolyte. The interconnected SiO 2 aerogel not only performs as a strong backbone strengthening the whole composite, but also offers large and continuous surfaces for strong anion adsorption, which produces a highly conductive pathway across the composite. As a consequence, a high modulus of ≈0.43 GPa and high ionic conductivity of ≈0.6 mS cm -1 at 30 °C are simultaneously achieved. Furthermore, LiFePO 4 -Li full cells with good cyclability and rate capability at ambient temperature are obtained. Full cells with cathode capacity up to 2.1 mAh cm -2 are also demonstrated. The aerogel-reinforced CPE represents a new design principle for solid-state electrolytes and offers opportunities for future all-solid-state Li batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid polymer electrolytes

DOEpatents

Abraham, K.M.; Alamgir, M.; Choe, H.S.

1995-12-12

This invention relates to Li ion (Li{sup +}) conductive solid polymer electrolytes composed of poly(vinyl sulfone) and lithium salts, and their use in all-solid-state rechargeable lithium ion batteries. The lithium salts comprise low lattice energy lithium salts such as LiN(CF{sub 3}SO{sub 2}){sub 2}, LiAsF{sub 6}, and LiClO{sub 4}. 2 figs.

Advanced Energy Storage and Conversion Devices

DTIC Science & Technology

2008-12-01

determined lithium-ion insertion mechanisms. 3.1 Background and Objectives Polymer electrolyte membrane fuel cells ( PEMFCs ) function by permitting...is one of the most critical components in the polymer electrolyte fuel cells. In recent years, PEMFCs have been identified as promising power...and residual hydrocarbons that are commonly produced by internal combustion engines. PEMFCs , due to their high efficiency and modularity of design

PEO based polymer composite with added acetamide, NaI/I2 as gel polymer electrolyte for dye sensitized solar cell applications

NASA Astrophysics Data System (ADS)

Narasimha Rao, B.; Padma suvarna, R.; Giribabu, L.; Raghavender, M.; kumar, V. Ramesh

2018-02-01

Poly (ethylene oxide) (PEO) based gel polymer electrolytes (GPEs) with added acetamide, NaI/I2 have been prepared for dye-sensitized solar cells application (DSSC). The Dye-sensitized solar cell investigated the performance of the optimized gel polymer electrolyte. GPEs synthesized by adding up of acetamide with different wt% in poly (ethylene oxide) (PEO) and poly (ethylene glycol) dimethyl ether (PEGDME) with NaI/I2. A maximum power conversion efficiency of 5.92% is achieved for PEO/PEGDME with 10 wt% acetamide in the photovoltaic performance under 100 mW/cm2 illumination and it exhibits maximum ionic conductivity (σ = 2.81×10-3 S/cm) among all electrolytes, compared to PEO without acetamide (η = 4.35%). The gain in open circuit voltage (Voc) was observed for GPEs due to the decrease in the recombination effect and electron lifetime increases by the addition of acetamide on the PEO. The fill factor (FF) is increased due to the growth in the ionic conductivity and amorphous nature of the GPE increases by the addition of acetamide on the PEO.

An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

PubMed Central

Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

2015-01-01

A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

Dispelling clichés at the nanoscale: the true effect of polymer electrolytes on the performance of dye-sensitized solar cells.

PubMed

Bella, Federico; Sacco, Adriano; Massaglia, Giulia; Chiodoni, Angelica; Pirri, Candido Fabrizio; Quaglio, Marzia

2015-07-28

In the field of dye-sensitized solar cells, polymer electrolytes are among the most studied materials due to their ability to ensure both high efficiency and stability, the latter being a critical point of these devices. Hundreds of polymeric matrices have been proposed over the years, and their functionalization with several groups, the variation of their molecular weight and the tuning of the crosslinking degree have been investigated. However, the true effect that polymeric matrices have on the cell parameters has often been addressed superficially, and hundreds of papers justify the obtained results with a simple bibliographic reference to other systems (sometimes completely different). This work proposes a system of nanoscale growth and crosslinking of a polymer electrolyte inside a nanostructured photoanode. Electrochemical and photovoltaic parameters are carefully monitored as a function of thickness and degree of penetration of the electrolyte. The results derived from this study refute many clichés generally accepted and taken for granted in many literature articles, and – for the first time – a compromise between the amount of polymer, cell efficiency and stability is achieved.

Biodegradation test of SPS-LS blends as polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Putri, Zufira; Arcana, I. Made

2014-03-01

Sulfonated polystyrene (SPS) can be applied as a proton exchange membrane fuel cell due to its fairly good chemical stability. In order to be applied as polymer electrolyte membrane fuel cells (PEMFCs), membrane polymer should have a good ionic conductivity, high proton conductivity, and high mechanical strength. Lignosulfonate (LS) is a complex biopolymer which has crosslinks and sulfonate groups. SPS-LS blends with addition of SiO2 are used to increase the proton conductivity and to improve the mechanical properties and thermal stability. However, the biodegradation test of SPS-LS blends is required to determine whether the application of these membranes to be applied as an environmentally friendly membrane. In this study, had been done the synthesis of SPS, biodegradability test of SPS-LS blends with variations of LS and SiO2 compositions. The biodegradation test was carried out in solid medium of Luria Bertani (LB) with an activated sludge used as a source of microorganism at incubation temperature of 37°C. Based on the results obtained indicated that SPS-LS-SiO2 blends are more decomposed by microorganism than SPS-LS blends. This result is supported by analysis of weight reduction percentage, functional groups with Fourier Transform Infrared (FTIR) Spectroscopy, and morphological surface with Scanning Electron Microscopy (SEM).

Inorganic-organic electrolyte materials for energy applications

NASA Astrophysics Data System (ADS)

Fei, Shih-To

This thesis research is devoted to the development of phosphazene-based electrolyte materials for use in various energy applications. Phosphazenes are inorganic-organic materials that provide unusal synthetic advantages and unique process features that make them useful in energy research. This particular thesis consists of six chapters and is focused on four specific aspects: lithium battery, solar cell, and fuel cell electrolytes, and artificial muscles. Chapter 1 is written as an introduction and review of phosphazene electrolytes used in energy applications. In this introduction the basic history and characteristics of the phosphazenes are discussed briefly, followed by examples of current and future applications of phosphazene electrolytes related to energy. Notes are included on how the rest of the chapters relate to previous work. Chapters 2 and 3 discuss the conductivity and fire safety of ethyleneoxy phosphazene gel electrolytes. The current highly flammable configurations for rechargeable lithium batteries generate serious safety concerns. Although commercial fire retardant additives have been investigated, they tend to decrease the overall efficiency of the battery. In these two chapters the discussion is focused on ionically conductive, non-halogenated lithium battery additives based on a methoxyethoxyethoxyphosphazene oligomer and the corresponding high polymer, both of which can increase the fire resistance of a battery while retaining a high energy efficiency. Conductivities in the range of 10 -4 Scm-1 have been obtained for self-extinguishing, ion-conductive methoxyethoxyethoxyphosphazene oligomers. The addition of 25 wt% high polymeric poly[bis(methoxyethoxyethoxy)phosphazene] to propylene carbonate electrolytes lowers the flammability by 90% while maintaining a good ionic conductivity of 2.5x10--3 Scm -1 Chapter 2 is focused more on the electrochemical properties of the electrolytes and how they compare to other similar materials, while Chapter 3 emphasizes the flammability studies. Chapter 4 expands the application of the ethyleneoxy phosphazene system to dye sensitized solar cell systems, and uses this material as a model for the study of electrode-electrolyte interfaces. We report here the results of our study on polymer electrolyte infiltration and its effect on dye-sensitized solar cells. In-depth studies have been made to compare the effects of different cell assembly procedures on the electrochemical properties as well as infiltration of electrolytes into various electrode designs. The first part of the study is based on the use of thermoplastic phosphazene electrolytes and how the overall fabrication procedure affects electrochemical performance, and the second is the use of cross-section microscopy to characterize the degree of electrolyte infiltration into various nanostructured titanium dioxide electrode surfaces. The results of this study should eventually improve the efficiency and longevity of thermally stable polymer dye solar cell systems. In Chapter 5 the effect of pendant polymer design on methanol fuel cell membrane performance was investigated. A synthetic method is described to produce a proton conductive polymer membrane with a polynorbornane backbone and inorganic-organic cyclic phosphazene pendent groups that bear sulfonic acid units. This hybrid polymer combines the inherent hydrophobicity and flexibility of the organic polymer with the tuning advantages of the cyclic phosphazene to produce a membrane with high proton conductivity and low methanol crossover at room temperature. The ion exchange capacity (IEC), the water swelling behavior of the polymer, and the effect of gamma radiation crosslinking were studied, together with the proton conductivity and methanol permeability of these materials. A typical membrane had an IEC of 0.329 mmolg-1 and had water swelling of 50 wt%. The maximum proton conductivity of 1.13x10 -4 Scm-1 at room temperature is less than values reported for some commercially available materials such as Nafion. However the average methanol permeability was around 10-9 cms-1, which is one hundred times smaller than the value for Nafion. Thus, the new polymers are candidates for low-temperature direct methanol fuel cell membranes. Finally, Chapter 6 focuses on the electroactivity of a mixed-substituent phosphazene electrolyte and its viability as an actuator material. We report here an electrochemically responsive polymer hydrogel based on ionic crosslinking. The crosslinking by metal cations and anionic carboxylic acid side groups can be controlled by redox reactions. The crosslinks dissociate when the cation crosslinker is reduced to a lower oxidation state and reform following oxidation, which leads to a reversible and localized swelling--contraction. By choosing biocompatible components and miniaturization designs, the system has potential in microrobotic and biomedical applications.

Comparative study of polymer and liquid electrolytes in quantum dot sensitized solar cells

NASA Astrophysics Data System (ADS)

Poudyal, Uma; Wang, Wenyong

We present the study of CdS/CdSe quantum dot sensitized solar cells (QDSSCs) in which Zn2SnO4\\ nanowires on the conductive glass are used as photoanode. The CdS/CdSe quantum dots (QDs) are deposited in the Zn2SnO4 photoanode by the Successive Ionic Layer Adsorption and Reaction (SILAR) method. CdS is first deposited on the nanowires after which it is further coated with 5 cycles of CdSe QDs. Finally, ZnS is coated on the QDs as a passivation layer. The QD sensitized photoanode are then used to assemble a solar device with the polymer and liquid electrolytes. The Incident Photon to Current Efficiency (IPCE) spectra are obtained for the CdS/CdSe coated nanowires. Further, a stability test of these devices is performed, using the polymer and liquid electrolytes, which provides insight to determine the better working electrolyte in the CdS/CdSe QDSSCs. Department of Energy.

Newly Elaborated Multipurpose Polymer Electrolyte Encompassing RTILs for Smart Energy-Efficient Devices.

PubMed

Nair, Jijeesh R; Porcarelli, Luca; Bella, Federico; Gerbaldi, Claudio

2015-06-17

Profoundly ion-conducting, self-standing, and tack-free ethylene oxide-based polymer electrolytes encompassing a room-temperature ionic liquid (RTIL) with specific amounts of lithium salt are successfully prepared via a rapid and easily upscalable process including a UV irradiation step. All prepared materials are thoroughly characterized in terms of their physical, chemical, and morphological properties and eventually galvanostatically cycled in lab-scale lithium batteries (LIBs) exploiting a novel direct polymerization procedure to get intimate electrode/electrolyte interfacial characteristics. The promising multipurpose characteristics of the newly elaborated materials are demonstrated by testing them in dye-sensitized solar cells (DSSCs), where the introduction of the iodine/iodide-based redox mediator in the polymer matrix assured the functioning of a lab-scale test cell with conversion efficiency exceeding 6% at 1 sun. The reported results enlighten the promising prospects of the material to be successfully implemented as stable, durable, and efficient electrolyte in next-generation energy conversion and storage devices.

BIPV-powered smart windows utilizing photovoltaic and electrochromic devices.

PubMed

Ma, Rong-Hua; Chen, Yu-Chia

2012-01-01

A BIPV-powered smart window comprising a building-integrated photovoltaic (BIPV) panel and an all-solid-state electrochromic (EC) stack is proposed. In the proposed device, the output voltage of the BIPV panel varies in accordance with the intensity of the incident light and is modulated in such a way as to generate the EC stack voltage required to maintain the indoor illuminance within a specified range. Two different EC stacks are fabricated and characterized, namely one stack comprising ITO/WO(3)/Ta(2)O(5)/ITO and one stack comprising ITO/WO(3)/lithium-polymer electrolyte/ITO. It is shown that of the two stacks, the ITO/WO(3)/lithium-polymer electrolyte/ITO stack has a larger absorptance (i.e., approximately 99% at a driving voltage of 3.5 V). The experimental results show that the smart window incorporating an ITO/WO(3)/lithium-polymer electrolyte/ITO stack with an electrolyte thickness of 1.0 μm provides an indoor illuminance range of 750-1,500 Lux under typical summertime conditions in Taiwan.

Intrinsically stretchable supercapacitors composed of polypyrrole electrodes and highly stretchable gel electrolyte.

PubMed

Zhao, Chen; Wang, Caiyun; Yue, Zhilian; Shu, Kewei; Wallace, Gordon G

2013-09-25

There has been an emerging interest in stretchable power sources compatible with flexible/wearable electronics. Such power sources must be able to withstand large mechanical strains and still maintain function. Here we report a highly stretchable H3PO4-poly(vinyl alcohol) (PVA) polymer electrolyte obtained by optimizing the polymer molecular weight and its weight ratio to H3PO4 in terms of conductivity and mechanical properties. The electrolyte demonstrates a high conductivity of 3.4 × 10(-3) S cm(-1), and a high fracture strain at 410% elongation. It is mechanically robust with a tensile strength of 2 MPa and a Young's modulus of 1 MPa, and displays a small plastic deformation (5%) after 1000 stretching cycles at 100% strain. A stretchable supercapacitor device has been developed based on buckled polypyrrole electrodes and the polymer electrolyte. The device shows only a small capacitance loss of 5.6% at 30% strain, and can retain 81% of the initial capacitance after 1000 cycles of such stretching.

Functional interface of polymer modified graphite anode

NASA Astrophysics Data System (ADS)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

Hybrid capacitor with activated carbon electrode, Ni(OH) 2 electrode and polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Nohara, Shinji; Asahina, Toshihide; Wada, Hajime; Furukawa, Naoji; Inoue, Hiroshi; Sugoh, Nozomu; Iwasaki, Hideharu; Iwakura, Chiaki

A new hybrid capacitor (HC) cell was assembled using an activated carbon (AC) negative electrode, an Ni(OH) 2 positive electrode and a polymer hydrogel electrolyte prepared from crosslinked potassium poly(acrylate) (PAAK) and KOH aqueous solution. The HC cell was characterized compared with an electric double layer capacitor (EDLC) using two AC electrodes and the polymer hydrogel electrolyte. It was found that the HC cell successfully worked in the larger voltage range and exhibited ca. 2.4 times higher capacitance than the EDLC cell. High-rate dischargeability of the HC cell was also superior to that of the EDLC cell. These improved characteristics strongly suggest that the HC cell can be a promising system of capacitors with high energy and power densities.

High rate lithium-sulfur battery enabled by sandwiched single ion conducting polymer electrolyte

PubMed Central

Sun, Yubao; Li, Gai; Lai, Yuanchu; Zeng, Danli; Cheng, Hansong

2016-01-01

Lithium-sulfur batteries are highly promising for electric energy storage with high energy density, abundant resources and low cost. However, the battery technologies have often suffered from a short cycle life and poor rate stability arising from the well-known “polysulfide shuttle” effect. Here, we report a novel cell design by sandwiching a sp3 boron based single ion conducting polymer electrolyte film between two carbon films to fabricate a composite separator for lithium-sulfur batteries. The dense negative charges uniformly distributed in the electrolyte membrane inherently prohibit transport of polysulfide anions formed in the cathode inside the polymer matrix and effectively blocks polysulfide shuttling. A battery assembled with the composite separator exhibits a remarkably long cycle life at high charge/discharge rates. PMID:26898772

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.

Safe battery solvents

DOEpatents

Harrup, Mason K.; Delmastro, Joseph R.; Stewart, Frederick F.; Luther, Thomas A.

2007-10-23

An ion transporting solvent maintains very low vapor pressure, contains flame retarding elements, and is nontoxic. The solvent in combination with common battery electrolyte salts can be used to replace the current carbonate electrolyte solution, creating a safer battery. It can also be used in combination with polymer gels or solid polymer electrolytes to produce polymer batteries with enhanced conductivity characteristics. The solvents may comprise a class of cyclic and acyclic low molecular weight phosphazenes compounds, comprising repeating phosphorus and nitrogen units forming a core backbone and ion-carrying pendent groups bound to the phosphorus. In preferred embodiments, the cyclic phosphazene comprises at least 3 phosphorus and nitrogen units, and the pendent groups are polyethers, polythioethers, polyether/polythioethers or any combination thereof, and/or other groups preferably comprising other atoms from Group 6B of the periodic table of elements.

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.

Structural, electrical properties and dielectric relaxations in Na+-ion-conducting solid polymer electrolyte.

PubMed

Arya, Anil; Sharma, A L

2018-04-25

In this paper, we have studied the structural, microstructural, electrical, dielectric properties and ion dynamics of a sodium-ion-conducting solid polymer electrolyte film comprising PEO 8 -NaPF 6 +  x wt. % succinonitrile. The structural and surface morphology properties have been investigated, respectively using x-ray diffraction and field emission scanning electron microscopy. The complex formation was examined using Fourier transform infrared spectroscopy, and the fraction of free anions/ion pairs obtained via deconvolution. The complex dielectric permittivity and loss tangent has been analyzed across the whole frequency window, and enables us to estimate the DC conductivity, dielectric strength, double layer capacitance and relaxation time. The presence of relaxing dipoles was determined by the addition of succinonitrile (wt./wt.) and the peak shift towards high frequency indicates the decrease of relaxation time. Further, relations among various relaxation times ([Formula: see text]) have been elucidated. The complex conductivity has been examined across the whole frequency window; it obeys the Universal Power Law, and displays strong dependency on succinonitrile content. The sigma representation ([Formula: see text]) was introduced in order to explore the ion dynamics by highlighting the dispersion region in the Cole-Cole plot ([Formula: see text]) in the lower frequency window; increase in the semicircle radius indicates a decrease of relaxation time. This observation is accompanied by enhancement in ionic conductivity and faster ion transport. A convincing, logical scheme to justify the experimental data has been proposed.

STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

DTIC Science & Technology

2013-03-28

positions leading us to utilize a two-step procedure in which the amines were treated with methylchloroformate before being fully reduced with lithium ...was carried out using lithium aluminum hydride before undergoing a similar two-step methylation as described above to yield bisferrocenyl ligand 16...of Ni-based complex 30. CV’s were ran in DCM with tetrabutylammonium hexafluorophosphate electrolyte and referenced to a ferrocene standard. In

The role of electrolyte and polyelectrolyte on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, at the air-water interface.

PubMed

Zhang, X L; Taylor, D J F; Thomas, R K; Penfold, J

2011-04-15

The role of the polyelectrolyte, poly(ethyleneimine), PEI, and the electrolytes NaCl and CaCl(2), on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, LAS, at the air-water interface have been investigated by neutron reflectivity and surface tension. The surface tension data for the PEI/LAS mixtures are substantially affected by pH and the addition of electrolyte, and are consistent with a strong adsorption of surface polymer/surfactant complexes down to relatively low surfactant concentrations. The effects are most pronounced at high pH, and this is confirmed by the adsorption data obtained directly from neutron reflectivity. However, the effects of the addition of PEI and electrolyte on the LAS adsorption are not as pronounced as previously reported for PEI/SDS mixtures. This is attributed primarily to the steric hindrance of the LAS phenyl group resulting in a reduction in the ion-dipole attraction between the LAS sulfonate and amine groups that dominates the interaction at high pH. Copyright © 2011 Elsevier Inc. All rights reserved.

Passivation-free solid state battery

DOEpatents

Abraham, Kuzhikalail M.; Peramunage, Dharmasena

1998-01-01

This invention pertains to passivation-free solid-state rechargeable batteries composed of Li.sub.4 Ti.sub.5 O.sub.12 anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2 and LiV.sub.2 O.sub.5 and their derivatives.

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.

High power density proton exchange membrane fuel cells

NASA Technical Reports Server (NTRS)

Murphy, Oliver J.; Hitchens, G. Duncan; Manko, David J.

1993-01-01

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Enhanced lithium battery with polyethylene oxide-based electrolyte containing silane-Al2 O3 ceramic filler.

PubMed

Zewde, Berhanu W; Admassie, Shimelis; Zimmermann, Jutta; Isfort, Christian Schulze; Scrosati, Bruno; Hassoun, Jusef

2013-08-01

A solid polymer electrolyte prepared by using a solvent-free, scalable technique is reported. The membrane is formed by low-energy ball milling followed by hot-pressing of dry powdered polyethylene oxide polymer, LiCF3 SO3 salt, and silane-treated Al2 O3 (Al2 O3 -ST) ceramic filler. The effects of the ceramic fillers on the properties of the ionically conducting solid electrolyte membrane are characterized by using electrochemical impedance spectroscopy, XRD, differential scanning calorimeter, SEM, and galvanostatic cycling in lithium cells with a LiFePO4 cathode. We demonstrate that the membrane containing Al2 O3 -ST ceramic filler performs well in terms of ionic conductivity, thermal properties, and lithium transference number. Furthermore, we show that the lithium cells, which use the new electrolyte together with the LiFePO4 electrode, operate within 65 and 90 °C with high efficiency and long cycle life. Hence, the Al2 O3 -ST ceramic can be efficiently used as a ceramic filler to enhance the performance of solid polymer electrolytes in lithium batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrode property of single-walled carbon nanotubes in all-solid-state lithium ion battery using polymer electrolyte

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

Sakamoto, Y.; Ishii, Y.; Kawasaki, S., E-mail: kawasaki.shinji@nitech.ac.jp

2016-07-06

Electrode properties of single-walled carbon nanotubes (SWCNTs) in an all-solid-state lithium ion battery were investigated using poly-ethylene oxide (PEO) solid electrolyte. Charge-discharge curves of SWCNTs in the solid electrolyte cell were successfully observed. It was found that PEO electrolyte decomposes on the surface of SWCNTs.

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

PubMed Central

Hu, Qichao; Caputo, Antonio; Sadoway, Donald R.

2013-01-01

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (<80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed. PMID:23963203

Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program

NASA Technical Reports Server (NTRS)

Bennett, William R.; Baldwin, Richard S.

2006-01-01

Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.

Solid-state graft copolymer electrolytes for lithium battery applications.

PubMed

Hu, Qichao; Caputo, Antonio; Sadoway, Donald R

2013-08-12

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (< 80 °C), flammable, and volatile organic electrolytes. These organic based electrolyte systems are viable at ambient temperatures, but require a cooling system to ensure that temperatures do not exceed 80 °C. These cooling systems tend to increase battery costs and can malfunction which can lead to battery malfunction and explosions, thus endangering human life. Increases in petroleum prices lead to a huge demand for safe, electric hybrid vehicles that are more economically viable to operate as oil prices continue to rise. Existing organic based electrolytes used in lithium ion batteries are not applicable to high temperature automotive applications. A safer alternative to organic electrolytes is solid polymer electrolytes. This work will highlight the synthesis for a graft copolymer electrolyte (GCE) poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). The conduction mechanism has been discussed and it has been demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence. Batteries containing commercially available LP30 organic (LiPF6 in ethylene carbonate (EC):dimethyl carbonate (DMC) at a 1:1 ratio) and GCE were cycled at ambient temperature. It was found that at ambient temperature, the batteries containing GCE showed a greater overpotential when compared to LP30 electrolyte. However at temperatures greater than 60 °C, the GCE cell exhibited much lower overpotential due to fast polymer electrolyte conductivity and nearly the full theoretical specific capacity of 170 mAh/g was accessed.

[Synthesis and Characterization of a Sugar Based Electrolyte for Thin-film Polymer Batteries

NASA Technical Reports Server (NTRS)

1998-01-01

The work performed during the current renewal period, March 1,1998 focused primarily on the synthesis and characterization of a sugar based electrolyte for thin-film polymer batteries. The initial phase of the project involved developing a suitable sugar to use as the monomer in the polymeric electrolyte synthesis. The monomer has been synthesized and characterized completely. Overall the yield of this material is high and it can be produced in relatively large quantity easily and in high purity. The scheme used for the preparation of the monomer is outlined along with pertinent yields.

Recent advances in solid polymer electrolyte fuel cell technology

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

Ticianelli, E.A.; Srinivasan, S.; Gonzalez, E.R.

1988-01-01

With methods used to advance solid polymer electrolyte fuel cell technology, we are close to obtaining the goal of 1 A/cm/sup 2/ at 0.7. Higher power densities have been reported (2 A/cm/sup 2/ at 0.5 V) but only with high catalyst loading electrodes (2 mg/cm/sup 2/ and 4 mg/cm/sup 2/ at anode and cathode, respectively) and using a Dow membrane with a better conductivity and water retention characteristics. Work is in progress to ascertain performances of cells with Dow membrane impregnated electrodes and Dow membrane electrolytes. 5 refs., 6 figs.

Synthesis and Characterization of Thin Film Lithium-Ion Batteries Using Polymer Electrolytes

NASA Technical Reports Server (NTRS)

Maranchi, Jeffrey P.; Kumta, Prashant N.; Hepp, Aloysius F.; Raffaelle, Ryne P.

2002-01-01

The present paper describes the integration of thin film electrodes with polymer electrolytes to form a complete thin film lithium-ion battery. Thin film batteries of the type, LiCoO2 [PAN, EC, PC, LiN(CF3SO2)2] SnO2 have been fabricated. The results of the synthesis and characterization studies will be presented and discussed.

Dielectric relaxations and conduction mechanisms in polyether-clay composite polymer electrolytes under high carbon dioxide pressure.

PubMed

Kitajima, Shunsuke; Bertasi, Federico; Vezzù, Keti; Negro, Enrico; Tominaga, Yoichi; Di Noto, Vito

2013-10-21

The composite material P(EO/EM)-Sa consisting of synthetic saponite (Sa) dispersed in poly[ethylene oxide-co-2-(2-methoxyethoxy)ethyl glycidyl ether] (P(EO/EM)) is studied by "in situ" measurements using broadband electrical spectroscopy (BES) under pressurized CO2 to characterize the dynamic behavior of conductivity and the dielectric relaxations of the ion host polymer matrix. It is revealed that there are three dielectric relaxation processes associated with: (I) the dipolar motions in the short oxyethylene side chains of P(EO/EM) (β); and (II) the segmental motion of the main chains comprising the polyether components (αfast, αslow). αslow is attributed to the slow α-relaxation of P(EO/EM) macromolecules, which is hindered by the strong coordination interactions with the ions. Two conduction processes are observed, σDC and σID, which are attributed, respectively, to the bulk conductivity and the interdomain conductivity. The temperature dependence of conductivity and relaxation processes reveals that αfast and αslow are strongly correlated with σDC and σID. The "in situ" BES measurements under pressurized CO2 indicate a fast decrease in σDC at the initial CO2 treatment time resulting from the decrease in the concentration of polyether-M(n+) complexes, which is driven by the CO2 permeation. The relaxation frequency (fR) of αslow at the initial CO2 treatment time increases and shows a steep rise with time with the same behavior of the αfast mode. It is demonstrated that the interactions between polyether chains of P(EO/EM) and cations in the polymer electrolyte layers embedded in Sa are probably weakened by the low permittivity of CO2 (ε = 1.08). Thus, the formation of ion pairs in the polymer electrolyte domains of P(EO/EM)-Sa occurs, with a corresponding reduction in the concentration of ion carriers.

Preliminary study on aluminum-air battery applying disposable soft drink cans and Arabic gum polymer

NASA Astrophysics Data System (ADS)

Alva, S.; Sundari, R.; Wijaya, H. F.; Majlan, E. H.; Sudaryanto; Arwati, I. G. A.; Sebayang, D.

2017-09-01

This study is in relation to preliminary investigation of aluminium-air battery using disposable soft drink cans as aluminium source for anode. The cathode uses commercial porous carbon sheet to trap oxygen from air. This work applies a commercial cashing to place carbon cathode, electrolyte, Arabic gum polymer, and aluminium anode in a sandwich-like arrangement to form the aluminium-air battery. The Arabic gum as electrolyte polymer membrane protects anode surface from corrosion due to aluminium oxide formation. The study result shows that the battery discharge test using constant current loading of 0.25 mA yields battery capacity of 0.437 mAh with over 100 minute battery life times at 4M NaOH electrolyte and 20 % Arabic gum polymer as the best performance in this investigation. This study gives significant advantage in association with beneficiation of disposable soft drink cans from municipal solid waste as aluminium source for battery anode.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

Self-doped molecular composite battery electrolytes

DOEpatents

Harrup, Mason K.; Wertsching, Alan K.; Stewart, Frederick F.

2003-04-08

This invention is in solid polymer-based electrolytes for battery applications. It uses molecular composite technology, coupled with unique preparation techniques to render a self-doped, stabilized electrolyte material suitable for inclusion in both primary and secondary batteries. In particular, a salt is incorporated in a nano-composite material formed by the in situ catalyzed condensation of a ceramic precursor in the presence of a solvated polymer material, utilizing a condensation agent comprised of at least one cation amenable to SPE applications. As such, the counterion in the condensation agent used in the formation of the molecular composite is already present as the electrolyte matrix develops. This procedure effectively decouples the cation loading levels required for maximum ionic conductivity from electrolyte physical properties associated with condensation agent loading levels by utilizing the inverse relationship discovered between condensation agent loading and the time domain of the aging step.

Spatially resolved, in situ potential measurements through porous electrodes as applied to fuel cells.

PubMed

Hess, Katherine C; Epting, William K; Litster, Shawn

2011-12-15

We report the development and use of a microstructured electrode scaffold (MES) to make spatially resolved, in situ, electrolyte potential measurements through the thickness of a polymer electrolyte fuel cell (PEFC) electrode. This new approach uses a microfabricated apparatus to analyze the coupled transport and electrochemical phenomena in porous electrodes at the microscale. In this study, the MES allows the fuel cell to run under near-standard operating conditions, while providing electrolyte potential measurements at discrete distances through the electrode's thickness. Here we use spatial distributions of electrolyte potential to evaluate the effects of Ohmic and mass transport resistances on the through-plane reaction distribution for various operating conditions. Additionally, we use the potential distributions to estimate the ionic conductivity of the electrode. Our results indicate the in situ conductivity is higher than typically estimated for PEFC electrodes based on bulk polymer electrolyte membrane (PEM) conductivity.

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.

Interfacial behavior of polymer electrolytes

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

Kerr, John; Kerr, John B.; Han, Yong Bong

2003-06-03

Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combinedmore » with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.« less

Electrical and electrochemical studies on sodium ion-based gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Isa, K. B. Md; Othman, L.; Hambali, D.; Osman, Z.

2017-09-01

Gel polymer electrolytes (GPEs) have captured great attention because of their unique properties such as good mechanical stability, high flexibility and high conductivity approachable to that of the liquid electrolytes. In this work, we have prepared sodium ion conducting gel polymer electrolyte (GPE) films consisting of polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) as a polymer host using the solution casting technique. Sodium trifluoromethane- sulfonate (NaCF3SO3) was used as an ionic salt and the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizing solvent. Impedance spectroscopy measurements were carried out to determine the ionic conductivity of the GPE films. The sample containing 20 wt.% of NaCF3SO3 salt exhibits the highest room temperature ionic conductivity of 2.50 × 10-3 S cm-1. The conductivity of the GPE films was found to depend on the salt concentration that added to the films. The ionic and cationic transference numbers of GPE films were estimated by DC polarization and the combination of AC and DC polarization method, respectively. The results had shown that both ionic and cationic transference numbers are consistent with the conductivity studies. The electrochemical stability of the GPE films was tested using linear sweep voltammetry (LSV) and the value of working voltage range appears to be high enough to be used as an electrolyte in sodium batteries. The cyclic voltammetry (CV) studies confirmed the sodium ion conduction in the GPE films.

Room-Temperature-Cured Copolymers for Lithium Battery Gel Electrolytes

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B.; Tigelaar, Dean M.

2009-01-01

Polyimide-PEO copolymers (PEO signifies polyethylene oxide) that have branched rod-coil molecular structures and that can be cured into film form at room temperature have been invented for use as gel electrolytes for lithium-ion electric-power cells. These copolymers offer an alternative to previously patented branched rod-coil polyimides that have been considered for use as polymer electrolytes and that must be cured at a temperature of 200 C. In order to obtain sufficient conductivity for lithium ions in practical applications at and below room temperature, it is necessary to imbibe such a polymer with a suitable carbonate solvent or ionic liquid, but the high-temperature cure makes it impossible to incorporate and retain such a liquid within the polymer molecular framework. By eliminating the high-temperature cure, the present invention makes it possible to incorporate the required liquid.

Photovoltaic and thermal properties of electrolytes based on electrospun poly(vinylidene fluoride-hexafluoro propylene)/poly(methyl methacrylate) nanofibers for dye-sensitized solar cells.

PubMed

Jang, Young-Wook; Won, Du-Hyun; Kim, Young-Keun; Hwang, Won-Pill; Jang, Sung-Il; Jeong, Sung-Hoon; Kim, Mi-Ra; Lee, Jin-Kook

2014-08-01

We prepared electrospun polymer nanofibers by electrospnning method and investigated about their applications to dye-sensitized solar cells (DSSCs). Electrospun polymer nanofibers applied to the polymer matrix in electrolyte for DSSCs. To improve the stiffness of polymer nanofiber, poly(vinylidene fluoride-hexafluoro propylene)/Poly(methyl methacrylate) (PVDF-HFP/PMMA) blend nanofibers were prepared and examined. In the electrospun PVDF-HFP/PMMA (1:1) blend nanofibers, the best results of VOC, JSC, FF, and efficiency of the DSSC devices showed 0.71 V, 12.8 mA/cm2, 0.61, and 5.56% under AM 1.5 illumination.

Self-standing gel polymer electrolyte for improving supercapacitor thermal and electrochemical stability

NASA Astrophysics Data System (ADS)

Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri

2018-07-01

Electrochemical energy storage is a very active research topic. However, the use of liquid electrolyte in such systems as supercacitors presents several drawbacks on security and packaging. One way to overcome these issues is to design supercapacitors using solid-state electrolytes. We report here the one-pot synthesis and the characterization of self-standing gel polymer electrolyte (SGPE) composed of semi-Interpenetrating Polymer Networks (semi-IPN) based on poly(ethylene oxide) (PEO) network and non cross-linked nitrile butadiene rubber (NBR), self-containing EMITFSI/γ-Butyrolactone (50/50 wt%/wt%) binary mixtures. The SGPE under the form of a thin film are then used as solid electrolyte and also as separator in supercapacitors with Single Wall Carbon Nanotubes (SWCNTs) bucky paper as electrodes. Thermal characterization revealed the suitability of all synthesized membrane in wide range of operating temperature. Electrochemical stabilities of SGPE were close to that of a cellulose separator system (ESW∼3.2-3.6 V) at 20 °C, and were relatively higher than a cellulose system at 100 °C: 2.1-2.5 V and 1.8 V respectively. Furthermore, floating experiments at 100 °C (holding voltage at 2 V) revealed the exceptionally high stability of SGPE, with a residual capacitance of 93% after 500 h. This high electrochemical performance demonstrated the potential of semi-IPN SGPE as separator/electrolyte for high performance supercapacitors.

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.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-06-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy.

Oral salt supplements to compensate for jejunostomy losses: comparison of sodium chloride capsules, glucose electrolyte solution, and glucose polymer electrolyte solution.

PubMed Central

Nightingale, J M; Lennard-Jones, J E; Walker, E R; Farthing, M J

1992-01-01

Six patients with jejunostomies and residual jejunal lengths of 105 to 250 cm took the same food and water each day for eight study days. In random order, three methods of salt replacement were tested, each over 48 hours, against a period without added salt. During the three test periods the patients took 120 mmol of sodium chloride daily, as salt in gelatine capsules, as an isotonic glucose electrolyte (280 mOsmol/kg; 30 kcal) solution, and as a glucose polymer (Maxijul) solution (280 mOsmol/kg; 200 kcal). The daily stomal output remained constant for each patient during the four test periods but varied between patients from 0.60 to 2.84 kg (daily intestinal fluid balance 0.74-2.61 kg). Without a salt supplement, three patients lost more sodium from the stoma than they took in by mouth (-25, -94, and -101 mmol/day) and the mean sodium balance for all six subjects was -16 mmol (range -101 to 79) daily. Extra salt was absorbed with each form of supplement (p less than 0.05); no patient with the glucose electrolyte solution (mean 96, range 0 to 226 mmol), but one patient with the glucose-polymer solution (mean 96, range -25 to 164 mmol) and two with the salt capsules (mean 66, range -8 to 145 mmol) were in negative balance. Two patients vomited with the salt capsules. There was only a small increase in energy absorption (mean 115 kcal) with the glucose polymer solution compared with the glucose electrolyte solution. A sipped glucose electrolyte solution seems to be the optimal mode of sodium replacement in patients with a high output jejunostomy. PMID:1624155

Novel, Solvent-Free, Single Ion-Conducting Polymer Electrolytes

DTIC Science & Technology

2007-10-31

the selected polymer electrolyte membrane and a LiFePO4 -based composite cathode film. The latter was prepared by blending the LiFePO4 active...following: charge Li+ + FePO4 + e LiFePO4 [1] discharge to which is associate a maximum...as separator in a Li/ LiFePO4 battery. . 1.Experimental. Calixpyrrole (CP, provided by the University of Warsaw), LiBOB (Libby) and PEO

Low temperature sulfur and sodium metal battery for grid-scale energy storage application

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

Liu, Gao; Wang, Dongdong

A re-chargeable battery comprising a non-dendrite forming sodium (Na)/potassium (K) liquid metal alloy anode, a sulfur and polyacrylonitrile (PAN) conductive polymer composite cathode, a polyethyleneoxide (PEO) solid electrolyte, a solid electrolyte interface (SEI) formed on the PEO solid electrolyte; and a cell housing, wherein the anode, cathode, and electrolyte are assembled into the cell housing with the PEO solid electrolyte disposed between the cathode and anode.

Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers

DOE PAGES

Adams, Marisa; Richmond, Victoria; Smith, Douglas; ...

2017-03-24

Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion formore » polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures T g reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in T g might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.« 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.

Transcap: A new integrated hybrid supercapacitor and electrolyte-gated transistor device (Presentation Recording)

NASA Astrophysics Data System (ADS)

Santato, Clara

2015-10-01

The boom in multifunctional, flexible, and portable electronics and the increasing need of low-energy cost and autonomy for applications ranging from wireless sensor networks for smart environments to biomedical applications are triggering research efforts towards the development of self-powered sustainable electronic devices. Within this context, the coupling of electronic devices (e.g. sensors, transistors) with small size energy storage systems (e.g. micro-batteries or micro-supercapacitors) is actively pursued. Micro-electrochemical supercapacitors are attracting much attention in electronics for their capability of delivering short power pulses with high stability over repeated charge/discharge cycling. For their high specific pseudocapacitance, electronically conducting polymers are well known as positive materials for hybrid supercapacitors featuring high surface carbon negative electrodes. The processability of both polymer and carbon is of great relevance for the development of flexible miniaturised devices. Electronically conducting polymers are even well known to feature an electronic conductivity that depends on their oxidation (p-doped state) and that it is modulated by the polymer potential. This property and the related pseudocapacitive response make polymer very attracting channel materials for electrolyte-gated (EG) transistors. Here, we propose a novel concept of "Trans-capacitor", an integrated device that exhibits the storage properties of a polymer/carbon hybrid supercapacitor and the low-voltage operation of an electrolyte-gated transistor.

Modeling of fixed-bed column studies for the adsorption of cadmium onto novel polymer-clay composite adsorbent.

PubMed

Unuabonah, Emmanuel I; Olu-Owolabi, Bamidele I; Fasuyi, Esther I; Adebowale, Kayode O

2010-07-15

Kaolinite clay was treated with polyvinyl alcohol to produce a novel water-stable composite called polymer-clay composite adsorbent. The modified adsorbent was found to have a maximum adsorption capacity of 20,400+/-13 mg/L (1236 mg/g) and a maximum adsorption rate constant of approximately = 7.45x10(-3)+/-0.0002 L/(min mg) at 50% breakthrough. Increase in bed height increased both the breakpoint and exhaustion point of the polymer-clay composite adsorbent. The time for the movement of the Mass Transfer Zone (delta) down the column was found to increase with increasing bed height. The presence of preadsorbed electrolyte and regeneration were found to reduce this time. Increased initial Cd(2+) concentration, presence of preadsorbed electrolyte, and regeneration of polymer-clay composite adsorbent reduced the volume of effluent treated. Premodification of polymer-clay composite adsorbent with Ca- and Na-electrolytes reduced the rate of adsorption of Cd(2+) onto polymer-clay composite and lowered the breakthrough time of the adsorbent. Regeneration and re-adsorption studies on the polymer-clay composite adsorbent presented a decrease in the bed volume treated at both the breakpoint and exhaustion points of the regenerated bed. Experimental data were observed to show stronger fits to the Bed Depth Service Time (BDST) model than the Thomas model. 2010 Elsevier B.V. All rights reserved.

Molecular Dynamics Simulations of Ion Transport and Mechanisms in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Mogurampelly, Santosh; Ganesan, Venkat

2015-03-01

Using all atom molecular dynamics and trajectory-extending kinetic Monte Carlo simulations, we study the influence of Al2O3 nanoparticles on the transport properties of Li+ ions in polymer electrolytes consisting of polyethylene oxide (PEO) melt solvated with LiBF4 salt. We observe that the nanoparticles have a strong influence on polymer segmental dynamics which in turn correlates with the mobility of Li+ ions. Explicitly, polymer segmental relaxation times and Li+ ion residence times around polymer were found to increase with the addition of nanoparticles. We also observe that increasing short range repulsive interactions between nanoparticles and polymer membrane leads to increasing polymer dynamics and ion mobility. Overall, our simulation results suggest that nanoparticle induced changes in conformational and dynamic properties of the polymer influences the ion mobilities in polymer electrolytes and suggests possible directions for using such findings to improve the polymer matrix conductivity. The authors acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing computing resources that have contributed to the research.

Passivation-free solid state battery

DOEpatents

Abraham, K.M.; Peramunage, D.

1998-06-16

This invention pertains to passivation-free solid-state rechargeable batteries composed of Li{sub 4}Ti{sub 5}O{sub 12} anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2} and LiV{sub 2}O{sub 5} and their derivatives. 5 figs.

Long-lasting solid-polymer electrolytic hygrometer

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1978-01-01

Device consists of hollow tube node of oxidation-resistant sulfonated fluorocarbon polymer. Tube absorbs moisture from air passing across inner and outer surfaces, causing change in polymer conductance. Change is related to change in water content in gas sample.

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.

Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Prakash, G. K. Surya; Smart, Marshall; Atti, Anthony R.; Olah, George A.; Narayanan, S. R.; Valdez, T.; Surampudi, S.

1996-01-01

Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications.

PubMed

Liew, Chiam-Wen; Ramesh, S

2014-05-21

Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF₆) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF₆) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02) × 10 -4 and (3.21 ± 0.01) × 10 -4 S∙cm -1 were achieved with adulteration of 50 wt% of BmImPF₆ and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system.

Electrochemical properties of lithium iron phosphate cathode material using polymer electrolyte

NASA Astrophysics Data System (ADS)

Kim, Jae-Kwang; Choi, Jae-Won; Cheruvally, Gouri; Shin, Yong-Jo; Ahn, Jou-Hyeon; Cho, Kwon-Koo; Ahn, Hyo-Jun; Kim, Ki-Won

2007-12-01

Carbon-coated lithium iron phosphate (LiFePO4/C) cathode material was synthesized by mechano-chemical activation method. The performance of LiFePO4/C in lithium battery was tested with an electrospun polymer-based electrolyte. Liquid electrolyte of 1M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC) (1 : 1vol) was incorporated in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-HFP)) microfibrous membrane to prepare the polymer electrolyte (PE). The cell based on Li|PE|Li FePO4/C exhibited an initial discharge capacity of 142 mAh g-1 at 0.1 C-rate at room temperature. Good cycling performance even under the high current density of 2 C could be obtained. Impedance spectroscopy was applied to investigate the material behavior during 0.1 C-rate charge-discharge cycling. When the fresh cell and the cell after different cycles were compared, impedance resistance was found to decrease with cycling. Impedance study indicated good cycle life for the cell when tested at room temperature.

Comparing Triflate and Hexafluorophosphate Anions of Ionic Liquids in Polymer Electrolytes for Supercapacitor Applications

PubMed Central

Liew, Chiam-Wen; Ramesh, S.

2014-01-01

Two different ionic liquid-based biopolymer electrolyte systems were prepared using a solution casting technique. Corn starch and lithium hexafluorophosphate (LiPF6) were employed as polymer and salt, respectively. Additionally, two different counteranions of ionic liquids, viz. 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) and 1-butyl-3-methylimidazolium trifluoromethanesulfonate (also known as 1-butyl-3-methylimidazolium triflate) (BmImTf) were used and studied in this present work. The maximum ionic conductivities of (1.47 ± 0.02) × 10−4 and (3.21 ± 0.01) × 10−4 S·cm−1 were achieved with adulteration of 50 wt% of BmImPF6 and 80 wt% of BmImTf, respectively at ambient temperature. Activated carbon-based electrodes were prepared and used in supercapacitor fabrication. Supercapacitors were then assembled using the most conducting polymer electrolyte from each system. The electrochemical properties of the supercapacitors were then analyzed. The supercapacitor containing the triflate-based biopolymer electrolyte depicted a higher specific capacitance with a wider electrochemical stability window compared to that of the hexafluorophosphate system. PMID:28788662

A long life 4 V class lithium-ion polymer battery with liquid-free polymer electrolyte

NASA Astrophysics Data System (ADS)

Kobayashi, Yo; Shono, Kumi; Kobayashi, Takeshi; Ohno, Yasutaka; Tabuchi, Masato; Oka, Yoshihiro; Nakamura, Tatsuya; Miyashiro, Hajime

2017-02-01

Ether-based solid polymer electrolyte (SPE) is one of the most well-known lithium ion conductors. Unlike the other inorganic electrolytes, SPE exhibits advantages of flexibility and large-area production, enabling low cost production of large size batteries. However, because the ether group is oxidized at 4 V versus Li/Li+ cathode, and due to its high irreversibility with the carbon anode, ether-based SPE was believed to be inapplicable to 4 V class lithium-ion batteries with carbon anode. Here we report a remarkably stable SPE in combination with a 4 V class cathode and carbon anode achieved by the proper design at the interface. The introduced boron-based lithium salt prohibits further oxidation of SPE at the cathode interface. The surface modification of graphite by the annealing of polyvinyl chloride mostly prohibits the continuous consumption of lithium at the graphite anode. Using above interface design, we achieved 60% capacity retention after 5400 cycles. The proposed battery provides a possible approach for realizing flammable electrolyte-free lithium-ion batteries, which achieve innovative safety improvements of large format battery systems for stationary use.

BIPV-Powered Smart Windows Utilizing Photovoltaic and Electrochromic Devices

PubMed Central

Ma, Rong-Hua; Chen, Yu-Chia

2012-01-01

A BIPV-powered smart window comprising a building-integrated photovoltaic (BIPV) panel and an all-solid-state electrochromic (EC) stack is proposed. In the proposed device, the output voltage of the BIPV panel varies in accordance with the intensity of the incident light and is modulated in such a way as to generate the EC stack voltage required to maintain the indoor illuminance within a specified range. Two different EC stacks are fabricated and characterized, namely one stack comprising ITO/WO3/Ta2O5/ITO and one stack comprising ITO/WO3/lithium-polymer electrolyte/ITO. It is shown that of the two stacks, the ITO/WO3/lithium-polymer electrolyte/ITO stack has a larger absorptance (i.e., approximately 99% at a driving voltage of 3.5 V). The experimental results show that the smart window incorporating an ITO/WO3/lithium-polymer electrolyte/ITO stack with an electrolyte thickness of 1.0 μm provides an indoor illuminance range of 750–1,500 Lux under typical summertime conditions in Taiwan. PMID:22368474

In Situ Study of Strain-Dependent Ion Conductivity of Stretchable Polyethylene Oxide Electrolyte

PubMed Central

Kelly, Taylor; Ghadi, Bahar Moradi; Berg, Sean; Ardebili, Haleh

2016-01-01

There is a strong need in developing stretchable batteries that can accommodate stretchable or irregularly shaped applications including medical implants, wearable devices and stretchable electronics. Stretchable solid polymer electrolytes are ideal candidates for creating fully stretchable lithium ion batteries mainly due to their mechanical and electrochemical stability, thin-film manufacturability and enhanced safety. However, the characteristics of ion conductivity of polymer electrolytes during tensile deformation are not well understood. Here, we investigate the effects of tensile strain on the ion conductivity of thin-film polyethylene oxide (PEO) through an in situ study. The results of this investigation demonstrate that both in-plane and through-plane ion conductivities of PEO undergo steady and linear growths with respect to the tensile strain. The coefficients of strain-dependent ion conductivity enhancement (CSDICE) for in-plane and through-plane conduction were found to be 28.5 and 27.2, respectively. Tensile stress-strain curves and polarization light microscopy (PLM) of the polymer electrolyte film reveal critical insights on the microstructural transformation of stretched PEO and the potential consequences on ionic conductivity. PMID:26831948

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Long-Life and High-Power Binder-Free Cathode Based on One-Step Synthesis of Radical Polymers with Multi-Pendant Groups.

PubMed

Chen, Yaoguang; Zhang, Yangfan; Liu, Xiu; Fan, Xuliang; Bai, Bing; Yang, Kang; Liang, Zhongxin; Zhang, Zishou; Mai, Kancheng

2018-05-16

The main bottlenecks for the widespread application of radical polymers in organic radical batteries are poor cycling stability, due to the dissolution of radical polymers into the electrolyte, and the low efficiency of multi-step synthesis strategies. Herein, a kind of electrolyte-resistant radical polymer bearing multi-pendant groups (poly(ethylene-alt-TEMPO maleate) (PETM)) is designed and synthesized through a one-step esterification reaction to graft 4-hydroxy-2,2,6,6-teramethylpiperidinyl-1-oxy into the commercially available poly(ethylene-alt-maleic anhydride). Interestingly, PETM is hardly soluble in the ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate-based electrolyte, showing an extremely low solubility of 0.59 mg mL -1 , but is easily soluble in tetrahydrofuran and N-Methyl pyrrolidone. The derived binder-free PETM cathode exhibits nearly 100% utilization of the grafted nitroxide radicals (88 mA h g -1 ) and excellent rate capability with almost invariant capacitance from 10 C to 40 C. Significantly, the PETM cathodes retain 94% of the initial capacity after 1000 cycles, outperforming most reported radical polymer-based cathodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.

Fluorinated carbonates are pursued as liquid electrolyte solvents for high-voltage Li-ion batteries. Here we report aggregation of [Li+(FEC)(3)](n) polymer species in fluoroethylene carbonate containing electrolytes and scrutinize the causes for this behavior.

Novel metal(II) coordination polymers based on N,N'-bis-(4-pyridyl)phthalamide as supercapacitor electrode materials in an aqueous electrolyte.

PubMed

Gong, Yun; Li, Jian; Jiang, Peng-Gang; Li, Qing-Fang; Lin, Jian-Hua

2013-02-07

Based on the redox-active L (N,N'-bis-(4-pyridyl)phthalamide) ligand, two porous MOFs formulated as Zn(6)(BPC)(6)(L)(3)·9DMF (H(2)BPC = 4,4'-biphenyldicarboxylic acid) (1) and Cd(2)(TDC)(2)(L)(2)·4H(2)O (H(2)TDC = 2,5-thiophenedicarboxylic acid) (2) were synthesized and structurally characterized by single-crystal X-ray diffractions. Complex 1 features a uninodal 5-connected 3-fold interpenetrated 3D framework with {4(6).6(4)}-bnn hexagonal BN topology. Complex 2 displays a uninodal 6-connected 2-fold interpenetrated 3D framework with {4(12).6(3)}-pcu topology. When complexes 1 and 2 are used as supercapacitor electrode materials, they can provide a large voltage window as high as 2.6 V in an aqueous electrolyte, and their specific capacitances are much more than the value for the bare carbon glassy electrode. It is observed that the more the current density, the less the specific capacitance for the two kinds of supercapacitor electrode materials. The two complexes show different thermal stabilities, UV absorption and photoluminescence properties.

Effect of The Addition of PEG and PVA Polymer for Gel Electrolytes in Dye-Sensitized Solar Cell (DSSC) with Chlorophyll as Dye Sensitizer

NASA Astrophysics Data System (ADS)

Seni, Ramadhanti S.; Puspitasari, Nurrisma; Endarko

2017-07-01

Dye-sensitized Solar Cell (DSSC) is a third-generation solar cell that consists of a working electrode, electrolyte and counter electrode. One of the most important parts of DSSC is an electrolyte that roles as a medium and regenerates the electron transport of electrons in the dye. However, the liquid electrolyte has a lack of stability in long-term use and easily evaporate or leak in DSSC. Therefore, this study aims to investigate an effect of the addition of polymer material such as PEG 1000, 4000 and PVA 60000 for fabricating a gel electrolyte to solve the problems of liquid electrolyte. The synthesized TiO2 nanoparticles used in this study was prepared using co-precipitation (CPT) method which produces TiO2 anatase phase with a crystal size of 11.1 nm. DSSC has been successfully conducted and analyzed to evaluate its performance. The results showed that the efficiency of DSSC cells using gel electrolyte prepared with PVA 60000 was better than a liquid electrolyte, PEG 1000, 4000, with the efficiency could be obtained at 0.083, 0.018, 0.033, and 0.054%, respectively. The results demonstrated that the addition PEG and/or PVA could be enhanced the performance of DSSC due to gel electrolyte produced current and voltage more stable compared to the liquid electrolyte.

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Zhao, Ning; Sun, Jiyang; Du, Fuming; Li, Yiqiu; Guo, Xiangxin

2017-12-01

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li6.4La3Zr1.4Ta0.6O12 particles interfacially wetted by [BMIM]TF2N of 1.8 μL cm-2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 104 Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10-4 S cm-1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li6.4La3Zr1.4Ta0.6O12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO4/Li and LiFe0.15Mn0.85PO4/Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries.

Solid polymer electrolyte (SPE) fuel cell technology program, phase 1/1A. [design and fabrication

NASA Technical Reports Server (NTRS)

1975-01-01

A solid polymer electrolyte fuel cell was studied for the purpose of improving the characteristics of the technology. Several facets were evaluated, namely: (1) reduced fuel cell costs; (2) reduced fuel cell weight; (3) improved fuel cell efficiency; and (4) increased systems compatibility. Demonstrated advances were incorporated into a full scale hardware design. A single cell unit was fabricated. A substantial degree of success was demonstrated.

Mathematical Modeling and Optimization Studies on Development of Fuel Cells for Multifarious Applications

DTIC Science & Technology

2010-05-12

multicomponent steady-state model for liquid -feed solid polymer electrolyte DBFCs. These fuel cells use sodium borohydride (NaBH4) in alkaline media...layers, diffusion layers and the polymer electrolyte membrane for a liquid feed DBFC. Diffusion of reactants within and between the pores is accounted...projected for futuristic portable applications. In this project we developed a three- dimensional, multicomponent steady-state model for liquid -feed solid

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

PubMed

Fu, Xiao-Bin; Yang, Guang; Wu, Jin-Ze; Wang, Jia-Chen; Chen, Qun; Yao, Ye-Feng

2018-01-05

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEO n /Li + (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li + salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li + ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li + and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tetraarylborate polymer networks as single-ion conducting solid electrolytes

DOE PAGES

Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; ...

2015-06-23

A new family of solid polymer electrolytes based upon anionic tetrakis(phenyl)borate tetrahedral nodes and linear bis-alkyne linkers is reported. Sonogashira polymerizations using tetrakis(4-iodophenyl)borate, tetrakis(4-iodo-2,3,5,6-tetrafluorophenyl)borate and tetrakis(4-bromo-2,3,5,6-tetrafluorophenyl)borate delivered highly cross-linked polymer networks with both 1,4-diethynylbeznene and a tri(ethylene glycol) substituted derivative. Promising initial conductivity metrics have been observed, including high room temperature conductivities (up to 2.7 × 10 -4 S cm -1), moderate activation energies (0.25–0.28 eV), and high lithium ion transport numbers (up to t Li+ = 0.93). Initial investigations into the effects of important materials parameters such as bulk morphology, porosity, fluorination, and other chemical modification, provide starting designmore » parameters for further development of this new class of solid electrolytes.« less

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.

Biodegradation test of SPS-LS blends as polymer electrolyte membrane fuel cells

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

Putri, Zufira, E-mail: zufira.putri@gmail.com, E-mail: arcana@chem.itb.ac.id; Arcana, I Made, E-mail: zufira.putri@gmail.com, E-mail: arcana@chem.itb.ac.id

Sulfonated polystyrene (SPS) can be applied as a proton exchange membrane fuel cell due to its fairly good chemical stability. In order to be applied as polymer electrolyte membrane fuel cells (PEMFCs), membrane polymer should have a good ionic conductivity, high proton conductivity, and high mechanical strength. Lignosulfonate (LS) is a complex biopolymer which has crosslinks and sulfonate groups. SPS-LS blends with addition of SiO{sub 2} are used to increase the proton conductivity and to improve the mechanical properties and thermal stability. However, the biodegradation test of SPS-LS blends is required to determine whether the application of these membranes tomore » be applied as an environmentally friendly membrane. In this study, had been done the synthesis of SPS, biodegradability test of SPS-LS blends with variations of LS and SiO{sub 2} compositions. The biodegradation test was carried out in solid medium of Luria Bertani (LB) with an activated sludge used as a source of microorganism at incubation temperature of 37°C. Based on the results obtained indicated that SPS-LS-SiO{sub 2} blends are more decomposed by microorganism than SPS-LS blends. This result is supported by analysis of weight reduction percentage, functional groups with Fourier Transform Infrared (FTIR) Spectroscopy, and morphological surface with Scanning Electron Microscopy (SEM)« less

Highly Flexible and Planar Supercapacitors Using Graphite Flakes/Polypyrrole in Polymer Lapping Film.

PubMed

Raj, C Justin; Kim, Byung Chul; Cho, Won-Je; Lee, Won-gil; Jung, Sang-Don; Kim, Yong Hee; Park, Sang Yeop; Yu, Kook Hyun

2015-06-24

Flexible supercapacitor electrodes have been fabricated by simple fabrication technique using graphite nanoflakes on polymer lapping films as flexible substrate. An additional thin layer of conducting polymer polypyrrole over the electrode improved the surface conductivity and exhibited excellent electrochemical performances. Such capacitor films showed better energy density and power density with a maximum capacitance value of 37 mF cm(-2) in a half cell configuration using 1 M H2SO4 electrolyte, 23 mF cm(-2) in full cell, and 6 mF cm(-2) as planar cell configuration using poly(vinyl alcohol) (PVA)/phosphoric acid (H3PO4) solid state electrolyte. Moreover, the graphite nanoflakes/polypyrrole over polymer lapping film demonstrated good flexibility and cyclic stability.

Electrokinetic properties of polymer colloids

NASA Technical Reports Server (NTRS)

Micale, F. J.; Fuenmayor, D. Y.

1986-01-01

The surface of polymer colloids, especially polystyrene latexes, were modified for the purpose of controlling the electrokinetic properties of the resulting colloids. Achievement required a knowledge of electrical double layer charging mechanism, as a function of the electrolyte conditions, at the polymer/water interface. The experimental approach is to control the recipe formulation in the emulsion polymerization process so as to systematically vary the strong acid group concentration on the surface of the polymer particles. The electrophoretic mobility of these model particles will then be measured as a function of surface group concentration and as a function of electrolyte concentration and type. An effort was also made to evaluate the electrophoretic mobility of polystyrene latexes made in space and to compare the results with latexes made on the ground.

Electrochemical supercapacitors

DOEpatents

Rudge, Andrew J.; Ferraris, John P.; Gottesfeld, Shimshon

1996-01-01

A new class of electrochemical capacitors provides in its charged state a positive electrode including an active material of a p-doped material and a negative electrode including an active material of an n-doped conducting polymer, where the p-doped and n-doped materials are separated by an electrolyte. In a preferred embodiment, the positive and negative electrode active materials are selected from conducting polymers consisting of polythiophene, polymers having an aryl group attached in the 3-position, polymers having aryl and alkyl groups independently attached in the 3- and 4-positions, and polymers synthesized from bridged dimers having polythiophene as the backbone. A preferred electrolyte is a tetraalykyl ammonium salt, such as tetramethylammonium trifluoromethane sulphonate (TMATFMS), that provides small ions that are mobile through the active material, is soluble in acetonitrile, and can be used in a variety of capacitor configurations.

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

NASA Technical Reports Server (NTRS)

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

2005-01-01

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Structural, electrical properties and dielectric relaxations in Na+-ion-conducting solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2018-04-01

In this paper, we have studied the structural, microstructural, electrical, dielectric properties and ion dynamics of a sodium-ion-conducting solid polymer electrolyte film comprising PEO8-NaPF6+  x wt. % succinonitrile. The structural and surface morphology properties have been investigated, respectively using x-ray diffraction and field emission scanning electron microscopy. The complex formation was examined using Fourier transform infrared spectroscopy, and the fraction of free anions/ion pairs obtained via deconvolution. The complex dielectric permittivity and loss tangent has been analyzed across the whole frequency window, and enables us to estimate the DC conductivity, dielectric strength, double layer capacitance and relaxation time. The presence of relaxing dipoles was determined by the addition of succinonitrile (wt./wt.) and the peak shift towards high frequency indicates the decrease of relaxation time. Further, relations among various relaxation times ({{τ }{{\\varepsilon \\prime}}}>~{{τ }tanδ }>{{τ }z}>{{τ }m} ) have been elucidated. The complex conductivity has been examined across the whole frequency window; it obeys the Universal Power Law, and displays strong dependency on succinonitrile content. The sigma representation ({{σ }\\prime\\prime}~versus~{{σ }\\prime} ) was introduced in order to explore the ion dynamics by highlighting the dispersion region in the Cole–Cole plot ({{\\varepsilon }\\prime\\prime}~versus~{{\\varepsilon }\\prime} ) in the lower frequency window; increase in the semicircle radius indicates a decrease of relaxation time. This observation is accompanied by enhancement in ionic conductivity and faster ion transport. A convincing, logical scheme to justify the experimental data has been proposed.

Mechanisms Underlying Ionic Mobilities in Nanocomposite Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Hanson, Benjamin; Pryamitsyn, Victor

2014-03-01

Recently, a number of experiments have demonstrated that addition of ceramics with nanoscale dimensions can lead to substantial improvements in the low temperature conductivity of the polymeric materials. However, the origin of such behaviors, and more generally, the manner by which nanoscale fillers impact the ion mobilities remain unresolved. In this communication, we report the results of atomistic molecular dynamics simulations which used multibody polarizable force-fields to study lithium ion diffusivities in an amorphous poly(ethylene-oxide) (PEO) melt containing well-dispersed TiO2 nanoparticles. We observed that the lithium ion diffusivities decrease with increased particle loading. Our analysis suggests that the ion mobilities are correlated to the nanoparticle-induced changes in the polymer segmental dynamics. Interestingly, the changes in polymer segmental dynamics were seen to be related to the nanoparticle's influence on the polymer conformational features. Overall, our results indicate that addition of nanoparticle fillers modify polymer conformations and the polymer segmental dynamics, and thereby influence the ion mobilities of polymer electrolytes.

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.

Electric double-layer capacitors with tea waste derived activated carbon electrodes and plastic crystal based flexible gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Suleman, M.; Deraman, M.; Othman, M. A. R.; Omar, R.; Hashim, M. A.; Basri, N. H.; Nor, N. S. M.; Dolah, B. N. M.; Hanappi, M. F. Y. M.; Hamdan, E.; Sazali, N. E. S.; Tajuddin, N. S. M.; Jasni, M. R. M.

2016-08-01

We report a novel configuration of symmetrical electric double-layer capacitors (EDLCs) comprising a plastic crystalline succinonitrile (SN) based flexible polymer gel electrolyte, incorporated with sodium trifluoromethane sulfonate (NaTf) immobilised in a host polymer poly (vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP). The cost-effective activated carbon powder possessing a specific surface area (SSA) of ~ 1700 m2g-1 containing a large proportion of meso-porosity has been derived from tea waste to use as supercapacitor electrodes. The high ionic conductivity (~3.6×10-3 S cm-1 at room temperature) and good electrochemical stability render the gel polymer electrolyte film a suitable candidate for the fabrication of EDLCs. The performance of the EDLCs has been tested by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge-discharge studies. The performance of the EDLC cell is found to be promising in terms of high values of specific capacitance (~270 F g-1), specific energy (~ 36 Wh kg-1), and power density (~ 33 kW kg-1).

Highly stable gel electrolytes for dye solar cells based on chemically engineered polymethacrylic hosts.

PubMed

De Gregorio, Gian Luca; Agosta, Rita; Giannuzzi, Roberto; Martina, Francesca; De Marco, Luisa; Manca, Michele; Gigli, Giuseppe

2012-03-25

Four different species of ionically conductive polymers were synthesized and successfully implemented to formulate novel quasi-solid electrolytes for dye solar cells. A power conversion efficiency superior to 85% of the correspondent liquid electrolyte as well as an excellent cell's stability was demonstrated after 500 days of storage.

Hydrophobic, Porous Battery Boxes

NASA Technical Reports Server (NTRS)

Bragg, Bobby J.; Casey, John E., Jr.

1995-01-01

Boxes made of porous, hydrophobic polymers developed to contain aqueous potassium hydroxide electrolyte solutions of zinc/air batteries while allowing air to diffuse in as needed for operation. Used on other types of batteries for in-cabin use in which electrolytes aqueous and from which gases generated during operation must be vented without allowing electrolytes to leak out.

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

Interfacial stability and electrochemical behavior of Li/LiFePO4 batteries using novel soft and weakly adhesive photo-ionogel electrolytes

NASA Astrophysics Data System (ADS)

Aidoud, D.; Etiemble, A.; Guy-Bouyssou, D.; Maire, E.; Le Bideau, J.; Guyomard, D.; Lestriez, B.

2016-10-01

We have developed flexible polymer-gel electrolytes based on a polyacrylate cross-linked matrix that confines an ionic liquid doped with a lithium salt. Free-standing solid electrolyte membrane is obtained after UV photo-polymerization of acrylic monomers dissolved inside the ionic liquid/lithium salt mixture. The liquid precursor of the photo-ionogel may also be directly deposited onto porous composite electrode, which results in all-solid state electrode/electrolyte stacking after UV illumination. Minor variations in the polymer component of the electrolyte formulation significantly affect the electrochemical behavior in LiFePO4/lithium and lithium/lithium cells. The rate performance increases with an increase of the ionic conductivity, which decreases with the polymer content and decreases with increasing oxygen content in the polyacrylate matrix. Their fairly low modulus endow them weak and beneficial pressure-sensitive-adhesive character. X-Rays Tomography shows that the solid-state photo-ionogel electrolytes keep their integrity upon cycling and that their surface remains smooth. The coulombic efficiency of LiFePO4/lithium cells increases with an increase of the adhesive strength of the photo-ionogel, suggesting a relationship between the contact intimacy at the lithium/photo-ionogel interface and the efficiency of the lithium striping/plating. In lithium/lithium cells, only the photo-ionogels with the higher adhesion strength are able to allow the reversible striping/plating of lithium.

Development of polypyrrole based solid-state on-chip microactuators using photolithography

NASA Astrophysics Data System (ADS)

Zhong, Yong; Lundemo, Staffan; Jager, Edwin W. H.

2018-07-01

There is a need for soft microactuators, especially for biomedical applications. We have developed a microfabrication process to create such soft, on-chip polymer based microactuators that can operate in air. The on-chip microactuators were fabricated using standard photolithographic techniques and wet etching, combined with special designed process to micropattern the electroactive polymer polypyrrole that drives the microactuators. By immobilizing a UV-patternable gel containing a liquid electrolyte on top of the electroactive polypyrrole layer, actuation in air was achieved although with reduced movement. Further optimization of the processing is currently on-going. The result shows the possibility to batch fabricate complex microsystems such as microrobotics and micromanipulators based on these solid-state on-chip microactuators using microfabrication methods including standard photolithographic processes.

DNA Based Electrochromic and Photovoltaic Cells

DTIC Science & Technology

2012-01-01

electrolyte/CeO2- TiO2 /ITO/glass configuration [29]. 2. Experimental 2.1 Gel polymeric electrolytes The electrolytes were prepared according to the...transparent membranes. Blend samples were also prepared by the addition of other macromolecules (gelatin), synthetic polymers, such as poly(ethylene...Electrochromic devices Electrochromic devices with the glass/ITO/WO3/DNA-based electrolyte/CeO2- TiO2 /ITO/glass configuration were obtained by assembling

Water-based thixotropic polymer gel electrolyte for dye-sensitized solar cells.

PubMed

Park, Se Jeong; Yoo, Kichoen; Kim, Jae-Yup; Kim, Jin Young; Lee, Doh-Kwon; Kim, Bongsoo; Kim, Honggon; Kim, Jong Hak; Cho, Jinhan; Ko, Min Jae

2013-05-28

For the practical application of dye-sensitized solar cells (DSSCs), it is important to replace the conventional organic solvents based electrolyte with environmentally friendly and stable ones, due to the toxicity and leakage problems. Here we report a noble water-based thixotropic polymer gel electrolyte containing xanthan gum, which satisfies both the environmentally friendliness and stability against leakage and water intrusion. For application in DSSCs, it was possible to infiltrate the prepared electrolyte into the mesoporous TiO2 electrode at the fluidic state, resulting in sufficient penetration. As a result, this electrolyte exhibited similar conversion efficiency (4.78% at 100 mW cm(-2)) and an enhanced long-term stability compared to a water-based liquid electrolyte. The effects of water on the photovoltaic properties were examined elaborately from the cyclic voltammetry curves and impedance spectra. Despite the positive shift in the conduction band potential of the TiO2 electrode, the open-circuit voltage was enhanced by addition of water in the electrolyte due to the greater positive shift in the I(-)/I3(-) redox potential. However, due to the dye desorption and decreased diffusion coefficient caused by the water content, the short-circuit photocurrent density was reduced. These results will provide great insight into the development of efficient and stable water-based electrolytes.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

PubMed

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

Ion conduction in high ion content PEO-based ionomers

NASA Astrophysics Data System (ADS)

Caldwell, David, II; Maranas, Janna

Solid Polymer Electrolytes (SPEs) can enable the design of batteries that are safer and have higher capacity than batteries with traditional volatile organic electrolytes. The current limitation for SPEs is their low conductivity, resulting from a conduction mechanism strongly coupled to the dynamics of the polymer host matrix. Our previous work indicated the possibility of a conduction mechanism through the use of ion aggregates. In order to investigate this mechanism, we performed a series of molecular dynamics simulations of PEO-based ionomers at high ion content. Our results indicate that conduction through ion aggregates are partially decoupled from polymer dynamics and could enable the development of higher conductive SPEs.

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.

The NASA "PERS" Program: Solid Polymer Electrolyte Development for Advanced Lithium-Based Batteries

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

In fiscal year 2000, The National Aeronautics and Space Administration (NASA) and the Air Force Research Laboratory (AFRL) established a collaborative effort to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The ultimate objective of this development program, which was referred to as the Polymer Energy Rechargeable System (PERS), was to establish a world-class technology capability and U.S. leadership in polymer-based battery technology for aerospace applications. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. Out of a total of 38 proposals received in response to a NASA Research Announcement (NRA) solicitation, 18 proposals (13 contracts and 5 grants) were selected for initial award to address these technical challenges. Brief summaries of technical approaches, results and accomplishments of the PERS Program development efforts are presented. With Agency support provided through FY 2004, the PERS Program efforts were concluded in 2005, as internal reorganizations and funding cuts resulted in shifting programmatic priorities within NASA. Technically, the PERS Program participants explored, to various degrees over the lifetime of the formal program, a variety of conceptual approaches for developing and demonstrating performance of a viable advanced solid polymer electrolyte possessing the desired attributes, as well as several participants addressing all components of an integrated cell configuration. Programmatically, the NASA PERS Program was very successful, even though the very challenging technical goals for achieving a viable solid polymer electrolyte material or the overall envisioned long-term, program objectives were not met due to funding reductions. The NASA PERS Program provided research opportunities and generated and disseminated a wealth of new scientific knowledge and technical competencies within the polymer electrolyte area.

Synthesis and characterization of aminated perfluoro polymer electrolytes

NASA Astrophysics Data System (ADS)

Page-Belknap, Zachary Stephan Glenn

Polymer electrolytes have been developed for use in anion exchange membrane fuel cells for years. However, due to the highly corrosive environment within these fuel cells, poor chemical stability of the polymers and low ion conductivity have led to high development costs and thus prevention from widespread commercialization. The work in this study aims to provide a solution to these problems through the synthesis and characterization of a novel polymer electrolyte. The 800 EW 3M PFSA sulfonyl fluoride precursor was aminated with 3-(dimethylamino)-1-propylamine to yield a functional polymer electrolyte following quaternization, referred to in this work as PFSa-PTMa. 1 M solutions of LiPF6, HCL, KOH, NaOH, CsOH, NaHCO3 and Na2CO3 were used to exchange the polymer to alternate counterion forms. Chemical structure analysis was performed using both FT and ATR infrared spectroscopy to confirm sulfonyl fluoride replacement and the absence of sulfonic acid sites. Mechanical testing of the polymer, following counterion exchange with KOH, at saturated conditions and 60 ºC exhibited a tensile strength of 13 +/- 2.0 MPa, a Young's modulus of 87 +/- 16 MPa and a degree of elongation reaching 75% +/- 9.1%, which indicated no mechanical degradation following exposure to a highly basic environment. Conductivities of the polymer in the Cl- and OH- counterion forms at saturated conditions and 90 ºC were observed at 26 +/- 8.0 mS cm-1 and 1.1 +/- 0.1 mS cm-1, respectively. OH- conductivities were slightly above those observed for CO32- and HCO 3- counterions at the same conditions, 0.63 +/- 0.18 and 0.66 +/- 0.21 mS cm-1 respectively. The ion exchange capacity (IEC) of the polymer in the Cl- counterion form was measured via titration at 0.57 meq g-1 which correlated to 11.2 +/- 0.10 water molecules per ion site when at 60ºC and 95% relative humidity. The IEC of the polymer in the OH- counterion form following titration expressed nearly negligible charge density, less than 0.01 meq g -1. The low OH- conductivities and IEC were attributed to the formation of a predominately zwitterionic polymer when exposed to a strong base. Removal of the sulfonamide proton following counterion exchange with a strong base and formation of a zwitterion was confirmed by FTIR with the absence of a primary amine stretch between 3000-3600 cm-1. 1H NMR analysis of small molecule analogues established that the sulfonamide site was not methylated during quaternization as evident by the exclusion of a strong singlet around 2.9 ppm. pH indication tests with Thymolphthalein illuminated the slight presence of free OH- ions within the polymer following counterion exchange thus validating the low IEC and formation of a predominately zwitterionic polymer. Recommended future work with this polymer electrolyte consists of fine tuning the polymer to be less or completely zwitterionic, pKa analysis of the sulfonamide linkage with small molecule analogues, implementation into microbial fuel cell and biological separation processes for pH regulation, and development as a support infrastructure for ionic liquids.

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

NASA Astrophysics Data System (ADS)

Wang, Yun; Chen, Ken S.

2016-05-01

In the present work, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Analysis is performed on a dimensionless parameter Da0 introduced in our previous paper [Y. Wang and K. S. Chen, Chemical Engineering Science 66 (2011) 3557-3567] and the parameter is further evaluated in a realistic fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

DOE PAGES

Wang, Yun; Chen, Ken S.

2016-03-21

In the present study, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Here, analysis is performed on a dimensionless parameter Da 0 introduced in our previous paper and the parameter is further evaluated in a realisticmore » fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da 0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.« less

Solid biopolymer electrolytes came from renewable biopolymer

NASA Astrophysics Data System (ADS)

Wang, Ning; Zhang, Xingxiang; Qiao, Zhijun; Liu, Haihui

2009-07-01

Solid polymer electrolytes (SPEs) have attracted many attentions as solid state ionic conductors, because of their advantages such as high energy density, electrochemical stability, and easy processing. SPEs obtained from starch have attracted many attentions in recent years because of its abundant, renewable, low price, biodegradable and biocompatible. In addition, the efficient utilization of biodegradable polymers came from renewable sources is becoming increasingly important due to diminishing resources of fossil fuels as well as white pollution caused by undegradable plastics based on petroleum. So N, N-dimethylacetamide (DMAc) with certain concentration ranges of lithium chloride (LiCl) is used as plasticizers of cornstarch. Li+ can complexes with the carbonyl atoms of DMAc molecules to produce a macro-cation and leave the Cl- free to hydrogen bond with the hydroxyl or carbonyl of starch. This competitive hydrogen bond formation serves to disrupt the intra- and intermolecular hydrogen bonding existed in starch. Therefore, melt extrusion process conditions are used to prepare conductive thermoplastic starch (TPS). The improvements of LiCl concentration increase the water absorption and conductance of TPS. The conductance of TPS containing 0.14 mol LiCl achieve to 10-0.5 S cm-1 with 18 wt% water content.

Conductivity study and fourier transform infrared (FTIR) characterization of methyl cellulose solid polymer electrolyte with sodium iodide conducting ion

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

Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom; Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor D.E.

2015-08-28

Sodium ion (Na{sup +}) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na{sup +} conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10{sup −11} S/cm.Themore » conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10{sup −5} S/cm.« less

Conductivity study and fourier transform infrared (FTIR) characterization of methyl cellulose solid polymer electrolyte with sodium iodide conducting ion

NASA Astrophysics Data System (ADS)

Abiddin, Jamal Farghali Bin Zainal; Ahmad, Azizah Hanom

2015-08-01

Sodium ion (Na+) based solid polymer electrolyte (SPE) has been prepared using solution cast technique with distilled water as solvent and Methylcellulose (MC) as a polymer host. Methylcellulose polymer was chosen as the polymer host due to the abundance of lone pair electrons in the carbonyl and C-O-C constituents, which in turn provide multiple hopping sites for the Na+ conducting ions. Variable compositions of sodium iodide (NaI) salt were prepared to investigate the optimum MC-NaI weight ratio. Results from Electrical Impedance Spectroscopy (EIS) technique show that pure methylcellulose has a low conductivity of 3.61 × 10-11 S/cm.The conductivity increases as NaI content increases up to optimum NaIcomposition of 40 wt%, which yields an average conductivity of 2.70 × 10-5 S/cm.

Computationally Guided Design of Polymer Electrolytes for Battery Applications

NASA Astrophysics Data System (ADS)

Wang, Zhen-Gang; Webb, Michael; Savoie, Brett; Miller, Thomas

We develop an efficient computational framework for guiding the design of polymer electrolytes for Li battery applications. Short-times molecular dynamics (MD) simulations are employed to identify key structural and dynamic features in the solvation and motion of Li ions, such as the structure of the solvation shells, the spatial distribution of solvation sites, and the polymer segmental mobility. Comparative studies on six polyester-based polymers and polyethylene oxide (PEO) yield good agreement with experimental data on the ion conductivities, and reveal significant differences in the ion diffusion mechanism between PEO and the polyesters. The molecular insights from the MD simulations are used to build a chemically specific coarse-grained model in the spirit of the dynamic bond percolation model of Druger, Ratner and Nitzan. We apply this coarse-grained model to characterize Li ion diffusion in several existing and yet-to-be synthesized polyethers that differ by oxygen content and backbone stiffness. Good agreement is obtained between the predictions of the coarse-grained model and long-timescale atomistic MD simulations, thus providing validation of the model. Our study predicts higher Li ion diffusivity in poly(trimethylene oxide-alt-ethylene oxide) than in PEO. These results demonstrate the potential of this computational framework for rapid screening of new polymer electrolytes based on ion diffusivity.

Quasi-Solid-State Rechargeable Li-O2 Batteries with High Safety and Long Cycle Life at Room Temperature.

PubMed

Cho, Sung Man; Shim, Jimin; Cho, Sung Ho; Kim, Jiwoong; Son, Byung Dae; Lee, Jong-Chan; Yoon, Woo Young

2018-05-09

As interest in electric vehicles and mass energy storage systems continues to grow, Li-O 2 batteries are attracting much attention as a candidate for next-generation energy storage systems owing to their high energy density. However, safety problems related to the use of lithium metal anodes have hampered the commercialization of Li-O 2 batteries. Herein, we introduced a quasi-solid polymer electrolyte with excellent electrochemical, chemical, and thermal stabilities into Li-O 2 batteries. The ion-conducting QSPE was prepared by gelling a polymer network matrix consisting of poly(ethylene glycol) methyl ether methacrylate, methacrylated tannic acid, lithium trifluoromethanesulfonate, and nanofumed silica with a small amount of liquid electrolyte. The quasi-solid-state Li-O 2 cell consisted of a lithium powder anode, a quasi-solid polymer electrolyte, and a Pd 3 Co/multiwalled carbon nanotube cathode, which enhanced the electrochemical performance of the cell. This cell, which exhibited improved safety owing to the suppression of lithium dendrite growth, achieved a lifetime of 125 cycles at room temperature. These results show that the introduction of a quasi-solid electrolyte is a potentially new alternative for the commercialization of solid-state Li-O 2 batteries.

Borotungstic Acid (BWA)-Polyacrylamide (PAM) Solid Polymer Electrolytes for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Foong, Yee Wei

Solid polymer electrolytes (SPEs) are key enablers for thin and flexible electrochemical capacitors in wearable technologies. Polyacrylamide (PAM) is one such promising hygroscopic polymer host, but its performance had not been optimized. This thesis enhanced PAM with borotungstic acid (BWA) as the heteropolyacid conductors. The BWA-PAM electrolyte achieved a high initial conductivity of ca. 27 mS cm-1, but suffered from a short service life (< 40% conductivity retention after 28 days) due to dehydration. BWA-PAM modified with acidic (H3PO4) and neutral (glycerol) plasticizers showed improved conductivity of ca. 30 mS cm-1 and service life (≥ 70% conductivity retention after 28 days). The high BWA and H3PO4 content accelerated the hydrolysis of PAM to polyacrylic acid, resulting in the undesirable precipitation of NH4+-substituted BWA; whereas, glycerol was found to suppress this reaction. The solid CNT-graphite cells with the optimized electrolytes demonstrated a capacitance of ca. 19.5 mF cm -2; a high rate capability (≥ 75% capacitance retention) at 1Vs -1; excellent cycle life (≥ 90% retention of its initial capacitance); and maintained ca. -85° phase angle over 10,000 charging-discharging cycles.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

NASA Astrophysics Data System (ADS)

Costa, Luciano T.; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-01

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li+ coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSIṡ1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

PubMed

Costa, Luciano T; Sun, Bing; Jeschull, Fabian; Brandell, Daniel

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend

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

Costa, Luciano T., E-mail: ltcosta@id.uff.br; Sun, Bing; Jeschull, Fabian

2015-07-14

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li{sup +} coordination and transportation were studied in the ternary electrolyte system, i.e., PEO{sub 16}LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generatedmore » significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.« less

Single-ion conducting diblock terpolymers for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Morris, Melody; Epps, Thomas H., III

Block polymer (BP) electrolytes provide an attractive route to overcome the competing constraints of high conductivity and mechanical/thermal stability in lithium-ion batteries through nanoscale self-assembly. For example, macromolecules can be engineered such that one domain conducts lithium ions and the other prevents lithium dendrite formation. Herein, we report on the behavior of a single-ion conducting BP electrolyte that was designed to facilitate the transport of lithium ions. These polymers differ from traditional salt-doped BP electrolytes, which require the addition of a lithium salt to bestow conductivity and typically suffer from substantial counterion motion that reduces efficiency. New single-ion BPs were synthesized, and the nanoscale morphologies were determined using small angle X-ray scattering and transmission electron microscopy. Electrolyte performance was measured using AC impedance spectroscopy and DC polarization, and the results were correlated to nanoscale morphology and ion content. Enhanced physical understanding of single-ion BPs was gained by connecting the ion mobility to the chemistry, chain structure, and ion content of the single-ion BP. These studies can be applied to other charged-neutral block polymers to elucidate the effects of ion content on self-assembly and macroscopic properties.

Studies on Ionic Conductivity and Electrochemical Stability of Plasticized Photopolymerized Polymer Electrolyte Membranes for Solid State Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

He, Ruixuan

In pursuit of safer and more flexible solid-state lithium ion batteries, solid polymer electrolytes have emerged as a promising candidate. The present dissertation entails exploration of solid plasticized, photopolymerized (i.e. ultraviolent-cured) polymer electrolyte membranes (PEM) for fulfilling the critical requirements of electrolytes, such as high ionic conductivity and good thermal and electrochemical stability, among others. Electrochemical performance of PEMs containing lithium ion half-cells was also investigated at different two temperatures. Phase diagram approach was adopted to guide the fabrication of two types of plasticized PEMs. Prepolymer poly (ethylene glycol) diacrylate (PEGDA) was used as a matrix for building an ionic conductive and mechanically sturdy network. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated as a source of lithium ions, while a solid plasticizer succinonitrile (SCN) and a liquid plasticizer tetraethylene glycol dimethyl ether (TEGDME) were incorporated in the respective systems. The important role of plasticizer on the enhancement of ionic conductivity (sigma) to the superionic conductive level (10-3 S/cm) was revealed in both systems. It is worth noting that photopolymerization induced crystallization (PIC) occurred during UV-curing in the SCN-rich region of the ternary PEGDA/LiTFSI/SCN ternary mixtures. The PEM thus formed contained a plastic crystal phase, which showed lower σ relative to their amorphous PEGDA/LiTFSI/TEGDME counterpart. Comparisons on other thermal and electrochemical properties of the two types of PEMs are presented in Chapter IV. For the PEGDA/LiTFSI/SCN PEMs, fundamental study was carried out to clarify the relationship between σ and glass transition temperature (T g). In lithium salt/polymer binary PEMs, increase in Tg and reduction in σ were observed; these may be attributed to ion-dipole complexation between dissociated lithium cations and ether oxygen upon salt addition. Notably, above the threshold salt concentration of 7 mol %, dual loss tangent peaks were observed in dynamic mechanical studies. These might be ascribed to segmental relaxations of ion-dipole complexed networks and that of polymer chains surrounding the undissociated lithium salt acting like "fillers". Upon SCN incorporation, these two peaks merged into one that was further suppressed below the Tg of the pure network, whereas σ improved to the superionic conductor level. The role of SCN on the σ enhancement as both plasticizer for the polymer network and ionizer for the salt is discussed in Chapter V. In order to improve the mechanical toughness of the highly conductive PEGDA/LiTFSI/SCN PEM, effects of prepolymer molecular weight on mechanical and electrochemical properties of PEMs were further investigated. By increasing molecular weight of PEGDA from 700 to 6000 g/mol, toughness and elongation at break were enhanced as expected. Interestingly, improved ionic conductivity was achieved simultaneously. The dual improvement may be attributed to the less chemical crosslinked points and the more flexible chain motion in the looser network of PEGDA6000-PEM relative to its PEGDA700 counterpart. Subsequently, high thermal stability and electrochemical stability of both types of PEMs, as well as the satisfactory room temperature charge/discharge cycling performance of PEM containing lithium ion half-cells were observed. The pertinent information is documented in Chapter VI. Finally, the investigation of the charge/discharge cycling performance of solid-state LiFePO4 half-cells at an elevated temperature of 60°C is discussed in Chapter VII. In the half-cells, particularly, SCN plasticized PEMs with and without electrolyte modifier lithium bis(oxalato)borate (LiBOB) were respectively employed. Rapid decline of capacity and increase of cell resistance were found in the unmodified PEM containing cell; however, these deteriorations were greatly suppressed upon LiBOB modification. Electrochemical and thermal compatibility of PEMs towards different electrodes were examined in several symmetric cells and half-cells. Detailed characterization on LiFePO 4 electrodes and PEMs retrieved from these cells implied that the observed battery failure might be triggered by an amide-forming side reaction that took place at the interface of a SCN plasticized PEM and a lithium electrode at high temperature. Of particular importance is the fact that this detrimental side reaction was effectively suppressed upon LiBOB electrolyte modifier addition. Plausible mechanisms are discussed.

An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes

PubMed Central

Zhao, Chen-Zi; Zhang, Xue-Qiang; Cheng, Xin-Bing; Zhang, Rui; Xu, Rui; Chen, Peng-Yu; Peng, Hong-Jie; Huang, Jia-Qi

2017-01-01

Lithium metal is strongly regarded as a promising electrode material in next-generation rechargeable batteries due to its extremely high theoretical specific capacity and lowest reduction potential. However, the safety issue and short lifespan induced by uncontrolled dendrite growth have hindered the practical applications of lithium metal anodes. Hence, we propose a flexible anion-immobilized ceramic–polymer composite electrolyte to inhibit lithium dendrites and construct safe batteries. Anions in the composite electrolyte are tethered by a polymer matrix and ceramic fillers, inducing a uniform distribution of space charges and lithium ions that contributes to a dendrite-free lithium deposition. The dissociation of anions and lithium ions also helps to reduce the polymer crystallinity, rendering stable and fast transportation of lithium ions. Ceramic fillers in the electrolyte extend the electrochemically stable window to as wide as 5.5 V and provide a barrier to short circuiting for realizing safe batteries at elevated temperature. The anion-immobilized electrolyte can be applied in all–solid-state batteries and exhibits a small polarization of 15 mV. Cooperated with LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathodes, the all–solid-state lithium metal batteries render excellent specific capacities of above 150 mAh⋅g−1 and well withstand mechanical bending. These results reveal a promising opportunity for safe and flexible next-generation lithium metal batteries. PMID:28973945

Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability.

PubMed

Shin, Dong Won; Guiver, Michael D; Lee, Young Moo

2017-03-22

A fundamental understanding of polymer microstructure is important in order to design novel polymer electrolyte membranes (PEMs) with excellent electrochemical performance and stabilities. Hydrocarbon-based polymers have distinct microstructure according to their chemical structure. The ionic clusters and/or channels play a critical role in PEMs, affecting ion conductivity and water transport, especially at medium temperature and low relative humidity (RH). In addition, physical properties such as water uptake and dimensional swelling behavior depend strongly on polymer morphology. Over the past few decades, much research has focused on the synthetic development and microstructural characterization of hydrocarbon-based PEM materials. Furthermore, blends, composites, pressing, shear field, electrical field, surface modification, and cross-linking have also been shown to be effective approaches to obtain/maintain well-defined PEM microstructure. This review summarizes recent work on developments in advanced PEMs with various chemical structures and architecture and the resulting polymer microstructures and morphologies that arise for potential application in fuel cell, lithium ion battery, redox flow battery, actuators, and electrodialysis.

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.

Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

2015-12-15

The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

The Effect of Structural Modifications on Ionic Conductivity in Newly-Designed Polyester Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Jung, Yuki; Coates, Geoff; Balsara, Nitash

2015-03-01

Gaining a fundamental understanding of the relationship between molecular structure and ionic conductivity of polymer electrolytes is an essential step toward designing next generation materials for battery applications. In this study, we use a systematic set of newly-designed polyesters with varying side-chain lengths and oxygen functional groups to elucidate the effects of structural modifications on the conductive properties of the corresponding electrolytes. Mixtures of polyesters and lithium bis(trifluromethanesulfonyl)imide (LiTFSI) were characterized using ac impedance spectroscopy to measure the ionic conductivity at various temperatures and salt concentrations. The relative conductivities of these electrolytes in the dilute limit are directly comparable to results of molecular dynamics simulations performed using the same polymers. The simulations correspond well with the experimental results, and provide molecular level insight about the solvation environment of the lithium ions and how the ions transport through these polyesters.

Dielectric studies on PVA/PVP blend polymer electrolyte films

NASA Astrophysics Data System (ADS)

Kumar, B. Ranjit; Basha, S. K. Shahenoor; Rao, M. C.

2018-05-01

Biodegradable blend polymer electrolytes of PVA/PVP with different wt% ratios of MgCl2.6H2O have been prepared using solution cast technique. Dielectric studies were performed on to the prepared films using HIOKI 3532-50 in the frequency range 5000 Hz - 50000 KHz. As increasing the frequency the dielectric constant gradually decreases and found to be high for the sample prepared at 30 wt%; this concludes that the drifting of ions is high giving raise to conductivity phenomenon.

Optical absorption studies on biodegradable PVA/PVP blend polymer electrolyte system

NASA Astrophysics Data System (ADS)

Basha, S. K. Shahenoor; Reddy, K. Veera Bhadra; Rao, M. C.

2018-05-01

Biodegradable blend polymer electrolytes of PVA/PVP with different wt% ratios of MgCl2.6H2O have been prepared using solution cast technique. Optical absorption studies were carried-out on to the prepared films at room temperature using JASCO V-670 Spectrophotometer in the wavelength region 200-600 nm. Due to the clusters between the vibrations of molecules a broad peak is obtained due to п-п* transition in the wavelength region 310-340 nm.

Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

NASA Technical Reports Server (NTRS)

1976-01-01

Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

In situ measurements of the optical absorption of dioxythiophene-based conjugated polymers

NASA Astrophysics Data System (ADS)

Hwang, J.; Schwendeman, I.; Ihas, B. C.; Clark, R. J.; Cornick, M.; Nikolou, M.; Argun, A.; Reynolds, J. R.; Tanner, D. B.

2011-05-01

Conjugated polymers can be reversibly doped by electrochemical means. This doping introduces new subband-gap optical absorption bands in the polymer while decreasing the band-gap absorption. To study this behavior, we have prepared an electrochemical cell allowing in situ measurements of the optical properties of the polymer. The cell consists of a thin polymer film deposited on gold-coated Mylar behind which is another polymer that serves as a counterelectrode. An infrared transparent window protects the upper polymer from ambient air. By adding a gel electrolyte and making electrical connections to the polymer-on-gold films, one may study electrochromism in a wide spectral range. As the cell voltage (the potential difference between the two electrodes) changes, the doping level of the conjugated polymer films is changed reversibly. Our experiments address electrochromism in poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-dimethylpropylenedioxythiophene) (PProDOT-Me2). This closed electrochemical cell allows the study of the doping induced subband-gap features (polaronic and bipolaronic modes) in these easily oxidized and highly redox switchable polymers. We also study the changes in cell spectra as a function of polymer thickness and investigate strategies to obtain cleaner spectra, minimizing the contributions of water and gel electrolyte features.

The Influence of Charged Species on the Phase Behavior, Self-Assembly, and Electrochemical Performance of Block Copolymer Electrolytes

NASA Astrophysics Data System (ADS)

Thelen, Jacob Lloyd

One of the major barriers to expanding the capacity of large-scale electrochemical energy storage within batteries is the threat of a catastrophic failure. Catastrophic battery pack failure can be initiated by a defect within a single battery cell. If the failure of a defective battery cell is not contained, the damage can spread and subsequently compromise the integrity of the entire battery back, as well as the safety of those in its surroundings. Replacing the volatile, flammable liquid electrolyte components found in most current lithium ion batteries with a solid polymer electrolyte (SPE) would significantly improve the cell-level safety of batteries; however, poor ionic conductivity and restricted operating temperatures compared to liquid electrolytes have plagued the practical application of SPEs. Rather than competing with the performance of liquid electrolytes directly, our approach to developing SPEs relies on increasing electrolyte functionality through the use of block copolymer architectures. Block copolymers, wherein two or more chemically dissimilar polymer chains are covalently bound, have a propensity to microphase separate into nanoscale domains that have physical properties similar to those of each of the different polymer chains. For instance, the block copolymer, polystyrene-b-poly(ethylene oxide) (SEO), has often been employed as a solid polymer electrolyte because the nanoscale domains of polystyrene (PS) can provide mechanical reinforcement, while the poly(ethylene oxide) microphases can solvate and conduct lithium ions. Block copolymer electrolytes (BCEs) formed from SEO/salt mixtures result in a material with the bulk mechanical properties of a solid, but with the ion conducting properties of a viscoelastic fluid. The efficacy SEO-based BCEs has been demonstrated; the enhanced mechanical functionality provided by the PS domains resist the propagation of dendritic lithium structures during battery operation, thus enabling the use of a lithium metal anode. The increase in the specific energy of a battery upon replacing a graphite anode with lithium metal can offset the losses in performance due to the poor ion conduction of SPEs. However, BCEs that enable the use of a lithium anode and have improved performance would represent a major breakthrough for the development of high capacity batteries. The electrochemical performance of BCEs has a complex relationship with the nature of the microphase separated domains, which is not well-understood. The objective of this dissertation is to provide fundamental insight into the nature of microphase separation and self-assembly of block copolymer electrolytes. Specifically, I will focus on how the ion-polymer interactions within a diverse set of BCEs dictate nanostructure. Combining such insight with knowledge of how nanostructure influences ion motion will enable the rational design of new BCEs with enhanced performance and functionality. In order to facilitate the study of BCE nanostructure, synchrotron-based X-ray scattering techniques were used to study samples over a wide range of length-scales under conditions relevant to the battery environment. The development of the experimental aspects of the X-ray scattering techniques, as well as an improved treatment of scattering data, played a pivotal role in the success of this work. The dissemination of those developments will be the focus of the first section. The thermodynamic impact of adding salt to a neutral diblock copolymer was studied in a model BCE composed of a low molecular weight SEO diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a common salt used in lithium batteries. In neutral block copolymers (BCPs), self-assembly is a thermodynamically driven process governed by a balance between unfavorable monomer contacts and the entropy of mixing. When the enthalpic and entropic contributions to free energy are similar in magnitude, a block copolymer can undergo a thermally reversible phase transition from an ordered to a disordered nanostructure. We used temperature-dependent small angle X-ray scattering (SAXS) to observe this transition in the model SEO/LiTFSI system. Unlike neutral BCPs, which to a first approximation are single component systems, the SEO/LiTFSI system demonstrated the thermodynamically stable coexistence phases of ordered lamellae and disordered polymer over a finite temperature window. Analysis of the lamellar domains revealed an increase in salt concentration during the ODT, indicating local salt partitioning due to the presence of nanostructure. The performance of BCEs can also be improved by chemically functionalizing one of the polymer blocks by covalently attaching the salt anion. Since the cation is the only mobile species, these materials are coined single-ion conducting block copolymers. Single ion conduction can improve the efficiency of battery operation. In order for cation motion to occur in single-ion conducting block copolymers, it must dissociate from the backbone of the anion-containing polymer block. This direct coupling of ion dissociation (and hence conduction) and nanostructure has interesting implications for BCE performance. (Abstract shortened by ProQuest.).

7Li NMR spectroscopy and ion conduction mechanism in mesoporous silica (SBA-15) composite poly(ethylene oxide) electrolyte

NASA Astrophysics Data System (ADS)

Reddy, M. Jaipal; Chu, Peter P.

A composite of mesoporous silica (SBA-15) with a polyethylene oxide (PEO) polymer electrolyte is examined for use in various electrochemical devices. Incorporation of SBA-15 in a PEO:LiClO 4 polymer electrolyte facilitates salt dissociation, enhances ion conductivity, and improves miscibility between organic and inorganic moieties. Optimized conductivity is found at 10 wt.% SBA-15 composition, above this concentration the conductivity is reduced due to aggregation of a SBA-15:Li rich phase. Heating above melt temperature of PEO allows more of the polymer segments to interact with SBA-15. This results in a greater degree of disorder upon cooling, and the ion conductivity is enhanced. A 7Li MAS NMR study reveals three types of lithium-ion coordination. Two major types of conduction mechanism can be identified: one through conventional amorphous PEO; a second via hopping in a sequential manner by replacing the nearby vacancies ('holes') on the surface (both interior and exterior) of the SBA-15 channels.

Composite polymer electrolytes based on MG49 and carboxymethyl cellulose from kenaf

NASA Astrophysics Data System (ADS)

Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan

2013-11-01

The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF3SO3 were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2-10 wt%) via solution-casting method. The conductivity was increased with carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10-7 Scm-1 upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

2016-05-01

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

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

Sengwa, R. J., E-mail: rjsengwa@rediffmail.com; Dhatarwal, Priyanka, E-mail: dhatarwalpriyanka@gmail.com; Choudhary, Shobhna, E-mail: shobhnachoudhary@rediffmail.com

2016-05-06

Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF{sub 4}) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governedmore » by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10{sup −6} S cm{sup −1} which suggests the suitability of the SPE film for rechargeable lithium batteries.« less

Hybrid solid polymer electrolyte from diapers as separator for electrochemical double layer capacitor (EDLC)

NASA Astrophysics Data System (ADS)

Hashim, Mohd Azman; Yatim, Nadhrah Md.; Mahmud, Nor Azura Che; Sazali, Nur Ezniera Shafieza; Hamdan, Ellisah; Yahya, Mohd Adib; Ngah, Che Wan Zanariah Che Wan; Suhaimi, Syahida

2018-06-01

EDLC was fabricated using hybrid solid polymer electrolyte from PVA-diapers and an activated carbon powder as electrode by using solution casting method. For comparison, four types of EDLC cells were constructed and tested. It was found that an EDLC with a PVA-diapers (60:40) polymer electrolyte exhibited much higher capacitance and longer cycle-life. The electrocapacitive properties of the supercapacitor (P50HD50, P60HD40, P70HD30 and P80HD20) were done using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge discharge (GCD). Results from these analysis showed that P60HD40 cell had recorded excellent rate capability and highest Csp value of 179 F g-1 (EIS), 50 F g-1 (CV), 328 F g-1 (GCD) respectively. Futher, results from ESR (GCD) analysis showed that P60HD40 composition of PVA/H3PO4 liquid electroyte gave a lower value of 88.05 Ω in the supercapacitor cell compared with another cells.

Sulfonated polystyrene and its characterization as a material of electrolyte polymer

NASA Astrophysics Data System (ADS)

Ngadiwiyana; Ismiyarto; Gunawan; Purbowatiningrum, RS; Prasetya, N. B. A.; Kusworo, T. D.; Susanto, H.

2018-05-01

The research of polystyrene modification from Styrofoam waste and its application as a main material of electrolyte polymer had been done. The sulfonation reaction of polystyrene was conducted using sulfuric acid as sufonation agent and the reactions were done with variation times of 1, 2, 3, 4 and 5 h. The characterization of the sulfonated products covered analysis of functional groups using FT-IR spectrophotometer, sulfonation degree, measurements of ion exchange capacity, conductivity and swelling degree. The sulfonated polystyrene product was white solid as confirmed by the spectra of FT-IR with the presence of wide band absorption of O=S=O at the wavenumber of 1080-1411 cm-1 as indication. The research showed the best sulfonated polystyrene prepared in 4 h as a material of electrolyte polymer, since it had the highest degree of sulfonation, ion exchange capacity, conductivity and swelling degree with the values were 28.52 %, 1.550 meg/g, 15,924.10-6 Ω-1cm-1 and 332.4 %, respectively.

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

PubMed

Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

2010-10-05

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

Sulfonated polyphenylene polymers

DOEpatents

Cornelius, Christopher J.; Fujimoto, Cy H.; Hickner, Michael A.

2007-11-27

Improved sulfonated polyphenylene compositions, improved polymer electrolyte membranes and nanocomposites formed there from for use in fuel cells are described herein. The improved compositions, membranes and nanocomposites formed there from overcome limitations of Nafion.RTM. membranes.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

1984-01-01

Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

Polymer membranes as separators for supercapacitors

NASA Astrophysics Data System (ADS)

Szubzda, Bronisław; Szmaja, Aleksandra; Ozimek, Mariusz; Mazurkiewicz, Sławomir

2014-12-01

The purpose of the studies described was to examine the influence of low-energy plasma modification of polyamide and polypropylene polymer nonwoven fabrics on the usable properties of supercapacitors when using these fabrics as the separator material. To achieve this goal the following investigations were carried out: testing the time required for electrolyte saturation of separators and the conductivity of the electrolyte contained in the separator, as well as electrochemical examinations of supercapacitor models in which the modified fabric separators were used. The tests conducted fully confirm the usability of this modification for cleaning the surface and improving the wettability of separators by the electrolyte, which in turn results in a significant decrease of the internal resistance of the supercapacitor, thus increasing the usable power of the device.

High optical and switching performance electrochromic devices based on a zinc oxide nanowire with poly(methyl methacrylate) gel electrolytes

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

Chun, Young Tea; Chu, Daping, E-mail: dpc31@cam.ac.uk; Neeves, Matthew

2014-11-10

High performance electrochromic devices have been fabricated and demonstrated utilizing a solid polymer electrolyte and zinc oxide (ZnO) nanowire (NW) array counter electrode. The poly(methyl methacrylate) based polymer electrolyte was spin coated upon hydrothermally grown ZnO NW array counter electrodes, while electron beam evaporated NiO{sub x} thin films formed the working electrodes. Excellent optical contrast and switching speeds were observed in the fabricated devices with active areas of 2 cm{sup 2}, exhibiting an optical contrast of 73.11% at the wavelength of 470 nm, combined with a fast switching time of 0.2 s and 0.4 s for bleaching and coloration, respectively.

Interphase Transformations at Metal (Copper, Iron)-Polymer Gel-Electrolyte Interfaces

NASA Astrophysics Data System (ADS)

Lyamina, G. V.; Dubinina, O. V.; Vaitulevich, E. A.; Mokrousov, G. M.

2018-07-01

The results from studies of the interface boundaries between metals (copper and iron) and gel electrolyte based on methacrylic copolymers are organized systematically. In contrast to processes in liquid electrolytes, a number of key features of the reactions that occur at such interfaces are revealed: a diffusion limiting stage; a lack of reverse reactions; and the formation of coordination compounds of metal ions with the functional groups of polymers, the stabilities of which are several orders of magnitude greater than that of coordination with their low-molecular weight counterparts. It is shown that processes which employ polymeric organogels can be used for the careful cleaning of the metal surfaces, and for the formation of a desired phase composition on the latter.

Composite Polymer-Garnet Solid State Electrolytes

NASA Astrophysics Data System (ADS)

Villa, Andres; Oduncu, Muhammed R.; Scofield, Gregory D.; Marinero, Ernesto E.; Forbey, Scott

Solid-state electrolytes provide a potential solution to the safety and reliability issues of Li-ion batteries. We have synthesized cubic-phase Li7-xLa3Zr2-xBixO12 compounds utilizing inexpensive, scalable Sol-gel synthesis and obtained ionic conductivities 1.2 x 10-4 S/cm at RT in not-fully densified pellets. In this work we report on the fabrication of composite polymer-garnet ceramic particle electrolytes to produce flexible membranes that can be integrated with standard battery electrodes without the need for a separator. As a first step we incorporated the ceramic particles into polyethylene oxide polymers (PEO) to form flexible membranes. Early results are encouraging yielding ionic conductivity values 1.0 x 10-5 S/cm at RT. To increment the conductivity in the membranes, we are optimizing amongst other: the ceramic particle size distribution and weight load, the polymer molecular weight and chemical composition and the solvated Li-salt composition and content. Unhindered ion transport across interfaces between the composites and the battery electrode materials is paramount for battery performance. To this end, we are investigating the effect of interface morphology, its atomic composition and exploring novel electrode structures that facilitate ionic transport.

Estimation of electrode ionomer oxygen permeability and ionomer-phase oxygen transport resistance in polymer electrolyte fuel cells.

PubMed

Sambandam, Satheesh; Parrondo, Javier; Ramani, Vijay

2013-09-28

The oxygen permeability of perfluorinated and hydrocarbon polymer electrolyte membranes (PEMs; Nafion®, SPEEK and SPSU), which are used as electrolytes and electrode ionomers in polymer electrolyte fuel cells (PEFCs), was estimated using chronoamperometry using a modified fuel cell set-up. A thin, cylindrical microelectrode was embedded into the PEM and used as the working electrode. The PEM was sandwiched between 2 gas diffusion electrodes, one of which was catalyzed and served as the counter and pseudo-reference electrode. Independently, from fuel cell experiments, the oxygen transport resistance arising due to transport through the ionomer film covering the catalyst active sites was estimated at the limiting current and decoupled from the overall mass transport resistance. The in situ oxygen permeability measured at 80 °C and 75% RH of perfluorinated ionomers such as Nafion® (3.85 × 10(12) mol cm(-1) s(-1)) was observed to be an order of magnitude higher than that of hydrocarbon-based PEMs such as SPEEK (0.27 × 10(12) mol cm(-1) s(-1)) and SPSU (0.15 × 10(12) mol cm(-1) s(-1)). The obtained oxygen transport (through ionomer film) resistance values (Nafion® - 1.6 s cm(-1), SPEEK - 2.2 s cm(-1) and SPSU - 3.0 s cm(-1); at 80 °C and 75% RH) correlated well with the measured oxygen permeabilities in these ion-containing polymers.

High precision slotted cavity measurement of a novel ceramic state polymer electrolyte

NASA Astrophysics Data System (ADS)

Quan, Wei; NurulAfsar, Mohammed

2018-01-01

Thin film materials are already used in a variety of microwave and higher frequency applications such as electrically tunable microwave devices, integrated circuits like MMICs, radomes, and radar absorbing coating. The determination of the dielectric properties of these films is thus of significant importance. The measurement of complex dielectric permittivity of thin films is very difficult at microwave, millimeter, and THz frequencies because both the amplitude change and phase shift are not large enough to evaluate the real part of the dielectric permittivity. A specially designed transverse slotted cavity for X-band microwave measurement has been designed and constructed to employ with a vector network analyzer to evaluate the real part of dielectric permittivity of thin films accurately and conveniently. Commercially available polymer thin films are measured to validate the methods.

Ionic conductivity and relaxation studies in PVDF-HFP:PMMA-based gel polymer blend electrolyte with LiClO4 salt

NASA Astrophysics Data System (ADS)

Gohel, Khushbu; Kanchan, D. K.

Poly(vinylidene fluoride-hexafluropropylene) (PVDF-HFP) and poly(methyl methacrylate) (PMMA)-based gel polymer electrolytes (GPEs) comprising propylene carbonate and diethyl carbonate mixed plasticizer with variation of lithium perchlorate (LiClO4) salt concentrations have been prepared using a solvent casting technique. Structural characterization has been carried out using XRD wherein diffraction pattern reveals the amorphous nature of sample up to 7.5wt.% salt and complexation of polymers and salt have been studied by FTIR analysis. Surface morphology of the samples has been studied using scanning electron microscope. Electrochemical impedance spectroscopy in the temperature range 303-363K has been carried out for electrical conductivity. The maximum room temperature conductivity of 2.83×10-4S cm-1 has been observed for the GPE incorporating 7.5wt.% LiClO4. The temperature dependence of ionic conductivity obeys the Arrhenius relation. The increase in ionic conductivity with change in temperatures and salt content is observed. Transport number measurement is carried out by Wagner’s DC polarization method. Loss tangent (tan δ) and imaginary part of modulus (M‧‧) corresponding to dielectric relaxation and conductivity relaxation respectively show faster relaxation process with increasing salt content up to optimum value of 7.5wt.% LiClO4. The modulus (M‧‧) shows that the conductivity relaxation is of non-Debye type (broader than Debye peak).

Comparison of starch and gelatin hydrogels for non-toxic supercapacitor electrolytes

NASA Astrophysics Data System (ADS)

Railanmaa, Anna; Lehtimäki, Suvi; Lupo, Donald

2017-06-01

Starch and gelatin are two of the most abundantly available natural polymers. Their non-toxicity, low cost, and compatibility with aqueous solvents make them ideal for use in ubiquitous, environmentally friendly electronics systems. This work presents the results of conductivity measurements through impedance spectroscopy for gelatin- and starch-based aqueous gel electrolytes. The NaCl-based gels were physically cross-linked. The conductivity values were 84.6 mS/cm at 1.5 mol L-1 and 71.5 mS/cm at 2 mol L-1 for gelatin and starch, respectively. The mechanical properties of gelatin were found preferable to those of starch, although they deteriorated significantly when the salt concentration exceeded 2 mol L-1. The ability of the gels to successfully act as a supercapacitor electrolyte was demonstrated with printed electrodes on plastic substrate. The devices were characterized through cyclic voltammetry measurements. The results imply that these polymer gel electrolytes are very promising for replacing the traditional aqueous liquid electrolytes in supercapacitors in applications where, for example, user and environmental safety is essential.

Lithium dendrite growth through solid polymer electrolyte membranes

NASA Astrophysics Data System (ADS)

Harry, Katherine; Schauser, Nicole; Balsara, Nitash

2015-03-01

Replacing the graphite-based anode in current batteries with a lithium foil will result in a qualitative increase in the energy density of lithium batteries. The primary reason for not adopting lithium-foil anodes is the formation of dendrites during cell charging. In this study, stop-motion X-ray microtomography experiments were used to directly monitor the growth of lithium dendrites during electrochemical cycling of symmetric lithium-lithium cells with a block copolymer electrolyte. In an attempt to understand the relationship between viscoelastic properties of the electrolyte on dendrite formation, a series of complementary experiments including cell cycling, tomography, ac impedance, and rheology, were conducted above and below the glass transition temperature of the non-conducting poly(styrene) block; the conducting phase is a mixture of rubbery poly(ethylene oxide) and a lithium salt. The tomography experiments enable quantification of the evolution of strain in the block copolymer electrolyte. Our work provides fundamental insight into the dynamics of electrochemical deposition of metallic films in contact with high modulus polymer electrolytes. Rational approaches for slowing down and, perhaps, eliminating dendrite growth are proposed.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors

PubMed Central

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

Supercapacitor Electrode Materials from Highly Porous Carbon Nanofibers with Tailored Pore Distributions

NASA Astrophysics Data System (ADS)

Chathurika Abeykoon, Nimali

Environmental and human health risks associated with the traditional methods of energy production (e.g., oil and gas) and intermittency and uncertainty of renewable sources (e.g., solar and wind) have led to exploring effective and alternative energy sources to meet the growing energy demands. Electricity based on energy storage devices are the most promising solutions for realization of these objectives. Among the energy storage devices, electrochemical double layer capacitors (EDLCs) or supercapacitors have become an attractive research interest due to their outstanding performance, especially high power densities, long cycle life and rapid charge and discharge times, which enables them to utilize in many applications including consumer electronics and transportation, where high power is needed. However, low energy density of supercapacitors is a major obstacle to compete with the commercially existing high energy density energy storage device such as batteries. The fabrication of advanced electrodes materials with very high surface area from novel precursors and utilization of electrolytes with higher operating voltages are essential to enhance energy density of supercapacitors. In this work, carbon nanofibers (CNFs) from different polymer precursors with new fabrication techniques are explored to develop highly porous carbon with tailored pore distributions to match with employed ionic liquid electrolytes (which possess high working voltages), to realize high energy storage capability. Novel electrode materials derived from electrospun immiscible polymer blends and synthesized copolymers and terpolymers were described. Pore distributions of CNFs were tailored by varying the composition of polymers in immiscible blends or varying the monomer ratios of copolymer or terpolymers. Chapter 1 gives the detailed introduction of supercapacitors including history and storage principle of EDLCs, fabrication of carbon nanofiber based electrodes and electrolytes employed for EDLCs. It also explains the necessity and the advantages of tailored high surface area nanofibers as an electrode materials for supercapacitors. Chapter 2 describes the preparation of high surface area carbon nanofibers using polymer blends containing PAN and PMMA and introduces an effective and simple strategy to improve the surface area of CNFs by using a sacrificial polymer, PMMA. Chapter 3 describes blending of high fractional free volume polymer, 6FDA-DAM: DABA (3:2) into PBI to increase surface area and by using the higher etch rate of 6FDA-DAM: DABA in the blend to optimize pore distribution of CNFs. Chapter 4 introduces a novel approach to increase surface area of CNFs without any physical or chemical activation by using an in situ porogen containing copolymer P(AN-co-IA). The concept developed here avoids unnecessary and complex extra activation steps when fabricating carbon nanofibers which leads to lower char yield and uncontrollable pore sizes. Chapter 5 describes enhancement of surface area by using terpolymer P(AN-VIM-IA) to develop a new precursor. This approach is further advantageous since terpolymer can combine superior electrochemical properties of homopolymer, PAN and P(AN- co-IA) and P(AN-co-VIM). Chapter 6 describes the use of commercially available small molecule compatibilizer 2-MI to tailor pore architecture of carbon fiber derived from the immiscible blend of PBI/6FDD to match with the ion sizes of ionic liquid electrolytes thereby increasing the surface area of the CNFs that is accessible to electrolytes.

Ceramic and polymeric solid electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

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

Chew, K. W.; Tan, C. G.; Osman, Z.

The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10{sup -10} Scm{sup -1} is obtained. This may be due tomore » the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -1}. Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.« less

Synthesis and characterization of ion transport behavior in Cu2+-conducting nano composite polymer electrolyte membranes

NASA Astrophysics Data System (ADS)

Bala Sahu, Tripti; Sahu, Manju; Karan, Shrabani; Mahipal, Y. K.; Sahu, D. K.; Agrawal, R. C.

2017-07-01

Synthesis and characterization of ion transport behavior in Cu2+-conducting nano composite polymer electrolyte (NCPE) films: [90PEO: 10Cu(CF3SO3)2]  +  x CuO have been reported. NCPE films have been formed by hot-press casting technique using solid polymer electrolyte (SPE) film composition: [90PEO: 10Cu(CF3SO3)2] as 1st-phase host and nanoparticles of CuO in varying wt.(%) as 2nd-phase active filler. SPE: [90PEO: 10Cu(CF3SO3)2] was identified earlier as highest conducting film with room temperature conductivity (σ rt) ~ 3.0 x 10-6 S cm-1, which is three orders of magnitude higher than that of pure polymer host PEO with σ rt ~ 3.2  ×  10-9 S cm-1. Filler particle concentration dependent conductivity study revealed NCPE film: [90PEO: 10Cu(CF3SO3)2]  +  3%CuO as optimum conducting composition (OCC) exhibiting σ rt ~ 1.14  ×  10-5 S cm-1. Hence, by the fractional dispersal of 2nd-phase active filler into 1st-phase SPE host, σ-enhancement of approximately an order of magnitude has further been obtained. Ion transport behavior in NCPE OCC film has been characterized in terms of basic ionic parameters viz. ionic conductivity (σ), total ionic transference (t ion)/cationic (t +) numbers. Temperature dependent conductivity measurement has also been done to explain the mechanism of ion transport and to compute activation energy (E a). Materials characterization and hence, confirmation of complexation of salt in polymeric host and/or dispersal of filler particles in SPE host have been done by scanning electron microscopy (SEM), energy dispersive x-ray spectrometer (EDS), x-ray diffraction (XRD), Fourier transform infra-red (FTIR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). All-solid-state battery in the cell configuration: Cu (Anode) || SPE host/NCPE OCC film || C  +  I2  +  Electrolyte) (Cathode) has been fabricated and cell performance has been studied under two load resistances viz. 60 and 100 kΩ. Each NCPE cell gave on an open circuit voltage (OCV) ~ 0.68 V. Some important battery parameters have also been evaluated from the plateau regions of cell potential discharge profiles.

Functional and Multifunctional Polymers: Materials for Smart Structures

NASA Technical Reports Server (NTRS)

Arnold, S.; Pratt, L. M.; Li, J.; Wuagaman, M.; Khan, I. M.

1996-01-01

The ultimate goal of the research in smart structures and smart materials is the development of a new generation of products/devices which will perform better than products/devices built from passive materials. There are a few examples of multilayer polymer systems which function as smart structures, e.g. a synthetic muscle which is a multilayer assembly of a poly(ethylene) layer, a gold layer, and a poly(pyrrole) layer immersed in a liquid electrolyte. Oxidation and reductions of the active pyrrole layer causes the assembly to reversibly deflect and mimic biological muscles. The drawback of such a setup is slow response times and the use of a liquid electrolyte. We have developed multifunctional polymers which will eliminate the use of a liquid electrolyte, and also because the functionalities of the polymers are within a few hundred angstroms, an improved response time to changes in the external field should be possible. Such multifunctional polymers may be classified as the futuristic 'smart materials.' These materials are composed of a number of different functionalities which work in a synergistic fashion to function as a device. The device performs on the application of an external field and such multifunctional polymers may be scientifically labeled as 'field responsive polymers.' Our group has undertaken a systematic approach to develop functional and multifunctional polymers capable of functioning as field responsive polymers. Our approach utilizes multicomponent polymer systems (block copolymers and graft copolymers), the strategy involves the preparation of block or graft copolymers where the functionalities are limited to different phases in a microphase separated system. Depending on the weight (or volume) fractions of each of the components, different microstructures are possible. And, because of the intimate contact between the functional components, an increase in the synergism between the functionalities may be observed. In this presentation, three examples of multifunctional polymers developed in our labs will be reported. The first class of multifunctional polymers are the microphase separated mixed (ionic and electronic) conducting or MIEC block copolymers. The second class being developed in our labs are the biocompatible conductive materials and the conductive fluids. The final class may be considered microwave active smart polymers.

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.

Designing a Novel Polymer Electrolyte for Improving the Electrode/Electrolyte Interface in Flexible All-Solid-State Electrical Double-Layer Capacitors.

PubMed

Wang, Jeng-An; Lu, Yi-Ting; Lin, Sheng-Chi; Wang, Yu-Sheng; Ma, Chen-Chi M; Hu, Chi-Chang

2018-05-30

A novel copolymer, polyurethane-poly(acrylic acid) (PAA), is successfully synthesized from poly(acrylic acid) (PAA) backbone cross-linked with waterborne polyurethane (WPU). This sticky polymer, which is neutralized with 1 M KOH and then soaked in 1 M KOH (denoted as WPU-PAAK-K), provides an ionic conductivity greater than 10 -2 S cm -1 and acts as a gel electrolyte perfectly improving the electrode/electrolyte interfaces in a flexible all-solid-state electrical double-layer capacitor (EDLC). The PAA backbone chains in the copolymer increase the amount of carboxyl groups and promote the segmental motion. The carboxyl groups enhance the water-uptake capacity, which facilitates the ion transport and promotes the ionic conductivity. The cross-linked agent, WPU chains, effectively maintains the rich water content and provides mechanical stickiness to bind two electrodes together. An acid-treated carbon paper (denoted as ACP) combining with such a gel polymer electrolyte demonstrates excellent capacitive behavior with a high areal capacitance of 211.6 mF cm -2 at 10 mV s -1 . A full cell consisting of ACP/WPU-PAAK-K/ACP displays a low equivalent series resistance of 0.44 Ω from the electrochemical impedance spectroscopic results. An all-solid-state ACP/WPU-PAAK-K/ACP EDLC provides an areal specific capacitance of 94.6 mF cm -2 at 1 mA cm -2 . This device under 180° bending shows a capacitance retention over 90%, revealing its remarkable flexibility.

Using Polymer Electrolyte Membrane Fuel Cells in a Hybrid Surface Ship Propulsion Plant to Increase Fuel Efficiency

DTIC Science & Technology

2010-06-01

cell ( PEMFC ), and the phosphoric acid fuel cell (PAFC). 2.3.1 Solid Oxide Fuel Cells (SOFC) The first type of fuel cell considered is the SOFC. This...durability issues for use within a given application. 2.3.2 Polymer Electrolyte Membrane Fuel Cells ( PEMFC ) The PEMFC operates by passing hydrogen that has...cells. Some advantages of PEMFC operating at such low temperatures is that the fuel cell doesn’t require as meticulous of a support system infrastructure

Increased water retention in polymer electrolyte membranes at elevated temperatures assisted by capillary condensation.

PubMed

Park, Moon Jeong; Downing, Kenneth H; Jackson, Andrew; Gomez, Enrique D; Minor, Andrew M; Cookson, David; Weber, Adam Z; Balsara, Nitash P

2007-11-01

We establish a new systematic methodology for controlling the water retention of polymer electrolyte membranes. Block copolymer membranes comprising hydrophilic phases with widths ranging from 2 to 5 nm become wetter as the temperature of the surrounding air is increased at constant relative humidity. The widths of the moist hydrophilic phases were measured by cryogenic electron microscopy experiments performed on humid membranes. Simple calculations suggest that capillary condensation is important at these length scales. The correlation between moisture content and proton conductivity of the membranes is demonstrated.

Electron beam irradiated polymer electrolyte film: Morphology, dielectric and AC conductivity studies

NASA Astrophysics Data System (ADS)

Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Ganesh, S.; Devendrappa, H.

2018-05-01

The polymer (PVdF-co-HFP: LiClO4=90:10, PHL10) electrolyte films prepared by solution casting method and studied morphology, dielectric properties and ac conductivity before and after electron beam (EB) irradiation. The polarized optical micrographs reveals size of spherulite reduced with increasing EB dose represents increase in amorphousity. The dielectric measurements were studied at different temperatures and observed increase with frequency at different temperatures upon EB irradiation. The ac conductivity increases with frequency due to effect of EB dose.

Molten Carbonate Fuel Cell Operation With Dual Fuel Flexibility

DTIC Science & Technology

2007-10-01

electrolyte membrane fuel cell ( PEMFC ). At the higher operating temperature, fuel reforming of natural gas can occur internally, eliminating the need...oxygen PAFC Phosphoric Acid Fuel Cell PEMFC Polymer Electrolyte Membrane Fuel Cell PDS Propane Desulfurization System ppm parts per million psig

Stabilization of Silicon Carbide (SiC) micro- and nanoparticle dispersions in the presence of concentrated electrolyte.

PubMed

Vilinska, Annamaria; Ponnurangam, Sathish; Chernyshova, Irina; Somasundaran, Ponisseril; Eroglu, Damla; Martinez, Jose; West, Alan C

2014-06-01

Achieving a stable and robust dispersion of ultrafine particles in concentrated electrolytes is challenging due to the shielding of electrostatic repulsion. Stable dispersion of ultrafine particles in concentrated electrolytes is critical for several applications, including electro-codeposition of ceramic particles in protective metal coatings. We achieved the steric stabilization of SiC micro- and nano-particles in highly concentrated electroplating Watts solutions using their controlled coating with linear and branched polyethyleneimines (PEI) as dispersants. Branched polyethyleneimine of 60,000 MW effectively disperses both microparticles and nanoparticles at a concentration of 1000 ppm. However, lower polymer dosages and smaller polymers fail to disperse, presumably due to insufficient coverage and bridging flocculation. Dispersion stability correlates well with the adsorption density of PEI on microparticles. We discuss the results in the framework of DLVO theory and suggest possible dispersion mechanisms. However, though the dispersion is enhanced with extended adsorption time, the residual PEI in solution adversely affects electroplating. We overcome this drawback by precoating the particles with the polymer and resuspending them in Watts solution. With this novel approach, we obtained robust dispersions. These results offer new possibilities to control dispersion at high electrolyte concentration, as well as bring new insights into the dispersion phenomenon. Copyright © 2014 Elsevier Inc. All rights reserved.

Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

NASA Astrophysics Data System (ADS)

Das, S.; Ghosh, A.

2016-06-01

In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

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

Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in

2014-01-28

Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO)more » (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.« less

Actuator device utilizing a conductive polymer gel

DOEpatents

Chinn, Douglas A.; Irvin, David J.

2004-02-03

A valve actuator based on a conductive polymer gel is disclosed. A nonconductive housing is provided having two separate chambers separated by a porous frit. The conductive polymer is held in one chamber and an electrolyte solution, used as a source of charged ions, is held in the second chamber. The ends of the housing a sealed with a flexible elastomer. The polymer gel is further provide with electrodes with which to apply an electrical potential across the gel in order to initiate an oxidation reaction which in turn drives anions across the porous frit and into the polymer gel, swelling the volume of the gel and simultaneously contracting the volume of the electrolyte solution. Because the two end chambers are sealed the flexible elastomer expands or contracts with the chamber volume change. By manipulating the potential across the gel the motion of the elastomer can be controlled to act as a "gate" to open or close a fluid channel and thereby control flow through that channel.

A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

PubMed Central

Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

2016-01-01

Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at −1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier. PMID:27687772

Enhanced performance of dye-sensitized solar cells based on organic dopant incorporated PVDF-HFP/PEO polymer blend electrolyte with g-C{sub 3}N{sub 4}/TiO{sub 2} photoanode

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

Senthil, R.A.; Theerthagiri, J.; Madhavan, J., E-mail: jagan.madhavan@gmail.com

This work describes the effect of 2-aminopyrimidine (2-APY) on poly(vinylidinefluoride-co-hexafluoropropylene) (PVDF-HFP)/polyethylene oxide (PEO) blend polymer electrolyte along with binary iodide salts (tetrabutylammonium iodide (TBAI) and potassium iodide (KI)) and iodine (I{sub 2}) were studied for enhancing the efficiency of the dye-sensitized solar cells (DSSCs) consisting of g-C{sub 3}N{sub 4}/TiO{sub 2} composite as photoanode. The g-C{sub 3}N{sub 4} was synthesized from low cost urea by thermal condensation method. It was used as a precursor to synthesize the various weight percentage ratios (5%, 10% and 15%) of g-C{sub 3}N{sub 4}/TiO{sub 2} composites by wet-impregnation method. The pure and 2-APY incorporated PVDF-HFP/PEO polymermore » blend electrolytes were arranged by wet chemical process (casting method) using DMF as a solvent. The synthesized g-C{sub 3}N{sub 4}/TiO{sub 2} composites and polymer blend electrolytes were studied and analyzed by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The ionic conductivity values of the pure and 2-APY incorporated PVDF-HFP/PEO blend electrolytes were estimated to be 4.53×10{sup −5} and 1.87×10{sup −4} Scm{sup −1} respectively. The UV–vis absorption spectroscopy was carried out for the pure and different wt% of g-C{sub 3}N{sub 4}/TiO{sub 2} composites coated FTO films after N3 dye-sensitization. The 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} composite film showed a maximum absorption compared to the others. The DSSC assembled with 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode using the pure polymer blend electrolyte exhibited a power conversion efficiency (PCE) of 3.17% , which was superior than that of DSSC based pure TiO{sub 2} (2.46%). However, the PCE was increased to 4.73% for the DSSC assembled using 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode with 2-APY incorporated polymer blend electrolyte. Hence, the present study is a successful attempt to provide a new pathway to enhance the performance of DSSCs. - Graphical abstract: In this study, the g-C{sub 3}N{sub 4} was synthesized from low cost urea and it was used as a precursor to synthesize of g-C{sub 3}N{sub 4}/TiO{sub 2} composite. The pure and 2-APY incorporated PVDF-HFP/PEO electrolytes were fabricated by solution casting method. A remarkably enhanced PCE of 4.73% was observed for 2-APY incorporated PVDF-HFP/PEO electrolyte with g-C{sub 3}N{sub 4}/TiO{sub 2} composite photoanode based DSSC. - Highlights: • 2-APY added PVDF-HFP/PEO electrolyte was prepared by solution casting method. • The g-C{sub 3}N{sub 4}/TiO{sub 2} composites were synthesized by wet-impregnation method. • DSSC with g-C{sub 3}N{sub 4}/TiO{sub 2} and 2-APY added electrolyte showed the efficiency of 4.73 %. • The g-C{sub 3}N{sub 4} and 2-APY can be a useful dopant to enhance the performance of DSSCs.« less

Direct methanol fuel cell and system

DOEpatents

Wilson, Mahlon S.

2004-10-26

A fuel cell having an anode and a cathode and a polymer electrolyte membrane located between anode and cathode gas diffusion backings uses a methanol vapor fuel supply. A permeable polymer electrolyte membrane having a permeability effective to sustain a carbon dioxide flux equivalent to at least 10 mA/cm.sup.2 provides for removal of carbon dioxide produced at the anode by reaction of methanol with water. Another aspect of the present invention includes a superabsorpent polymer material placed in proximity to the anode gas diffusion backing to hold liquid methanol or liquid methanol solution without wetting the anode gas diffusion backing so that methanol vapor from the liquid methanol or liquid methanol-water solution is supplied to the membrane.

Novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 for high temperature fuel cell

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sonai, Atsuo

Three novel proton conducting polymer electrolytes based on polyparabanic acid doped with H 3PO 4 were synthesized and their use in high temperature fuel cells characterized. The precursor polymers, PMD-Im, POD-Im and PDMDP-Im, were synthesized by cyclization polymerization of diisocynanates. After doping with H 3PO 4, the ionic conductivity and the thermal degradation were studied by using the AC impedance method and thermal gravimetric analysis, respectively. These membranes showed high ionic conductivity of the order of 10 -2 S cm -1 at 423 K with good thermal stability. Their application to fuel cells was demonstrated and polarization curves were obtained at 423 K were obtained without humidification.

Synthesis and characterization of sulfonate polystyrene-lignosulfonate-alumina (SPS-LS-Al{sub 2}O{sub 3}) polyblends as electrolyte membranes for fuel cell

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

Gonggo, Siang Tandi, E-mail: standigonggo@yahoo.com

2015-09-30

The new type of electrolyte membrane materials has been prepared by blend sulfonated polystyrene (SPS), lignosulfonate (LS), and alumina (SPS-LS-Al{sub 2}O{sub 3}) by casting polymer solution. The resulting polymer electrolyte membranes were then characterized by functional groups analysis, mechanical properties, water uptake, ion exchange capacity, and proton conductivity. SPS-LS-Al{sub 2}O{sub 3} membranes with alumina composition various have been proven qualitatively by analysis of functional groups. Increasing the Al{sub 2}O{sub 3} ratio resulted in higher ion exchange capacity (IEC), mechanical strength and proton conductivity, but water uptake decreased. The SPS-LS-Al{sub 2}O{sub 3} blend showed higher proton conductivity than Nafion 117.

Morphology and conductivity of PEO-based polymers having various end functional groups

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Mandal, Prithwiraj; Park, Moon Jeong

Poly(ethylene oxide) (PEO)-based polymers have been considered most promising candidates of polymer electrolytes for lithium batteries owing to the high ionic conductivity of PEO/lithium salt complexes. This positive aspect prompted researchers to investigate PEO-containing block copolymers prepared by linking mechanically robust block to PEO covalently. Given that the microphase separation of block copolymers can affect both mechanical properties and ion transport properties, various strategies have been reported to tune the morphology of PEO-containing block copolymers. In the present study, we describe a simple means for modulating the morphologies of PEO-based block copolymers with an aim to improve ion transport properties. By varying terminal groups of PEO in block copolymers, the disordered morphology can be readily transformed into ordered lamellae or gyroid phases, depending on the type and number density of end group. In particular, the existence of terminal groups resulted in a large reduction in crystallinity of PEO chains and thereby increasing room temperature ionic conductivity.