Sulfonated Copper Phthalocyanine/Sulfonated Polysulfone Composite Membrane for Ionic Polymer Actuators with High Power Density and Fast Response Time.

PubMed

Kwon, Taehoon; Cho, Hyeongrae; Lee, Jang-Woo; Henkensmeier, Dirk; Kang, Youngjong; Koo, Chong Min

2017-08-30

Ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA) are assembled into bending ionic polymer actuators. CuPCSA is an organic filler with very high sulfonation degree (IEC = 4.5 mmol H + /g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane, probably due to its good dispersibility in SPAES-containing solutions. SPAES/CuPCSA actuators exhibit larger ion conductivity (102 mS cm -1 ), tensile modulus (208 MPa), strength (101 MPa), and strain (1.21%), exceptionally faster response to electrical stimuli, and larger mechanical power density (3028 W m -3 ) than ever reported for ion-conducting polymer actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next-generation transducers with high power density, which are currently developed, e.g., for underwater propulsion and endoscopic surgery.

Variation of Ionic Conductivity with Annealing Temperature in Argyrodite Solid Electrolytes

NASA Astrophysics Data System (ADS)

Rao, R. Prasada; Chen, Maohua; Adams, Stefan

2013-07-01

In situ neutron diffraction studies of argyrodite-type Li6PS5X (X = Cl, Br, I) were conducted for mechanically milled sample to reveal the formation and growth of crystalline phases. These studies indicated the formation of crystals in all the compounds started from as low as 80°C. The Rietveld refinements of the resulting crystalline phases at 150°C indicate the formation of the argyrodite structure. Structure refinements using high-intensity neutron diffraction provide insight into the influence of disorder on the fast ionic conductivity. Besides the disorder in the lithium distribution, it is the disorder in the S2-/Cl- or S2-/Br- distribution that we find to promote ion mobility. Among the samples studied Li6PS5Br, annealed at 250°C, exhibited the highest ionic conductivity, 1.05 × 10-3 S/cm at room temperature. An all solid state battery with Li4Ti5O12/Li6PS5Br/Li exhibited 57 mAh/g first discharge capacity at 75°C with 91% coulombic efficiency after 60 cycles.

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

On the origin of high ionic conductivity in Na-doped SrSiO 3

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

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

On the origin of high ionic conductivity in Na-doped SrSiO 3

DOE PAGES

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen; ...

2016-02-17

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

A hybrid nanosensor for TNT vapor detection.

PubMed

Díaz Aguilar, Alvaro; Forzani, Erica S; Leright, Mathew; Tsow, Francis; Cagan, Avi; Iglesias, Rodrigo A; Nagahara, Larry A; Amlani, Islamshah; Tsui, Raymond; Tao, N J

2010-02-10

Real-time detection of trace chemicals, such as explosives, in a complex environment containing various interferents has been a difficult challenge. We describe here a hybrid nanosensor based on the electrochemical reduction of TNT and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts-per-trillion level TNT in the presence of various interferents within a few minutes.

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

AC impedance spectroscopy of NASICON type Na3Fe2(PO4)3 ceramic

NASA Astrophysics Data System (ADS)

Mandal, Biswajit; Thakur, A. K.

2018-05-01

Super ionic conductors (e.g.; A3M2(XO4)3, A=Li, Na) have received attention in applied research due to their interesting electrochemical property and inherently high ionic conductivity [1]. However, structural and compatibility requirements for fast ion transport is stringent and it plays a crucial role. In A3M2(XO4)3, a suitable cage formation in the crystal framework due to corner sharing arrangement of XO4 tetrahedra and MO6 octahedra creates voids that acts as host/guest site for cation transport. In this work, we report Nasicon structure Na3Fe2(PO4)3 (NFP) prepared via sol-gel route mediated by citric acid. Structural analysis confirmed that NFP sample belongs to monoclinic crystal structure having Cc space group (S. G. No 9) with lattice parameters, a=15.106 Å, b=8.722 Å, c=8.775 Å and β=124.96°. Electrical properties of the prepared sample have been studied by AC impedance spectroscopy technique. The AC conductivity results indicated typical signature of ionically conducting system.

Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

NASA Astrophysics Data System (ADS)

Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

2018-03-01

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

Interplay of Transport and Morphology in Nanostructured Ion-Containing Polymers

NASA Astrophysics Data System (ADS)

Park, Moon Jeong

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

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

Microwave-assisted reactive sintering and lithium ion conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte

NASA Astrophysics Data System (ADS)

Hallopeau, Leopold; Bregiroux, Damien; Rousse, Gwenaëlle; Portehault, David; Stevens, Philippe; Toussaint, Gwenaëlle; Laberty-Robert, Christel

2018-02-01

Li1.3Al0.3Ti1.7(PO4)3 (LATP) materials are made of a three-dimensional framework of TiO6 octahedra and PO4 tetrahedra, which provides several positions for Li+ ions. The resulting high ionic conductivity is promising to yield electrolytes for all-solid-state Li-ion batteries. In order to elaborate dense ceramics, conventional sintering methods often use high temperature (≥1000 °C) with long dwelling times (several hours) to achieve high relative density (∼90%). In this work, an innovative synthesis and processing approach is proposed. A fast and easy processing technique called microwave-assisted reactive sintering is used to both synthesize and sinter LATP ceramics with suitable properties in one single step. Pure and crystalline LATP ceramics can be achieved in only 10 min at 890 °C starting from amorphous, compacted LATP's precursors powders. Despite a relative density of 88%, the ionic conductivity measured at ambient temperature (3.15 × 10-4 S cm-1) is among the best reported so far. The study of the activation energy for Li+ conduction confirms the high quality of the ceramic (purity and crystallinity) achieved by using this new approach, thus emphasizing its interest for making ion-conducting ceramics in a simple and fast way.

High Electromechanical Response of Ionic Polymer Actuators with Controlled-Morphology Aligned Carbon Nanotube/Nafion Nanocomposite Electrodes

PubMed Central

Liu, Sheng; Liu, Yang; Cebeci, Hülya; de Villoria, Roberto Guzmán; Lin, Jun-Hong

2011-01-01

Recent advances in fabricating controlled-morphology vertically aligned carbon nanotubes (VA-CNTs) with ultrahigh volume fraction create unique opportunities for markedly improving the electromechanical performance of ionic polymer conductor network composite (IPCNC) actuators. Continuous paths through inter-VA-CNT channels allow fast ion transport, and high electrical conduction of the aligned CNTs in the composite electrodes lead to fast device actuation speed (>10% strain/second). One critical issue in developing advanced actuator materials is how to suppress the strain that does not contribute to the actuation (unwanted strain) thereby reducing actuation efficiency. Here our experiments demonstrate that the VA-CNTs give an anisotropic elastic response in the composite electrodes, which suppresses the unwanted strain and markedly enhances the actuation strain (>8% strain under 4 volts). The results reported here suggest pathways for optimizing the electrode morphology in IPCNCs using ultra-high volume fraction VA-CNTs to further enhanced performance. PMID:21765822

The Na+/K+ pump is an important modulator of refractoriness and rotor dynamics in human atrial tissue.

PubMed

Sánchez, Carlos; Corrias, Alberto; Bueno-Orovio, Alfonso; Davies, Mark; Swinton, Jonathan; Jacobson, Ingemar; Laguna, Pablo; Pueyo, Esther; Rodríguez, Blanca

2012-03-01

Pharmacological treatment of atrial fibrillation (AF) exhibits limited efficacy. Further developments require a comprehensive characterization of ionic modulators of electrophysiology in human atria. Our aim is to systematically investigate the relative importance of ionic properties in modulating excitability, refractoriness, and rotor dynamics in human atria before and after AF-related electrical remodeling (AFER). Computer simulations of single cell and tissue atrial electrophysiology were conducted using two human atrial action potential (AP) models. Changes in AP, refractory period (RP), conduction velocity (CV), and rotor dynamics caused by alterations in key properties of all atrial ionic currents were characterized before and after AFER. Results show that the investigated human atrial electrophysiological properties are primarily modulated by maximal value of Na(+)/K(+) pump current (G(NaK)) as well as conductances of inward rectifier potassium current (G(K1)) and fast inward sodium current (G(Na)). G(NaK) plays a fundamental role through both electrogenic and homeostatic modulation of AP duration (APD), APD restitution, RP, and reentrant dominant frequency (DF). G(K1) controls DF through modulation of AP, APD restitution, RP, and CV. G(Na) is key in determining DF through alteration of CV and RP, particularly in AFER. Changes in ionic currents have qualitatively similar effects in control and AFER, but effects are smaller in AFER. The systematic analysis conducted in this study unravels the important role of the Na(+)/K(+) pump current in determining human atrial electrophysiology.

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

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

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

Computational and Experimental Investigations of Na-Ion Conduction in Cubic Na 3PSe 4

DOE PAGES

Bo, Shou -Hang; Wang, Yan; Kim, Jae Chul; ...

2015-11-17

All-solid-state Na-ion batteries that operate at or close to room temperature are a promising next-generation battery technology with enhanced safety and reduced manufacturing cost. An indispensable component of this technology is the solid-state electrolyte that allows rapid shuttling of the mobile cation (i.e., Na +) between the cathode and anode. However, there are very few fast Na-ion conductors with ionic conductivity approaching that of the liquid counterparts (i.e., 1 mS cm –1). In this work, we present the synthesis and characterization of a fast Na-ion conductor, cubic Na 3PSe 4. This material possesses a room-temperature ionic conductivity exceeding 0.1 mSmore » cm –1 and does not require high-temperature sintering to minimize grain boundary resistance, making it a promising solid-state electrolyte candidate for all-solid-state Na-ion battery applications. On the basis of density functional theory, nudged elastic band, and molecular dynamics investigations, we demonstrate that the framework of cubic Na 3PSe 4 only permits rapid Na + diffusion with the presence of defects, and that the formation of the Na vacancy (charge-balanced by slight Se 2– oxidation) is more energetically favorable among the various defects considered. This finding provides important guidelines to further improve Na-ion conductivity in this class of materials.« less

Stability and ionic mobility in argyrodite-related lithium-ion solid electrolytes.

PubMed

Chen, Hao Min; Maohua, Chen; Adams, Stefan

2015-07-07

In the search for fast lithium-ion conducting solids for the development of safe rechargeable all-solid-state batteries with high energy density, thiophosphates and related compounds have been demonstrated to be particularly promising both because of their record ionic conductivities and their typically low charge transfer resistances. In this work we explore a wide range of known and predicted thiophosphates with a particular focus on the cubic argyrodite phase with a robust three-dimensional network of ion migration pathways. Structural and hydrolysis stability are calculated employing density functional method in combination with a generally applicable method of predicting the relevant critical reaction. The activation energy for ion migration in these argyrodites is then calculated using the empirical bond valence pathway method developed in our group, while bandgaps of selected argyrodites are calculated as a basis for assessing the electrochemical window. Findings for the lithium compounds are also compared to those of previously known copper argyrodites and hypothetical sodium argyrodites. Therefrom, guidelines for experimental work are derived to yield phases with the optimum balance between chemical stability and ionic conductivity in the search for practical lithium and sodium solid electrolyte materials.

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator

PubMed Central

Wu, Guan; Hu, Ying; Liu, Yang; Zhao, Jingjing; Chen, Xueli; Whoehling, Vincent; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Chen, Wei

2015-01-01

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g−1) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m−1) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance. PMID:26028354

Correlation of anisotropy and directional conduction in β-Li 3PS 4 fast Li + conductor

DOE PAGES

Chen, Yan; Cai, Lu; Liu, Zengcai; ...

2015-07-06

Our letter reports the correlation of anisotropy and directional conduction in the fast Li + conductor β-Li 3PS 4, one of the low-symmetry crystalline electrolyte candidates. The material has both high conductivity and good stability that serves well for the large-scale energy storage applications of all-solid-state lithium ion batteries. The anisotropic physical properties, demonstrated here by the thermal expansion coefficients, are crucial for compatibility in the solid-state system and battery performance. Neutron and X-ray powder diffraction measurements were done to determine the crystal structure and thermal stability. Moreover, the crystallographic b-axis was revealed as a fast expansion direction, while negligiblemore » thermal expansion was observed along the a-axis around the battery operating temperatures. The anisotropic behavior has its structural origin from the Li + conduction channels with incomplete Li occupancy and a flexible connection of LiS 4 and PS 4 tetrahedra within the framework. This indicates a strong correlation in the direction of the ionic transport in the low-symmetry Li + conductor.« less

Probing DNA in nanopores via tunneling: from sequencing to ``quantum'' analogies

NASA Astrophysics Data System (ADS)

di Ventra, Massimiliano

2012-02-01

Fast and low-cost DNA sequencing methods would revolutionize medicine: a person could have his/her full genome sequenced so that drugs could be tailored to his/her specific illnesses; doctors could know in advance patients' likelihood to develop a given ailment; cures to major diseases could be found faster [1]. However, this goal of ``personalized medicine'' is hampered today by the high cost and slow speed of DNA sequencing methods. In this talk, I will discuss the sequencing protocol we suggest which requires the measurement of the distributions of transverse currents during the translocation of single-stranded DNA into nanopores [2-5]. I will support our conclusions with a combination of molecular dynamics simulations coupled to quantum mechanical calculations of electrical current in experimentally realizable systems [2-5]. I will also discuss recent experiments that support these theoretical predictions. In addition, I will show how this relatively unexplored area of research at the interface between solids, liquids, and biomolecules at the nanometer length scale is a fertile ground to study quantum phenomena that have a classical counterpart, such as ionic quasi-particles, ionic ``quantized'' conductance [6,7] and Coulomb blockade [8]. Work supported in part by NIH. [4pt] [1] M. Zwolak, M. Di Ventra, Physical Approaches to DNA Sequencing and Detection, Rev. Mod. Phys. 80, 141 (2008).[0pt] [2] M. Zwolak and M. Di Ventra, Electronic signature of DNA nucleotides via transverse transport, Nano Lett. 5, 421 (2005).[0pt] [3] J. Lagerqvist, M. Zwolak, and M. Di Ventra, Fast DNA sequencing via transverse electronic transport, Nano Lett. 6, 779 (2006).[0pt] [4] J. Lagerqvist, M. Zwolak, and M. Di Ventra, Influence of the environment and probes on rapid DNA sequencing via transverse electronic transport, Biophys. J. 93, 2384 (2007).[0pt] [5] M. Krems, M. Zwolak, Y.V. Pershin, and M. Di Ventra, Effect of noise on DNA sequencing via transverse electronic transport, Biophys. J. 97, 1990, (2009).[0pt] [6] M. Zwolak, J. Lagerqvist, and M. Di Ventra, Ionic conductance quantization in nanopores, Phys. Rev.Lett. 103, 128102 (2009).[0pt] [7] M. Zwolak, J. Wilson, and M. Di Ventra, Dehydration and ionic conductance quantization in nanopores, J. Phys. Cond. Matt. 22 454126 (2011). [0pt] [8] M. Krems and M. Di Ventra, Ionic Coulomb blockade in nanopores arXiv:1103.2749.

Grotthuss Transport of Iodide in EMIM/I3 Ionic Crystal.

PubMed

McDaniel, Jesse G; Yethiraj, Arun

2018-01-11

Highly ionic environments can mediate unusual chemical reactions that would otherwise be considered impossible based on chemical intuition. For example, the formation of a chemical bond between two iodide anions to form a divalent polyiodide anion is seemingly prohibited due to Coulombic repulsion. Using ab initio molecular dynamics simulations, we show that in the 1-ethyl-3-methylimidazolium (EMIM)/I 3 ionic crystal, the reactive formation of divalent and even trivalent polyiodide anions occurs with extremely small energetic barriers, due to the electrostatic field of the ionic lattice. A practical consequence of this anomalous reactivity is that iodide anions are efficiently transported within the crystal through a "Grotthuss-exchange" mechanism involving bond-breaking and forming events. We characterize two distinct transport pathways, involving both I 4 2- and I 7 3- intermediates, with fast transport of iodide resulting from the release of an I - anion on the opposite side of the intermediate species from the initial bond formation. The ordered cation arrangement in the crystal provides the necessary electrostatic screening for close approach of anions, suggesting a new counterintuitive approach to obtain high ionic conductivity. This new design principle could be used to develop better solid-state electrolytes for batteries, fuel cells, and supercapacitors.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Strongly enhanced oxygen ion transport through samarium-doped CeO 2 nanopillars in nanocomposite films

DOE PAGES

Yang, Sangmo; Lee, Shinbuhm; Jian, Jie; ...

2015-10-08

Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO 2 embedded in supporting matrices of SrTiO 3. The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeOmore » 2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO 2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness.« less

Fast Ignition and Sustained Combustion of Ionic Liquids

NASA Technical Reports Server (NTRS)

Joshi, Prakash B. (Inventor); Piper, Lawrence G. (Inventor); Oakes, David B. (Inventor); Sabourin, Justin L. (Inventor); Hicks, Adam J. (Inventor); Green, B. David (Inventor); Tsinberg, Anait (Inventor); Dokhan, Allan (Inventor)

2016-01-01

A catalyst free method of igniting an ionic liquid is provided. The method can include mixing a liquid hypergol with a HAN (Hydroxylammonium nitrate)-based ionic liquid to ignite the HAN-based ionic liquid in the absence of a catalyst. The HAN-based ionic liquid and the liquid hypergol can be injected into a combustion chamber. The HAN-based ionic liquid and the liquid hypergol can impinge upon a stagnation plate positioned at top portion of the combustion chamber.

Depolarization of the conductance-voltage relationship in the NaV1.5 mutant, E1784K, is due to altered fast inactivation

PubMed Central

Yu, Alec; Zhu, Wandi; Silva, Jonathan R.; Ruben, Peter C.

2017-01-01

E1784K is the most common mixed long QT syndrome/Brugada syndrome mutant in the cardiac voltage-gated sodium channel NaV1.5. E1784K shifts the midpoint of the channel conductance-voltage relationship to more depolarized membrane potentials and accelerates the rate of channel fast inactivation. The depolarizing shift in the midpoint of the conductance curve in E1784K is exacerbated by low extracellular pH. We tested whether the E1784K mutant shifts the channel conductance curve to more depolarized membrane potentials by affecting the channel voltage-sensors. We measured ionic currents and gating currents at pH 7.4 and pH 6.0 in Xenopus laevis oocytes. Contrary to our expectation, the movement of gating charges is shifted to more hyperpolarized membrane potentials by E1784K. Voltage-clamp fluorimetry experiments show that this gating charge shift is due to the movement of the DIVS4 voltage-sensor being shifted to more hyperpolarized membrane potentials. Using a model and experiments on fast inactivation-deficient channels, we show that changes to the rate and voltage-dependence of fast inactivation are sufficient to shift the conductance curve in E1784K. Our results localize the effects of E1784K to DIVS4, and provide novel insight into the role of the DIV-VSD in regulating the voltage-dependencies of activation and fast inactivation. PMID:28898267

Depolarization of the conductance-voltage relationship in the NaV1.5 mutant, E1784K, is due to altered fast inactivation.

PubMed

Peters, Colin H; Yu, Alec; Zhu, Wandi; Silva, Jonathan R; Ruben, Peter C

2017-01-01

E1784K is the most common mixed long QT syndrome/Brugada syndrome mutant in the cardiac voltage-gated sodium channel NaV1.5. E1784K shifts the midpoint of the channel conductance-voltage relationship to more depolarized membrane potentials and accelerates the rate of channel fast inactivation. The depolarizing shift in the midpoint of the conductance curve in E1784K is exacerbated by low extracellular pH. We tested whether the E1784K mutant shifts the channel conductance curve to more depolarized membrane potentials by affecting the channel voltage-sensors. We measured ionic currents and gating currents at pH 7.4 and pH 6.0 in Xenopus laevis oocytes. Contrary to our expectation, the movement of gating charges is shifted to more hyperpolarized membrane potentials by E1784K. Voltage-clamp fluorimetry experiments show that this gating charge shift is due to the movement of the DIVS4 voltage-sensor being shifted to more hyperpolarized membrane potentials. Using a model and experiments on fast inactivation-deficient channels, we show that changes to the rate and voltage-dependence of fast inactivation are sufficient to shift the conductance curve in E1784K. Our results localize the effects of E1784K to DIVS4, and provide novel insight into the role of the DIV-VSD in regulating the voltage-dependencies of activation and fast inactivation.

Computational, Experimental and Engineering Foundations of Ionic Channels as Miniaturized Sensors, Devices and Systems

DTIC Science & Technology

2003-10-01

made in an ensemble of channels of unknown orientation and number, preventing quantitative analysis . • Currents have been compared among continuum PNP...microfluidic) analysis of ion channels to obtain fundamental insights into the selectivity, conductivity, and sensitivity of ion channels [19], [6...1.1 Develop fast and efficient simulators for steady-state analysis of continuum model for extraction of I-V curves. 1.2 Create

The performance of fast-moving low-voltage electromechanical actuators based on single-walled carbon nanotubes and ionic liquids

NASA Astrophysics Data System (ADS)

Mukai, Ken; Asaka, Kinji; Hata, Kenji; Oike, Hideaki

2011-12-01

In this paper, we study the details of the mechanical and electrical properties of polymer-free single-walled carbon nanotube (SWNT) sheets containing different contents of ionic liquids (ILs). The polymer-free SWNT sheets were prepared by a previously reported finding that millimeter-long 'super-growth' carbon nanotubes (SG-SWNTs), produced by a water-assisted modified chemical vapor deposition (CVD) method, associate together tightly with ILs, affording a free-standing sheet with a superb conductivity. The Young's modulus, breaking strength and the electrical conductivity of the SG-SWNT sheet with 67 wt% 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMITFSI) showed large values, 0.63 GPa, 20 MPa, and 147 S cm-1, respectively, although it has large amounts of ILs. We also measure the frequency dependence of the displacement of the actuator composed of SG-SWNT sheets sandwiching an ionic-gel electrolyte layer (SG-SWNT actuator). At more than 50 wt% of EMITFSI content, the frequency response of the actuation of the SG-SWNT actuator is flat up to around 100 Hz. The results of the displacement measurements are discussed in relation to the mechanical and electrical properties of the SG-SWNT actuators.

Electrodiffusion kinetics of ionic transport in a simple membrane channel.

PubMed

Valent, Ivan; Petrovič, Pavol; Neogrády, Pavel; Schreiber, Igor; Marek, Miloš

2013-11-21

We employ numerical techniques for solving time-dependent full Poisson-Nernst-Planck (PNP) equations in 2D to analyze transient behavior of a simple ion channel subject to a sudden electric potential jump across the membrane (voltage clamp). Calculated spatiotemporal profiles of the ionic concentrations and electric potential show that two principal exponential processes can be distinguished in the electrodiffusion kinetics, in agreement with original Planck's predictions. The initial fast process corresponds to the dielectric relaxation, while the steady state is approached in a second slower exponential process attributed to the nonlinear ionic redistribution. Effects of the model parameters such as the channel length, height of the potential step, boundary concentrations, permittivity of the channel interior, and ionic mobilities on electrodiffusion kinetics are studied. Numerical solutions are used to determine spatiotemporal profiles of the electric field, ionic fluxes, and both the conductive and displacement currents. We demonstrate that the displacement current is a significant transient component of the total electric current through the channel. The presented results provide additional information about the classical voltage-clamp problem and offer further physical insights into the mechanism of electrodiffusion. The used numerical approach can be readily extended to multi-ionic models with a more structured domain geometry in 2D or 3D, and it is directly applicable to other systems, such as synthetic nanopores, nanofluidic channels, and nanopipettes.

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

PubMed Central

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-01-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

NASA Astrophysics Data System (ADS)

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-09-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

Forging Fast Ion Conducting Nanochannels with Swift Heavy Ions: The Correlated Role of Local Electronic and Atomic Structure

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

Sachan, Ritesh; Cooper, Valentino R.; Liu, Bin

2016-12-19

Atomically disordered oxides have attracted significant attention in recent years due to the possibility of enhanced ionic conductivity. However, the correlation between atomic disorder, corresponding electronic structure, and the resulting oxygen diffusivity is not well understood. The disordered variants of the ordered pyrochlore structure in gadolinium titanate (Gd 2Ti 2O 7) are seen as a particularly interesting prospect due to intrinsic presence of a vacant oxygen site in the unit atomic structure, which could provide a channel for fast oxygen conduction. In this paper, we provide insights into the subangstrom scale on the disordering-induced variations in the local atomic environmentmore » and its effect on the electronic structure in high-energy ion irradiation-induced disordered nanochannels, which can be utilized as pathways for fast oxygen ion transport. With the help of an atomic plane-by-plane-resolved analyses, the work shows how the presence of various types of TiO x polyhedral that exist in the amorphous and disordered crystalline phase modify the electronic structures relative to the ordered pyrochlore phase in Gd 2Ti 2O 7. Finally, the correlated molecular dynamics simulations on the disordered structures show a remarkable enhancement in oxygen diffusivity as compared with ordered pyrochlore lattice and make that a suitable candidate for applications requiring fast oxygen conduction.« less

Solid State Ionic Materials - Proceedings of the 4th Asian Conference on Solid State Ionics

NASA Astrophysics Data System (ADS)

Chowdari, B. V. R.; Yahaya, M.; Talib, I. A.; Salleh, M. M.

1994-07-01

The Table of Contents for the full book PDF is as follows: * Preface * I. INVITED PAPERS * Diffusion of Cations and Anions in Solid Electrolytes * Silver Ion Conductors in the Crystalline State * NMR Studies of Superionic Conductors * Hall Effect and Thermoelectric Power in High Tc Hg-Ba-Ca-Cu-O Ceramics * Solid Electrolyte Materials Prepared by Sol-Gel Chemistry * Preparation of Proton-Conducting Gel Films and their Application to Electrochromic Devices * Thin Film Fuel Cells * Zirconia based Solid Oxide Ion Conductors in Solid Oxide Fuel Cells * The Influence of Anion Substitution on Some Phosphate-based Ion Conducting Glasses * Lithium Intercalation in Carbon Electrodes and its Relevance in Rocking Chair Batteries * Chemical Sensors using Proton Conducting Ceramics * NMR/NQR Studies of Y-Ba-Cu-O Superconductors * Silver Molybdate Glasses and Battery Systems * New Highly Conducting Polymer Ionics and their Application in Electrochemical Devices * Study of Li Electrokinetics on Oligomeric Electrolytes using Microelectrodes * Calculation of Conductivity for Mixed-Phase Electrolytes PEO-MX-Immiscible Additive by Means of Effective Medium Theory * II. CONTRIBUTED PAPERS * Phase Relationship and Electrical Conductivity of Sr-V-O System with Vanadium Suboxide * Amorphous Li+ Ionic Conductors in Li2SO4-Li2O-P2O5 System * Fast Ion Transport in KCl-Al2O3 Composites * The Effect of the Second Phase Precipitation on the Ionic Conductivity of Zr0.85Mg0.15O1.85 * Conductivity Measurements and Phase Relationships in CaCl2-CaHCl Solid Electrolyte * Relationships Between Crystal Structure and Sodium Ion Conductivity in Na7Fe4(AsO4)6 and Na3Al2(AsO4)3 * Electrical Conductivity and Solubility Limit of Ti4+ Ion in Na1+x TiyZr2-ySixP3-xO12 System * Study on Sodium Fast Ion Conductors of Na1+3xAlxTi2-xSi2xP3-2xO12 System * Influences of Zirconia on the Properties of β''-Alumina Ceramics * Decay of Luminescence from Cr3+ Ions in β-Alumina * Lithium Ion Conductivity in the Li4XO4-Li2SO4 (X=Si, Ge, Ti) Systems * A DSC and Conductivity Study of the Influence of Cesium Ion on the Beta-Alpha Transition in Silver Iodide * Phase Diagrams, Stoichiometries and Properties of Bi4V2O11:M2+ Solid Electrolytes * Physical Properties of Electrodeposited Silver Chromotungstate * Pseudopotential Study of Bonding in the Superionic Material AgI: The Effect of Statistical Distribution of Mobile Ions * Cubic Phase Dominant Region in Submicron BaTiO3 Particles * The Crystallization of CoZr Amorphous Alloys via Electrical Resistivity * Cation Ratio Related Properties of Synthetic Mg/Al Layered Double Hydroxide and it's Nanocomposite * DC Conductivity of Nano-Particles of Silver Iodide * Effect of Anomalous Diffusion on Quasielastic Scattering in Superionic Conductors * Computer Simulation Study of Conductivity Enhancement in Superionic-Insulator Composites * Dynamics of Superionic Silver and Copper Iodide Salt Melts * Influence of Dopant Salt AgI, Glass Modifier Ag2O and Glass Formers (SeO3 + MoO3) on Electrical Conductivity in Quaternary Glassy System * Fast Ion Conductivity in the Presence of Competitive Network Formers * Role of Alkali Ions in Borate Glasses * Inelastic Light Scattering in Cadmium Borate Glasses * Investigation on Transport Properties of Mixed Glass System 0.75 [0.75AgI:0.25AgCl]. 0.25[Ag2O:CrO3] * Conduction Mechanism in Lithium Tellurite Glasses * Optimized Silver Tungstoarsenate Glass Electrolyte * Stabilized Superfine Zirconia Powder Prepared by Sol-Gel Process * Study of New PAN-based Electrolytes * Electrical and Thermal Characterization of PVA based Polymer Electrolytes * Conductive Electroactive Polymers: Versatile Solid State Ionic Materials * The Role of Ag2O Addition on the Superconducting Properties of Y-124 Compound * Absorption Spectra Studies of the C60 Films on Transition Metal Film Substrates * Effect of Alumina Dispersal on the Conductivity and Crystallite Size of Polymer Electrolyte * New Mixed Galss-Polymer Solid Electrolytes * The Sputtered La0.5Sr0.5MnO3-Yttria Stabilized Zirconia Composite Electrode in Solid Oxide Fuel Cells * A Solid Electrochemical Ferro Sensor for Molten Matte * SnO2-based Sensor for H2S Monitoring-Electrical Conductivity Measurements and Device Testing * Humidity Sensor using Potassium Tungsten Bronze Synthesized from Peroxo-Polytungstic Acid * Study on Li/LiClO4/V6O13 Test Cells * Fabrication and Characterisation of Some Solid Electrolyte Cells Containing CuI and Silver Oxysalts * Solid State Battery of Proton Conducting Sodium Thiosulphate Pentahydrate * Low Temperature Synthesis of LiMn2O4 for Secondary Lithium Batteries * Effect of Different Cathode Active Materials on Battery Performance with Silver Molybdate Electrolyte Partially Substituted with Zinc Oxide * Fabrication and Characterization of Electrochemical Cells based on Silver Molybdoarsenate and Silver Tungstoarsenate Glass Electrolytes * Lorentz Force Dependence of Dissipation in a Granular Superconductor * Late Entry (Invited paper) * Simultaneous Voltammetry and Spectroscopy of Polyaniline in Propylene Carbonate * Author Index * Tentative List of Participants

One-volt-driven superfast polymer actuators based on single-ion conductors

PubMed Central

Kim, Onnuri; Kim, Hoon; Choi, U. Hyeok; Park, Moon Jeong

2016-01-01

The key challenges in the advancement of actuator technologies related to artificial muscles include fast-response time, low operation voltages and durability. Although several researchers have tackled these challenges over the last few decades, no breakthrough has been made. Here we describe a platform for the development of soft actuators that moves a few millimetres under 1 V in air, with a superfast response time of tens of milliseconds. An essential component of this actuator is the single-ion-conducting polymers that contain well-defined ionic domains through the introduction of zwitterions; this achieved an exceptionally high dielectric constant of 76 and a 300-fold enhancement in ionic conductivity. Moreover, the actuator demonstrated long-term durability, with negligible changes in the actuator stroke over 20,000 cycles in air. Owing to its low-power consumption (only 4 mW), we believe that this actuator could pave the way for cutting-edge biomimetic technologies in the future. PMID:27857067

Kinetic Studies of Reactions in Solution Using Fast Mass Spectrometry

DTIC Science & Technology

2013-08-13

dicyanamide ionic liquids Hypergolic fuels, or hypergols, can be ignited by exposure to an oxidizing agent under ambient conditions and are a common...DCA) based ionic liquids are a less volatile alternative that are less viscous than most ionic liquids ; however, ignition of these compounds...Condensates upon Hypergolic Ignition of Dicyanamide Ionic Liquids ," Angew. Chem. Int. Ed. 50, 8634–8637 (2011). (7) R. H. Perry, D. I. Bellovin, E

Thickness dependence of curvature, strain, and response time in ionic electroactive polymer actuators fabricated via layer-by-layer assembly

NASA Astrophysics Data System (ADS)

Montazami, Reza; Liu, Sheng; Liu, Yang; Wang, Dong; Zhang, Qiming; Heflin, James R.

2011-05-01

Ionic electroactive polymer (IEAP) actuators containing porous conductive network composites (CNCs) and ionic liquids can result in high strain and fast response times. Incorporation of spherical gold nanoparticles in the CNC enhances conductivity and porosity, while maintaining relatively small thickness. This leads to improved mechanical strain and bending curvature of the actuators. We have employed the layer-by-layer self-assembly technique to fabricate a CNC with enhanced curvature (0.43 mm-1) and large net intrinsic strain (6.1%). The results demonstrate that curvature and net strain of IEAP actuators due to motion of the anions increase linearly with the thickness of the CNC as a result of the increased volume in which the anions can be stored. In addition, after subtracting the curvature of a bare Nafion actuator without a CNC, it is found that the net intrinsic strain of the CNC layer is independent of thickness for the range of 20-80 nm, indicating that the entire CNC volume contributes equivalently to the actuator motion. Furthermore, the response time of the actuator due to anion motion is independent of CNC thickness, suggesting that traversal through the Nafion membrane is the limiting factor in the anion motion.

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

Chen, Yan; Cai, Lu; An, Ke, E-mail: kean@ornl.gov

This letter reports the correlation of anisotropy and directional conduction in the fast Li{sup +} conductor β-Li{sub 3}PS{sub 4}, one of the low-symmetry crystalline electrolyte candidates. The material has both high conductivity and good stability that serves well for the large-scale energy storage applications of all-solid-state lithium ion batteries. The anisotropic physical properties, demonstrated here by the thermal expansion coefficients, are crucial for compatibility in the solid-state system and battery performance. Neutron and X-ray powder diffraction measurements were done to determine the crystal structure and thermal stability. The crystallographic b-axis was revealed as a fast expansion direction, while negligible thermalmore » expansion was observed along the a-axis around the battery operating temperatures. The anisotropic behavior has its structural origin from the Li{sup +} conduction channels with incomplete Li occupancy and a flexible connection of LiS{sub 4} and PS{sub 4} tetrahedra within the framework. This indicates a strong correlation in the direction of the ionic transport in the low-symmetry Li{sup +} conductor.« less

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

Chen, Yan; Cai, Lu; Liu, Zengcai

Our letter reports the correlation of anisotropy and directional conduction in the fast Li + conductor β-Li 3PS 4, one of the low-symmetry crystalline electrolyte candidates. The material has both high conductivity and good stability that serves well for the large-scale energy storage applications of all-solid-state lithium ion batteries. The anisotropic physical properties, demonstrated here by the thermal expansion coefficients, are crucial for compatibility in the solid-state system and battery performance. Neutron and X-ray powder diffraction measurements were done to determine the crystal structure and thermal stability. Moreover, the crystallographic b-axis was revealed as a fast expansion direction, while negligiblemore » thermal expansion was observed along the a-axis around the battery operating temperatures. The anisotropic behavior has its structural origin from the Li + conduction channels with incomplete Li occupancy and a flexible connection of LiS 4 and PS 4 tetrahedra within the framework. This indicates a strong correlation in the direction of the ionic transport in the low-symmetry Li + conductor.« less

A microdot multilayer oxide device: let us tune the strain-ionic transport interaction.

PubMed

Schweiger, Sebastian; Kubicek, Markus; Messerschmitt, Felix; Murer, Christoph; Rupp, Jennifer L M

2014-05-27

In this paper, we present a strategy to use interfacial strain in multilayer heterostructures to tune their resistive response and ionic transport as active component in an oxide-based multilayer microdot device on chip. For this, fabrication of strained multilayer microdot devices with sideways attached electrodes is reported with the material system Gd0.1Ce0.9O(2-δ)/Er2O3. The fast ionic conducting Gd0.1Ce0.9O(2-δ) single layers are altered in lattice strain by the electrically insulating erbia phases of a microdot. The strain activated volume of the Gd0.1Ce0.9O(2-δ) is investigated by changing the number of individual layers from 1 to 60 while keeping the microdot at a constant thickness; i.e., the proportion of strained volume was systematically varied. Electrical measurements showed that the activation energy of the devices could be altered by Δ0.31 eV by changing the compressive strain of a microdot ceria-based phase by more than 1.16%. The electrical conductivity data is analyzed and interpreted with a strain volume model and defect thermodynamics. Additionally, an equivalent circuit model is presented for sideways contacted multilayer microdots. We give a proof-of-concept for microdot contacting to capture real strain-ionic transport effects and reveal that for classic top-electrode contacting the effect is nil, highlighting the need for sideways electric contacting on a nanoscopic scale. The near order ionic transport interaction is supported by Raman spectroscopy measurements. These were conducted and analyzed together with fully relaxed single thin film samples. Strain states are described relative to the strain activated volumes of Gd0.1Ce0.9O(2-δ) in the microdot multilayer. These findings reveal that strain engineering in microfabricated devices allows altering the ionic conduction over a wide range beyond classic doping strategies for single films. The reported fabrication route and concept of strained multilayer microdots is a promising path for applying strained multilayer oxides as active new building blocks relevant for a broad range of microelectrochemical devices, e.g., resistive switching memory prototypes, resistive or electrochemical sensors, or as active catalytic solid state surface components for microfuel cells or all-solid-state batteries.

Structural and Na-ion conduction characteristics of Na 3PS xSe 4–x

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

Bo, Shou -Hang; Wang, Yan; Ceder, Gerbrand

The recent discovery of the isostructrual cubic Na 3PS 4 and Na 3PSe 4 as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na 3PS xSe 4–x. Synthesis of Na 3PS 4 under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na 3PS xSe 4–x identifiedmore » a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na 3PS xSe 4–x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.« less

Structural and Na-ion conduction characteristics of Na 3 PS x Se 4-x

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

Bo, Shou-Hang; Wang, Yan; Ceder, Gerbrand

The recent discovery of the isostructrual cubic Na 3PS 4 and Na 3PSe 4 as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na 3PS xSe 4-x. Synthesis of Na 3PS 4 under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na 3PS xSe 4-x more » identified a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na 3PS xSe 4-x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.« less

Structural and Na-ion conduction characteristics of Na 3PS xSe 4–x

DOE PAGES

Bo, Shou -Hang; Wang, Yan; Ceder, Gerbrand

2016-05-19

The recent discovery of the isostructrual cubic Na 3PS 4 and Na 3PSe 4 as fast Na-ion conductors provided a general structural framework for the exploration of new sodium superionic conductors. In this work, we systematically investigated the structures and ionic conduction characteristics of a series of compounds with the general chemical formula of Na 3PS xSe 4–x. Synthesis of Na 3PS 4 under different conditions (e.g., temperature, reaction vessel, mass of the precursors) reveals the reactivity of the precursors with the reaction tubes, producing different polymorphs. X-ray diffraction studies on the solid solution phases Na 3PS xSe 4–x identifiedmore » a tetragonal-to-cubic phase transition with increasing Se concentration. This observation is consistent with the computed stability of the tetragonal and cubic polymorphs, where the energy difference between the two polymorphs becomes very close to zero in Se-rich compositions. Furthermore, ab initio molecular dynamic simulations suggest that the fast Na-ion conduction in Na 3PS xSe 4–x may not be causally related with the symmetry or the composition of these phases. The formation of defects, instead, enables fast Na-ion conduction in this class of materials.« less

Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes

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

Arges, Christopher G.; Kambe, Yu; Dolejsi, Moshe

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEsmore » with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per mu m(2) to 20 terminal defects per mu m(2) ( a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.« less

Implementation of a fast 16-Bit dynamic clamp using LabVIEW-RT.

PubMed

Kullmann, Paul H M; Wheeler, Diek W; Beacom, Joshua; Horn, John P

2004-01-01

The dynamic-clamp method provides a powerful electrophysiological tool for creating virtual ionic conductances in living cells and studying their influence on membrane potential. Here we describe G-clamp, a new way to implement a dynamic clamp using the real-time version of the Lab-VIEW programming environment together with a Windows host, an embedded microprocessor that runs a real-time operating system and a multifunction data-acquisition board. The software includes descriptions of a fast voltage-dependent sodium conductance, delayed rectifier, M-type and A-type potassium conductances, and a leak conductance. The system can also read synaptic conductance waveforms from preassembled data files. These virtual conductances can be reliably implemented at speeds < or =43 kHz while simultaneously saving two channels of data with 16-bit precision. G-clamp also includes utilities for measuring current-voltage relations, synaptic strength, and synaptic gain. Taking an approach built on a commercially available software/hardware platform has resulted in a system that is easy to assemble and upgrade. In addition, the graphical programming structure of LabVIEW should make it relatively easy for others to adapt G-clamp for new experimental applications.

Kinematically stable bipedal locomotion using ionic polymer-metal composite actuators

NASA Astrophysics Data System (ADS)

Hosseinipour, Milad; Elahinia, Mohammad

2013-08-01

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

Protein Self-Assemblies That Can Generate, Hold, and Discharge Electric Potential in Response to Changes in Relative Humidity.

PubMed

Carter, Nathan A; Grove, Tijana Z

2018-05-30

Generation of electric potential upon external stimulus has attracted much attention for the development of highly functional sensors and devices. Herein, we report large-displacement, fast actuation in the self-assembled engineered repeat protein Consensus Tetratricopeptide Repeat protein (CTPR18) materials. The ionic nature of the CTPR18 protein coupled to the long-range alignment upon self-assembly results in the measured conductivity of 7.1 × 10 -2 S cm -1 , one of the highest reported for protein materials. The change of through-thickness morphological gradient in the self-assembled materials provides the means to select between faster, highly water-sensitive actuation or vastly increased mechanical strength. Tuning of the mode of motion, e.g., bending, twisting, and folding, is achieved by changing the morphological director. We further show that the highly ionic character of CTPR18 gives rise to piezo-like behavior in these materials, exemplified by low-voltage, ionically driven actuation and mechanically driven generation/discharge of voltage. This work contributes to our understanding of the emergence of stimuli-responsiveness in biopolymer assemblies.

Carbon Redox-Polymer-Gel Hybrid Supercapacitors.

PubMed

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

2016-02-26

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

Ionic mechanisms and receptor properties underlying the responses of molluscan neurones to 5-hydroxytryptamine

PubMed Central

Gerschenfeld, H. M.; Tritsch, Danièle Paupardin

1974-01-01

1. Molluscan neurones have been found to show six different types of response (three excitatory and three inhibitory) to the iontophoretic application of 5-hydroxytryptamine (5-HT). The pharmacological properties of the receptors and the ionic mechanisms associated with these responses have been analysed. 2. Four of the responses to 5-HT (named A, A′, B and C) are consequent upon an increase in membrane conductance whereas the other two (named α and β) are caused by a decrease in membrane conductance. 3. The A-response to 5-HT consists of a `fast' depolarization due to an increase mainly in Na+-conductance; the A′-response is a `slow' depolarization also associated with a Na+-conductance increase. Receptors mediating the A- and A′-depolarizations have different pharmacological properties and may exist side by side on the same neurone. 4. Both the B- and C-responses are inhibitory. The B-response is a `slow' hyperpolarization due to an increase in K+-conductance, the C-response is a fast hyperpolarization associated with an increase in Cl--conductance. 5. The α-response to 5-HT is a depolarization which becomes reduced in amplitude with cell hyperpolarization and reverses at -75 mV; it is caused by a decrease in K+-conductance. The β-response is an hyperpolarization which increases in amplitude with cell hyperpolarization and reverses at -20/-30 mV. It results from a decrease in conductance to both Na+ and K+ ions. 6. The receptors involved in the 5-HT responses associated with a conductance increase may be recognized by the action of specific antagonists: 7-methyltryptamine blocks only the A-receptors, 5-methoxygramine only the B-receptors and neostigmine only the C-receptors. Curare blocks the A- and C-receptors and bufotenine, the A-, A′- and B-receptors. No specific antagonists have yet been found for the 5-HT responses caused by a conductance decrease. 7. The significance of the multiplicity of receptors is discussed. Their functional significance at synapses is analysed in the following paper. PMID:4155767

Flexible poly(ethylene carbonate)/garnet composite solid electrolyte reinforced by poly(vinylidene fluoride-hexafluoropropylene) for lithium metal batteries

NASA Astrophysics Data System (ADS)

He, Zijian; Chen, Long; Zhang, Bochen; Liu, Yongchang; Fan, Li-Zhen

2018-07-01

Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li6.25Al0.25La3Zr2O12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number (tLi+). PEC, as a fast ion-conducting polymer, possesses high tLi+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high tLi+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO4|Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g-1 and good cycling stability at 55 °C.

New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics.

PubMed

Drüschler, Marcel; Borisenko, Natalia; Wallauer, Jens; Winter, Christian; Huber, Benedikt; Endres, Frank; Roling, Bernhard

2012-04-21

Ionic liquids are of high interest for the development of safe electrolytes in modern electrochemical cells, such as batteries, supercapacitors and dye-sensitised solar cells. However, electrochemical applications of ionic liquids are still hindered by the limited understanding of the interface between electrode materials and ionic liquids. In this article, we first review the state of the art in both experiment and theory. Then we illustrate some general trends by taking the interface between the extremely pure ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate and an Au(111) electrode as an example. For the study of this interface, electrochemical impedance spectroscopy was combined with in situ STM and in situ AFM techniques. In addition, we present new results for the temperature dependence of the interfacial capacitance and dynamics. Since the interfacial dynamics are characterised by different processes taking place on different time scales, the temperature dependence of the dynamics can only be reliably studied by recording and carefully analysing broadband capacitance spectra. Single-frequency experiments may lead to artefacts in the temperature dependence of the interfacial capacitance. We demonstrate that the fast capacitive process exhibits a Vogel-Fulcher-Tamman temperature dependence, since its time scale is governed by the ionic conductivity of the ionic liquid. In contrast, the slower capacitive process appears to be Arrhenius activated. This suggests that the time scale of this process is determined by a temperature-independent barrier, which may be related to structural reorganisations of the Au surface and/or to charge redistributions in the strongly bound innermost ion layer. This journal is © the Owner Societies 2012

Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II) Ions and Histidine-Containing Peptides.

PubMed

Li, Hsin-Yi; Chen, Chien-Yuan; Cheng, Hui-Ting; Chu, Yen-Ho

2016-10-13

Based on a common structural core of 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5- a ]pyridine, a number of bicyclic triazolium ionic liquids 1 - 3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1 , 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II) ions and, for the first time, histidine-containing peptides.

Bioinspired Ultrastrong Solid Electrolytes with Fast Proton Conduction along 2D Channels.

PubMed

He, Guangwei; Xu, Mingzhao; Zhao, Jing; Jiang, Shengtao; Wang, Shaofei; Li, Zhen; He, Xueyi; Huang, Tong; Cao, Moyuan; Wu, Hong; Guiver, Michael D; Jiang, Zhongyi

2017-07-01

Solid electrolytes have attracted much attention due to their great prospects in a number of energy- and environment-related applications including fuel cells. Fast ion transport and superior mechanical properties of solid electrolytes are both of critical significance for these devices to operate with high efficiency and long-term stability. To address a common tradeoff relationship between ionic conductivity and mechanical properties, electrolyte membranes with proton-conducting 2D channels and nacre-inspired architecture are reported. An unprecedented combination of high proton conductivity (326 mS cm -1 at 80 °C) and superior mechanical properties (tensile strength of 250 MPa) are achieved due to the integration of exceptionally continuous 2D channels and nacre-inspired brick-and-mortar architecture into one materials system. Moreover, the membrane exhibits higher power density than Nafion 212 membrane, but with a comparative weight of only ≈0.1, indicating potential savings in system weight and cost. Considering the extraordinary properties and independent tunability of ion conduction and mechanical properties, this bioinspired approach may pave the way for the design of next-generation high-performance solid electrolytes with nacre-like architecture. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Ionic Liquids in Electro-active Devices (ILED)

DTIC Science & Technology

2013-12-12

Polyesters: Structure-Property Relationships in Thermal Behavior, Ionic Conductivity , and Morphology , Advanced Functional Materials, (01 2010...and Ionic Conductivities , Macromolecular Chemistry and Physics, (10 2011): . doi: M. Green, C. Schreiner, T. Long. Thermal , Rheological, and Ion...block giving thermal stability and ionic conductivity . Table 1 shows the molecular weight analysis of the triblock copolymers with increasing

Low-Dimensional Oxygen Vacancy Ordering and Diffusion in SrCrO 3$-$δ

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

Ong, Phuong-Vu; Du, Yingge; Sushko, Peter V.

2017-04-06

We investigate the formation mechanisms of vacancy-ordered phase and collective mass transport in epitaxial SrCrO 3$-$δ films using ab initio simulations within the density functional theory formalism. We show that as concentration of oxygen vacancies (V O’s) increases, they form one-dimensional (1D) chains that feature Cr-centered tetrahedra. Aggregation of these 1D V O-chains results in the formation of (111)-oriented oxygen-deficient planes (V O-planes) and an extended vacancy-ordered phase observed in recent experiments. We discuss atomic scale mechanisms enabling the quasi-2D V O aggregates to expand along and translate across (111) planes. The corresponding lowest activation energy pathways necessarily involve rotationmore » of Cr-centered tetrahedra, which emerges as a universal feature of fast ionic conduction in complex oxides. These findings explain reversible oxidation and reduction in SrCrO 3$-$δ at low-temperatures and provide insights into transient behavior necessary to harness ionic conductive oxides for high performance and low-temperature electrochemical reactors.« less

Fast-slow asymptotics for a Markov chain model of fast sodium current

NASA Astrophysics Data System (ADS)

Starý, Tomáš; Biktashev, Vadim N.

2017-09-01

We explore the feasibility of using fast-slow asymptotics to eliminate the computational stiffness of discrete-state, continuous-time deterministic Markov chain models of ionic channels underlying cardiac excitability. We focus on a Markov chain model of fast sodium current, and investigate its asymptotic behaviour with respect to small parameters identified in different ways.

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.

Structural and electrical properties of NASICON type solid electrolyte nanoscaled glass-ceramic powder by mechanical milling for thin film batteries.

PubMed

Patil, Vaishali; Patil, Arun; Yoon, Seok-Jin; Choi, Ji-Won

2013-05-01

During last two decades, lithium-based glasses have been studied extensively as electrolytes for solid-state secondary batteries. For practical use, solid electrolyte must have high ionic conductivity as well as chemical, thermal and electrochemical stability. Recent progresses have focused on glass electrolytes due to advantages over crystalline solid. Glass electrolytes are generally classified into two types oxide glass and sulfide glass. Oxide glasses do not react with electrode materials and this chemical inertness is advantageous for cycle performances of battery. In this study, major effort has been focused on the improvement of the ion conductivity of nanosized LiAlTi(PO4)3 oxide electrolyte prepared by mechanical milling (MM) method. After heating at 1000 degrees C the material shows good crystallinity and ionic conductivity with low electronic conductivity. In LiTi2(PO4)3, Ti4+ ions are partially substituted by Al3+ ions by heat-treatment of Li20-Al2O3-TiO2-P2O5 glasses at 1000 degrees C for 10 h. The conductivity of this material is 1.09 x 10(-3) S/cm at room temp. The glass-ceramics show fast ion conduction and low E(a) value. It is suggested that high conductivity, easy fabrication and low cost make this glass-ceramics promising to be used as inorganic solid electrolyte for all-solid-state Li rechargeable batteries.

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.

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.

Ultra-high density aligned Carbon-nanotube with controled nano-morphology for supercapacitors

NASA Astrophysics Data System (ADS)

Ghaffari, Mehdi; Zhao, Ran; Liu, Yang; Zhou, Yue; Cheng, Jiping; Guzman de Villoria, Roberto; Wardle, B. L.; Zhang, Q. M.

2012-02-01

Recent advances in fabricating controlled-morphology vertically aligned carbon nanotubes (VA-CNTs) with ultrahigh volume fractioncreate unique opportunities for developing unconventional supercapacitors with ultra-high energy density, power density, and long charge/discharge cycle life.Continuous paths through inter-VA-CNT channels allow fast ion transport, and high electrical conduction of the aligned CNTs in the composite electrodes lead to fast discharge speed. We investigate the charge-discharge characteristics of VA-CNTs with >20 vol% of CNT and ionic liquids as electrolytes. By employing both the electric and electromechanical spectroscopes, as well as nanostructured materials characterization, the ion transport and storage behaviors in porous electrodes are studied. The results suggest pathways for optimizing the electrode morphology in supercapacitorsusing ultra-high volume fraction VA-CNTs to further enhance performance.

Carbon Redox-Polymer-Gel Hybrid Supercapacitors

PubMed Central

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

2016-01-01

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

Highly efficient conductivity modulation of cinnamate-based light-responsive ionic liquids in aqueous solutions.

PubMed

Yang, Jie; Wang, Huiyong; Wang, Jianji; Zhang, Yue; Guo, Zhongjia

2014-12-11

A new class of cinnamate-based light-responsive ionic liquids was synthesized and characterized, and these ionic liquids with longer alkyl chains showed a remarkable increase in ionic conductivity under UV light irradiation in aqueous solutions.

Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

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

He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.

2011-08-01

The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationshipmore » between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.« less

Coherency strain and its effect on ionic conductivity and diffusion in solid electrolytes--an improved model for nanocrystalline thin films and a review of experimental data.

PubMed

Korte, C; Keppner, J; Peters, A; Schichtel, N; Aydin, H; Janek, J

2014-11-28

A phenomenological and analytical model for the influence of strain effects on atomic transport in columnar thin films is presented. A model system consisting of two types of crystalline thin films with coherent interfaces is assumed. Biaxial mechanical strain ε0 is caused by lattice misfit of the two phases. The conjoined films consist of columnar crystallites with a small diameter l. Strain relaxation by local elastic deformation, parallel to the hetero-interface, is possible along the columnar grain boundaries. The spatial extent δ0 of the strained hetero-interface regions can be calculated, assuming an exponential decay of the deformation-forces. The effect of the strain field on the local ionic transport in a thin film is then calculated by using the thermodynamic relation between (isostatic) pressure and free activation enthalpy ΔG(#). An expression describing the total ionic transport relative to bulk transport of a thin film or a multilayer as a function of the layer thickness is obtained as an integral average over strained and unstrained regions. The expression depends only on known material constants such as Young modulus Y, Poisson ratio ν and activation volume ΔV(#), which can be combined as dimensionless parameters. The model is successfully used to describe own experimental data from conductivity and diffusion studies. In the second part of the paper a comprehensive literature overview of experimental studies on (fast) ion transport in thin films and multilayers along solid-solid hetero-interfaces is presented. By comparing and reviewing the data the observed interface effects can be classified into three groups: (i) transport along interfaces between extrinsic ionic conductors (and insulator), (ii) transport along an open surface of an extrinsic ionic conductor and (iii) transport along interfaces between intrinsic ionic conductors. The observed effects in these groups differ by about five orders of magnitude in a very consistent way. The modified interface transport in group (i) is most probably caused by strain effects, misfit dislocations or disordered transition regions.

Communication: Influence of nanophase segregation on ion transport in room temperature ionic liquids

DOE PAGES

Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; ...

2016-04-21

In this paper, we report measurements of the ionic conductivity, shear viscosity, and structural dynamics in a homologous series of quaternary ammonium ionic liquids (ILs) and a prototypical imidazolium-based IL over a wide range of temperatures down to the glass transition. We find that the ionic conductivity of these materials generally decreases, while the shear viscosity correspondingly increases, with increasing volume fraction of aliphatic side groups. Upon crossing an aliphatic volume fraction of ~0.40, we observe a sharp, order-of-magnitude decrease in ionic conductivity and enhancement of viscosity, which coincides with the presence of long-lived, nanometer-sized alkyl aggregates. These strong changesmore » in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Finally, our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.« less

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

PubMed

Li, Zhiyong; Yuan, Xiaoqing; Feng, Ying; Chen, Yongkui; Zhao, Yuling; Wang, Huiyong; Xu, Qingli; Wang, Jianji

2018-05-09

Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

Ionic Conductivity and Air Stability of Al-Doped Li₇La₃Zr₂O₁₂ Sintered in Alumina and Pt Crucibles.

PubMed

Xia, Wenhao; Xu, Biyi; Duan, Huanan; Guo, Yiping; Kang, Hongmei; Li, Hua; Liu, Hezhou

2016-03-02

Li7La3Zr2O12 (LLZO) is a promising electrolyte material for all-solid-state battery due to its high ionic conductivity and good stability with metallic lithium. In this article, we studied the effect of crucibles on the ionic conductivity and air stability by synthesizing 0.25Al doped LLZO pellets in Pt crucibles and alumina crucibles, respectively. The results show that the composition and microstructure of the pellets play important roles influencing the ionic conductivity, relative density, and air stability. Specifically, the 0.25Al-LLZO pellets sintered in Pt crucibles exhibit a high relative density (∼96%) and high ionic conductivity (4.48 × 10(-4) S cm(-1)). The ionic conductivity maintains 3.6 × 10(-4) S cm(-1) after 3-month air exposure. In contrast, the ionic conductivity of the pellets from alumina crucibles is about 1.81 × 10(-4) S cm(-1) and drops to 2.39 × 10(-5) S cm(-1) 3 months later. The large grains and the reduced grain boundaries in the pellets sintered in Pt crucibles are favorable to obtain high ionic conductivity and good air stability. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results suggest that the formation of Li2CO3 on the pellet surface is probably another main reason, which is also closely related to the relative density and the amount of grain boundary within the pellets. This work stresses the importance of synthesis parameters, crucibles included, to obtain the LLZO electrolyte with high ionic conductivity and good air stability.

Correlating morphology to dc conductivity in polymerized ionic liquids

NASA Astrophysics Data System (ADS)

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

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

Dielectric Studies on Thermally Evaporated CEF3 Thin Film

NASA Astrophysics Data System (ADS)

Selvasekarapandian, S.; Gowtham, M.; Bhuvaneswari, M. S.

In recent years rare earth compounds especially their fluorides have drawn particular attention as electrochemical gas sensors. Lanthanum and cerium fluoride based sensors have been investigated for sensing the fluorine, oxygen, and carbon monoxide because of their high chemical stability and high ionic conductivity. The fast response and good sensitivity of these sensors rely on the ion conduction properties of these thin films. In the present work Cerium Fluoride thin film has been prepared by vacuum thermal evaporation method. The electrical characterization is carried out using the Impedance spectroscopy method in the frequency range of 50 Hz to 5 MHz. The temperature dependence of ionic conductivity obeys the Arrhenius behavior and the activation energy Ea is found to be 0.3eV. The modulus and the dielectric spectra analysis reveal the non - Debye nature and the distribution of relaxation time due to the presence of grain and grain boundaries in the film. The relaxation energy Ed has been calculated from the dielectric spectra. The similar value of activation and relaxation energies suggests that the charge carriers that are responsible for bulk conductivity and relaxation process are the same. The optical measurement done in the wavelength range of 400-2500 nm confirms that the CeF3 thin film is highly transparent and the band gap energy is found to be 3.5 eV.

Measuring blocking force to interpret ionic mechanisms within bucky-gel actuators

NASA Astrophysics Data System (ADS)

Kruusamäe, Karl; Sugino, Takushi; Asaka, Kinji

2015-04-01

Bucky-gel laminates are tri-layer structures where polymeric electrolyte film is sandwiched between two compliant electrode layers of carbon nanotubes and ionic liquid. The resulting ionic and capacitive structures, being regarded as a type of electromechanically active polymers (EAP), have the perspective of becoming soft bending actuators in the fields such as biomimetic robotics or lab-on-chip technology. A typical electromechanical step response of a bucky-gel actuator in a cantilever configuration exhibits a fast bending displacement followed by some reverse motion referred to as the back-relaxation. It has been proposed that the bending but also the back-relaxation of bucky-gel laminates occur due to the relocation of cations and anions within the tri-layer structure. A great number of modeling about ionic EAP materials aims to predict the amplitude of free bending or the blocking force of the actuator. However, as the bucky-gel laminates are viscoelastic, the translation from generated force to bending amplitude is not always straightforward - it can take the form of an integro-differential equation with speed (i.e. the amplitude and type of the input signal) and temperature (i.e. the electronic conductivity of the material and driving current) as just some of the parameters. In this study we propose to use a so-called two carrier-model to analyze the electromechanical response of a bucky-gel actuator. After modifying the electrical equivalent circuit, the time domain response of blocking force is measured to elaborate the ionic mechanisms during the work-cycle of bucky-gel actuator.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Effect of Mixed Glass Former on Ionic Conductivity of Silver Boro Tungstate glass system x[0.75AgI:0.25AgCl]: (1-x) [Ag2O-{B2O3:WO3}

NASA Astrophysics Data System (ADS)

Dehariya, Harsha; Kumar, R.; Polu, A. R.

2012-05-01

The idea to explore new 'Superionic Electrolytes', "Fast ionic conductors" is due to their tremendous potential applications in solid state electrochemical devices viz. solid state batteries, fuel cells, sensors, super capacitors. Superionic glasses have attracted great deal of attention due to their several advantageous over their crystalline counterparts such as high ionic conductivity, easy preparation, wide selection of compositions, isotropic properties and high stability etc [4-7]. Large numbers of silver ion based glasses have been reported in the literature for the glassy system of AgI:Ag2O: MxOy (MxOy = B2O3, SiO2, P2O5, GeO2, V2O5, As2O5, CrO3, SeO2, MoO3 & TeO3 etc many of them shows high silver ion conductivity [8]. Ion transport behavior of Silver Boro Tungstate glass system x[0.75AgI:0.25AgCl]: (1-x) [Ag2O{B2O3:WO3}], where 0 <= x <= 1 in molar wt% prepared by melt quench technique were reported. The new host [0.75AgI:0.25AgCl] was used as a better alternate in place of conventional host salt AgI. Conductivity measurement were carried out on this glass system as a function of frequency from 50 Hz to 5 MHz, over a temperature range of 27°C to 200°C, for different compositions by Impedance spectroscopy. The composition 0.7[0.75AgI:0.25AgCl]: 0.3[Ag2O{B2O3:WO3}] shows the highest conductivity of the order of σrt ~ 2.76 × 10-2 S/cm, referred to as the Optimum Conducting Composition (OCC). The enhancement in the conductivity has been obtained by mixed former effect. XRD result shows that the system is completely amorphous. Temperature dependence of conductivity of all compositions were studied & reported. Activation energies (Ea) were also evaluated from the slope of .Log(σ) vs 1000/T, Arrhenius plots.

DFT-based ab initio MD simulation of the ionic conduction in doped ZrO₂ systems under epitaxial strain.

PubMed

Oka, M; Kamisaka, H; Fukumura, T; Hasegawa, T

2015-11-21

The oxygen ionic conduction in ZrO2 systems under tensile epitaxial strain was investigated by performing ab initio molecular dynamics (MD) calculations based on density functional theory (DFT) to elucidate the essential factors in the colossal ionic conductivity observed in the yttria stabilized ZrO2 (YSZ)/SrTiO3 heterostructure. Three factors were evaluated: lattice strain, oxygen vacancies, and dopants. Phonon calculations based on density functional perturbation theory (DFPT) were used to obtain the most stable structure for nondoped ZrO2 under 7% tensile strain along the a- and b-axes. This structure has the space group Pbcn, which is entirely different from that of cubic ZrO2, suggesting that previous ab initio MD calculations assuming cubic ZrO2 may have overestimated the ionic conductivity due to relaxation from the initial structure to the stable structure (Pbcn). Our MD calculations revealed that the ionic conductivity is enhanced only when tensile strain and oxygen vacancies are incorporated, although the presently obtained diffusion constant is far below the range for the colossal ionic conduction experimentally observed. The enhanced ionic conductivity is due to the combined effects of oxygen sublattice formation induced by strain and deformation of this sublattice by oxygen vacancies.

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-01

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ˜75 F g-1, ˜987 kW kg-1 and ˜27 W h kg-1, respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (˜158 F g-1) and energy density (˜53 W h kg-1). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices.

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes.

PubMed

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-20

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ~75 F g(-1), ~987 kW kg(-1) and ~27 W h kg(-1), respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (~158 F g(-1)) and energy density (~53 W h kg(-1)). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices. © 2012 IOP Publishing Ltd

Statistical variances of diffusional properties from ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

He, Xingfeng; Zhu, Yizhou; Epstein, Alexander; Mo, Yifei

2018-12-01

Ab initio molecular dynamics (AIMD) simulation is widely employed in studying diffusion mechanisms and in quantifying diffusional properties of materials. However, AIMD simulations are often limited to a few hundred atoms and a short, sub-nanosecond physical timescale, which leads to models that include only a limited number of diffusion events. As a result, the diffusional properties obtained from AIMD simulations are often plagued by poor statistics. In this paper, we re-examine the process to estimate diffusivity and ionic conductivity from the AIMD simulations and establish the procedure to minimize the fitting errors. In addition, we propose methods for quantifying the statistical variance of the diffusivity and ionic conductivity from the number of diffusion events observed during the AIMD simulation. Since an adequate number of diffusion events must be sampled, AIMD simulations should be sufficiently long and can only be performed on materials with reasonably fast diffusion. We chart the ranges of materials and physical conditions that can be accessible by AIMD simulations in studying diffusional properties. Our work provides the foundation for quantifying the statistical confidence levels of diffusion results from AIMD simulations and for correctly employing this powerful technique.

Fundamentals of ionic conductivity relaxation gained from study of procaine hydrochloride and procainamide hydrochloride at ambient and elevated pressure.

PubMed

Wojnarowska, Z; Swiety-Pospiech, A; Grzybowska, K; Hawelek, L; Paluch, M; Ngai, K L

2012-04-28

The pharmaceuticals, procaine hydrochloride and procainamide hydrochloride, are glass-forming as well as ionically conducting materials. We have made dielectric measurements at ambient and elevated pressures to characterize the dynamics of the ion conductivity relaxation in these pharmaceuticals, and calorimetric measurements for the structural relaxation. Perhaps due to their special chemical and physical structures, novel features are found in the ionic conductivity relaxation of these pharmaceuticals. Data of conductivity relaxation in most ionic conductors when represented by the electric loss modulus usually show a single resolved peak in the electric modulus loss M(")(f) spectra. However, in procaine hydrochloride and procainamide hydrochloride we find in addition another resolved loss peak at higher frequencies over a temperature range spanning across T(g). The situation is analogous to many non-ionic glass-formers showing the presence of the structural α-relaxation together with the Johari-Goldstein (JG) β-relaxation. Naturally the analogy leads us to name the slower and faster processes resolved in procaine hydrochloride and procainamide hydrochloride as the primary α-conductivity relaxation and the secondary β-conductivity relaxation, respectively. The analogy of the β-conductivity relaxation in procaine HCl and procainamide HCl with JG β-relaxation in non-ionic glass-formers goes further by the finding that the β-conductivity is strongly related to the α-conductivity relaxation at temperatures above and below T(g). At elevated pressure but compensated by raising temperature to maintain α-conductivity relaxation time constant, the data show invariance of the ratio between the β- and the α-conductivity relaxation times to changes of thermodynamic condition. This property indicates that the β-conductivity relaxation has fundamental importance and is indispensable as the precursor of the α-conductivity relaxation, analogous to the relation found between the Johari-Goldstein β-relaxation and the structural α-relaxation in non-ionic glass-forming systems. The novel features of the ionic conductivity relaxation are brought out by presenting the measurements in terms of the electric modulus or permittivity. If presented in terms of conductivity, the novel features are lost. This warns against insisting that a log-log plot of conductivity vs. frequency is optimal to reveal and interpret the dynamics of ionic conductors.

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

Conductivity Scaling Relationships of Nanostructured Membranes based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing

NASA Astrophysics Data System (ADS)

Sanoja, Gabriel; Popere, Bhooshan; Beckingham, Bryan; Evans, Christopher; Lynd, Nathaniel; Segalman, Rachel

Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated block copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS- b - PIL with constant volume fraction of ionic liquid moieties (fIL ~ 0.39). These materials self-assemble into ordered lamellar morphologies with variable domain spacing (23-59 nm) as demonstrated by SAXS. PS- b - PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing. The conductivity scaling relationship demonstrated in this work suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit lower water uptake (λ = 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of these materials makes them promising candidates for solar-fuels electrochemical devices.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Anomalous frequency-dependent ionic conductivity of lesion-laden human-brain tissue

NASA Astrophysics Data System (ADS)

Emin, David; Akhtari, Massoud; Fallah, Aria; Vinters, Harry V.; Mathern, Gary W.

2017-10-01

We study the effect of lesions on our four-electrode measurements of the ionic conductivity of (˜1 cm3) samples of human brain excised from patients undergoing pediatric epilepsy surgery. For most (˜94%) samples, the low-frequency ionic conductivity rises upon increasing the applied frequency. We attributed this behavior to the long-range (˜0.4 mm) diffusion of solvated sodium cations before encountering intrinsic impenetrable blockages such as cell membranes, blood vessels, and cell walls. By contrast, the low-frequency ionic conductivity of some (˜6%) brain-tissue samples falls with increasing applied frequency. We attribute this unusual frequency-dependence to the electric-field induced liberation of sodium cations from traps introduced by the unusually severe pathology observed in samples from these patients. Thus, the anomalous frequency-dependence of the ionic conductivity indicates trap-producing brain lesions.

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.

Enhancement of the ionic conductivity of olivine by the water incorporation based on the Mg diffusivity

NASA Astrophysics Data System (ADS)

Katsura, T.; Fei, H.; Koizumi, S.; Sakamoto, N.; Yurimoto, H.

2016-12-01

Although the water corporation has been considered to enhance the electrical conductivity of olivine by the proton conduction, the magnitude of the proton conduction is relatively small at asthenospheric temperatures because of its smaller activation energy than those of the small polaron and ionic conductions. However, the water incorporation could enhance the ionic conduction, because it should increase the defect density in the Mg sites. Since the ionic conductivity is proportional to the diffusivity, we have measured the self-diffusion coefficients of Mg in forsterite as a function of pressure, temperature and water content. We annealed fine-grained polycrystalline aggregates of forsterite with water contents up to 300 ppm, on whose polished plane a 25Mg-enriched Mg2SiO4 thin film was made, at pressures of 1 to 13 GPa and temperatures of 1100 to 1300 K. The lattice and grain-boundary diffusion coefficients were calculated simultaneously using profiles obtained by the depth analysis of SIMS. Experimental results gave the activation energy of 280 ± 30 and 360 ± 30 kJ/mol, activation volumes of 4.3 ± 0.3 and 3.9 ± 0.7 cm3/mol, and water content exponents of 1.2 ± 0.2 and 1.0 ± 0.1 for the lattice and grain-boundary diffusions, respectively. Using the ionic conduction data by Constable [2006] and Yoshino et al. [2009], and the water and pressure effects on Mg diffusivity in this study, the ionic conduction is found by 2 orders of magnitude higher than the small polaron and proton conductions under oceanic-asthenosphere conditions. Thus, the high conductivity of the oceanic asthenosphere will be governed by the water-enhanced ionic conduction. The negative pressure dependence of the Mg diffusivity and the gradual temperature increase in the asthenosphere will produce a conductivity maximum at the top of the asthenosphere. The high-conductivity layer at the top of the asthenosphere observed under very young oceanic plates can be attributed to this ionic conduction maximum.

Origin of high Li⁺ conduction in doped Li₇La₃Zr₂O₁₂ garnets

DOE PAGES

Chen, Yan; Rangasamy, Ezhiylmurugan; Liang, Chengdu; ...

2015-08-06

Substitution of a native ion in the crystals with a foreign ion that differs in valence ( aliovalent doping) has been widely attempted to upgrade solid-state ionic conductors for various charge carriers including O²⁻, H⁺, Li⁺, Na⁺, etc. The doping helps promote the high-conductive framework and dredge the tunnel for fast ion transport. The garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a fast Li⁺ solid conductor, which received much attention as an electrolyte candidate for all-solid-state lithium ion batteries, showing great potential to offer high energy density and minimize battery safety concerns to meet extensive applications in large energy storage systems such asmore » those for electric vehicles and aerospace. In the Li-stuffed garnet framework of LLZO, the 3D pathway formed by the incompletely occupied tetrahedral sites bridged by a single octahedron enables the superior Li⁺ conductivity. For optimal performance, many aliovalent-doping efforts have been made throughout metal elements (Al³⁺, Ta⁵⁺) and metalloid elements (Ga³⁺, Te⁶⁺) in the periodic table with various valences to stabilize the high-conductive phase and increase the Li vacancy concentration.« less

Mesh-structured N-doped graphene@Sb2Se3 hybrids as an anode for large capacity sodium-ion batteries.

PubMed

Zhao, Wenxi; Li, Chang Ming

2017-02-15

A mesh-structured N-doped graphene@Sb 2 Se 3 (NGS) hybrid was one-pot prepared to realize N-doping, nanostructuring and hybridization for a sodium-ion battery anode to deliver much larger reversible specific capacity, faster interfacial electron transfer rate, better ionic and electronic transport, higher rate performance and longer cycle life stability in comparison to the plain Sb 2 Se 3 one. The better performance is ascribed to the unique intertwined porous mash-like structure associated with a strong synergistic effect of N-doped graphene for dramatic improvement of electronic and ionic conductivity by the unique porous structure, the specific capacity of graphene from N doping and fast interfacial electron transfer rate by N-doping induced surface effect and the structure-shortening insertion/desertion pathway of Na + . The detail electrochemical process on the NGS electrode is proposed and analyzed in terms of the experimental results. Copyright © 2016 Elsevier Inc. All rights reserved.

Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems

NASA Astrophysics Data System (ADS)

Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B.

2014-12-01

The thermal, transport, rheological and flammability properties of electrolyte mixtures, proposed for safer lithium-ion battery systems, were investigated as a function of the mole composition. The blends were composed of a lithium salt (LiTFSI), organic solvents (namely EC, DEC) and an ionic liquid (PYR13TFSI). The main goal is to combine the fast ion transport properties of the organic compounds with the safe issues of the non-flammable and non-volatile ionic liquids. Preliminary tests in batteries have evidenced cycling performance approaching that observed in commercial organic electrolytes.

Bucky gel actuators optimization towards haptic applications

NASA Astrophysics Data System (ADS)

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

2014-03-01

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

Extensional ionomeric polymer conductor composite actuators with ionic liquids

NASA Astrophysics Data System (ADS)

Liu, Sheng; Lin, Minren; Zhang, Qiming

2008-03-01

Although the Ionic Polymer-Metal Composite (IPMC) actuators developed up to date are in the form of bending actuators, development of extensional actuators based on IMPC is highly desirable from practical applications and fundamental understanding points of view. This talk presents the design, fabrication and characterization of a recent work on an extensional Ionic Polymer-Metal Composite actuator. The extensional actuator consists of the Nafion ionomer as the matrix and the sub-micron size RuO II particles as the conductive filler for the conductor/ionomr composites. In this investigation, several ionic liquids (IL) were investigated. For a Nafion/RuO II composite with 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf) IL, it was found that as the ions are driven into the ionomer/RuO II composite (the composite under negative voltage), an extensional strain of 0.9% was observed; while as the ions were expelled from the ionomer/RuO II composite (under positive voltage), a contraction of -1.2% was observed. The results indicate that multiple ions are participating in charge transport and actuation process. In this paper, we also discuss several design considerations for future extensional actuators with fast response, much improved strain and stress level. Especially an actuator based on multilayer configuration can significantly increase the electric field level in the actuator and consequently significantly improve the actuator speed. The extensional actuator investigated here provides a unique platform to investigate various phenomena related to ion transport and their interaction with the ionomer/conductor matrix to realize high electromechanical performance.

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

NASA Astrophysics Data System (ADS)

Xiao, Ruijuan; Li, Hong; Chen, Liquan

2015-09-01

Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

Composite mixed oxide ionic and electronic conductors for hydrogen separation

DOEpatents

Gopalan, Srikanth [Westborough, MA; Pal, Uday B [Dover, MA; Karthikeyan, Annamalai [Quincy, MA; Hengdong, Cui [Allston, MA

2009-09-15

A mixed ionic and electronic conducting membrane includes a two-phase solid state ceramic composite, wherein the first phase comprises an oxygen ion conductor and the second phase comprises an n-type electronically conductive oxide, wherein the electronically conductive oxide is stable at an oxygen partial pressure as low as 10.sup.-20 atm and has an electronic conductivity of at least 1 S/cm. A hydrogen separation system and related methods using the mixed ionic and electronic conducting membrane are described.

Hydrophobic ionic liquids for quantitative bacterial cell lysis with subsequent DNA quantification.

PubMed

Fuchs-Telka, Sabine; Fister, Susanne; Mester, Patrick-Julian; Wagner, Martin; Rossmanith, Peter

2017-02-01

DNA is one of the most frequently analyzed molecules in the life sciences. In this article we describe a simple and fast protocol for quantitative DNA isolation from bacteria based on hydrophobic ionic liquid supported cell lysis at elevated temperatures (120-150 °C) for subsequent PCR-based analysis. From a set of five hydrophobic ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was identified as the most suitable for quantitative cell lysis and DNA extraction because of limited quantitative PCR inhibition by the aqueous eluate as well as no detectable DNA uptake. The newly developed method was able to efficiently lyse Gram-negative bacterial cells, whereas Gram-positive cells were protected by their thick cell wall. The performance of the final protocol resulted in quantitative DNA extraction efficiencies for Gram-negative bacteria similar to those obtained with a commercial kit, whereas the number of handling steps, and especially the time required, was dramatically reduced. Graphical Abstract After careful evaluation of five hydrophobic ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMPyr + ][Ntf 2 - ]) was identified as the most suitable ionic liquid for quantitative cell lysis and DNA extraction. When used for Gram-negative bacteria, the protocol presented is simple and very fast and achieves DNA extraction efficiencies similar to those obtained with a commercial kit. ddH 2 O double-distilled water, qPCR quantitative PCR.

Effects of impurity doping on ionic conductivity and polarization phenomenon in TlBr

NASA Astrophysics Data System (ADS)

Du, Mao-Hua

2013-02-01

Ionic conductivity due to vacancy diffusion and the resulting polarization phenomenon are major challenges to the development of TlBr radiation detector. It had been proposed that impurity doping of TlBr can suppress the ionic conductivity because the impurities can getter vacancies to form neutral complexes. This paper shows that the isolated vacancies can maintain their equilibrium concentrations even at room temperature, rendering any gettering methods ineffective. The main effect of doping is to change the Fermi level and consequently the vacancy concentration. The minimal ionic conductivity is reached at the donor concentration of [D+] = 4 × 1016 cm-3.

Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution.

PubMed

Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

2016-05-19

Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room-Temperature Ionic Liquids. 1. Variation of Anionic Species.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2015-12-03

A series of room temperature ionic liquids (RTILs) based on 1-ethyl-3-methylimidazolium ([emim](+)) with different aprotic heterocyclic anions (AHAs) were synthesized and characterized as potential electrolyte candidates for lithium ion batteries. The density and transport properties of these ILs were measured over the temperature range between 283.15 and 343.15 K at ambient pressure. The temperature dependence of the transport properties (viscosity, ionic conductivity, self-diffusion coefficient, and molar conductivity) is fit well by the Vogel-Fulcher-Tamman (VFT) equation. The best-fit VFT parameters, as well as linear fits to the density, are reported. The ionicity of these ILs was quantified by the ratio of the molar conductivity obtained from the ionic conductivity and molar concentration to that calculated from the self-diffusion coefficients using the Nernst-Einstein equation. The results of this study, which is based on ILs composed of both a planar cation and planar anions, show that many of the [emim][AHA] ILs exhibit very good conductivity for their viscosities and provide insight into the design of ILs with enhanced dynamics that may be suitable for electrolyte applications.

Rapid Measurement of Room Temperature Ionic Liquid Electrochemical Gas Sensor using Transient Double Potential Amperometry

PubMed Central

Wan, Hao; Yin, Heyu; Mason, Andrew J.

2016-01-01

Intense study on gas sensors has been conducted to implement fast gas sensing with high sensitivity, reliability and long lifetime. This paper presents a rapid amperometric method for gas sensing based on a room temperature ionic liquid electrochemical gas sensor. To implement a miniaturized sensor with a fast response time, a three electrode system with gold interdigitated electrodes was fabricated by photolithography on a porous polytetrafluoroethylene substrate that greatly enhances gas diffusion. Furthermore, based on the reversible reaction of oxygen, a new transient double potential amperometry (DPA) was explored for electrochemical analysis to decrease the measurement time and reverse reaction by-products that could cause current drift. Parameters in transient DPA including oxidation potential, oxidation period, reduction period and sample point were investigated to study their influence on the performance of the sensor. Oxygen measurement could be accomplished in 4 s, and the sensor presented a sensitivity of 0.2863 μA/[%O2] and a linearity of 0.9943 when tested in air samples with different oxygen concentrations. Repeatability and long-term stability were also investigated, and the sensor was shown to exhibit good reliability. In comparison to conventional constant potential amperometry, transient DPA was shown to reduce relative standard deviation by 63.2%. With transient DPA, the sensitivity, linearity, repeatability, measurement time and current drift characteristics demonstrated by the presented gas sensor are promising for acute exposure applications. PMID:28603384

Rapid Measurement of Room Temperature Ionic Liquid Electrochemical Gas Sensor using Transient Double Potential Amperometry.

PubMed

Wan, Hao; Yin, Heyu; Mason, Andrew J

2017-04-01

Intense study on gas sensors has been conducted to implement fast gas sensing with high sensitivity, reliability and long lifetime. This paper presents a rapid amperometric method for gas sensing based on a room temperature ionic liquid electrochemical gas sensor. To implement a miniaturized sensor with a fast response time, a three electrode system with gold interdigitated electrodes was fabricated by photolithography on a porous polytetrafluoroethylene substrate that greatly enhances gas diffusion. Furthermore, based on the reversible reaction of oxygen, a new transient double potential amperometry (DPA) was explored for electrochemical analysis to decrease the measurement time and reverse reaction by-products that could cause current drift. Parameters in transient DPA including oxidation potential, oxidation period, reduction period and sample point were investigated to study their influence on the performance of the sensor. Oxygen measurement could be accomplished in 4 s, and the sensor presented a sensitivity of 0.2863 μA/[%O 2 ] and a linearity of 0.9943 when tested in air samples with different oxygen concentrations. Repeatability and long-term stability were also investigated, and the sensor was shown to exhibit good reliability. In comparison to conventional constant potential amperometry, transient DPA was shown to reduce relative standard deviation by 63.2%. With transient DPA, the sensitivity, linearity, repeatability, measurement time and current drift characteristics demonstrated by the presented gas sensor are promising for acute exposure applications.

Local Structural Investigations, Defect Formation, and Ionic Conductivity of the Lithium Ionic Conductor Li 4 P 2 S 6

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

Dietrich, Christian; Sadowski, Marcel; Sicolo, Sabrina

Glassy, glass–ceramic, and crystalline lithium thiophosphates have attracted interest in their use as solid electrolytes in all-solid-state batteries. Despite similar structural motifs, including PS 4 3–, P 2S 6 4–, and P 2S 7 4– polyhedra, these materials exhibit a wide range of possible compositions, crystal structures, and ionic conductivities. Here, we present a combined approach of Bragg diffraction, pair distribution function analysis, Raman spectroscopy, and 31P magic angle spinning nuclear magnetic resonance spectroscopy to study the underlying crystal structure of Li 4P 2S 6. In this work, we show that the material crystallizes in a planar structural arrangement asmore » a glass ceramic composite, explaining the observed relatively low ionic conductivity, depending on the fraction of glass content. Calculations based on density functional theory provide an understanding of occurring diffusion pathways and ionic conductivity of this Li + ionic conductor.« less

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

PubMed

Yamaguchi, Tsuyoshi; Yonezawa, Takuya; Koda, Shinobu

2015-07-15

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Insulated Conducting Cantilevered Nanotips and Two-Chamber Recording System for High Resolution Ion Sensing AFM

PubMed Central

Meckes, Brian; Arce, Fernando Teran; Connelly, Laura S.; Lal, Ratnesh

2014-01-01

Biological membranes contain ion channels, which are nanoscale pores allowing controlled ionic transport and mediating key biological functions underlying normal/abnormal living. Synthetic membranes with defined pores are being developed to control various processes, including filtration of pollutants, charge transport for energy storage, and separation of fluids and molecules. Although ionic transport (currents) can be measured with single channel resolution, imaging their structure and ionic currents simultaneously is difficult. Atomic force microscopy enables high resolution imaging of nanoscale structures and can be modified to measure ionic currents simultaneously. Moreover, the ionic currents can also be used to image structures. A simple method for fabricating conducting AFM cantilevers to image pore structures at high resolution is reported. Tungsten microwires with nanoscale tips are insulated except at the apex. This allows simultaneous imaging via cantilever deflections in normal AFM force feedback mode as well as measuring localized ionic currents. These novel probes measure ionic currents as small as picoampere while providing nanoscale spatial resolution surface topography and is suitable for measuring ionic currents and conductance of biological ion channels. PMID:24663394

A methodology for achieving high-speed rates for artificial conductance injection in electrically excitable biological cells.

PubMed

Butera, R J; Wilson, C G; Delnegro, C A; Smith, J C

2001-12-01

We present a novel approach to implementing the dynamic-clamp protocol (Sharp et al., 1993), commonly used in neurophysiology and cardiac electrophysiology experiments. Our approach is based on real-time extensions to the Linux operating system. Conventional PC-based approaches have typically utilized single-cycle computational rates of 10 kHz or slower. In thispaper, we demonstrate reliable cycle-to-cycle rates as fast as 50 kHz. Our system, which we call model reference current injection (MRCI); pronounced merci is also capable of episodic logging of internal state variables and interactive manipulation of model parameters. The limiting factor in achieving high speeds was not processor speed or model complexity, but cycle jitter inherent in the CPU/motherboard performance. We demonstrate these high speeds and flexibility with two examples: 1) adding action-potential ionic currents to a mammalian neuron under whole-cell patch-clamp and 2) altering a cell's intrinsic dynamics via MRCI while simultaneously coupling it via artificial synapses to an internal computational model cell. These higher rates greatly extend the applicability of this technique to the study of fast electrophysiological currents such fast a currents and fast excitatory/inhibitory synapses.

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

NASA Astrophysics Data System (ADS)

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

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

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Ionic Liquid as an Effective Additive for Rechargeable Magnesium Batteries

DOE PAGES

Pan, Baofei; Lau, Ka -Cheong; Vaughey, John T.; ...

2017-03-02

Here, the effect of the addition of an ionic liquid DEME•TFSI to an electrolyte solution of Mg(HMDS) 2-MgCl 2 in THF was studied electrochemically and spectroscopically. Reversible magnesium deposition/dissolution was achieved with the DEME•TFSI-modified electrolyte. This electrolyte shows higher ionic conductivity, and a linear relationship was observed between the ionic conductivity and the concentration of DEME•TFSI in THF solution of Mg(HMDS) 2-MgCl 2. Mg-Mo 6S 8 coin cells have also been successfully cycled using Mg(HMDS) 2-MgCl 2 electrolyte with the addition of DEME•TFSI. Raman and NMR spectroscopy suggest that DEME•TFSI facilitates magnesium deposition/dissolution by improving ionic conductivity of the electrolyte.

Ionic Conduction in Lithium Ion Battery Composite Electrode Governs Cross-sectional Reaction Distribution

PubMed Central

Orikasa, Yuki; Gogyo, Yuma; Yamashige, Hisao; Katayama, Misaki; Chen, Kezheng; Mori, Takuya; Yamamoto, Kentaro; Masese, Titus; Inada, Yasuhiro; Ohta, Toshiaki; Siroma, Zyun; Kato, Shiro; Kinoshita, Hajime; Arai, Hajime; Ogumi, Zempachi; Uchimoto, Yoshiharu

2016-01-01

Composite electrodes containing active materials, carbon and binder are widely used in lithium-ion batteries. Since the electrode reaction occurs preferentially in regions with lower resistance, reaction distribution can be happened within composite electrodes. We investigate the relationship between the reaction distribution with depth direction and electronic/ionic conductivity in composite electrodes with changing electrode porosities. Two dimensional X-ray absorption spectroscopy shows that the reaction distribution is happened in lower porosity electrodes. Our developed 6-probe method can measure electronic/ionic conductivity in composite electrodes. The ionic conductivity is decreased for lower porosity electrodes, which governs the reaction distribution of composite electrodes and their performances. PMID:27193448

Scaling effects in sodium zirconium silicate phosphate (Na 1+ xZr 2Si xP 3- xO 12) ion-conducting thin films

DOE PAGES

Ihlefeld, Jon F.; Gurniak, Emily; Jones, Brad H.; ...

2016-05-04

Preparation of sodium zirconium silicate phosphate (NaSICon), Na 1+xZr 2Si xP 3–xO 12 (0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 × 10 –5 S/cm. In conclusion, themore » decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.« less

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.

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.

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

Transport Properties Of PbI2 Doped Silver Oxysalt Based Amorphous Solid Electrolytes

NASA Astrophysics Data System (ADS)

Shrisanjaykumar Jayswal, Manishkumar

Solid electrolytes are a class of materials that conduct electricity by means of motion of ions like Ag+, Na+, Li +, Cu+, H+, F-, O -2 etc. in solid phase. The host materials include crystalline, polycrystalline, glasses, polymers and composites. Ion conducting glasses are one of the most sought after solid electrolytes that are useful in various electrochemical applications like solid state batteries, gas sensors, supercapacitors, electrochromic devices, to name a few. Since the discovery of fast silver ion transport in silver oxyhalide glasses at the end of the 1960s, many glasses showing large ionic conductivity up to 10-4 10-2 S/cm at room temperature have been developed, chiefly silver and copper ion conductors. The silver ion conducting glasses owe their high ionic conductivity mainly to stabilized alpha-AgI. AgI, as we know, undergoes a structural phase transition from wurtzite (beta phase) at room temperature to body centered cubic (alpha phase) structure at temperatures higher than 146 °C. The alpha-AgI possesses approximately six order of higher ionic conductivity than beta-AgI. The high ionic conductivity of alpha-AgI is attributed to its molten sublattice type of structure, which facilitates easy Ag+ ion migration, like a liquid. And hence, several attempts have been made to stabilize it at room temperature in crystalline as well as non-crystalline hosts like oxide and non-oxide glasses. Recently, in order to stabilize AgI in glasses, instead of directly doping it, indirect routes have also been explored. Where, a metal iodide salt along with silver oxide or silver phosphate is taken and an exchange reaction permitted by Hard and Soft, Acid and Base (HSAB) principle occurs between the two and AgI and metal oxide form in the glass forming melt. Work done in the present thesis has been organized in seven chapters as follows: Chapter 1: A review and background information of different solid electrolyte materials and their development is presented. Along with that a detailed review on fast ion conducting glasses is included. At the end of the chapter, the aim of the present work has been given. Chapter 2: A discussion about various theoretical models to explain fast ion conduction mechanism in superionic conductors in general and superionic conducting glasses in particular is given. In addition to that, impedance spectroscopy and its various formalisms are discussed. Chapter 3: This chapter describes the method of preparation of the glass samples and various characterizations and techniques to study their various properties. Chapter 4: Physical properties of the prepared glass samples are studied and discussed in this chapter. The glass samples are found to be fully amorphous as exhibited by x-ray diffraction studies. The density of the prepared samples is increasing consistently with increasing PbI 2 content in the glass. For glass series (a), the molar volume also increases with PbI2 content. However, for glass series (b) and (c), molar volume is reducing with increasing PbI2 content, showing that glass is getting compacted with increasing PbI2 content. Chapter 5: Transport properties of the prepared glass samples have been investigated using impedance spectroscopy and its various formalisms. The chapter discusses DC conductivity, AC conductivity, dielectric permittivity and modulus analysis of the obtained impedance spectra. The sigma' spectra were scaled using Summerfield scaling law using sigmaDCT as the scaling factor for frequency axis and a well defined Time-Temperature Superposition (TTS) is observed as a function of temperature. The dielectric spectra show the presence of a dielectric relaxation in all glass samples. The dielectric permittivity, epsilon', spectra were scaled using the scaling law given by Sidebottom. The modulus spectra exhibit non-Debye relaxation of Ag+ ions and could be explained using KWW (Kohlrausch-Williams-Watts) decay function. Scaling analysis of the modulus spectra as a function of temperature suggest of invariance of ion relaxation process with changing temperatures. Chapter 6: Solid state battery studies: This chapter discusses about "solid state batteries" prepared by using the best conducting glass composition, from each glass Battery discharge characteristics, polarization measurements and other battery parameters like battery capacity, power density, energy, specific power etc. have been evaluated and summarized. Chapter 7: A summary of the work done and future prospects are discussed. (Abstract shortened by ProQuest.).

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.

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.

The second evolution of ionic liquids: from solvents and separations to advanced materials--energetic examples from the ionic liquid cookbook.

PubMed

Smiglak, Marcin; Metlen, Andreas; Rogers, Robin D

2007-11-01

In this Account of the small portion of the recent research in ionic liquids (ILs) by the Rogers Group, we fast forward through the first evolution of IL research, where ILs were studied for their unique set of physical properties and the resulting potential for tunable "green solvents", to the second evolution of ILs, where the tunability of the cation and anion independently offers almost unlimited access to targeted combinations of physical and chemical properties. This approach is demonstrated here with the field of energetic ionic liquids (EILs), which utilizes this design flexibility to find safe synthetic routes to ILs with high energy content and targeted physical properties.

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition.

PubMed

Shiotani, Shinya; Ohara, Koji; Tsukasaki, Hirofumi; Mori, Shigeo; Kanno, Ryoji

2017-08-01

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

Lightweight, Room-Temperature CO2 Gas Sensor Based on Rare-Earth Metal-Free Composites-An Impedance Study.

PubMed

Willa, Christoph; Schmid, Alexander; Briand, Danick; Yuan, Jiayin; Koziej, Dorota

2017-08-02

We report a light, flexible, and low-power poly(ionic liquid)/alumina composite CO 2 sensor. We monitor the direct-current resistance changes as a function of CO 2 concentration and relative humidity and demonstrate fast and reversible sensing kinetics. Moreover, on the basis of the alternating-current impedance measurements we propose a sensing mechanism related to proton conduction and gas diffusion. The findings presented herein will promote the development of organic/inorganic composite CO 2 gas sensors. In the future, such sensors will be useful for numerous practical applications ranging from indoor air quality control to the monitoring of manufacturing processes.

Anisotropic amplification of proton transport in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2017-07-01

Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Ion-mediated enhancement of xylem hydraulic conductivity in four Acer species: relationships with ecological and anatomical features.

PubMed

Nardini, Andrea; Dimasi, Federica; Klepsch, Matthias; Jansen, Steven

2012-12-01

The 'ionic effect', i.e., changes in xylem hydraulic conductivity (k(xyl)) due to variation of the ionic sap composition in vessels, was studied in four Acer species growing in contrasting environments differing in water availability. Hydraulic measurements of the ionic effect were performed together with measurements on the sap electrical conductivity, leaf water potential and vessel anatomy. The low ionic effect recorded in Acer pseudoplatanus L. and Acer campestre L. (15.8 and 14.7%, respectively), which represented two species from shady and humid habitats, was associated with a low vessel grouping index, high sap electrical conductivity and least negative leaf water potential. Opposite traits were found for Acer monspessulanum L. and Acer platanoides L., which showed an ionic effect of 23.6 and 23.1%, respectively, and represent species adapted to higher irradiance and/or lower water availability. These findings from closely related species provide additional support that the ionic effect could function as a compensation mechanism for embolism-induced loss of k(xyl), either as a result of high evaporative demand or increased risk of hydraulic failure.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

NASA Astrophysics Data System (ADS)

Sutto, Thomas E.; De Long, Hugh C.; Trulove, Paul C.

2002-11-01

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Communication: Dimensionality of the ionic conduction pathways in glass and the mixed-alkali effect.

PubMed

Novy, Melissa; Avila-Paredes, Hugo; Kim, Sangtae; Sen, Sabyasachi

2015-12-28

A revised empirical relationship between the power law exponent of ac conductivity dispersion and the dimensionality of the ionic conduction pathway is established on the basis of electrical impedance spectroscopic (EIS) measurements on crystalline ionic conductors. These results imply that the "universal" ac conductivity dispersion observed in glassy solids is associated with ionic transport along fractal pathways. EIS measurements on single-alkali glasses indicate that the dimensionality of this pathway D is ∼2.5, while in mixed-alkali glasses, D is lower and goes through a minimum value of ∼2.2 when the concentrations of the two alkalis become equal. D and σ display similar variation with alkali composition, thus suggesting a topological origin of the mixed-alkali effect.

AC conductivity scaling behavior in grain and grain boundary response regime of fast lithium ionic conductors

NASA Astrophysics Data System (ADS)

Mariappan, C. R.

2014-05-01

AC conductivity spectra of Li-analogues NASICON-type Li1.5Al0.5Ge1.5P3O12 (LAGP), Li-Al-Ti-P-O (LATP) glass-ceramics and garnet-type Li7La2Ta2O13 (LLTO) ceramic are analyzed by universal power law and Summerfield scaling approaches. The activation energies and pre-exponential factors of total and grain conductivities are following the Meyer-Neldel (M-N) rule for NASICON-type materials. However, the garnet-type LLTO material deviates from the M-N rule line of NASICON-type materials. The frequency- and temperature-dependent conductivity spectra of LAGP and LLTO are superimposed by Summerfield scaling. The scaled conductivity curves of LATP are not superimposed at the grain boundary response region. The superimposed conductivity curves are observed at cross-over frequencies of grain boundary response region for LATP by incorporating the exp ( {{{ - (EAt - EAg )} {{{ - (EAt - EAg )} {kT}}} ) factor along with Summerfield scaling factors on the frequency axis, where EAt and EAg are the activation energies of total and grain conductivities, respectively.

Biredox ionic liquids with solid-like redox density in the liquid state for high-energy supercapacitors.

PubMed

Mourad, Eléonore; Coustan, Laura; Lannelongue, Pierre; Zigah, Dodzi; Mehdi, Ahmad; Vioux, André; Freunberger, Stefan A; Favier, Frédéric; Fontaine, Olivier

2017-04-01

Kinetics of electrochemical reactions are several orders of magnitude slower in solids than in liquids as a result of the much lower ion diffusivity. Yet, the solid state maximizes the density of redox species, which is at least two orders of magnitude lower in liquids because of solubility limitations. With regard to electrochemical energy storage devices, this leads to high-energy batteries with limited power and high-power supercapacitors with a well-known energy deficiency. For such devices the ideal system should endow the liquid state with a density of redox species close to the solid state. Here we report an approach based on biredox ionic liquids to achieve bulk-like redox density at liquid-like fast kinetics. The cation and anion of these biredox ionic liquids bear moieties that undergo very fast reversible redox reactions. As a first demonstration of their potential for high-capacity/high-rate charge storage, we used them in redox supercapacitors. These ionic liquids are able to decouple charge storage from an ion-accessible electrode surface, by storing significant charge in the pores of the electrodes, to minimize self-discharge and leakage current as a result of retaining the redox species in the pores, and to raise working voltage due to their wide electrochemical window.

Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors.

PubMed

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-04-10

Mixed ionic-electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2-δ-CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2-δ-Ce0.8Gd0.2O2-δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic-electronic conductor composites through processing induced modifications of the grain boundary defect distribution.

Influence of Electrical and Ionic Conductivities of Organic Electronic Ion Pump on Acetylcholine Exchange Performance

PubMed Central

Abdullayeva, Nazrin; Sankir, Mehmet

2017-01-01

By using an easy and effective method of depositing conjugated polymers (PEDOT:PSS) on flexible substrates, a new design for organic bioelectronic devices has been developed. The purpose was to build up a system that mimics the motion of neurotransmitters in the synaptic cleft by obtaining an electrical to chemical signal transport. Fourier transform infrared (FTIR) spectroscopy and Raman measurements have demonstrated that electrochemical overoxidation region which separates the pristine PEDOT:PSS electrodes and allows ionic conduction has been achieved successfully. The influence of both electrical and ionic conductivities on organic electronic ion pump (OEIP) performances has been studied. The ultimate goal was to achieve the highest equilibrium current density at the lowest applied voltage via enhancing the electrical conductivity of PEDOT:PSS and ionic conductivity of electrochemically overoxidized region. The highest equilibrium current density, which corresponds to 4.81 × 1017 number of ions of acetylcholine was about 41 μA cm−2 observed for the OEIP with the electrical conductivities of 54 S cm−1. This was a threshold electrical conductivity beyond which the OEIP performances were not changed much. Once Nafion™ has been applied for enhancing the ionic conductivity, the equilibrium current density increased about ten times and reached up to 408 μA cm−2. Therefore, it has been demonstrated that the OEIP performance mainly scales with the ionic conductivity. A straightforward method of producing organic bioelectronics is proposed here may provide a clue for their effortless mass production in the near future. PMID:28772946

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

Pressure and temperature dependences of the ionic conductivities of the thallous halidesTlCl, TlBr, and TlI

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

Samara, G.A.

1981-01-15

Detailed studies of the pressure and temperature dependences of the ionic conductivities of TlCl and TlBr have allowed determination of the lattice volume relaxations and energies associated with the formation and motion of Schottky defects in these crystals. The volume relaxations deduced from the conductivity are found to be comparable in magnitude with values calculated from the strain energy model and a dynamical model. The association energy of Tl/sup +/ vacancies and divalent impurities was also determined for TlBr. A particularly important result is the finding that for these CsCl-type crystals the relaxation of the lattice associated with vacancy formationmore » is outward. Earlier studies on ionic crystals having the NaCl structure have yielded a similar result. This outward relaxation thus appears to be a general result for ionic crystals of both the NaCl and CsCl types (and possibly other ionic lattice types), in disagreement with earlier theoretical calculations which show that the relaxation should be inward for all models of ionic vacancies investigated. The conductivity of TlI was studied in both the (low temperature and pressure) orthorhombic phase as well as in the cubic CsCl-type phase. There is a large electronic contribution to the conductivity in the orthorhombic phase. An interesting result for all three materials is the observation in the cubic phase of a pressure-induced transition from ionic to electronic conduction. This is in qualitative agreement with what is known about the pressure dependences of the electronic structure of these materials.« less

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.

Effect of Structure on Transport Properties (Viscosity, Ionic Conductivity, and Self-Diffusion Coefficient) of Aprotic Heterocyclic Anion (AHA) Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in the Phosphonium Cation.

PubMed

Sun, Liyuan; Morales-Collazo, Oscar; Xia, Han; Brennecke, Joan F

2016-06-30

A series of room-temperature ionic liquids (ILs) composed of triethyl(alkyl)phosphonium cations paired with three different aprotic heterocyclic anions (AHAs) (alkyl = butyl ([P2224](+)) and octyl ([P2228](+))) were prepared to investigate the effect of cationic alkyl chain length on transport properties. The transport properties and density of these ILs were measured from 283.15 to 343.15 K at ambient pressure. The dependence of the transport properties (viscosity, ionic conductivity, diffusivity, and molar conductivity) on temperature can be described by the Vogel-Fulcher-Tamman (VFT) equation. The ratio of the molar conductivity obtained from the molar concentration and ionic conductivity measurements to that calculated from self-diffusion coefficients (measured by pulsed gradient spin-echo nuclear magnetic resonance spectroscopy) using the Nernst-Einstein equation was used to quantify the ionicity of these ILs. The molar conductivity ratio decreases with increasing number of carbon atoms in the alkyl chain, indicating that the reduced Coulombic interactions resulting from lower density are more than balanced by the increased van der Waals interactions between the alkyl chains. The results of this study may provide insight into the design of ILs with enhanced dynamics that may be suitable as electrolytes in lithium ion batteries and other electrochemical applications.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

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.

Solid state ionics: a Japan perspective

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu

2017-12-01

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term 'solid state ionics' was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1-xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm-1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm-1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology.

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

PubMed

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

Enhancement in ionic conductivity on solid polymer electrolytes containing large conducting species

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

Praveen, D.; Damle, Ramakrishna

2016-05-23

Solid Polymer Electrolytes (SPEs) lack better conducting properties at ambient temperatures. Various methods to enhance their ionic conductivity like irradiation with swift heavy ions, γ-rays, swift electrons and quenching at low temperature etc., have been explored in the literature. Among these, one of the oldest methods is incorporation of different conducting species into the polymer matrix and/or addition of nano-sized inert particles into SPEs. Various new salts like LiBr, Mg(ClO{sub 4}){sub 2}, NH{sub 4}I etc., have already been tried in the past with some success. Also various nanoparticles like Al{sub 2}O{sub 3}, TiO{sub 2} etc., have been tried in themore » past. In this article, we have investigated an SPE containing Rubidium as a conducting species. Rubidium has a larger ionic size compared to lithium and sodium ions which have been investigated in the recent past. In the present article, we have investigated the conductivity of large sized conducting species and shown the enhancement in the ionic conductivity by addition of nano-sized inert particles.« less

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

PubMed

Shojaatalhosseini, Mansoureh; Elamin, Khalid; Swenson, Jan

2017-10-19

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

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

None

Progress is reported on fundamental research in: crystal physics, reactions at metal surfaces, spectroscopy of ionic media, structure of metals, theory of alloying, physical properties, sintering, deformation of crystalline solids, x ray diffraction, metallurgy of superconducting materials, and electron microscope studies. Long-randge applied research studies were conducted for: zirconium metallurgy, materials compatibility, solid reactions, fuel element development, mechanical properties, non-destructive testing, and high-temperature materials. Reactor development support work was carried out for: gas-cooled reactor program, molten-salt reactor, high-flux isotope reactor, space-power program, thorium-utilization program, advanced-test reactor, Army Package Power Reactor, Enrico Fermi fast-breeder reactor, and water desalination program. Other programmore » activities, for which research was conducted, included: thermonuclear project, transuraniunn program, and post-irradiation examination laboratory. Separate abstracts were prepared for 30 sections of the report. (B.O.G.)« less

Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

NASA Astrophysics Data System (ADS)

Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

2015-07-01

Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

Insight into fast ion migration kinetics of a new hybrid single Li-ion conductor based on aluminate complexes for solid-state Li-ion batteries.

PubMed

Feng, Yancong; Tan, Rui; Zhao, Yan; Gao, Rongtan; Yang, Luyi; Yang, Jinlong; Li, Hao; Zhou, Guofu; Chen, Haibiao; Pan, Feng

2018-03-29

A novel hybrid single Li-ion conductor (SLIC) for a Li-ion solid electrolyte was prepared by mixing aluminate complexes-polyethylene glycol (LiAl-PEG) and polyethylene oxide (PEO) for solid-state Li-ion batteries. The LiAl-PEG/PEO blend possesses high thermal stability and electrochemical stability with an oxidation decomposition voltage up to 4.8 V. Notably, this hybrid SLIC exhibits not only excellent Li-ion migration kinetics, but also good ionic conductivity as high as 4.0 × 10-5 and 2.6 × 10-4 S cm-1 at 30 and 100 °C, respectively, which is much higher than previously reported SLICs. Importantly, by the combination of molecular dynamics simulations and experiment measurements, the mechanisms of Li-ion migration across the SLIC (LiAl-PEG), the salt-in-polymer (LiClO4/PEO) and the optimized SLIC (LiAl-PEG/PEO) were systematically investigated for the first time. The new hopping transport mechanism was verified for the SLIC system at the nanoscale. As for the hybrid SLIC, PEO chains enhance the segmental mobility of the ether-chains bonded with Al atoms, improve the ionicity, and provide extra ionic paths for Li transfer, resulting in the optimized Li-ion migration kinetics of LiAl-PEG/PEO.

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

Enhanced Electrochemical Performance of Fast Ionic Conductor LiTi2(PO4)3-Coated LiNi1/3Co1/3Mn1/3O2 Cathode Material.

PubMed

Zhang, Lu-Lu; Wang, Ji-Qing; Yang, Xue-Lin; Liang, Gan; Li, Tao; Yu, Peng-Lin; Ma, Di

2018-04-11

Layered LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM333) is successfully coated by fast ionic conductor LiTi 2 (PO 4 ) 3 (LTP) via a wet chemical method. The effects of LTP on the physicochemical properties and electrochemical performance are studied. The results reveal that a highly layered structure of NCM333 can be well maintained with less cation mixing after LTP coating. LTP of about 5 nm thickness is coated on the surface of NCM333. Such an LTP coating layer can effectively suppress the side reactions between NCM333 and electrolyte but will not hinder the lithium ion transmission. As a result, LTP-coated NCM333 owns an improved capability and cyclic performance, for example, NCM333/LTP delivers an initial capacity as high as 121.0 mA h g -1 with a capacity retention ratio of 82.3% after 200 cycles at 10 C, whereas NCM333 only has an initial capacity of 120.4 mA h g -1 with a very low capacity retention ratio of 66.4%. This method of using a fast ionic conductor like LTP as a coating material may provide a simple and effective strategy to modify those electrode materials with poor cyclic performance.

The effect of pH and ionic strength of dissolution media on in-vitro release of two model drugs of different solubilities from HPMC matrices.

PubMed

Asare-Addo, Kofi; Conway, Barbara R; Larhrib, Hassan; Levina, Marina; Rajabi-Siahboomi, Ali R; Tetteh, John; Boateng, Joshua; Nokhodchi, Ali

2013-11-01

The evaluation of the effects of different media ionic strengths and pH on the release of hydrochlorothiazide, a poorly soluble drug, and diltiazem hydrochloride, a cationic and soluble drug, from a gel forming hydrophilic polymeric matrix was the objective of this study. The drug to polymer ratio of formulated tablets was 4:1. Hydrochlorothiazide or diltiazem HCl extended release (ER) matrices containing hypromellose (hydroxypropyl methylcellulose (HPMC)) were evaluated in media with a pH range of 1.2-7.5, using an automated USP type III, Bio-Dis dissolution apparatus. The ionic strength of the media was varied over a range of 0-0.4M to simulate the gastrointestinal fed and fasted states and various physiological pH conditions. Sodium chloride was used for ionic regulation due to its ability to salt out polymers in the midrange of the lyotropic series. The results showed that the ionic strength had a profound effect on the drug release from the diltiazem HCl K100LV matrices. The K4M, K15M and K100M tablets however withstood the effects of media ionic strength and showed a decrease in drug release to occur with an increase in ionic strength. For example, drug release after the 1h mark for the K100M matrices in water was 36%. Drug release in pH 1.2 after 1h was 30%. An increase of the pH 1.2 ionic strength to 0.4M saw a reduction of drug release to 26%. This was the general trend for the K4M and K15M matrices as well. The similarity factor f2 was calculated using drug release in water as a reference. Despite similarity occurring for all the diltiazem HCl matrices in the pH 1.2 media (f2=64-72), increases of ionic strength at 0.2M and 0.4M brought about dissimilarity. The hydrochlorothiazide tablet matrices showed similarity at all the ionic strength tested for all polymers (f2=56-81). The values of f2 however reduced with increasing ionic strengths. DSC hydration results explained the hydrochlorothiazide release from their HPMC matrices. There was an increase in bound water as ionic strengths increased. Texture analysis was employed to determine the gel strength and also to explain the drug release for the diltiazem hydrochloride. This methodology can be used as a valuable tool for predicting potential ionic effects related to in vivo fed and fasted states on drug release from hydrophilic ER matrices. Copyright © 2013 Elsevier B.V. All rights reserved.

Fast sodium ionic conduction in Na2B10H10-Na2B12H12 pseudo-binary complex hydride and application to a bulk-type all-solid-state battery

NASA Astrophysics Data System (ADS)

Yoshida, Koji; Sato, Toyoto; Unemoto, Atsushi; Matsuo, Motoaki; Ikeshoji, Tamio; Udovic, Terrence J.; Orimo, Shin-ichi

2017-03-01

In the present work, we developed highly sodium-ion conductive Na2B10H10-Na2B12H12 pseudo-binary complex hydride via mechanically ball-milling admixtures of the pure Na2B10H10 and Na2B12H12 components. Both of these components show a monoclinic phase at room temperature, but ball-milled mixtures partially stabilized highly ion-conductive, disordered cubic phases, whose fraction and favored structural symmetry (body-centered cubic or face-centered cubic) depended on the conditions of mechanical ball-milling and molar ratio of the component compounds. First-principles molecular-dynamics simulations demonstrated that the total energy of the closo-borane mixtures and pure materials is quite close, helping to explain the observed stabilization of the mixed compounds. The ionic conductivity of the closo-borane mixtures appeared to be correlated with the fraction of the body-centered-cubic phase, exhibiting a maximum at a molar ratio of Na2B10H10:Na2B12H12 = 1:3. A conductivity as high as log(σ/S cm-1) = -3.5 was observed for the above ratio at 303 K, being approximately 2-3 orders of magnitude higher than that of either pure material. A bulk-type all-solid-state sodium-ion battery with a closo-borane-mixture electrolyte, sodium-metal negative-electrode, and TiS2 positive-electrode demonstrated a high specific capacity, close to the theoretical value of NaTiS2 formation and a stable discharge/charge cycling for at least eleven cycles, with a high discharge capacity retention ratio above 91% from the second cycle.

Dielectric study on mixtures of ionic liquids.

PubMed

Thoms, E; Sippel, P; Reuter, D; Weiß, M; Loidl, A; Krohns, S

2017-08-07

Ionic liquids are promising candidates for electrolytes in energy-storage systems. We demonstrate that mixing two ionic liquids allows to precisely tune their physical properties, like the dc conductivity. Moreover, these mixtures enable the gradual modification of the fragility parameter, which is believed to be a measure of the complexity of the energy landscape in supercooled liquids. The physical origin of this index is still under debate; therefore, mixing ionic liquids can provide further insights. From the chemical point of view, tuning ionic liquids via mixing is an easy and thus an economic way. For this study, we performed detailed investigations by broadband dielectric spectroscopy and differential scanning calorimetry on two mixing series of ionic liquids. One series combines an imidazole based with a pyridine based ionic liquid and the other two different anions in an imidazole based ionic liquid. The analysis of the glass-transition temperatures and the thorough evaluations of the measured dielectric permittivity and conductivity spectra reveal that the dynamics in mixtures of ionic liquids are well defined by the fractions of their parent compounds.

Conductivities of the ionic complexes of two cyclic polyethers

NASA Technical Reports Server (NTRS)

Fielder, W. L.; Odonnell, P. M.

1975-01-01

The conductivities of the solid potassium thiocyanate complex of both dicyclohexyl-18-crown-6 and dibenzo-18-crown-6 were measured at 300K (27 C). Saturated aqueous potassium thiocyanate and graphite were used as ion-transporting and ion-blocking electrodes, respectively. The ionic conductivity predominated for both samples, but it was many orders of magnitude smaller than the value previously reported. The ionic conductivity of the dicyclohexyl complex (the better conductor) was 0.000003 ohm/cm. Crown complexes, in general, do not appear promising as potassium ion solid electrolytes contrary to claims in the patent literature.

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.

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

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2007-10-11

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.

Role of succinonitrile in improving ionic conductivity of sodium-ion conductive polymer electrolyte

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Mohapatra, Saumya R.

2018-05-01

Sodium ion conducting solid polymer electrolytes were prepared using poly (ethylene oxide) (PEO) as polymer matrix, sodium perchlorate (NaClO4) as salt and succinonitrile (SN) as a plasticizer by solution casting technique. By blending a plastic crystal such as succinonitrile (SN) with PEO-NaClO4 electrolyte system, we aimed at improving the ionic conductivity by weakening the ether oxygen-Na+ interactions. The XRD and FTIR studies revealed structural and micro-structural changes in the blended electrolytes which aids in improving ionic conductivity. Also, DSC measurements showed improved segmental motion in the blended polymer electrolytes due to plasticizing effect of SN. The maximum ionic conductivity observed at room temperature is 1.13×10-5 S cm-1 merely for 7 wt. % of SN, which is one order higher than pure polymer-salt complex. The thermo-gravimetric analysis (TGA) suggests that blending of SN with polymer electrolyte had no detrimental effect on its thermal stability.

Properties of the Nafion membrane impregnated with hydroxyl ammonium based ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, Valeriy; Kleperis, Janis; Pavlovica, Sanita; Vaivars, Guntars

2012-08-01

In this work, the Nafion 112 membrane impregnated with nine various hydroxyl ammonium based ionic liquids have been investigated. The used ionic liquids were combined from hydroxyl ammonium cations (2-hydroxyethylammonium/HEA, bis(2- hydroxyethyl)ammonium/BHEA, tris(2-hydroxyethyl)ammonium/THEA) and carboxylate anions (formate, acetate, lactate). The membranes are characterized by conductivity and thermal stability measurements. It was found, that almost all composites have 10 times higher ion conductivity than a pure Nafion 112 at 90 °C in ambient environment due to the higher thermal stability. The thermal stability of Nafion membrane was increased by all studied nine ionic liquids. In this work, only biodegradable ionic liquids were used for composite preparation.

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects.

PubMed

Pastor, María Jesús; Cuerva, Cristián; Campo, José A; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-05-12

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOO R(n)pyH ]⁺ and BF₄ - , ReO₄ - , NO₃ - , CF₃SO₃ - , CuCl₄ 2- counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOO R(12)pyH ][ReO₄] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl₄ 2- salts exhibit the best LC properties followed by the ReO₄ - ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO₄ - , and CuCl₄ 2- families, and for the solid phase in one of the non-mesomorphic Cl - salts. The highest ionic conductivity was found for the smectic mesophase of the ReO₄ - containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure.

Flow-induced immobilization of glucose oxidase in nonionic micellar nanogels for glucose sensing.

PubMed

Cardiel, Joshua J; Zhao, Ya; Tonggu, Lige; Wang, Liguo; Chung, Jae-Hyun; Shen, Amy Q

2014-10-21

A simple microfluidic platform was utilized to immobilize glucose oxidase (GOx) in a nonionic micellar scaffold. The immobilization of GOx was verified by using a combination of cryogenic electron microscopy (cryo-EM), scanning electron microscopy (SEM), and ultraviolet spectroscopy (UV) techniques. Chronoamperometric measurements were conducted on nanogel-GOx scaffolds under different glucose concentrations, exhibiting linear amperometric responses. Without impacting the lifetime and denaturation of GOx, the nonionic nanogel provides a favorable microenvironment for GOx in biological media. This flow-induced immobilization method in a nonionic nanogel host matrix opens up new pathways for designing a simple, fast, biocompatible, and cost-effective process to immobilize biomolecules that are averse to ionic environments.

Lightweight, Room-Temperature CO2 Gas Sensor Based on Rare-Earth Metal-Free Composites—An Impedance Study

PubMed Central

2017-01-01

We report a light, flexible, and low-power poly(ionic liquid)/alumina composite CO2 sensor. We monitor the direct-current resistance changes as a function of CO2 concentration and relative humidity and demonstrate fast and reversible sensing kinetics. Moreover, on the basis of the alternating-current impedance measurements we propose a sensing mechanism related to proton conduction and gas diffusion. The findings presented herein will promote the development of organic/inorganic composite CO2 gas sensors. In the future, such sensors will be useful for numerous practical applications ranging from indoor air quality control to the monitoring of manufacturing processes. PMID:28726384

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Dutta, Rituraj; Kumar, Ashok

2016-10-01

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

Electronic functions of solid-to-liquid interfaces of organic semiconductor crystals and ionic liquid

NASA Astrophysics Data System (ADS)

Takeya, J.

2008-10-01

The environment of surface electrons at 'solid-to-liquid' interfaces is somewhat extreme, subjected to intense local electric fields or harsh chemical pressures that high-density ionic charge or polarization of mobile molecules create. In this proceedings, we argue functions of electronic carriers generated at the surface of organic semiconductor crystals in response to the local electric fields in the very vicinity of the interface to ionic liquid. The ionic liquids (ILs), or room temperature molten salts, are gaining considerable interest in the recent decade at the prospect of nonvolatile 'green solvents', with the development of chemically stable and nontoxic compounds. Moreover, such materials are also applied to electrolytes for lithium ion batteries and electric double-layer (EDL) capacitors. Our present solid-to-liquid interfaces of rubrene single crystals and ionic liquids work as fast-switching organic field-effect transistors (OFETs) with the highest transconductance, i.e. the most efficient response of the output current to the input voltage, among the OFETs ever built.

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

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.

Effect of nanochitosan and succinonitrile on the AC ionic conductivity of plasticized nanocomposite solid polymer electrolytes (PNCSPE)

NASA Astrophysics Data System (ADS)

Karuppasamy, K.; Vani, C. Vijil; Nichelson, A.; Balakumar, S.; Shajan, X. Sahaya

2013-06-01

In the present study, the filler chitosan was converted into nanochitosan by ionotropic gelation method. Plasticized nanocomposite solid polymer electrolytes (PNCSPE) composed of poly ethylene oxide as host polymer, LiBOB (lithium bis(oxalatoborate)) as salt, SN as plasticizer and nanochitosan as filler were prepared by membrane hot-press technique. Succinonitrile and nanochitosan incorporation in PEO-LiBOB matrix enhanced the room temperature ionic conductivity. The highest ionic conductivities were found to be in the order of 10-3.2 S/cm.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C.A.; Xu, K.; Liu, C.

1996-01-16

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

Lithium ion conducting ionic electrolytes

DOEpatents

Angell, C. Austen; Xu, Kang; Liu, Changle

1996-01-01

A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

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

PubMed

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

2017-07-01

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

NMR Studies of Mass Transport in New Conducting Media for Fuel Cells

DTIC Science & Technology

2009-01-01

PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the short range by spin-lattice...structural environments of muticomponent PEM films, for example those containing phosphoric acid and ionic liquids . Dynamical processes are probed at the...correlation between water diffusivity and proton conductivity in the nanocomposites Transport properties of several ionic liquids (IL’s) and membranes

Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

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

Fan, Fei; Wang, Yangyang; Hong, Tao

2015-07-17

Polymerized ionic liquids (PolyILs) are promising candidates for energy storage and electrochemical devices applications. Understanding their ionic transport mechanism is the key for designing highly conductive PolyILs. By using broadband dielectric spectroscopy (BDS), rheology, and differential scanning calorimetry (DSC), a systematic study has been carried out to provide a better understanding of the ionic transport mechanism in PolyILs with different pendant groups. The variation of pendant groups results in different dielectric, mechanical, and thermal properties of these PolyILs. The Walden plot analysis shows that the data points for all these PolyILs fall above the ideal Walden line, and the deviationmore » from the ideal line increases upon approaching the glass transition temperature (T g). Moreover, the conductivity for these PolyILs at their Tgs are much higher than the usually reported value 10 15 S/cm for polymer electrolytes, in which the ionic transport is closely coupled to the segmental dynamics. These results indicate a decoupling of ionic conductivity from the segmental relaxation in these materials. The degree of decoupling increases with the increase of the fragility of polymer segmental relaxation. Finally, we relate this observation to a decrease in polymer packing efficiency with an increase in fragility.« less

Penning ionization electron spectroscopy of CO 2 clusters in collision with metastable rare gas atoms

NASA Astrophysics Data System (ADS)

Maruyama, Ryo; Tanaka, Hideyasu; Yamakita, Yoshihiro; Misaizu, Fuminori; Ohno, Koichi

2000-09-01

Penning ionization electron spectra (PIES) of CO 2 clusters have been observed for the first time. An unusually fast electron band with excess kinetic energies of 1.4-2.9 eV with respect to the monomer band for the ionic X state was observed for CO 2 clusters in collision with He*(2 3S) atoms. While for PIES with Ne*(3 3P), no such unusual band was observed. The unusual band is ascribed to autoionization into stable structures of ionic clusters to which direct ionization processes are almost impossible due to very small Franck-Condon overlaps associated with a very large geometry difference between the ionic and neutral clusters.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

DOE PAGES

Seol, Daehee; Seo, Hosung; Jesse, Stephen; ...

2015-08-19

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Jesse, Stephen

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. Finally, these results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

Nanoscale mapping of electromechanical response in ionic conductive ceramics with piezoelectric inclusions

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

Seol, Daehee; Seo, Hosung; Kim, Yunseok, E-mail: yunseokkim@skku.edu

Electromechanical (EM) response in ion conductive ceramics with piezoelectric inclusions was spatially explored using strain-based atomic force microscopy. Since the sample is composed of two dominant phases of ionic and piezoelectric phases, it allows us to explore two different EM responses of electrically induced ionic response and piezoresponse over the same surface. Furthermore, EM response of the ionic phase, i.e., electrochemical strain, was quantitatively investigated from the comparison with that of the piezoelectric phase, i.e., piezoresponse. These results could provide additional information on the EM properties, including the electrochemical strain at nanoscale.

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.

Electrochemistry of poly(3,4-ethylenedioxythiophene)-polyaniline/ Prussian blue electrochromic devices containing an ionic liquid based gel electrolyte film.

PubMed

Deepa, Melepurath; Awadhia, Arvind; Bhandari, Shweta

2009-07-21

Electrochromic devices based on poly(3,4-ethylenedioxythiophene) (PEDOT) as the cathodic coloring electrode and polyaniline (PANI) or Prussian blue (PB) as the counter electrode containing a highly conductive, self-supporting, distensible and transparent polymer-gel electrolyte film encapsulating an ionic liquid, 1-butyl-1-methylpyrrolidiniumbis-(trifluoromethylsulfonyl)imide, have been fabricated. Polarization, charge transfer and diffusion processes control the electrochemistry of the functional electrodes during coloration and bleaching and these phenomena differ when PEDOT and PANI/PB were employed alternately as working electrodes. While the electrochemical impedance response shows good similitude for PEDOT and PANI electrodes, the responses of PEDOT and PB were significantly different in the PEDOT-PB device, especially during reduction of PB, wherein the overall amplitude of the impedance response is enormous. Large values of the coloration efficiency maxima of 281 cm2 C(-1) (lambda = 583 nm) and 274 cm2 C(-1) (lambda = 602 nm), achieved at -1.0 and -1.5 V for the PEDOT PANI and PEDOT-PB devices have been correlated to the particularly low magnitude of charge transfer resistance and high polarization capacitance operative at the PEDOT ionic liquid based electrolyte interface at these dc potentials, thus allowing facile ion-transport and consequently resulting in enhanced absorption modulation. Moderately fast switching kinetics and the ability of these devices to sustain about 2500 cycles of clear-to-dark and dark-to-clear without incurring major losses in the optical contrast, along with the ease of construction of these cells in terms of high scalability and reproducibility of the synthetic procedure for fabrication of the electrochromic films and the ionic liquid based gel electrolyte film, are indicators of the promise these devices hold for practical applications like electrochromic windows and displays.

Effect of alcaline cations in zeolites on their dielectric properties.

PubMed

Legras, Benoît; Polaert, Isabelle; Estel, Lionel; Thomas, Michel

2012-01-01

The effect on dielectric properties of alkaline cations Li+, Na+ and K+ incorporated in a zeolite Faujasite structure X or Y, has been investigated. Two major phenomena have been proved to occur: ionic conductivity and rotational polarization of the water molecules adsorbed. The polarizability of the cation which is directly linked to its radius, affects ionic conductivity as well as rotational polarization. Li cations are more strongly Linked to the framework than K+ and Na+ and induce a lower ionic conductivity. K+ is weakly fixed and induces a ionic conductivity even at low solvation level. At low water content, the cation nature and number mainly control the free rotation of the water molecules and affect the relaxation frequency. Close to saturation, the water molecules are mainly linked together by H bonds: the cation nature and number do not really affect the global dielectric properties anymore.

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.

Is Geometric Frustration-Induced Disorder a Recipe for High Ionic Conductivity?

PubMed

Düvel, Andre; Heitjans, Paul; Fedorov, Pavel; Scholz, Gudrun; Cibin, Giannantonio; Chadwick, Alan V; Pickup, David M; Ramos, Silvia; Sayle, Lewis W L; Sayle, Emma K L; Sayle, Thi X T; Sayle, Dean C

2017-04-26

Ionic conductivity is ubiquitous to many industrially important applications such as fuel cells, batteries, sensors, and catalysis. Tunable conductivity in these systems is therefore key to their commercial viability. Here, we show that geometric frustration can be exploited as a vehicle for conductivity tuning. In particular, we imposed geometric frustration upon a prototypical system, CaF 2 , by ball milling it with BaF 2 , to create nanostructured Ba 1-x Ca x F 2 solid solutions and increased its ionic conductivity by over 5 orders of magnitude. By mirroring each experiment with MD simulation, including "simulating synthesis", we reveal that geometric frustration confers, on a system at ambient temperature, structural and dynamical attributes that are typically associated with heating a material above its superionic transition temperature. These include structural disorder, excess volume, pseudovacancy arrays, and collective transport mechanisms; we show that the excess volume correlates with ionic conductivity for the Ba 1-x Ca x F 2 system. We also present evidence that geometric frustration-induced conductivity is a general phenomenon, which may help explain the high ionic conductivity in doped fluorite-structured oxides such as ceria and zirconia, with application for solid oxide fuel cells. A review on geometric frustration [ Nature 2015 , 521 , 303 ] remarks that classical crystallography is inadequate to describe systems with correlated disorder, but that correlated disorder has clear crystallographic signatures. Here, we identify two possible crystallographic signatures of geometric frustration: excess volume and correlated "snake-like" ionic transport; the latter infers correlated disorder. In particular, as one ion in the chain moves, all the other (correlated) ions in the chain move simultaneously. Critically, our simulations reveal snake-like chains, over 40 Å in length, which indicates long-range correlation in our disordered systems. Similarly, collective transport in glassy materials is well documented [for example, J. Chem. Phys. 2013 , 138 , 12A538 ]. Possible crystallographic nomenclatures, to be used to describe long-range order in disordered systems, may include, for example, the shape, length, and branching of the "snake" arrays. Such characterizations may ultimately provide insight and differences between long-range order in disordered, amorphous, or liquid states and processes such as ionic conductivity, melting, and crystallization.

Electrolyte with Low Polysulfide Solubility for Li-S Batteries

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

Sun, Ke; Wu, Qin; Tong, Xiao

Here, Li-S battery is one of the most promising next generation rechargeable battery technologies due to its high theoretical energy density and low material cost. While its success is impeded by the low energy efficiency and fast capacity fade primarily caused by the discharge intermediates, Li-polysulfides (PS), dissolution in the electrolyte. Mitigation of PS dissolution in electrolyte involves the search of new electrolyte solvent system that exhibits poor solvation to the PS while still have good solvation ability to the electrolyte salt for high ionic conductivity. Applying co-solvents with reduced solvating power but compatible with the state of art Li-Smore » battery’s ether-based electrolyte is one of the most promising concepts. This route is also advantageous of having a low scale-up cost. With the aids of Quantum Chemical Calculation, we have identified high carbon-to-oxygen (C/O) ratio ethers as co-solvent in the new electrolytes that effectively impede PS dissolution while still maintaining high ionic conductivity. Significantly improved cycle life and cycling Coulombic efficiency are observed for Li-S cells using the new composite electrolytes. Anode analysis with different methods also demonstrate that reducing electrolyte’s PS solubility results in less sulfur total amount on the lithium anode surface and lower ratio of the longer-chain PS, which is probably a sign of suppressed side reactions between the anode and PS in the electrolyte.« less

Electrolyte with Low Polysulfide Solubility for Li-S Batteries

DOE PAGES

Sun, Ke; Wu, Qin; Tong, Xiao; ...

2018-05-23

Here, Li-S battery is one of the most promising next generation rechargeable battery technologies due to its high theoretical energy density and low material cost. While its success is impeded by the low energy efficiency and fast capacity fade primarily caused by the discharge intermediates, Li-polysulfides (PS), dissolution in the electrolyte. Mitigation of PS dissolution in electrolyte involves the search of new electrolyte solvent system that exhibits poor solvation to the PS while still have good solvation ability to the electrolyte salt for high ionic conductivity. Applying co-solvents with reduced solvating power but compatible with the state of art Li-Smore » battery’s ether-based electrolyte is one of the most promising concepts. This route is also advantageous of having a low scale-up cost. With the aids of Quantum Chemical Calculation, we have identified high carbon-to-oxygen (C/O) ratio ethers as co-solvent in the new electrolytes that effectively impede PS dissolution while still maintaining high ionic conductivity. Significantly improved cycle life and cycling Coulombic efficiency are observed for Li-S cells using the new composite electrolytes. Anode analysis with different methods also demonstrate that reducing electrolyte’s PS solubility results in less sulfur total amount on the lithium anode surface and lower ratio of the longer-chain PS, which is probably a sign of suppressed side reactions between the anode and PS in the electrolyte.« less

Understanding the impact of nanoscale aggregation on charge transport and structural dynamics in room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Griffin, Philip; Holt, Adam; Wang, Yangyang; Sokolov, Alexei

2015-03-01

Amphiphilic room temperature ionic liquids (ILs) segregate on the nanoscale, forming intricate networks of charge-rich ionic domains intercalated with charge-poor aliphatic domains. While this structural phenomenon has been well established through x-ray diffraction studies and atomistic MD simulations, the precise effects of nanophase segregation on ion transport and structural dynamics in ILs remains poorly understood. Using a combination of broadband dielectric spectroscopy, light scattering spectroscopy, and rheology, we have characterized the ionic conductivity, structural dynamics, and shear viscosity of a homologous series of quaternary ammonium ionic liquids over a wide temperature range. Upon increasing the length and volume fraction of the alkyl side chains of these quaternary ammonium ILs, ionic conductivity decreases precipitously, although no corresponding slowing of the structural dynamics is observed. Instead, we identify the dynamical signature of supramolecular aggregates. Our results directly demonstrate the role that chemical structure and ionic aggregation plays in determining the charge transport properties of amphiphilic ILs.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

Ionic liquids and their solid-state analogues as materials for energy generation and storage

NASA Astrophysics Data System (ADS)

Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

2016-02-01

Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

Use of Monte Carlo simulation for the interpretation and analysis of diffuse scattering

NASA Astrophysics Data System (ADS)

Welberry, T. R.; Chan, E. J.; Goossens, D. J.; Heerdegen, A. P.

2010-02-01

With the development of computer simulation methods there is, for the first time, the possibility of having a single general method that can be used for any diffuse scattering problem in any type of system. As computers get ever faster it is expected that current methods will become increasingly powerful and applicable to a wider and wider range of problems and materials and provide results in increasingly fine detail. In this article we discuss two contrasting recent examples. The first is concerned with the two polymorphic forms of the pharmaceutical compound benzocaine. The strong and highly structured diffuse scattering in these is shown to be symptomatic of the presence of highly correlated molecular motions. The second concerns Ag+ fast ion conduction in the pearceite/polybasite family of mineral solid electrolytes. Here Monte-Carlo simulation is used to model the diffuse scattering and gain insight into how the ionic conduction arises.

Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles.

PubMed

Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

2017-05-12

Through first-principles calculations and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS_{2}O_{2} are found in different temperature ranges. Phonon and molecular dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calculations. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic conductivity and a wide electrochemical window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.

Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles

NASA Astrophysics Data System (ADS)

Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

2017-05-01

Through first-principles calculations and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS2O2 are found in different temperature ranges. Phonon and molecular dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calculations. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic conductivity and a wide electrochemical window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.

Computer aided design of nano-structured materials with tailored ionic conductivities.

PubMed

Sayle, Dean C; Doig, James A; Parker, Stephen C; Watson, Graeme W; Sayle, Thi X T

2005-01-07

We show, using simulation techniques, that the high ionic conductivity in BaF2/CaF2 heterolayers is because the interfaces reduce the activation energy barriers to mobility and increase the number of charge carriers.

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.

Direct current dielectrophoretic manipulation of the ionic liquid droplets in water.

PubMed

Zhao, Kai; Li, Dongqing

2018-07-13

The ionic liquids (ILs) as the environmentally benign solvents show great potentials in microemulsion carrier systems and have been widely used in the biochemical and pharmaceutical fields. In the work, the ionic liquid-in-water microemulsions were fabricated by using two kinds of hydrophobic ionic liquid, 1-Butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF 6 ] and 1-Hexyl-3-methylimidazolium hexafluorophosphate [Hmim][PF 6 ] with Tween 20. The ionic liquid droplets in water experience the dielectrophoretic (DEP) forces induced by applying electrical field via a nano-orifice and a micron orifice on the opposite channel walls of a microchannel. The dielectrophoretic behaviors of the ionic liquid-in-water emulsion droplets were investigated under direct current (DC) electric field. The positive and negative DEP behaviors of the ionic liquid-in-water droplets varying with the electrical conductivity of the suspending medium were investigated and two kinds of the ionic liquid droplets of similar sizes were separated by their different DEP behaviors. In addition, the separation of the ionic liquid-in-water droplets by size was conducted. This paper, for the first time to our knowledge, presents the DC-DEP manipulation of the ionic liquid-in-water emulsion droplets by size and by type. This method provides a platform to manipulate the ionic liquid droplets individually. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrical screening procedure for solid ionic conductors

NASA Technical Reports Server (NTRS)

Kautz, H. E.; Singer, J.; Fielder, W. L.; Fordyce, J. S.

1973-01-01

An electrical screening method has been developed for preliminary evaluation of polycrystalline specimens of candidates for use as solid ionic conductive electrolytes in batteries. The procedure measures dielectric loss and capacitance, from which are calculated an ac conductivity attributed provisionally to ions and an activation energy for that conductivity. Electronic conductivity is directly measured. The screening procedure applied to sodium beta-alumina yielded acceptable values for conductivity and activation energy.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko

2000-08-01

The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte

NASA Astrophysics Data System (ADS)

Kang, Joonhee; Chung, Habin; Doh, Chilhoon; Kang, Byoungwoo; Han, Byungchan

2015-10-01

Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34% of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.

Influence of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses

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

El Moudane, M., E-mail: m.elmoudane@gmail.com; El Maniani, M.; Sabbar, A.

2015-12-15

Highlights: • Results of ionic conductivities of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. • Determination of glass transition temperature using DSC method. • Study of temperature and frequency on ionic conductivity of Li{sub 3}PO{sub 4}–Pb{sub 3}(PO{sub 4}){sub 2}–BiPO{sub 4} phosphate glasses. - Abstract: Lithium–Lead–Bismuth phosphates glasses having, a composition 30Li{sub 3}PO{sub 4}–(70 − x)Pb{sub 3}(PO{sub 4}){sub 2}–xBiPO{sub 4} (45 ≤ x ≤ 60 mol%) were prepared by using the melt quenching method 1000 °C. The thermal stability of theses glasses increases with the substitution of Bi{sub 2}O{sub 3} with PbO. The ionic conductivity of all compositions havemore » been measured over a wide temperature (200–500 °C) and frequency range (1–106 Hz). The ionic conductivity data below and above T{sub g} follows Arrhenius and Vogel–Tamman–Fulcher (VTF) relationship, respectively. The activation energies are estimated and discussed. The dependence in frequency of AC conductivity is found to obey Jonscher’s relation.« less

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids

NASA Astrophysics Data System (ADS)

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situscanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situSTM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situmicroscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM). Electronic supplementary information (ESI) available: In situ image of PEDOT in [HMIm]FAP and in situ studies of PEDOT grown in [EMIm]TFSA and redox behavior of PEDOT. See DOI: 10.1039/c0nr00579g

Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.

PubMed

Shen, Li; Wu, Hao Bin; Liu, Fang; Brosmer, Jonathan L; Shen, Gurong; Wang, Xiaofeng; Zink, Jeffrey I; Xiao, Qiangfeng; Cai, Mei; Wang, Ge; Lu, Yunfeng; Dunn, Bruce

2018-06-01

Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CO2 Responsive Imidazolium-Type Poly(Ionic Liquid) Gels.

PubMed

Zhang, Jing; Xu, Dan; Guo, Jiangna; Sun, Zhe; Qian, Wenjing; Zhang, Ye; Yan, Feng

2016-07-01

Poly(ionic liquid) (PIL) gels with CO2 stimulus responsiveness have been synthesized through the copolymerization of an imidazolium-type ionic liquid monomer with 2-(dimethyl amino) ethyl methacrylate. Upon bubbling with CO2 gas, the prepared PIL solution is converted to a transparent and stable gel, which can be turned back to the initial solution state after N2 bubbling. The reversible sol-gel phase transition behavior is proved by the reversible values of viscosity and ionic conductivity. The possible mechanism for such a reversible sol-gel phase transition is demonstrated by NMR, conductivity, and rheological measurements. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Water Dissolvable Electrolyte with an Ionic Liquid for Eco-Friendly Electronics.

PubMed

Yamada, Shunsuke; Toshiyoshi, Hiroshi

2018-06-21

A water-dissolvable electrolyte is developed by combining an ionic liquid (IL) with poly(vinyl alcohol) (PVA), which decays over time by contact with water. An IL generally consists of two species of ions (anion and cation), and forms an electrical double layer (EDL) of a large electrostatic capacitance due to the ions accumulated in the vicinity of a conductive electrode when voltage is applied. In a similar manner, the ionic gel developed in this work forms an EDL due to the ions suspended in the conjugated polymer network while maintaining the gel form. Test measurements show a large capacitance of 13 µF cm -2 within the potential window of the IL. The ionic gel shows an electrical conductance of 20 µS cm -1 due to the ionic conduction, which depends on the weight ratio of the IL with respect to the polymer. The developed ionic gel dissolves into water in 16 h. Potential application includes the electrolyte in disposable electronics such as distributed sensors and energy harvesters that are supposed to be harmless to environment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductance valve and pressure-to-conductance transducer method and apparatus

DOEpatents

Schoeniger, Joseph S.; Cummings, Eric B.; Brennan, James S.

2005-01-18

A device for interrupting or throttling undesired ionic transport through a fluid network is disclosed. The device acts as a fluid valve by reversibly generating a fixed "bubble" in the conducting solvent solution carried by the network. The device comprises a porous hydrophobic structure filling a portion of a connecting channel within the network and optionally incorporates flow restrictor elements at either end of the porous structure that function as pressure isolation barriers, and a fluid reservoir connected to the region of the channel containing the porous structure. Also included is a pressure pump connected to the fluid reservoir. The device operates by causing the pump to vary the hydraulic pressure to a quantity of solvent solution held within the reservoir and porous structure. At high pressures, most or all of the pores of the structure are filled with conducting liquid so the ionic conductance is high. At lower pressures, only a fraction of the pores are filled with liquid, so ionic conductivity is lower. Below a threshold pressure, the porous structure contains only vapor, so there is no liquid conduction path. The device therefore effectively throttles ionic transport through the porous structure and acts as a "conductance valve" or "pressure-to-conductance" transducer within the network.

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.

Ionic liquids gels: Soft materials for environmental remediation.

PubMed

Marullo, Salvatore; Rizzo, Carla; Dintcheva, Nadka T; Giannici, Francesco; D'Anna, Francesca

2018-05-01

Nanostructured sorbents and, in particular, supramolecular gels are emerging as efficient materials for the removal of toxic contaminants from water, like industrial dyes. It is also known that ionic liquids can dissolve significant amounts of dyes. Consequently, supramolecular ionic liquids gels could be highly efficient sorbents for dyes removal. This would also contribute to overcome the drawbacks associated with dye removal by liquid-liquid extraction with neat ionic liquids which would require large volumes of extractant and a more difficult separation of the phases. Herein we employed novel supramolecular ionic liquid gels based on diimidazolium salts bearing naturally occurring or biomass derived anions, to adsorb cationic and anionic dyes from wastewaters. We also carried out a detailed investigation of thermal, structural, morphological and rheological features of our gels to identify which of them are key in designing better sorbents for environmental remediation. The most effective gels showed fast and thorough removal of cationic dyes like Rhodamine B. These gels could also be reused up to 20 times without any loss in removal efficiency. Overall, our ionic gels outperform most of gel-based sorbents systems so far reported in literature. Copyright © 2018 Elsevier Inc. All rights reserved.

High Packing Density Unidirectional Arrays of Vertically Aligned Graphene with Enhanced Areal Capacitance for High-Power Micro-Supercapacitors.

PubMed

Zheng, Shuanghao; Li, Zhilin; Wu, Zhong-Shuai; Dong, Yanfeng; Zhou, Feng; Wang, Sen; Fu, Qiang; Sun, Chenglin; Guo, Liwei; Bao, Xinhe

2017-04-25

Interfacial integration of a shape-engineered electrode with a strongly bonded current collector is the key for minimizing both ionic and electronic resistance and then developing high-power supercapacitors. Herein, we demonstrated the construction of high-power micro-supercapacitors (VG-MSCs) based on high-density unidirectional arrays of vertically aligned graphene (VG) nanosheets, derived from a thermally decomposed SiC substrate. The as-grown VG arrays showed a standing basal plane orientation grown on a (0001̅) SiC substrate, tailored thickness (3.5-28 μm), high-density structurally ordering alignment of graphene consisting of 1-5 layers, vertically oriented edges, open intersheet channels, high electrical conductivity (192 S cm -1 ), and strong bonding of the VG edges to the SiC substrate. As a result, the demonstrated VG-MSCs displayed a high areal capacitance of ∼7.3 mF cm -2 and a fast frequency response with a short time constant of 9 ms. Furthermore, VG-MSCs in both an aqueous polymer gel electrolyte and nonaqueous ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate operated well at high scan rates of up to 200 V s -1 . More importantly, VG-MSCs offered a high power density of ∼15 W cm -3 in gel electrolyte and ∼61 W cm -3 in ionic liquid. Therefore, this strategy of producing high-density unidirectional VG nanosheets directly bonded on a SiC current collector demonstrated the feasibility of manufacturing high-power compact supercapacitors.

Highly Conductive Anion Exchange Block Copolymers

DTIC Science & Technology

We are developing a comprehensive fundamental understanding of the interplay between transport and morphology in newly synthesized hydroxide...conducting block copolymers. We are synthesizing hydroxide conducting block copolymers of various (1) morphology types, (2) ionic concentrations, and (3...ionic domain sizes. We are carefully characterizing the morphology and transport properties using both conventional and new advanced in situ techniques

Thickness Dependency of Thin Film Samaria Doped Ceria for Oxygen Sensing

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

Sanghavi, Rahul P.; Nandasiri, Manjula I.; Kuchibhatla, Satyanarayana V N T

High temperature oxygen sensors are widely used for exhaust gas monitoring in automobiles. This particular study explores the use of thin film single crystalline samaria doped ceria as the oxygen sensing material. Desired signal to noise ratio can be achieved in a material system with high conductivity. From previous studies it is established that 6 atomic percent samarium doping is the optimum concentration for thin film samaria doped ceria to achieve high ionic conductivity. In this study, the conductivity of the 6 atomic percent samaria doped ceria thin film is measured as a function of the sensing film thickness. Hysteresismore » and dynamic response of this sensing platform is tested for a range of oxygen pressures from 0.001 Torr to 100 Torr for temperatures above 673 K. An attempt has been made to understand the physics behind the thickness dependent conductivity behavior of this sensing platform by developing a hypothetical operating model and through COMSOL simulations. This study can be used to identify the parameters required to construct a fast, reliable and compact high temperature oxygen sensor.« less

Nanoscale Ionic Liquids

DTIC Science & Technology

2006-11-01

Technical Report 11 December 2005 - 30 November 2006 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Nanoscale Ionic Liquids 5b. GRANT NUMBER FA9550-06-1-0012...Title: Nanoscale Ionic Liquids Principal Investigator: Emmanuel P. Giannelis Address: Materials Science and Engineering, Bard Hall, Cornell University...based fluids exhibit high ionic conductivity. The NFs are typically synthesized by grafting a charged, oligomeric corona onto the nanoparticle cores

Terahertz Investigations of Extraordinarily Efficient Conduction in a Redox Active Ionic Liquid.

NASA Astrophysics Data System (ADS)

Thorsmolle, Verner; Brauer, Jan; Rothenberger, Guido; Kuang, Daibin; Zakeeruddin, Shaik; Grätzel, Michael; Moser, Jacques

2009-03-01

Iodine added to iodide-based ionic liquids leads to extraordinarily efficient charge transport, vastly exceeding expectancy for such viscous systems. Using terahertz time-domain spectroscopy, in conjunction with dc conductivity and viscosity measurements we unravel the conductivity pathways in 1-methyl-3-propylimidazolium iodide melts. Applying low temperatures, we demonstrate for the first time conduction entirely due to a Grotthus bond-exchange mechanism at iodine concentrations higher than 3.9 M. The terahertz and transport results are reconciled in a model providing a quantitative description of the conduction by physical diffusion and the Grotthus bond-exchange process. These novel results are of great importance for the fundamental understanding of conduction in molten salts and for applications where ionic liquids are used as charge-transporting media such as in batteries and dye-sensitized solar cells.

[Advances of poly (ionic liquid) materials in separation science].

PubMed

Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

2015-11-01

Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials.

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

Structural control of mixed ionic and electronic transport in conducting polymers

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

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

First-principles investigations of ionic conduction in Li and Na borohydrides

NASA Astrophysics Data System (ADS)

Varley, Joel; Heo, Tae-Wook; Ray, Keith; Bonev, Stanimir; Wood, Brandon

Recent experimental studies have identified a family of alkali borohydride materials that exhibit superionic transition temperatures approaching room temperature and ionic conductivities exceeding 0.1 S/cm-1, making them highly promising solid electrolytes for next-generation batteries. Despite the rapid advances in improving the superionic conductivity in these materials, an understanding of the exact mechanisms driving the transport remains unknown. Here we use ab initio molecular dynamics calculations to address this issue by characterizing the diffusivity of the Li and Na species in a representative set of closoborane ionic conductors. We investigate both the Na and Li-containing borohydrides with icosahedral (B12H12) and double-capped square antiprism (B10H10) anion species and discuss the trends in ionic conductivity as a function of stoichiometry and the incorporation of various dopants. Our results support the borohydrides as a subset of a larger family of very promising solid electrolytes and identify strategies to improving the conductivity in these materials. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Structural control of mixed ionic and electronic transport in conducting polymers

DOE PAGES

Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; ...

2016-04-19

Poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate), PEDOT:PSS, has been utilized for over two decades as a stable, solution-processable hole conductor. While its hole transport properties have been the subject of intense investigation, recent work has turned to PEDOT:PSS as a mixed ionic/electronic conductor in applications including bioelectronics, energy storage and management, and soft robotics. Conducting polymers can efficiently transport both holes and ions when sufficiently hydrated, however, little is known about the role of morphology on mixed conduction. Here, we show that bulk ionic and electronic mobilities are simultaneously affected by processing-induced changes in nano- and meso-scale structure in PEDOT:PSS films. Wemore » quantify domain composition, and find that domain purification on addition of dispersion co-solvents limits ion mobility, even while electronic conductivity improves. We show that an optimal morphology allows for the balanced ionic and electronic transport that is critical for prototypical mixed conductor devices. As a result, these findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.« less

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

Intercalated hybrid of kaolinite with KH2PO4 showing high ionic conductivity (∼10-4 S cm-1) at room temperature

NASA Astrophysics Data System (ADS)

Liu, Shao-Xian; Xue, Chen; Yang, Hao; Huang, Xiao-Qing; Zou, Yang; Ding, Yan-Ni; Li, Li; Ren, Xiao-Ming

2017-12-01

In this paper, we present the study of preparation and ionic conductance for an intercalated hybrid of kaolinite with potassium dihydrogen. The intercalation efficiency is high up to ca. 90%. The intercalated hybrid has been characterized by powder X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The ionic conductivity (σ) of the hybrid material is strongly dependent on the moisture in the environment, with σ = 8.4 × 10-10 S cm-1 at 293 K and gradually increases to 7.16 × 10-9 S cm-1 under N2 atmosphere (anhydrous environment) at 353 K as well as an activation energy of Ea = 0.618 e V, whereas σ = 2.19 × 10-4 S cm-1 at 100% relative humidity and 293 K with Ea = 0.44 eV. The mechanism that the moisture affects the ionic conductance of the intercalated hybrid is further discussed.

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

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.

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

Diketonylpyridinium Cations as a Support of New Ionic Liquid Crystals and Ion-Conductive Materials: Analysis of Counter-Ion Effects

PubMed Central

Pastor, María Jesús; Cuerva, Cristián; Campo, José A.; Schmidt, Rainer; Torres, María Rosario; Cano, Mercedes

2016-01-01

Ionic liquid crystals (ILCs) allow the combination of the high ionic conductivity of ionic liquids (ILs) with the supramolecular organization of liquid crystals (LCs). ILCs salts were obtained by the assembly of long-chained diketonylpyridinium cations of the type [HOOR(n)pyH]+ and BF4−, ReO4−, NO3−, CF3SO3−, CuCl42− counter-ions. We have studied the thermal behavior of five series of compounds by differential scanning calorimetry (DSC) and hot stage polarized light optical microscopy (POM). All materials show thermotropic mesomorphism as well as crystalline polymorphism. X-ray diffraction of the [HOOR(12)pyH][ReO4] crystal reveals a layered structure with alternating polar and apolar sublayers. The mesophases also exhibit a lamellar arrangement detected by variable temperature powder X-ray diffraction. The CuCl42− salts exhibit the best LC properties followed by the ReO4− ones due to low melting temperature and wide range of existence. The conductivity was probed for the mesophases in one species each from the ReO4−, and CuCl42− families, and for the solid phase in one of the non-mesomorphic Cl− salts. The highest ionic conductivity was found for the smectic mesophase of the ReO4− containing salt, whereas the solid phases of all salts were dominated by electronic contributions. The ionic conductivity may be favored by the mesophase lamellar structure. PMID:28773485

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.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

Specialist gelator for ionic liquids.

PubMed

Hanabusa, Kenji; Fukui, Hiroaki; Suzuki, Masahiro; Shirai, Hirofusa

2005-11-08

Cyclo(l-beta-3,7-dimethyloctylasparaginyl-L-phenylalanyl) (1) and cyclo(L-beta-2-ethylhexylasparaginyl-L-phenylalanyl) (2), prepared from L-asparaginyl-L-phenylalanine methyl ester, have been found to be specialist gelators for ionic liquids. They can gel a wide variety of ionic liquids, including imizazolium, pyridinium, pyrazolidinium, piperidinium, morpholinium, and ammonium salts. The mean minimum gel concentrations (MGCs) necessary to make gels at 25 degrees C were determined for ionic liquids. The gel strength increased at a rate nearly proportional to the concentration of added gelator. The strength of the transparent gel of 1-butylpyridinium tetrafluoroborate ([C(4)py]BF(4)), prepared at a concentration of 60 g L(-1) (gelator 1/[C(4)py]BF(4)), was ca. 1500 g cm(-2). FT-IR spectroscopy indicated that a driving force for gelation was intermolecular hydrogen bonding between amides and that the phase transition from gel to liquid upon heating was brought about by the collapse of hydrogen bonding. The gels formed from ionic liquids were very thermally stable; no melting occurs up to 140 degrees C when the gels were prepared at a concentration of 70 g L(-1) (gelator/ionic liquid). The ionic conductivities of the gels were nearly the same as those of pure ionic liquids. The gelator had electrochemical stability and a wide electrochemical window. When the gels were prepared from ionic liquids containing propylene carbonate, the ionic conductivities of the resulting gels increased to levels rather higher than those of pure ionic liquids. The gelators also gelled ionic liquids containing supporting electrolytes.

Continuous synthesis of peralkylated imidazoles and their transformation into ionic liquids with improved (electro)chemical stabilities.

PubMed

Maton, Cedric; De Vos, Nils; Roman, Bart I; Vanecht, Evert; Brooks, Neil R; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

2012-09-17

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one-pot modified Debus-Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non-substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid analysis of ultraviolet filters using dispersive liquid-liquid microextraction coupled to headspace gas chromatography and mass spectrometry.

PubMed

Pierson, Stephen A; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-05-29

An ionic-liquid-based in situ dispersive liquid-liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7-10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D macroporous graphene frameworks for supercapacitors with high energy and power densities.

PubMed

Choi, Bong Gill; Yang, Minho; Hong, Won Hi; Choi, Jang Wook; Huh, Yun Suk

2012-05-22

In order to develop energy storage devices with high power and energy densities, electrodes should hold well-defined pathways for efficient ionic and electronic transport. Herein, we demonstrate high-performance supercapacitors by building a three-dimensional (3D) macroporous structure that consists of chemically modified graphene (CMG). These 3D macroporous electrodes, namely, embossed-CMG (e-CMG) films, were fabricated by using polystyrene colloidal particles as a sacrificial template. Furthermore, for further capacitance boost, a thin layer of MnO(2) was additionally deposited onto e-CMG. The porous graphene structure with a large surface area facilitates fast ionic transport within the electrode while preserving decent electronic conductivity and thus endows MnO(2)/e-CMG composite electrodes with excellent electrochemical properties such as a specific capacitance of 389 F/g at 1 A/g and 97.7% capacitance retention upon a current increase to 35 A/g. Moreover, when the MnO(2)/e-CMG composite electrode was asymmetrically assembled with an e-CMG electrode, the assembled full cell shows remarkable cell performance: energy density of 44 Wh/kg, power density of 25 kW/kg, and excellent cycle life.

Computational modeling of the structure and the ionic conductivity of the solid electrolyte materials Li3AsS4 and its Ge substitutions

NASA Astrophysics Data System (ADS)

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

Oak Ridge National Laboratory (G. Sahu et al.) reported that the substitution of Ge into Li3AsS4 leads to the composition Li3.334Ge0.334As0.666S4 with impressively high ionic conductivity . We use ab initio calculations to examine the structural relationships and the ionic conductivity mechanisms for pure Li3AsS4, Li3.334Ge0.334As0.666S4, and other compositions of these electrolytes. Supported by NSF Grant DMR-1105485 and 1507942 and WFU's DEAC cluster.

Temperature dependence of electrical conduction in PEMA-EMITFSI film

NASA Astrophysics Data System (ADS)

Zain, N. F.; Megat Hasnan, M. M. I.; Sabri, M. F. M.; Said, S. M.; Mohamed, N. S.; Salleh, F.

2018-04-01

Transparent and flexible film of poly (ethyl methacrylate) incorporated with 1-ethyl-3-methyl imidazolium bis(trifluorosulfonyl) imide ionic liquid (PEMA-EMITFSI) with thickness between 100 and 200 µm was fabricated by using solution casting technique. From the ionic transport measurement, it is confirmed that the electrical conduction in PEMA-EMITFSI film is mainly contributed by ionic transport. Moreover, the temperature-dependence of electrical conductivity measurement for 7 days reveals that the electrical properties of PEMA-EMITFSI film could be able to withstand a number of thermal cycles and be lasting for a period of time for potentially used as thermoelectric material through thermal heating.

Synthesis, structure, and ionic conductivity of solid solution, Li10+δM1+δP2-δS12 (M = Si, Sn).

PubMed

Hori, Satoshi; Suzuki, Kota; Hirayama, Masaaki; Kato, Yuki; Saito, Toshiya; Yonemura, Masao; Kanno, Ryoji

2014-01-01

Solid solutions of the silicon and tin analogous phases of the superionic conductor Li(10)MP(2)S(12) (M = Si, Sn) were synthesized by a conventional solid-state reaction in an evacuated silica tube at 823 K. The ranges of the solid solutions were determined to be 0.20 < δ < 0.43 and -0.25 < δ < -0.01 in Li(10+δ)M(1+δ)P(2-δ)S(12) (0.525 ≤k≤ 0.60 and 0.67 ≤k≤ 0.75 in Li(4-k)M(1-k)PkS(4)) for the Si and Sn systems, respectively. The ionic conductivity of these systems varied as a function of the changing M ions: the Si and Sn systems showed lower conductivity than the Ge system, Li(10+δ)Ge(1+δ)P(2-δ)S(12). The conductivity change for different elements might be due to the lattice size and lithium content affecting the ionic conduction. The relationship between ionic conduction, structure, and lithium concentration is discussed based on the structural and electrochemical information for the silicon, germanium, and tin systems.

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.

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

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

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

A Quaternary Sodium Superionic Conductor - Na 10.8Sn 1.9PS 11.8

DOE PAGES

Yu, Zhaoxin; Shang, Shun -Li; Gao, Yue; ...

2018-01-31

Sulfide-based Na-ion conductors are promising candidates as solid-state electrolytes (SSEs) for fabrication of solid-state Na-ion batteries (NIBs) because of their high ionic conductivities and low grain boundary resistance. Currently, most of the sulfide-based Na-ion conductors with high conductivities are focused on Na 3PS 4 phases and its derivatives. It is desirable to develop Na-ion conductors with new composition and crystal structure to achieve superior ionic conductivities. Here we report a new quaternary Na-ion conductor, Na 10.8Sn 1.9PS 11.8, exhibiting a high ionic conductivity of 0.67 mS cm –1 at 25 °C. This high ionic conductivity originates from the presence ofmore » a large number of intrinsic Na-vacancies and three-dimensional Na-ion conduction pathways, which has been confirmed by single-crystal X-ray diffraction and first-principles calculations. In conclusion, the Na 10.8Sn 1.9PS 11.8 phase is further evaluated as an electrolyte in a Na-Sn alloy/TiS 2 battery, demonstrating its potential application in all-solid-state NIBs.« less

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.

New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

DOE PAGES

Fang, Youxing; Jiang, Xueguang; Dai, Sheng; ...

2015-07-14

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10 -4 S cm -1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

High Current Ionic Diode Using Homogeneously Charged Asymmetric Nanochannel Network Membrane.

PubMed

Choi, Eunpyo; Wang, Cong; Chang, Gyu Tae; Park, Jungyul

2016-04-13

A high current ionic diode is achieved using an asymmetric nanochannel network membrane (NCNM) constructed by soft lithography and in situ self-assembly of nanoparticles with uniform surface charge. The asymmetric NCNM exhibits high rectified currents without losing a rectification ratio because of its ionic selectivity gradient and differentiated electrical conductance. Asymmetric ionic transport is analyzed with diode-like I-V curves and visualized via fluorescent dyes, which is closely correlated with ionic selectivity and ion distribution according to variation of NCNM geometries.

New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

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

Fang, Youxing; Jiang, Xueguang; Dai, Sheng

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10 -4 S cm -1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

Mg2B2O5 Nanowire Enabled Multifunctional Solid-State Electrolytes with High Ionic Conductivity, Excellent Mechanical Properties, and Flame-Retardant Performance.

PubMed

Sheng, Ouwei; Jin, Chengbin; Luo, Jianmin; Yuan, Huadong; Huang, Hui; Gan, Yongping; Zhang, Jun; Xia, Yang; Liang, Chu; Zhang, Wenkui; Tao, Xinyong

2018-05-09

High ionic conductivity, satisfactory mechanical properties, and wide electrochemical windows are crucial factors for composite electrolytes employed in solid-state lithium-ion batteries (SSLIBs). Based on these considerations, we fabricate Mg 2 B 2 O 5 nanowire enabled poly(ethylene oxide) (PEO)-based solid-state electrolytes (SSEs). Notably, these SSEs have enhanced ionic conductivity and a large electrochemical window. The elevated ionic conductivity is attributed to the improved motion of PEO chains and the increased Li migrating pathway on the interface between Mg 2 B 2 O 5 and PEO-LiTFSI. Moreover, the interaction between Mg 2 B 2 O 5 and -SO 2 - in TFSI - anions could also benefit the improvement of conductivity. In addition, the SSEs containing Mg 2 B 2 O 5 nanowires exhibit improved the mechanical properties and flame-retardant performance, which are all superior to the pristine PEO-LiTFSI electrolyte. When these multifunctional SSEs are paired with LiFePO 4 cathodes and lithium metal anodes, the SSLIBs show better rate performance and higher cyclic capacity of 150, 106, and 50 mAh g -1 under 0.2 C at 50, 40, and 30 °C. This strategy of employing Mg 2 B 2 O 5 nanowires provides the design guidelines of assembling multifunctional SSLIBs with high ionic conductivity, excellent mechanical properties, and flame-retardant performance at the same time.

Solid state ionics: a Japan perspective

PubMed Central

Yamamoto, Osamu

2017-01-01

Abstract The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term ‘solid state ionics’ was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1–xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm–1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm–1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology. PMID:28804526

Effect of SiO2 addition and gamma irradiation on the lithium borate glasses

NASA Astrophysics Data System (ADS)

Raut, A. P.; Deshpande, V. K.

2018-01-01

The physical properties like density, glass transition temperature (Tg), and ionic conductivity of lithium borate (LB) glasses with SiO2 addition were measured before and after gamma irradiation. Remarkable changes in properties have been obtained in the physical properties of LB glasses with SiO2 addition and after gamma irradiation. The increase in density and glass transition temperature of LB glasses with SiO2 addition has been explained with the help of increase in density of cross linking due to SiO4 tetrahedra formation. The increase in ionic conductivity with SiO2 addition was explained with the help of ‘mixed glass former effect’. The increase in density and Tg of LB glasses with SiO2 addition after gamma irradiation has been attributed to fragmentation of bigger ring structure into smaller rings, which increases the density of cross linking and hence compaction. The exposure of gamma irradiation has lead to decrease in ionic conductivity of LB glasses with SiO2 addition. The atomic displacement caused by gamma irradiation resulted in filling of interstices and decrease in trapping sites. This explains the obtained decrease in ionic conductivity after gamma irradiation of glasses. The obtained results of effect of SiO2 addition and gamma irradiation on the density, Tg and ionic conductivity has been supported by FTIR results.

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Polymerized Paired Ions as Polymeric Ionic Liquid-Proton Conductivity.

PubMed

Gu, Hong; Yan, Feng; Texter, John

2016-07-01

A new polymerized ionic liquid has been derived by photopolymerization of a stimuli-responsive ionic liquid surfactant, ILAMPS, which is composed of polymerizable, paired ions. The cation is 1-methyl-3-[11-(acryloyloxy)undecyl] imidazolium (IL), and the anion is 2-acrylamido-2-methyl-1-propanesulfonate (AMPS). This ion combination is a new ionic liquid. The resulting hygroscopic resins are highly polarizable, suitable for sensor design and for ultracapacitor fabrication and proton conducting. Interactions of imidazolium with anions provide basis for stimuli-responsiveness, and are used to promote proton transport. Doping with one equivalent of HPF6 at 0% relative humidity produces a 100-fold increase in proton conductivity at 100-125 °C and activation energies for proton transport lower than those of Nafion at water loadings less than 5 per sulfonate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

DOE PAGES

Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund; Stacy, Eric W.; ...

2016-09-28

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach ismore » introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.« less

Conductivity relaxation and charge transport of trihexyl tetradecyl phosphonium dicyanamide ionic liquid by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Thasneema K., K.; Thayyil, M. Shahin; Krishna Kumar N., S.; Govindaraj, G.; Saheer, V. C.

2018-04-01

Usually ionic liquids consists of a large organic cation with low symmetry such as imidazolium, pyridinium, quaternary ammonium or phosponium etc combined with enormously wide range of inorganic or organic symmetric anion with melting point below 100. Ionic liquids existing in an extremely large number of possible ion pair combinations. It offers a very wide range of thermo physical properties led to the concept of designer solvents for specific applications. Due to the features of high chemical and thermal stability, low vapor pressure non flammability high ionic conductivity, and they show a good solvent ability towards a great variety of organic or inorganic compounds, ionic liquids have a widespread use in many areas such as batteries, fuel cell, solar cells, super capacitors etc. The main focus of this work is the study of molecular dynamics and conductivity relaxation of amorphous Trihexyl tetradecyl phosphonium dicyanamide ([P14,6,6,6][N(CN)2]) ionic liquid which is proved as a better electrolyte in super capacitors, over a wide frequency 10-2 Hz to 107 Hz and the temperature range between 123k and 265 k by means of Broadband Dielectric Spectroscopy. We observe alpha conductivity relaxation and secondary relaxation above and below Glass Transition Temperature. The experimental results were analyzed using electric modulus representation. The analysis emphasis the inter molecular interaction and the nature of glass forming system, whether it is fragile or strong system. The ionic liquid shows a fragile behavior and the fragility index m=123.59. TGA result of the sample exhibit a good resistance to thermal decomposition, up to 300°C.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Improved ionic conductivity of lithium-zinc-tellurite glass-ceramic electrolytes

NASA Astrophysics Data System (ADS)

Widanarto, W.; Ramdhan, A. M.; Ghoshal, S. K.; Effendi, M.; Cahyanto, W. T.; Warsito

An enhancement in the secondary battery safety demands the optimum synthesis of glass-ceramics electrolytes with modified ionic conductivity. To achieve improved ionic conductivity and safer operation of the battery, we synthesized Li2O included zinc-tellurite glass-ceramics based electrolytes of chemical composition (85-x)TeO2·xLi2O·15ZnO, where x = 0, 5, 10, 15 mol%. Samples were prepared using the melt quenching method at 800 °C followed by thermal annealing at 320 °C for 3 h and characterized. The effects of varying temperature, alternating current (AC) frequency and Li2O concentration on the structure and ionic conductivity of such glass-ceramics were determined. The SEM images of the annealed glass-ceramic electrolytes displayed rough surface with a uniform distribution of nucleated crystal flakes with sizes less than 1 μm. X-ray diffraction analysis confirmed the well crystalline nature of achieved electrolytes. Incorporation of Li2O in the electrolytes was found to generate some new crystalline phases including hexagonal Li6(TeO6), monoclinic Zn2Te3O8 and monoclinic Li2Te2O5. The estimated crystallite size of the electrolyte was ranged from ≈40 to 80 nm. AC impedance measurement revealed that the variation in the temperatures, Li2O contents, and high AC frequencies have a significant influence on the ionic conductivity of the electrolytes. Furthermore, electrolyte doped with 15 mol% of Li2O exhibited the optimum performance with an ionic conductivity ≈2.4 × 10-7 S cm-1 at the frequency of 54 Hz and in the temperature range of 323-473 K. This enhancement in the conductivity was attributed to the sizable alteration in the ions vibration and ruptures of covalent bonds in the electrolytes network structures.

The lanthanum gallate-based mixed conducting perovskite ceramics

NASA Astrophysics Data System (ADS)

Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

2005-01-01

The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

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.

Ion conduction in crystalline superionic solids and its applications

NASA Astrophysics Data System (ADS)

Chandra, Angesh

2014-06-01

Superionic solids an area of multidisciplinary research activity, incorporates to study the physical, chemical and technological aspects of rapid ion movements within the bulk of the special class of ionic materials. It is an emerging area of materials science, as these solids show tremendous technological scopes to develop wide variety of solid state electrochemical devices such as batteries, fuel cells, supercapacitors, sensors, electrochromic displays (ECDs), memories, etc. These devices have wide range of applicabilities viz. power sources for IC microchips to transport vehicles, novel sensors for controlling atmospheric pollution, new kind of memories for computers, smart windows/display panels, etc. The field grew with a rapid pace since then, especially with regards to designing new materials as well as to explore their device potentialities. Amongst the known superionic solids, fast Ag+ ion conducting crystalline solid electrolytes are attracted special attention due to their relatively higher room temperature conductivity as well as ease of materials handling/synthesis. Ion conduction in these electrolytes is very much interesting part of today. In the present review article, the ion conducting phenomenon and some device applications of crystalline/polycrystalline superionic solid electrolytes have been reviewed in brief. Synthesis and characterization tools have also been discussed in the present review article.

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions

DOE PAGES

Tang, Wan Si; Unemoto, Atsushi; Zhou, Wei; ...

2015-10-08

Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2B 12H 12, which contains large, icosahedral, divalent B 12H 12 2– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2B 12H 12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11H 12 and NaCB 11H 12 salts, which contain icosahedral, monovalent CB 11H 12–more » anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm –1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.« less

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.

Surface polymerization of (3,4-ethylenedioxythiophene) probed by in situ scanning tunneling microscopy on Au(111) in ionic liquids.

PubMed

Ahmad, Shahzada; Carstens, Timo; Berger, Rüdiger; Butt, Hans-Jürgen; Endres, Frank

2011-01-01

The electropolymerization of 3,4-ethylenedioxythiophene (EDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) was investigated in the air and water-stable ionic liquids 1-hexyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate [HMIm]FAP and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide [EMIm]TFSA. In situ scanning tunnelling microscopy (STM) results show that the electropolymerization of EDOT in the ionic liquid can be probed on the nanoscale. In contrast to present understanding, it was observed that the EDOT can be oxidised in ionic liquids well below its oxidation potential and the under potential growth of polymer was visualized by in situ STM. These results serve as the first study to confirm the under potential growth of conducting polymers in ionic liquids. Furthermore, ex situ microscopy measurements were performed. Quite a high current of 670 nA was observed on the nanoscale by conductive scanning force microscopy (CSFM).

Influence Of Zwitterions on Properties and Morphology of Ionomers: Implications for Electro-Active Applications

DTIC Science & Technology

2010-08-01

membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in composites with similar mechanical performance, but 1. REPORT DATE (DD-MM...TERMS zwitterionomer, thermal mechanical property, morphology, ionic liquid , ionic conductivity, transducer Tianyu Wu, Rebecca H. Brown, Andrew J. Duncan...expected entanglement concentration. Swelling of the zwitterionomer membranes in EMIm ES ionic liquid at 10 wt% IL concentration resulted in

Microsiemens or Milligrams: Measures of Ionic Mixtures ...

EPA Pesticide Factsheets

In December of 2016, EPA released the Draft Field-Based Methods for Developing Aquatic Life Criteria for Specific Conductivity for public comment. Once final, states and authorized tribes may use these methods to derive field-based ecoregional ambient Aquatic Life Ambient Water Quality Criteria (AWQC) for specific conductivity (SC) in flowing waters. The methods provide flexible approaches for developing science-based SC criteria that reflect ecoregional or state specific factors. The concentration of a dissolved salt mixture can be measured in a number of ways including measurement of total dissolved solids, freezing point depression, refractive index, density, or the sum of the concentrations of individually measured ions. For the draft method, SC was selected as the measure because SC is a measure of all ions in the mixture; the measurement technology is fast, inexpensive, and accurate, and it measures only dissolved ions. When developing water quality criteria for major ions, some stakeholders may prefer to identify the ionic constituents as a measure of exposure instead of SC. A field-based method was used to derive example chronic and acute water quality criteria for SC and two anions a common mixture of ions (bicarbonate plus sulfate, [HCO3−] + [SO42−] in mg/L) that represent common mixtures in streams. These two anions are sufficient to model the ion mixture and SC (R2 = 0.94). Using [HCO3−] + [SO42−] does not imply that these two anions are the

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Acidic Ionic Liquids.

PubMed

Amarasekara, Ananda S

2016-05-25

Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

A self-forming composite electrolyte for solid-state sodium battery with ultra-long cycle life

DOE PAGES

Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; ...

2016-10-31

Replacing organic liquid electrolyte with inorganic solid electrolytes (SE) can potentially address the inherent safety problems in conventional rechargeable batteries. Furthermore, all-solid-state batteries have been plagues by the relatively low ionic conductivity of solid electrolytes and large charge-transfer resistance resulted from solid-solid interfaces between electrode materials and solid electrolytes. Here we report a new design strategy for improving the ionic conductivity of solid electrolyte by self-forming a composite material. An optimized Na + ion conducting composite electrolyte derived from the NASICON structure was successfully synthesized, yielding ultra-high ionic conductivity of 3.4 mS cm –1 at 25°C and 14 ms cmmore » –1 at 80°C.« less

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

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

PubMed

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

2011-01-21

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

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

PubMed Central

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

2011-01-01

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

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.

Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

DOEpatents

Van Calcar, Pamela; Mackay, Richard; Sammells, Anthony F.

2002-01-01

The invention relates to mixed phase materials for the preparation of catalytic membranes which exhibit ionic and electronic conduction and which exhibit improved mechanical strength compared to single phase ionic and electronic conducting materials. The mixed phase materials are useful for forming gas impermeable membranes either as dense ceramic membranes or as dense thin films coated onto porous substrates. The membranes and materials of this invention are useful in catalytic membrane reactors in a variety of applications including synthesis gas production. One or more crystalline second phases are present in the mixed phase material at a level sufficient to enhance the mechanical strength of the mixture to provide membranes for practical application in CMRs.

Cellulose ionics: switching ionic diode responses by surface charge in reconstituted cellulose films.

PubMed

Aaronson, Barak D B; Wigmore, David; Johns, Marcus A; Scott, Janet L; Polikarpov, Igor; Marken, Frank

2017-09-25

Cellulose films as well as chitosan-modified cellulose films of approximately 5 μm thickness, reconstituted from ionic liquid media onto a poly(ethylene-terephthalate) (PET, 6 μm thickness) film with a 5, 10, 20, or 40 μm diameter laser-drilled microhole, show significant current rectification in aqueous NaCl. Reconstituted α-cellulose films provide "cationic diodes" (due to predominant cation conductivity) whereas chitosan-doped cellulose shows "anionic diode" effects (due to predominant anion conductivity). The current rectification, or "ionic diode" behaviour, is investigated as a function of NaCl concentration, pH, microhole diameter, and molecular weight of the chitosan dopant. Future applications are envisaged exploiting the surface charge induced switching of diode currents for signal amplification in sensing.

Fabrication of core-shell structured magnetic nanocellulose base polymeric ionic liquid for effective biosorption of Congo red dye.

PubMed

Beyki, Mostafa Hossein; Bayat, Mehrnoosh; Shemirani, Farzaneh

2016-10-01

Ionic liquids are considered to be a class of environmentally friendly compounds as combination of them with bioresource polymeric substances such as; cellulose, constitute emerging coating materials. Biosorption by polymeric ionic liquids exhibits an attractive green way that involves low cost and irrespective of toxicity. As a result, a novel polymeric ionic liquid has been developed by the reaction of one step synthesized Fe3O4-cellulose nanohybrid, epichlorohydrin and 1-methylimidazole and employed as a green sorbent for efficient biosorption of Congo red dye. Effective parameters on dye removing as well as their interactions were determined with response surface methodology (RSM). Congo red adsorption showed fast equilibrium time (11min) with maximum uptake of 131mgg(-1). Isotherm study revealed that Langmuir adsorption model can better describe dye adsorption behavior. Regeneration of the sorbent was performed with a mixture of methanol-acetone-NaOH (3.0molL(-1)) solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biredox ionic liquids: new opportunities toward high performance supercapacitors.

PubMed

Bodin, C; Mourad, E; Zigah, D; Le Vot, S; Freunberger, S A; Favier, F; Fontaine, O

2018-01-01

Nowadays commercial supercapacitors are based on purely capacitive storage at the porous carbons that are used for the electrodes. However, the limits that capacitive storage imposes on energy density calls to investigate new materials to improve the capacitance of the device. This new type of electrodes (e.g., RuO 2 , MnO 2 …) involves pseudo-capacitive faradaic redox processes with the solid material. Ion exchange with solid materials is, however, much slower than the adsorption process in capacitive storage and inevitably leads to significant loss of power. Faradaic process in the liquid state, in contrast can be similarly fast as capacitive processes due to the fast ion transport. Designing new devices with liquid like dynamics and improved specific capacitance is challenging. We present a new approach to increase the specific capacitance using biredox ionic liquids, where redox moieties are tethered to the electrolyte ions, allowing high redox concentrations and significant pseudo-capacitive storage in the liquid state. Anions and cations are functionalized with anthraquinone (AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) moieties, respectively. Glassy carbon, carbon-onion, and commercial activated carbon electrodes that exhibit different double layer structures and thus different diffusion dynamics were used to simultaneously study the electrochemical response of biredox ionic liquids at the positive and negative electrode.

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

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

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

Application of Ionic Liquids in Hydrometallurgy

PubMed Central

Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

2014-01-01

Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

PubMed

Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella

2015-08-28

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Flake-like oxygen-deficient lithium vanadium oxides as a high ionic and electronic conductive cathode material for high-power Li-ion battery

NASA Astrophysics Data System (ADS)

Li, Jing-quan; Han, Chong; Jing, Mao-xiang; Yang, Hua; Shen, Xiang-qian; Qin, Shi-biao

2018-06-01

Low electronic and ionic conductivity for LiV3O8 cathode material could lead to poor cycling stability and rate capability, which are considered as the main restraint for its application in Li-ion battery. A novel flake-like LiV3O7.9 material modified by high ionic and electronic conductive Li0.3V2O5/C was fabricated via electrospinning and controlled thermal sintering processes. This oxygen-deficient LiV3O7.9/Li0.3V2O5-C composite electrode sintered at 500 °C exhibits improved rate and cycle stability. The electrode possesses a retention capacity of 151.9mAh/g after 500 cycles at 5C and 84.8mAh/g after 1000 cycles at 10C, respectively. The improvement of the electrochemical performance could be attributed to the synergistic effects of flake-like morphology, oxygen-deficiency and surface modification of Li0.3V2O5/C, which increase the ionic and electronic conductivity of LiV3O8.

Aerospace Power Scholarly Research Program. Delivery Order 0011: Modeling Lithium-Ion Conducting Channel

DTIC Science & Technology

2005-12-01

Brinkmann, D. NMR, DSC, and conductivity study of a poly (ethylene oxide) complex electrolyte: PEO(LiClO4)x, Sol. St. Ionics 1986, 18-19, 295. (27...Electrochemical Characterizations of Dilithium Octacyanophthalocyanine Langmuir - Blodgett films, Langmuir 2002, 18, 2223. 20 ...phthalocyanine (Li2Pc) has been used in this development since it can undergo molecular self-assembly to form the ionic ally conducting channel. The

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.

Influence of reactivation on the electrochemical performances of activated carbon based on coconut shell.

PubMed

Geng, Xin; Li, Lixiang; Zhang, Meiling; An, Baigang; Zhu, Xiaoming

2013-12-01

Coconut shell-based activated carbon (AC) were prepared by CO2 activation, and then the ACs with higher mesopore ratio were obtained by steam activation and by impregnating iron catalyst followed by steam activation, respectively. The AC with the highest mesopore ratio (AChmr) shows superior capacitive behavior, power output and high-frequency performance in supercapacitors. The results should attribute to the connection of its wide micropores and mesopores larger than 3 nm, which is more favorable for fast ionic transportation. The pore size distribution exhibits that the mesopore ratios of the ACs are significantly increased by reactivation of steam or catalyst up to 75% and 78%, respectively. As evidenced by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic measurements, the AChmr shows superior capacitive behaviors, conductivity and performance of electrolytic ionic transportation. The response current densities are evidently enhanced through the cyclic voltammery test at 50 mV/sec scan rate. The electrochemical impedance spectroscopy demonstrates that the conductivity and ion transport performance of the ACs are improved. The specific capacitances of the ACs were increased from 140 to 240 F/g at 500 mA/g current density. The AChmr can provide much higher power density while still maintaining good energy density, and demonstrate excellent high-frequency performances. The pore structure and conductivity of the AChmr also improve the cycleability and self-discharge of supercapacitors. Such AChmr exhibits a great potential in supercapacitors, particularly for applications where high power output and good high-frequency capacitive performances are required. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Ionomer Design, Synthesis and Characterization for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph H.

2013-03-01

For ionic actuators and battery separators, it is vital to utilize single-ion conductors that avoid the detrimental polarization of other ions; the commonly studied dual-ion conductors simply will not be used in the next generation of materials for these applications. Ab initio quantum chemistry calculations at 0 K in vacuum characterize ion interactions and ion solvation by various functional groups, allowing identification of constituents with weak interactions to be incorporated in ionomers for facile ion transport. Simple ideas for estimating the ion interactions and solvation at practical temperatures and dielectric constants are presented that indicate the rank ordering observed at 0 K in vacuum should be preserved. Hence, such ab initio calculations are useful for screening the plethora of combinations of polymer-ion, counterion and polar functional groups, to decide which are worthy of synthesis for new ionomers. Single-ion conducting ionomers are synthesized based on these calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for ionic actuators and battery separators. Characterization by X-ray scattering, dielectric spectroscopy, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. Examples are shown of how ab initio calculations can be used to understand experimental observations of dielectric constant, glass transition temperature and conductivity of polymerized ionic liquids with counterions being either lithium, sodium, fluoride, hydroxide (for batteries) or bulky ionic liquids (for ionic actuators). This work was supported by the Department of Energy under Grant BES-DE-FG02-07ER46409.

Poly(methylene blue) functionalized graphene modified carbon ionic liquid electrode for the electrochemical detection of dopamine.

PubMed

Sun, Wei; Wang, Yuhua; Zhang, Yuanyuan; Ju, Xiaomei; Li, Guangjiu; Sun, Zhenfan

2012-11-02

An ionic liquid 1-butylpyridinium hexafluorophosphate based carbon ionic liquid electrode (CILE) was used as the substrate electrode and a poly(methylene blue) (PMB) functionalized graphene (GR) composite film was co-electrodeposited on CILE surface by cyclic voltammetry. The PMB-GR/CILE exhibited better electrochemical performances with higher conductivity and lower electron transfer resistance. Electrochemical behavior of dopamine (DA) was further investigated by cyclic voltammetry and a pair of well-defined redox peaks appeared with the peak-to-peak separation (ΔE(p)) as 0.058V in 0.1 mol L(-1) pH 6.0 phosphate buffer solution, which proved a fast quasi-reversible electron transfer process on the modified electrode. Electrochemical parameters of DA on PMB-GR/CILE were calculated with the electron transfer number as 1.83, the charge transfer coefficients as 0.70, the apparent heterogeneous electron transfer rate constant as 1.72 s(-1) and the diffusional coefficient (D) as 3.45×10(-4) cm(2) s(-1), respectively. Under the optimal conditions with differential pulse voltammetric measurement, the linear relationship between the oxidation peak current of DA and its concentration was obtained in the range from 0.02 to 800.0 μmol L(-1) with the detection limit as 5.6 nmol L(-1) (3σ). The coexisting substances exhibited no interference and PMB-GR/CILE was applied to the detection of DA injection samples and human urine samples with satisfactory results. Copyright © 2012 Elsevier B.V. All rights reserved.

Importance of liquid fragility for energy applications of ionic liquids

NASA Astrophysics Data System (ADS)

Sippel, Pit; Lunkenheimer, Peter; Krohns, Stephan; Thoms, Erik; Loidl, Alois

Ionic liquids (ILs) are salts that are liquid at ambient temperatures. The strong electrostatic forces between their molecular ions result, e.g., in low volatility and high stability for many members of this huge material class. For this reason they bear a high potential for new advancements in applications, e.g., as electrolytes in energy-storage devices such as supercapacitors or batteries, where the ionic conductivity is an essential figure of merit. Most ILs show dynamic properties typical for glassy matter, which dominate many of their physical properties. An important method to study these dynamical glass-properties is dielectric spectroscopy that can access relaxation times of dynamic processes and the conductivity in a broad frequency and temperature range. In the present contribution, we present results on a large variety of ionic liquids showing that the conductivity of ILs depends in a systematic way not only on their glass temperature but also on the so-called fragility, characterizing the non-canonical super-Arrhenius temperature dependence of their ionic mobility. This work was supported by the Deutsche Forschungsgemeinschaft via Research Unit FOR1394 and by the BMBF via ENREKON 03EK3015.

Understanding ion association states and molecular dynamics using infrared spectroscopy

NASA Astrophysics Data System (ADS)

Masser, Hanqing

A molecular level understanding of the ion transport mechanism within polymer electrolytes is crucial to the further development for advanced energy storage applications. This can be achieved by the identification and quantitative measurement of different ion species in the system and further relating them to the ion conductivity. In the first part of this thesis, research is presented towards understanding the ion association states (free ions, ion pairs and ion aggregates) in ionomer systems, and the correlation of ion association states, ion conduction, polymer dynamics, and morphology. Ion conductivity in ionomers can be improved by lowering glass transition temperature, increasing polymer ion solvation ability, and adjusting ionomer structural variables such as ion content, cation type and side chain structure. These effects are studied in three ionomer systems respectively, using a combination of characterization methods. Fourier Transform Infrared Spectroscopy (FTIR) identifies and quantifies the ion association states. Dielectric Spectroscopy (DRS) characterizes ion conductivity and polymer and ion dynamics. X-ray scattering reveals changes in morphology. The influence of a cation solvating plasticizer on a polyester ionomer is systematically investigated with respect to ion association states, ion and polymer dynamics and morphology. A decrease in the number ratio of ion aggregates with increased plasticizer content and a slight increase at elevated temperature are observed in FTIR. Similar results are also detected by X-ray scattering. As determined from dielectric spectroscopy, ion conductivity increases with plasticizer content, in accordance with the decrease in glass transition temperature. Research on copolymer of poly(ethylene oxide) (PEO) and poly(tetramethylene oxide) (PTMO) based ionomers further develops an understanding of the trade-off between ion solvation and segmental dynamics. Upon the incorporation of PTMO, the majority of the PTMO microphase separates from the PEO-rich microphase, and ionic groups are preferentially solvated by PEO chains and reside in the PEO-rich microphase. As the ratio of PTMO increases, the fraction of aggregates increases, resulting in more highly coordinated aggregation states. Results on ion association states are in good agreement with previous results on ion conductivity, polymer dynamics and morphology. The effects of ion content, cation type and ionic side chain structure on ion association states are systemically studied in a series of ionomers with short ethylene oxide and ionic sulfonated styrene side chains, and then correlated to the ion and polymer dynamic characterization. It is found that ionomers with modest ion content, large cation and styrene ionic side chain have the most "free ions" and ion pairs, and highest ion conductivity. Ion conduction in ionomers is optimized by systematically changing their chemical structures. In addition to knowledge of ion association states, a IR band shape also contains information on molecular dynamics. In companion investigation, the vibrational relaxation and dynamic transitions of conformationally insensitive normal modes in two different polymer systems (atactic polystyrene and deuterated poly(methyl methacrylate)) are studied. The information on vibrational relaxations is resolved by conducting precisely controlled FTIR experiments, applying specialized curve resolving data analysis, and calculating time correlation functions through numerical Fourier transformation. The vibrational relaxations of these modes can be described by a two process model: a fast process on the time scale of 0.01 ps, which is inhomogeneously broadened by a slow process on the time scale of picoseconds.

Solid state electrolyte composites based on complex hydrides and metal doped fullerenes/fulleranes for batteries and electrochemical applications

DOEpatents

Zidan, Ragaiy; Teprovich, Jr., Joseph A.; Colon-Mercado, Hector R.; Greenway, Scott D.

2018-05-01

A LiBH₄--C₆₀ nanocomposite that displays fast lithium ionic conduction in the solid state is provided. The material is a homogenous nanocomposite that contains both LiBH₄ and a hydrogenated fullerene species. In the presence of C₆₀, the lithium ion mobility of LiBH₄ is significantly enhanced in the as prepared state when compared to pure LiBH₄. After the material is annealed the lithium ion mobility is further enhanced. Constant current cycling demonstrated that the material is stable in the presence of metallic lithium electrodes. The material can serve as a solid state electrolyte in a solid-state lithium ion battery.

Determination of triazine herbicides in juice samples by microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography.

PubMed

Su, Rui; Li, Dan; Wu, Lijie; Han, Jing; Lian, Wenhui; Wang, Keren; Yang, Hongmei

2017-07-01

A novel microextraction method, termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high-performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1-hexyl-3-methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1-butyl-3-methylimidazolium tetrafluoroborate. In addition, an ion-pairing agent (NH 4 PF 6 ) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00-250.00 μg/L, with the correlation coefficients of 0.9982-0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7-105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Realisation of an all solid state lithium battery using solid high temperature plastic crystal electrolytes exhibiting liquid like conductivity.

PubMed

Shekibi, Youssof; Rüther, Thomas; Huang, Junhua; Hollenkamp, Anthony F

2012-04-07

Replacement of volatile and combustible electrolytes in conventional lithium batteries is desirable for two reasons: safety concerns and increase in specific energy. In this work we consider the use of an ionic organic plastic crystal material (IOPC), N-ethyl-N-methylpyrrolidinium tetrafluoroborate, [C2mpyr][BF(4)], as a solid-state electrolyte for lithium battery applications. The effect of inclusion of 1 to 33 mol% lithium tetrafluoroborate, LiBF(4), into [C2mpyr][BF(4)] has been investigated over a wide temperature range by differential scanning calorimetry (DSC), impedance spectroscopy, cyclic voltammetry and cycling of full Li|LiFePO(4) batteries. The increases in ionic conductivity by orders of magnitude observed at higher temperature are most likely associated with an increase in Li ion mobility in the highest plastic phase. At concentrations >5 mol% LiBF(4) the ionic conductivity of these solid-state composites is comparable to the ionic conductivity of room temperature ionic liquids. Galvanostatic cycling of Li|Li symmetrical cells showed that the reversibility of the lithium metal redox reaction at the interface of this plastic crystal electrolyte is sufficient for lithium battery applications. For the first time we demonstrate an all solid state lithium battery incorporating solid electrolytes based on IOPC as opposed to conventional flammable organic solvents.

Ionic Conductivity Increased by Two Orders of Magnitude in Micrometer-Thick Vertical Yttria-Stabilized ZrO 2 Nanocomposite Films

DOE PAGES

Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; ...

2015-09-03

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO 2 (YSZ) nanocolumns, strain coupled to a SrTiO 3 matrix. We also enhanced the ionic conductivity of these nanocolumnsby over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, “oxygen migration highways” are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling ofmore » the YSZ nanocolumns to the SrTiO 3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO 2 nanocolumns within the SrTiO 3 matrix. Furthermore, this intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10 –2 Ω –1 cm –1 were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.« less

Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

NASA Astrophysics Data System (ADS)

Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

2016-09-01

Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

PubMed

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

2017-06-01

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

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

DOE PAGES

Fan, Fei; Wang, Weiyu; Holt, Adam P.; ...

2016-06-07

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

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

Fan, Fei; Wang, Weiyu; Holt, Adam P.

The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

Research@ARL: Materials Modeling at Multiple Scales. Volume 3, Issue 2

DTIC Science & Technology

2014-07-01

possessing high ionic conductivity , low viscosity, and good thermal and electrochemical stability and, importantly, being compatible with electrodes. As... thermal and electrical properties. ARL conducts extensive research in graphene and other 2D materials such as BN, ZnO, and hybrid graphene-polyethylene...contribution at temperatures below 393 K. Thus, below 393 K, Li2EDC essentially acts as a single ion conductor . The isotropic ionic conductivity from MD

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

NASA Astrophysics Data System (ADS)

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; Zhao, Meng-Qiang; Shpigel, Netanel; Levi, Mikhael D.; Halim, Joseph; Taberna, Pierre-Louis; Barsoum, Michel W.; Simon, Patrice; Gogotsi, Yury

2017-08-01

The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g-1 at scan rates of 10 V s-1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ˜1,500 F cm-3 reaching the previously unmatched volumetric performance of RuO2.

An unusual slowdown of fast diffusion in a room temperature

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

Chathoth,; Mamontov, Eugene; Fulvio, Pasquale F

2013-01-01

Using quasielastic neutron scattering in the temperature range from 290 to 350 K, we show that the diffusive motions in a room temperature ionic liquid [H2NC(dma)2][BETI] become faster for a fraction of cations when the liquid is confined in a mesoporous carbon. This applies to both the localized and long-range translational diffusive motions of the highly mobile cations, although the former exhibit an unusual trend of slowing-down as the temperature is increased, until the localized diffusivity is reduced to the bulk ionic liquid value at a temperature of 350 K.

Nonhumidified intermediate temperature fuel cells using protic ionic liquids.

PubMed

Lee, Seung-Yul; Ogawa, Atsushi; Kanno, Michihiro; Nakamoto, Hirofumi; Yasuda, Tomohiro; Watanabe, Masayoshi

2010-07-21

In this paper, the characterization of a protic ionic liquid, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]), as a proton conductor for a fuel cell and the fabrication of a membrane-type fuel cell system using [dema][TfO] under nonhumidified conditions at intermediate temperatures are described in detail. In terms of physicochemical and electrochemical properties, [dema][TfO] exhibits high activity for fuel cell electrode reactions (i.e., the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR)) at a Pt electrode, and the open circuit voltage (OCV) of a liquid fuel cell is 1.03 V at 150 degrees C, as has reported in ref 27. However, diethylmethylammonium bis(trifluoromethane sulfonyl)amide ([dema][NTf(2)]) has relatively low HOR and ORR activity, and thus, the OCV is ca. 0.7 V, although [dema][NTf(2)] and [dema][TfO] have an identical cation ([dema]) and similar thermal and bulk-transport properties. Proton conduction occurs mainly via the vehicle mechanism in [dema][TfO] and the proton transference number (t(+)) is 0.5-0.6. This relatively low t(+) appears to be more disadvantageous for a proton conductor than for other electrolytes such as hydrated sulfonated polymer electrolyte membranes (t(+) = 1.0). However, fast proton-exchange reactions occur between ammonium cations and amines in a model compound. This indicates that the proton-exchange mechanism contributes to the fuel cell system under operation, where deprotonated amines are continuously generated by the cathodic reaction, and that polarization of the cell is avoided. Six-membered sulfonated polyimides in the diethylmethylammonium form exhibit excellent compatibility with [dema][TfO]. The composite membranes can be obtained up to a [dema][TfO] content of 80 wt % and exhibit good thermal stability, high ionic conductivity, and mechanical strength and gas permeation comparable to those of hydrated Nafion. H(2)/O(2) fuel cells prepared using the composite membranes can successfully operate at temperatures from 30 to 140 degrees C under nonhumidified conditions, and a current density of 250 mA cm(-2) is achieved at 120 degrees C. The protic ionic liquid and its composite membrane are a possible candidate for an electrolyte of a H(2)/O(2) fuel cell that operates under nonhumidified conditions.

The Effect of Ionic Strength on the Solubility of an Electrolyte

ERIC Educational Resources Information Center

Willey, Joan D.

2004-01-01

A simple experiment was conducted for studying and demonstrating visually and dramatically the effect of ionic strength on the solubility of an electrolyte is described. It is seen that the experiment visually illustrates the effect of ionic strength on electrolyte solubility by the appearance of the two solutions and by the difference in the…

Thermal boundary conductance of hydrophilic and hydrophobic ionic liquids

NASA Astrophysics Data System (ADS)

Oyake, Takafumi; Sakata, Masanori; Yada, Susumu; Shiomi, Junichiro

2015-03-01

A solid/liquid interface plays a critical role for understanding mechanisms of biological and physical science. Moreover, carrier density of the surface is dramatically enhanced by electric double layer with ionic liquid, salt in the liquid state. Here, we have measured the thermal boundary conductance (TBC) across an interface of gold thin film and ionic liquid by using time-domain thermoreflectance technique. Following the prior researches, we have identified the TBC of two interfaces. One is gold and hydrophilic ionic liquid, N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate (DEME-BF4), which is a hydrophilic ionic liquid, and the other is N,N-Diethyl-N-methyl-N-(2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI), which is a hydrophobic ionic liquid. We found that the TBC between gold and DEME-TFIS (19 MWm-2K-1) is surprisingly lower than the interface between gold and DEME-BF4 (45 MWm-2K-1). With these data, the importance of the wetting angle and ion concentration for the thermal transport at the solid/ionic liquid interface is discussed. Part of this work is financially supported by Japan Society for the Promotion of Science (JSPS) and Japan Science and Technology Agency. The author is financially supported by JSPS Fellowship.

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

Extremely dense microstructure and enhanced ionic conductivity in hot-isostatic pressing treated cubic garnet-type solid electrolyte of Ga2O3-doped Li7La3Zr2O12

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming’En; Hu, Zhiwei; Zhu, Jiliang

A large number of pores and a low relative density that are frequently observed in solid electrolytes reduce severely their ionic conductivity and thus limit their applicability. Here, we report on the use of hot isostatic pressing (HIP) for ameliorating the garnet-type lithium-ion conducting solid electrolyte of Ga2O3-doped Li7La3Zr2O12 (Ga-LLZO) with nominal composition of Li6.55Ga0.15La3Zr2O12. The Ga-LLZO pellets were conventionally sintered at 1075∘C for 12h, and then were followed by HIP treatment at 120MPa and 1160∘C under an Ar atmosphere. It is found that the HIP-treated Ga-LLZO shows an extremely dense microstructure and a significantly enhanced ionic conductivity. Coherent with the increase in relative density from 90.5% (untreated) to 97.5% (HIP-treated), the ionic conductivity of the HIP-treated Ga-LLZO reaches as high as 1.13×10‑3S/cm at room temperature (25∘C), being two times higher than that of 4.58×10‑4S/cm for the untreated one.

Miniaturized Planar Room Temperature Ionic Liquid Electrochemical Gas Sensor for Rapid Multiple Gas Pollutants Monitoring.

PubMed

Wan, Hao; Yin, Heyu; Lin, Lu; Zeng, Xiangqun; Mason, Andrew J

2018-02-01

The growing impact of airborne pollutants and explosive gases on human health and occupational safety has escalated the demand of sensors to monitor hazardous gases. This paper presents a new miniaturized planar electrochemical gas sensor for rapid measurement of multiple gaseous hazards. The gas sensor features a porous polytetrafluoroethylene substrate that enables fast gas diffusion and room temperature ionic liquid as the electrolyte. Metal sputtering was utilized for platinum electrodes fabrication to enhance adhesion between the electrodes and the substrate. Together with carefully selected electrochemical methods, the miniaturized gas sensor is capable of measuring multiple gases including oxygen, methane, ozone and sulfur dioxide that are important to human health and safety. Compared to its manually-assembled Clark-cell predecessor, this sensor provides better sensitivity, linearity and repeatability, as validated for oxygen monitoring. With solid performance, fast response and miniaturized size, this sensor is promising for deployment in wearable devices for real-time point-of-exposure gas pollutant monitoring.

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.

Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

PubMed

Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

2009-06-01

A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

Carbon/PTFE Electrode for Lithium/Air-Water Batteries

DTIC Science & Technology

2007-03-01

non-electronically conducting ceramic membrane impervious to water but with a high ionic conductivity for lithium-ions. LiTixAly(PO4)3 is one such...example of a ceramic composition that has been used in this manner. The lithium ion can be thought of as being solvated by the ceramic membrane as it...through 5) provides current. To balance the overall charge in the reaction, positive lithium ions flow 1 through an ionically conducting ceramic

Influence of microstructure and AlPO4 secondary-phase on the ionic conductivity of Li1.3Al0.3Ti1.7(PO4)3 solid-state electrolyte

NASA Astrophysics Data System (ADS)

Yu, Shicheng; Mertens, Andreas; Gao, Xin; Gunduz, Deniz Cihan; Schierholz, Roland; Benning, Svenja; Hausen, Florian; Mertens, Josef; Kungl, Hans; Tempel, Hermann; Eichel, Rüdiger-A.

2016-09-01

A ceramic solid-state electrolyte of lithium aluminum titanium phosphate with the composition of Li1.3Al0.3Ti1.7(PO4)3 (LATP) was synthesized by a sol-gel method using a pre-dissolved Ti-source. The annealed LATP powders were subsequently processed in a binder-free dry forming method and sintered under air for the pellet preparation. Phase purity, density, microstructure as well as ionic conductivity of the specimen were characterized. The highest density (2.77gṡcm-3) with an ionic conductivity of 1.88×10-4 Sṡcm-1 (at 30∘C) was reached at a sintering temperature of 1100∘C. Conductivity of LATP ceramic electrolyte is believed to be significantly affected by both, the AlPO4 secondary phase content and the ceramic electrolyte microstructure. It has been found that with increasing sintering temperature, the secondary-phase content of AlPO4 increased. For sintering temperatures above 1000∘C, the secondary phase has only a minor impact, and the ionic conductivity is predominantly determined by the microstructure of the pellet, i.e. the correlation between density, porosity and particle size. In that respect, it has been demonstrated, that the conductivity increases with increasing particle size in this temperature range and density.

Ionic Conduction in Nanocrystalline Materials

DTIC Science & Technology

2000-02-10

In the following, we review studies performed films prepared by a polymer precursor process on on stabilized zirconia ceramics with grain sizes alumina ... titania , is reviewed. While it remains too early to make firm conclusions, the following observations are made. Additives which contribute to ion blocking...Keywords: Ionic conductivity; Nanocrystalline; Zirconia; Ceria; Titania ; Defects 1. Introduction tivity by nearly two orders of magnitude [6]. Given the

Ion transport with charge-protected and non-charge-protected cations using the compensated Arrhenius formalism. Part 2. Relationship between ionic conductivity and diffusion.

PubMed

Petrowsky, Matt; Fleshman, Allison; Bopege, Dharshani N; Frech, Roger

2012-08-09

Temperature-dependent ionic conductivities and cation/anion self-diffusion coefficients are measured for four electrolyte families: TbaTf-linear primary alcohols, LiTf-linear primary alcohols, TbaTf-n-alkyl acetates, and LiTf-n-alkyl acetates. The Nernst-Einstein equation does not adequately describe the data. Instead, the compensated Arrhenius formalism is applied to both conductivity and diffusion data. General trends based on temperature and alkyl chain length are observed when conductivity is plotted against cation or anion diffusion coefficient, but there is no clear pattern to the data. However, plotting conductivity exponential prefactors against those for diffusion results in four distinct curves, one each for the alcohol and acetate families described above. Furthermore, the TbaTf-alcohol and TbaTf-acetate data are "in line" with each other. The conductivity prefactors for the LiTf-alcohol data are smaller than those for the TbaTf data. The LiTf-acetate data have the lowest conductivity prefactors. This trend in prefactors mirrors the observed trend in degree of ionic association for these electrolytes.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts.

PubMed

Tripathy, Satya N; Wojnarowska, Zaneta; Knapik, Justyna; Shirota, Hideaki; Biswas, Ranjit; Paluch, Marian

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10(-1)-10(6) Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transition temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai's coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.

High Conductivity, High Strength Solid Electrolytes Formed by in Situ Encapsulation of Ionic Liquids in Nanofibrillar Methyl Cellulose Networks.

PubMed

Mantravadi, Ramya; Chinnam, Parameswara Rao; Dikin, Dmitriy A; Wunder, Stephanie L

2016-06-01

Strong, solid polymer electrolyte ion gels, with moduli in the MPa range, a capacitance of 2 μF/cm(2), and high ambient ionic conductivities (>1 × 10(-3) S/cm), all at room temperature, have been prepared from butyl-N-methyl pyrrolidinium bis(trifluoromethylsulfonyl) imide (PYR14TFSI) and methyl cellulose (MC). These properties are particularly attractive for supercapacitor applications. The ion gels are prepared by codissolution of PYR14TFSI and MC in N,N-dimethylformamide (DMF), which after heating and subsequent cooling form a gel. Evaporation of DMF leave thin, flexible, self-standing ion gels with up to 97 wt % PYR14TFSI, which have the highest combined moduli and ionic conductivity of ion gels to date, with an excellent electrochemical stability window (5.6 V). These favorable properties are attributed to the immiscibility of PYR14TFSI in MC, which permits the ionic conductivity to be independent of the MC at low MC content, and the in situ formation of a volume spanning network of semicrystalline MC nanofibers, which have a high glass transition temperature (Tg = 190 °C) and remain crystalline until they degrade at 300 °C.

Preparation and electrochemical characterization of ionic-conducting lithium lanthanum titanate oxide/polyacrylonitrile submicron composite fiber-based lithium-ion battery separators

NASA Astrophysics Data System (ADS)

Liang, Yinzheng; Ji, Liwen; Guo, Bingkun; Lin, Zhan; Yao, Yingfang; Li, Ying; Alcoutlabi, Mataz; Qiu, Yiping; Zhang, Xiangwu

Lithium lanthanum titanate oxide (LLTO)/polyacrylonitrile (PAN) submicron composite fiber-based membranes were prepared by electrospinning dispersions of LLTO ceramic particles in PAN solutions. These ionic-conducting LLTO/PAN composite fiber-based membranes can be directly used as lithium-ion battery separators due to their unique porous structure. Ionic conductivities were evaluated after soaking the electrospun LLTO/PAN composite fiber-based membranes in a liquid electrolyte, 1 M lithium hexafluorophosphate (LiPF 6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). It was found that, among membranes with various LLTO contents, 15 wt.% LLTO/PAN composite fiber-based membranes provided the highest ionic conductivity, 1.95 × 10 -3 S cm -1. Compared with pure PAN fiber membranes, LLTO/PAN composite fiber-based membranes had greater liquid electrolyte uptake, higher electrochemical stability window, and lower interfacial resistance with lithium. In addition, lithium//1 M LiPF 6/EC/EMC//lithium iron phosphate cells containing LLTO/PAN composite fiber-based membranes as the separator exhibited high discharge specific capacity of 162 mAh g -1 and good cycling performance at 0.2 C rate at room temperature.

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.

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

PubMed

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.

New generation Li+ NASICON glass-ceramics for solid state Li+ ion battery applications

NASA Astrophysics Data System (ADS)

Sharma, Neelakshi; Dalvi, Anshuman

2018-04-01

Lithiumion conducting NASICON glass-ceramics have been prepared by a novel planetary ball milling assisted synthesis route. Structural, thermal and electrical investigations have been carried out on the novel composites composed of LiTi(PO4)3 (LTP) and 50[Li2SO4]-50[Li2O-P2O5] ionic glass reveal interesting results. Composites were prepared keeping the concentration of the ionic glass fixed at 20 wt%. X-ray diffraction and diffe rential thermal analysis confirm the glass-ceramic formation. Moreover, the structure of LTP remains intact during the glass -ceramic formation. Electrical conductivity of the glass-ceramic composite is found to be higher than that of the pristine glass (50LSLP) and LTP. The bulk and grain boundary conductivities of LTP exhibit improvement in composite. Owing to high ionic conductivity and thermal stability, novel glass -ceramic seems to be a promising candidate for all solid-state battery applications.

Water uptake, ionic conductivity and swelling properties of anion-exchange membrane

NASA Astrophysics Data System (ADS)

Duan, Qiongjuan; Ge, Shanhai; Wang, Chao-Yang

2013-12-01

Water uptake, ionic conductivity and dimensional change of the anion-exchange membrane made by Tokuyama Corporation (A201 membrane) are investigated at different temperatures and water activities. Specifically, the amount of water taken up by membranes exposed to water vapor and membranes soaked in liquid water is determined. The water uptake of the A201 membrane increases with water content as well as temperature. In addition, water sorption data shows Schroeder's paradox for the AEMs investigated. The swelling properties of the A201 membrane exhibit improved dimensional stability compared with Nafion membrane. Water sorption of the A201 membrane occurs with a substantial negative excess volume of mixing. The threshold value of hydrophilic fraction in the A201 membrane for ionic conductivity is around 0.34, above which, the conductivity begins to rise quickly. This indicates that a change in the connectivity of the hydrophilic domains occurs when hydrophilic fraction approaches 0.34.

Electronically and ionically conductive porous material and method for manufacture of resin wafers therefrom

DOEpatents

Lin, YuPo J [Naperville, IL; Henry, Michael P [Batavia, IL; Snyder, Seth W [Lincolnwood, IL

2011-07-12

An electrically and ionically conductive porous material including a thermoplastic binder and one or more of anion exchange moieties or cation exchange moieties or mixtures thereof and/or one or more of a protein capture resin and an electrically conductive material. The thermoplastic binder immobilizes the moieties with respect to each other but does not substantially coat the moieties and forms the electrically conductive porous material. A wafer of the material and a method of making the material and wafer are disclosed.

Comparative Investigation of the Ionicity of Aprotic and Protic Ionic Liquids in Molecular Solvents by using Conductometry and NMR Spectroscopy.

PubMed

Thawarkar, Sachin; Khupse, Nageshwar D; Kumar, Anil

2016-04-04

Electrical conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of binary mixtures of aprotic and protic imidazolium-based ionic liquids with water, dimethyl sulfoxide, and ethylene glycol were measured from 293.15 to 323.15 K. The temperature dependence study reveals typical Arrhenius behavior. The ionicities of aprotic ionic liquids were observed to be higher than those of protic ionic liquids in these solvents. The aprotic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, [bmIm][BF4 ], displays 100 % ionicity in both water and ethylene glycol. The protic ionic liquids in both water and ethylene glycol are classed as good ionic candidates, whereas in DMSO they are classed as having a poor ionic nature. The solvation dynamics of the ionic species of the ionic liquids are illustrated on the basis of the (1) H NMR chemical shifts of the ionic liquids. The self-diffusion coefficients D of the cation and anion of [HmIm][CH3 COO] in D2 O and in [D6 ]DMSO are determined by using (1) H nuclei with pulsed field gradient spin-echo NMR spectroscopy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors.

PubMed

Pastor, María Jesús; Sánchez, Ignacio; Campo, José A; Schmidt, Rainer; Cano, Mercedes

2018-04-03

Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl - , BF₄ - , ReO₄ - , p -CH₃-₆H₄SO₃ - (PTS) and CF₃SO₃ - (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H₂pz R(4),R(4) ][ReO₄]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl - and BF₄ - ) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity.

Super ionic conductive glass

DOEpatents

Susman, Sherman; Volin, Kenneth J.

1984-01-01

An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Lithium-Air and ionic Liquids

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

Kellar, Michael

2015-09-01

The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to themore » typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.« less

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.

Ion transferring in polyelectrolyte networks in electric fields

NASA Astrophysics Data System (ADS)

Li, Honghao; Erbas, Aykut; Zwanikken, Jos; Olvera de La Cruz, Monica

Ion-conducting polyelectrolyte gels have drawn the attention of many researchers in the last few decades as they have wide applications not only in lithium batteries but also as stretchable, transparent ionic conductor or ionic cables devices. However, ion dynamics in polyelectrolyte gels has been much less studied analytically or computationally due to the complicated interplay of long-range electrostatic and short-range interactions. Here we propose a coarse-grained non-equilibrium molecular dynamics simulation to study the ion dynamics in polyelectrolyte gels under external electric fields. We found a nonlinear response region where the molar conductivity of polyelectrolyte gels increases with external fields. We propose counterion redistribution under electric fields as the driving mechanism. We also found the ionic conductivity to be modulated by changing polylelectrolyte network topology such as the chain length. Our discovery reveals the essential difference of ion dynamics between electrolytes and polyelectrolyte gels. These results will expand our understanding in charged polymeric systems and help in designing ion-conducting devices with higher conductivity.

Retention of neodymium by dolomite at variable ionic strength as probed by batch and column experiments.

PubMed

Emerson, H P; Zengotita, F; Richmann, M; Katsenovich, Y; Reed, D T; Dittrich, T M

2018-10-01

The results presented in this paper highlight the complexity of adsorption and incorporation processes of Nd with dolomite and significantly improve upon previous work investigating trivalent actinide and lanthanide interactions with dolomite. Both batch and mini column experiments were conducted at variable ionic strength. These data highlight the strong chemisorption of Nd to the dolomite surface (equilibrium K d 's > 3000 mL/g) and suggest that equilibrium adsorption processes may not be affected by ionic strength based on similar results at 0.1 and 5.0 M ionic strength in column breakthrough and equilibrium batch (>5 days) results. Mini column experiments conducted over approximately one year also represent a significant development in measurement of sorption of Nd in the presence of flow as previous large-scale column experiments did not achieve breakthrough likely due to the high loading capacity of dolomite for Nd (up to 240 μg/g). Batch experiments in the absence of flow show that the rate of Nd removal increases with increasing ionic strength (up to 5.0 M) with greater removal at greater ionic strength for a 24 h sampling point. We suggest that the increasing ionic strength induces increased mineral dissolution and re-precipitation caused by changes in activity with ionic strength that lead to increased removal of Nd through co-precipitation processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Method to detect the end-point for PCR DNA amplification using an ionically labeled probe and measuring impedance change

DOEpatents

Miles, Robin R [Danville, CA; Belgrader, Phillip [Severna Park, MD; Fuller, Christopher D [Oakland, CA

2007-01-02

Impedance measurements are used to detect the end-point for PCR DNA amplification. A pair of spaced electrodes are located on a surface of a microfluidic channel and an AC or DC voltage is applied across the electrodes to produce an electric field. An ionically labeled probe will attach to a complementary DNA segment, and a polymerase enzyme will release the ionic label. This causes the conductivity of the solution in the area of the electrode to change. This change in conductivity is measured as a change in the impedance been the two electrodes.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors

NASA Astrophysics Data System (ADS)

Marple, M. A. T.; Avila-Paredes, H.; Kim, S.; Sen, S.

2018-05-01

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Atomistic interpretation of the ac-dc crossover frequency in crystalline and glassy ionic conductors.

PubMed

Marple, M A T; Avila-Paredes, H; Kim, S; Sen, S

2018-05-28

A comprehensive analysis of the ionic dynamics in a wide variety of crystalline and glassy ionic conductors, obtained in recent studies using a combination of electrochemical impedance and nuclear magnetic resonance spectroscopic techniques, is presented. These results demonstrate that the crossover frequency, between the frequency-independent dc conductivity and the frequency-dependent ac conductivity, corresponds to the time scale of "successful" diffusive hops of the mobile ions between the trapping sites in the structure. These inter-site hops are typically compound in nature and consist of several elementary hops in the intervening region between the neighboring trapping sites.

Covalently bonded ionic liquid onto cellulose for fast adsorption and efficient separation of Cr(VI): Batch, column and mechanism investigation.

PubMed

Dong, Zhen; Zhao, Long

2018-06-01

Combining the advantages of both cellulose and ionic liquid, ionic liquid functionalized cellulose (ILFC) as adsorbent was prepared through radiation grafting glycidyl methacrylate onto cellulose microsphere following by reaction with ionic liquid 1-aminopropyl-3-methyl imidazolium nitrate. Its adsorption properties towards Cr(VI) were investigated in batch and column experiments. In batch experiments, the adsorption kinetics was well fitted with pseudo-second-order mode with equilibrium time of 2 h and the adsorption capacity reached 181.8 mg/g at pH 2 calculated from Langmuir model. In fixed column, both Yoon-Nelson and Thomas models gave satisfactory fit to experimental data and breakthrough curves, and equilibrium adsorption capacity calculated by Thomas model was 161.0 mg/g. Moreover, ILFC exhibited high selectivity towards Cr(VI) even in synthetic chrome-plating wastewater. Besides, adsorption/desorption test revealed ILFC can be regenerated and reused several times without obvious decrease in adsorbed amount. The adsorption process was demonstrated to anion exchange-reduction mechanism via XPS analysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Visualization of TlBr ionic transport mechanism by the Accelerated Device Degradation technique

NASA Astrophysics Data System (ADS)

Datta, Amlan; Becla, Piotr; Motakef, Shariar

2015-06-01

Thallium Bromide (TlBr) is a promising gamma radiation semiconductor detector material. However, it is an ionic semiconductor and suffers from polarization. As a result, TlBr devices degrade rapidly at room temperature. Polarization is associated with the flow of ionic current in the crystal under electrical bias, leading to the accumulation of charged ions at the device's electrical contacts. We report a fast and reliable direct characterization technique to identify the effects of various growth and post-growth process modifications on the polarization process. The Accelerated Device Degradation (ADD) characterization technique allows direct observation of nucleation and propagation of ionic transport channels within the TlBr crystals under applied bias. These channels are observed to be initiated both directly under the electrode as well as away from it. The propagation direction is always towards the anode indicating that Br- is the mobile diffusing species within the defect channels. The effective migration energy of the Br- ions was calculated to be 0.33±0.03 eV, which is consistent with other theoretical and experimental results.

Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

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

Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.

2015-01-01

Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2more » produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.« less

Impedance analysis on PVA/PVP: GO blend nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Rao, M. C.; Basha, S. K. Shahenoor; Kumar, B. Ranjit

2018-05-01

Nanocomposite polymer films have been prepared by doping Graphene oxide (GO) in PVA/PVP blend polymers by solution cast technique. AC conductivity studies were performed on to the prepared nanocomposite films and the maximum ionic conductivity is found to be 6.13x10-4 Scm-1 for (0.30:0.3) wt% of nanocomposite polymer film at room temperature. The maximum ionic conductivity of nanocomposite polymer films of PVA/PVP: GO holds great promise in potential applications.

Raman studies on molecular and ionic forms in solid layers of nitrogen dioxide - Temperature and light induced effects

NASA Astrophysics Data System (ADS)

Givan, A.; Loewenschuss, A.

1990-12-01

Raman spectra of zero-pressure-formed N2O4 solid layers are reported. Sample composition is extremely dependent upon deposition conditions. For ordered and pure solid N2O4(D2h), produced by slow NO2 deposition, temperature cycling over the range in which the solid is stable shows no significant spectral changes and does not result in autoionization, as argued in a previous Raman study. Fast and low temperature deposited layers are amorphous and multicomponent, showing bands of disordered and isomeric molecular N2O4 and of ionic NO + NO3, nitrosonium nitrate. For nitrosonium nitrate, three solid modifications can be characterized spectroscopically. In the amorphous phase, a light induced, temperature dependent, reversible transition between molecular and ionic nitrogen tetroxide is observed below 150 K. The paths leading to nitrosonium nitrate formation are examined.

Surface hopping investigation of the relaxation dynamics in radical cations

DOE PAGES

Assmann, Mariana; Weinacht, Thomas; Matsika, Spiridoula

2016-01-19

Ionization processes can lead to the formation of radical cations with population in several ionic states. In this study, we examine the dynamics of three radical cations starting from an excited ionic state using trajectory surface hopping dynamics in combination with multiconfigurational electronic structure methods. The efficiency of relaxation to the ground state is examined in an effort to understand better whether fragmentation of cations is likely to occur directly on excited states or after relaxation to the ground state. The results on cyclohexadiene, hexatriene, and uracil indicate that relaxation to the ground ionic state is very fast in thesemore » systems, while fragmentation before relaxation is rare. Ultrafast relaxation is facilitated by the close proximity of electronic states and the presence of two- and three-state conical intersections. Furthermore, examining the properties of the systems in the Franck-Condon region can give some insight into the subsequent dynamics.« less

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

DOE PAGES

Lin, Ye; Fang, Shumin; Su, Dong; ...

2015-04-10

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

Microphase separation and the formation of ion conductivity channels in poly(ionic liquid)s: A coarse-grained molecular dynamics study

NASA Astrophysics Data System (ADS)

Weyman, Alexander; Bier, Markus; Holm, Christian; Smiatek, Jens

2018-05-01

We study generic properties of poly(ionic liquid)s (PILs) via coarse-grained molecular dynamics simulations in bulk solution and under confinement. The influence of different side chain lengths on the spatial properties of the PIL systems and on the ionic transport mechanism is investigated in detail. Our results reveal the formation of apolar and polar nanodomains with increasing side chain length in good agreement with previous results for molecular ionic liquids. The ion transport numbers are unaffected by the occurrence of these domains, and the corresponding values highlight the potential role of PILs as single-ion conductors in electrochemical devices. In contrast to bulk behavior, a pronounced formation of ion conductivity channels in confined systems is initiated in close vicinity to the boundaries. We observe higher ion conductivities in these channels for increasing PIL side chain lengths in comparison with bulk values and provide an explanation for this effect. The appearance of these domains points to an improved application of PILs in modern polymer electrolyte batteries.

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

PubMed Central

Lin, Ye; Fang, Shumin; Su, Dong; Brinkman, Kyle S; Chen, Fanglin

2015-01-01

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce0.8Gd0.2O2−δ–CoFe2O4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopant and depletion of oxygen vacancies at the Ce0.8Gd0.2O2−δ–Ce0.8Gd0.2O2−δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. This work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution. PMID:25857355

Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

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

Lin, Ye; Fang, Shumin; Su, Dong

Mixed ionic–electronic conductors are widely used in devices for energy conversion and storage. Grain boundaries in these materials have nanoscale spatial dimensions, which can generate substantial resistance to ionic transport due to dopant segregation. Here, we report the concept of targeted phase formation in a Ce 0.8Gd 0.2O 2₋δ–CoFe 2O 4 composite that serves to enhance the grain boundary ionic conductivity. Using transmission electron microscopy and spectroscopy approaches, we probe the grain boundary charge distribution and chemical environments altered by the phase reaction between the two constituents. The formation of an emergent phase successfully avoids segregation of the Gd dopantmore » and depletion of oxygen vacancies at the Ce 0.8Gd 0.2O 2₋δ–Ce 0.8Gd 0.2O 2₋δ grain boundary. This results in superior grain boundary ionic conductivity as demonstrated by the enhanced oxygen permeation flux. Lastly, this work illustrates the control of mesoscale level transport properties in mixed ionic–electronic conductor composites through processing induced modifications of the grain boundary defect distribution.« less

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

PubMed

Kerner, Ross A; Rand, Barry P

2018-01-04

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

Ionic conductors for solid oxide fuel cells

DOEpatents

Krumpelt, Michael; Bloom, Ira D.; Pullockaran, Jose D.; Myles, Kevin M.

1993-01-01

An electrolyte that operates at temperatures ranging from 600.degree. C. to 800.degree. C. is provided. The electrolyte conducts charge ionically as well as electronically. The ionic conductors include molecular framework structures having planes or channels large enough to transport oxides or hydrated protons and having net-positive or net-negative charges. Representative molecular framework structures include substituted aluminum phosphates, orthosilicates, silicoaluminates, cordierites, apatites, sodalites, and hollandites.

A novel bio electro active alginate-aniline tetramer/ agarose scaffold for tissue engineering: synthesis, characterization, drug release and cell culture study.

PubMed

Atoufi, Zhale; Zarrintaj, Payam; Motlagh, Ghodratollah Hashemi; Amiri, Anahita; Bagher, Zohreh; Kamrava, Seyed Kamran

2017-10-01

In this study, synthesis of a novel biocompatible stimuli-responsive conducting hydrogel based on agarose/alginate-aniline tetramer with the capability of a tailored electrically controlled drug-release for neuroregeneration is investigated. First, aniline tetramer is synthesized and grafted onto sodium alginate. Then, this material is added to agarose as an electrical conductivity modifier to obtain Agarose/alginate-aniline tetramer hydrogel. The synthesized materials are characterized by H NMR and FTIR. The hydrogels are prepared with varying content of aniline tetramer and their swelling-deswelling and shape memory behavior is evaluated. The electroactivity and ionic conductivity of hydrogels against temperature is measured. The sample with 10% aniline tetramer (AT10) reveals the highest ionic conductivity. In MTT and SEM assays, AT10 shows the best cell viability and cell proliferation due to its highest ionic conductivity highlighting the fact that electrical stimuli cell signaling. Hydrogels also represent great potentials for passive and electro-stimulated dexamethasone release. These results demonstrate that the newly developed conducting hydrogels are promising materials for neuroregenerative medicine.

Superionic Conductivity of Sm3+, Pr3+, and Nd3+ Triple-Doped Ceria through Bulk and Surface Two-Step Doping Approach.

PubMed

Liu, Yanyan; Fan, Liangdong; Cai, Yixiao; Zhang, Wei; Wang, Baoyuan; Zhu, Bin

2017-07-19

Sufficiently high oxygen ion conductivity of electrolyte is critical for good performance of low-temperature solid oxide fuel cells (LT-SOFCs). Notably, material conductivity, reliability, and manufacturing cost are the major barriers hindering LT-SOFC commercialization. Generally, surface properties control the physical and chemical functionalities of materials. Hereby, we report a Sm 3+ , Pr 3+ , and Nd 3+ triple-doped ceria, exhibiting the highest ionic conductivity among reported doped-ceria oxides, 0.125 S cm -1 at 600 °C. It was designed using a two-step wet-chemical coprecipitation method to realize a desired doping for Sm 3+ at the bulk and Pr 3+ /Nd 3+ at surface domains (abbreviated as PNSDC). The redox couple Pr 3+ /Pr 4+ contributes to the extraordinary ionic conductivity. Moreover, the mechanism for ionic conductivity enhancement is demonstrated. The above findings reveal that a joint bulk and surface doping methodology for ceria is a feasible approach to develop new oxide-ion conductors with high impacts on advanced LT-SOFCs.

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors

PubMed Central

Leistenschneider, Desirée; Jäckel, Nicolas; Hippauf, Felix; Presser, Volker

2017-01-01

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g−1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g−1 in organic and 138 F g−1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g−1 in EMIM-BF4. PMID:28781699

Dual-responsive soft actuators based on self-assembled polymers

NASA Astrophysics Data System (ADS)

Kim, Seung Jae; Park, Moon Jeong

Electroactive polymer actuators (EAPs) have been extensively studied for biomimetic technologies such as artificial muscles and soft robotics. While a large deformation can be achievable from EAPs under relatively low-driving voltages, the slow response time has long been a fundamental drawback of EAPs. Here, we investigate a new soft actuator capable of responding two different external stimuli. The actuator is composed of electroactive polymer and light-responsive polymer. We have employed ionic block copolymers having well-connected ion-conduction channels to raise response to electric-field. Light-responsive polymers were additionally incorporated into them to control the deformation of the actuator in an independent manner. Noteworthy observation in the present study is that the dual-responsive polymers resulted in synergetic achievement of high bending strain and fast response time, which marked a significant improvement from the conventional EAPs.

Millimeter-wave irradiation heating for operation of doped CeO2 electrolyte-supported single solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Che Abdullah, Salmie Suhana Binti; Teranishi, Takashi; Hayashi, Hidetaka; Kishimoto, Akira

2018-01-01

High operation temperature of solid oxide fuel cell (SOFC) results in high cell and operation cost, time consuming and fast cell degradation. Developing high performance SOFC that operates at lower temperature is required. Here we demonstrate 24 GHz microwave as a rapid heating source to replace conventional heating method for SOFC operation using 20 mol% Sm doped CeO2 electrolyte-supported single cell. The tested cell shows improvement of 62% in maximum power density at 630 °C under microwave heating. This improvement governs by bulk conductivity of the electrolyte. Investigation of ionic transference number reveals that the value is unchanged under microwave irradiation, confirming the charge carrier is dominated by oxygen ion species. This work shows a potential new concept of high performance as well as cost and energy effective SOFC.

Preoptimised VB: a fast method for the ground and excited states of ionic clusters I. Localised preoptimisation for (ArCO) +, (ArN 2) + and N 4+

NASA Astrophysics Data System (ADS)

Langenberg, J. H.; Bucur, I. B.; Archirel, P.

1997-09-01

We show that in the simple case of van der Waals ionic clusters, the optimisation of orbitals within VB can be easily simulated with the help of pseudopotentials. The procedure yields the ground and the first excited states of the cluster simultaneously. This makes the calculation of potential energy surfaces for tri- and tetraatomic clusters possible, with very acceptable computation times. We give potential curves for (ArCO) +, (ArN 2) + and N 4+. An application to the simulation of the SCF method is shown for Na +H 2O.

Effects of Polymer Structure and Relaxations on Ionic Conductivity in Anion Exchange Membranes with Quaternary Ammonium Functional Groups

NASA Astrophysics Data System (ADS)

Maes, Ashley M.

Anion exchange membranes (AEMs) are of considerable interest to developers and researchers of electrochemical conversion and storage devices such as anion exchange membrane fuel cells (AAEMFCs), alkaline polymer electrolyte electrolysers, redox flow batteries and bioelectrochemical devices. AEMs are generally in competition with more established proton exchange membranes (PEMs), but offer the potential for reduction of materials costs and greater fuel flexibility across these applications. This work includes an introduction to AEMs in the context of fuel cell technologies and some key techniques for AEM characterization. There are many synthetic strategies to incorporate cationic functional groups, which promote anion transport, into a polymer matrix. Two membrane chemistries are investigated in the following chapters. The first is based on a simple synthesis procedure that produced a membrane consisting of random, crosslinked polypropylene- ran-polyethyleneimine with quaternary ammonium functional groups. This membrane had moderate chloride ionic conductivity of 0.03 S cm -1 at 95 °C and high water uptake with minimal dimensional swelling. However, the lack of control of crosslink location and density during synthesis produced a material with a very random nature, making it a poor candidate for more fundamental transport studies. The second membrane chemistry is a block copolymer with a hydrophobic and hydrophilic block. The hydrophobic block was selected to provide favorable mechanical and barrier characteristics while a hydrophilic block was selected to provide water uptake and anion conducting functionalities. Poly(vinyl benzyl trimethyl ammonium bromide)-b-poly(methylbutylene) ([PVBTMA][Br]- b-PMB) was synthesized by partners at the University of Massachusetts-Amherst with varied degrees of functionalization (DF) along the hydrophilic block, resulting in ion exchange capacities ranging from 0.77 to 2.20 mmol g -1. Water uptake, in-plane ionic conductivity and membrane morphology were measured across a series of membranes with the original bromide (Br -) counter-ion. These bulk materials characterization experiments demonstrated that this polymer structure produces well-ordered lamellar morphology with moderate water uptake and competitive ionic conductivity (ca. 40 mS cm-1 at 90 °C and 95% relative humidity). These characteristics make it an appropriate candidate for the following more fundamental investigations of ionic conductivity mechanisms. Broadband electrical spectroscopy (BES) was conducted on one [PVBTMA][Br]- b-PMB sample in the Br- form and analyzed in conjunction with thermal stability and relaxation experiments in Chapter 4. We were able to propose two separate ionic conductivity mechanisms and relate each to physical attributes of the polymer structure. A significant thermal transition was observed at Tdelta , which resulted in a dramatic drop in conductivity. In a continued effort to characterize the ionic conductivity of these block-copolymer membranes, another BES study was conducted on three samples with varying DFs. Samples were converted to hydroxide (OH- ) form so we could contrast the Br- conductivity mechanisms to those in a more relevant counter-ion form. After analysis of the electric response of the material, combined with the thermal analysis by TGA, MDSC and DMA, conductivity mechanisms were described. As in the Br- study, conductivity involves two distinct conduction pathways, sigmaEP and sigmaIP,1. Importantly, we again observed a drop in conductivity at Tdelta in each of these samples, with Tdelta decreasing as the density of functional groups along the hydrophilic block increased. It is undesirable for this transition to occur during operation in a fuel cell or other electrochemical device, so future work to investigate strategies for inhibition are recommended.

Nonequilibrium Simulations of Ion Dynamics in Ionomer Melts

NASA Astrophysics Data System (ADS)

Frischknecht, Amalie

Ionomers, polymers containing a small fraction of covalently bound ionic groups, are of interest as possible electrolytes in batteries. However, to date ionomers do not have sufficiently high conductivities for practical application, most likely because the ions tend to form aggregates, leading to slow ion transport. To build a better understanding of the relationships among ionomer chemistry, morphology, and ion transport, we have performed a series of molecular dynamics simulations and connected aspects of these simulations with experiment. In previous work using both atomistic and coarse-grained models, we showed that precise ionomers (with a fixed spacing between ionic groups along the polymer backbone) exhibit a range of ionic aggregate morphologies, from discrete clusters to percolated aggregates. In this talk I will describe recent simulations of our coarse-grained ionomer melts in an applied electric field. From a constant applied field, we are able to extract the ion mobilities and hence conductivities. We find that ionomers with percolated ionic aggregate morphologies have higher ion mobilities and hence higher conductivities. Application of an oscillating electric field enables us to calculate the frequency-dependent conductivity of the model ionomer melts. The real part of the conductivity has a high frequency peak associated with plasma oscillations, and a very broad low frequency peak associated with ion motions in ionic aggregates. I will end with comments on the connections to atomistic simulations and to experimental probes of ion dynamics. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Synergistic Impacts of Electrolyte Adsorption on the Thermoelectric Properties of Single-Walled Carbon Nanotubes.

PubMed

Nakano, Motohiro; Nakashima, Takuya; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki

2017-08-01

Single-walled carbon nanotubes are promising candidates for light-weight and flexible energy materials. Recently, the thermoelectric properties of single-walled carbon nanotubes have been dramatically improved by ionic liquid addition; however, controlling factors remain unsolved. Here the thermoelectric properties of single-walled carbon nanotubes enhanced by electrolytes are investigated. Complementary characterization with absorption, Raman, and X-ray photoelectron spectroscopy reveals that shallow hole doping plays a partial role in the enhanced electrical conductivity. The molecular factors controlling the thermoelectric properties of carbon nanotubes are systematically investigated in terms of the ionic functionalities of ionic liquids. It is revealed that appropriate ionic liquids show a synergistic enhancement in conductivity and the Seebeck coefficient. The discovery of significantly precise doping enables the generation of thermoelectric power factor exceeding 460 µW m - 1 K -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of ionic transport in sodium scandium phosphate (NSP) and related compounds

NASA Astrophysics Data System (ADS)

Bhat, Kaustubh; Blügel, Stefan; Lustfeld, Hans

Sodium ionic conductors offer significant advantages for application in large scale energy storage systems. In this study, we investigate the different pathways available for sodium ion conduction in NSP and calculate energy barriers for ionic transport using Density Functional Theory (DFT) and the Nudged Elastic Band Method. We identify the structural parameters that reduce the energy barrier, by calculating the influence of positive and negative external pressure on the energy barrier. Lattice strain can be introduced by cation or anion substitution within the NASICON structure. We substitute the scandium atom with other trivalent atoms such as aluminium and yttrium, and calculate the resulting energy barriers. Sodium thiophosphate (Na3PS4) has previously shown about two orders of magnitude higher ionic conductivity than sodium phosphate (Na3PO4). We investigate the effect of substituting oxygen with sulphur in NSP. We acknowledge discussions with our experimental colleagues F. Tietz and M. Guin toward this work

Solid State Ionics: from Michael Faraday to green energy-the European dimension.

PubMed

Funke, Klaus

2013-08-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag 2 S and PbF 2 and coined terms such as cation and anion , electrode and electrolyte . In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an 'evolving scheme of materials science', point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987.

Solid State Ionics: from Michael Faraday to green energy—the European dimension

PubMed Central

Funke, Klaus

2013-01-01

Solid State Ionics has its roots essentially in Europe. First foundations were laid by Michael Faraday who discovered the solid electrolytes Ag2S and PbF2 and coined terms such as cation and anion, electrode and electrolyte. In the 19th and early 20th centuries, the main lines of development toward Solid State Ionics, pursued in Europe, concerned the linear laws of transport, structural analysis, disorder and entropy and the electrochemical storage and conversion of energy. Fundamental contributions were then made by Walther Nernst, who derived the Nernst equation and detected ionic conduction in heterovalently doped zirconia, which he utilized in his Nernst lamp. Another big step forward was the discovery of the extraordinary properties of alpha silver iodide in 1914. In the late 1920s and early 1930s, the concept of point defects was established by Yakov Il'ich Frenkel, Walter Schottky and Carl Wagner, including the development of point-defect thermodynamics by Schottky and Wagner. In terms of point defects, ionic (and electronic) transport in ionic crystals became easy to visualize. In an ‘evolving scheme of materials science’, point disorder precedes structural disorder, as displayed by the AgI-type solid electrolytes (and other ionic crystals), by ion-conducting glasses, polymer electrolytes and nano-composites. During the last few decades, much progress has been made in finding and investigating novel solid electrolytes and in using them for the preservation of our environment, in particular in advanced solid state battery systems, fuel cells and sensors. Since 1972, international conferences have been held in the field of Solid State Ionics, and the International Society for Solid State Ionics was founded at one of them, held at Garmisch-Partenkirchen, Germany, in 1987. PMID:27877585

Conductivity of gel polymer electrolytes doped with solutions of phosphonic acid or protic ionic liquids

NASA Astrophysics Data System (ADS)

Shmukler, Liudmila E.; Fadeeva, Yuliya A.; Glushenkova, Ekaterina V.; Nguyen, Van Thuc; Safonova, Liubov P.

2018-04-01

The proton-conducting gel electrolytes (PCGEs) based on PMMA, PVdF or PVdF-HFP doped with solutions of phosphonic acid or ammonium based protic ionic liquids (PILs) in DMF have been synthesized. Rather high values of the conductivity (10-4-10-3 S cm-1) have been reached at low dopant concentrations (up to 1 mol l-1). The influence of the nature of both polymeric matrix and dopant as well as dopant concentration on the conductivity values was discussed. It was established that the dependence of conductivity on the nature of dopant, but not the polymeric matrix, was more pronounced.

Development of ionic gels using thiol-based monomers in ionic liquid

NASA Astrophysics Data System (ADS)

Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu

2016-04-01

Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.

Synergistic Effects of Mixing Sulfone and Ionic Liquid as Safe Electrolytes for Lithium Sulfur Batteries

DOE PAGES

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; ...

2014-11-26

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAhg- 1 (second cycle) by using 40% 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-Npropylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60% 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower thanmore » that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAhg 1 even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity.« less

Guar gum as biosourced building block to generate highly conductive and elastic ionogels with poly(ionic liquid) and ionic liquid.

PubMed

Zhang, Biao; Sudre, Guillaume; Quintard, Guilhem; Serghei, Anatoli; David, Laurent; Bernard, Julien; Fleury, Etienne; Charlot, Aurélia

2017-02-10

In this study, we report on the simple and straightforward preparation of ionogels arising from the addition of guar gum (a plant-based polysaccharide) in a solution of precisely-defined poly(ionic liquid) chains (PIL) in imidazolium-based ionic liquid (IL). The development of intermolecular polar interactions (mainly hydrogen bonds) and topologic chain entanglements induces the formation of physical biohybrid ionogels, whose elastic properties can be easily tuned by varying the composition (up to 30000Pa). The combined presence of guar gum and PIL confers excellent dimensional stability to the ionogels with no IL exudation combined with high thermal properties (up to 310°C). The resulting materials are shown to exhibit gel scattering profiles and high conductivities (> 10 -4 S/cm at 30°C). The benefit linked to the formation of guar/PIL associations in IL medium enables to find a good compromise between the mechanical cohesion and the mobility ensuring the ionic transport. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rational design of mixed ionic and electronic conducting perovskite oxides for solid oxide fuel cell anode materials: A case study for doped SrTiO3

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

Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu

2014-01-01

The effect of p- and n-type dopants on ionic and electronic conductivity of SrTiO3 based perovskites were investigated both computationally and experimentally. Specifically, we performed density functional theory (DFT) calculations of Na- and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 systems. Constrained ab initio thermodynamic calculations were used to evaluate the phase stability and reducibility of doped SrTiO3 under both oxidizing and reducing synthesis conditions, as well as under anodic solid oxide fuel cell (SOFC) conditions. The density of states (DOS) of these materials was analyzed to study the effects of p- and n-doping on the electronic conductivity. Furthermore, Na-more » and La-doped SrTiO3 and Na- and Nb-doped SrTiO3 samples were experimentally prepared and the conductivity was measured to confirm our computational predictions. The experimental observations are in very good agreement with the theoretical predictions that doping n-doped SrTiO3 with small amounts of p-type dopants promotes both the ionic and electronic conductivity of the material. This doping strategy is valid independent of p- and n-doping site and permits the synthesis of perovskite based mixed ionic/electronic conductors.« less

Super ionic conductive glass

DOEpatents

Susman, S.; Volin, K.J.

Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Grain Boundary Engineering of Lithium-Ion-Conducting Lithium Lanthanum Titanate for Lithium-Air Batteries

DTIC Science & Technology

2015-01-01

Tojo T, Sakurai Y. Synthesis and lithium - ion conductivity for perovskite-type Li3/8Sr7/16Ta3/4Zr1/4O3 solid electrolyte by powder-bed sintering...battery performance is limited by the electrolytic membrane, which needs high Li-ionic conductivity. Lithium lanthanum titanate (Li3xLa(2/3)-xTiO3, or...of the A-site ions and lithium ion conductivity in the perovskite solid solution La0.67-xLi3xTiO3 (x=0.11). Journal of Solid State Ionics. 1999;121

Characterization of Thallium Bromide (TlBr) for Room Temperature Radiation Detectors

NASA Astrophysics Data System (ADS)

Smith, Holland McTyeire

Thallium bromide (TlBr) has emerged as a remarkably well-suited material for room temperature radiation detection. The unique combination of high-Z elements, high density, suitable band gap, and excellent electrical transport properties present in TlBr have brought device performance up to par with CdZnTe (CZT), the current market-leading room temperature radiation detector material. TlBr research is at an earlier stage than that of CZT, giving hope that the material will see even further improvement in electronic properties. Improving a resistive semiconductor material requires knowledge of deep levels present in the material and the effects of these deep levels on transport properties. Very few deep level studies have been conducted on TlBr, and none with the depth required to generate useful growth suggestions. In this dissertation, deep levels in nominally undoped and doped TlBr samples are studied with electrical and optical methods. Photo-Induced Conductivity Transient Spectroscopy (PICTS) is used to discover many deep levels in TlBr electrically. These levels are compared to sub-band gap optical transitions originating from defects observed in emission spectra. The results of this research indicate that the origin of resistivity in TlBr is likely due to deep level defects pinning the Fermi level at least ˜0.7 eV from either the conduction or valence band edge. The effect of dopants and deep levels on transport in TlBr is assessed with microwave photoconductivity decay analysis. It is found that Pb-, Se-, and O-doping decreases carrier lifetime in TlBr, whereas C-doping does not. TlBr exhibits weak ionic conductivity at room temperature, which both negatively affects the leakage current of detectors and leads to device degradation over time. Researchers are actively looking for ways to reduce or eliminate the ionic conductivity, but are faced with an intriguing challenge of materials engineering: is it possible to mitigate the ionic conduction of TlBr without harming the excellent electronic transport properties? Doping TlBr in order to control the ionic conductivity has been proposed and shown to be effective in reducing dark ionic current, but the electronic effects of the dopants has not been previously studied in detail. In this dissertation, the electronic effects of dopants introduced for ionic reasons are evaluated.

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

Synthesis of Long-Chain-Branched (LCB) Polysulfones for Multifunctional Transport Membranes

DTIC Science & Technology

2010-09-01

R.; Dutta, N. K. Interfacial Interactions in Aprotic Ionic Liquid Based Protonic Membrane and Its Correlation with High Temperature Conductivity...rigidity. The series of novel polymers was characterized for chemical structure, thermal transitions, and molecular weight. Ionic conductivity was tested...Although much progress exists based on perfluorosulfonated platforms ( Nafion , σ ≈ 10-1 – 10-2 S/cm) new and more complicated parameters arise as

Ionic Conductivity, Structural Deformation and Programmable Anisotropy of DNA Origami in Electric Field

PubMed Central

Li, Chen-Yu; Hemmig, Elisa A.; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia

2015-01-01

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules—a DNA origami plate— placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg2+ ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA. PMID:25623807

Ionic conductivity, structural deformation, and programmable anisotropy of DNA origami in electric field.

PubMed

Li, Chen-Yu; Hemmig, Elisa A; Kong, Jinglin; Yoo, Jejoong; Hernández-Ainsa, Silvia; Keyser, Ulrich F; Aksimentiev, Aleksei

2015-02-24

The DNA origami technique can enable functionalization of inorganic structures for single-molecule electric current recordings. Experiments have shown that several layers of DNA molecules, a DNA origami plate, placed on top of a solid-state nanopore is permeable to ions. Here, we report a comprehensive characterization of the ionic conductivity of DNA origami plates by means of all-atom molecular dynamics (MD) simulations and nanocapillary electric current recordings. Using the MD method, we characterize the ionic conductivity of several origami constructs, revealing the local distribution of ions, the distribution of the electrostatic potential and contribution of different molecular species to the current. The simulations determine the dependence of the ionic conductivity on the applied voltage, the number of DNA layers, the nucleotide content and the lattice type of the plates. We demonstrate that increasing the concentration of Mg(2+) ions makes the origami plates more compact, reducing their conductivity. The conductance of a DNA origami plate on top of a solid-state nanopore is determined by the two competing effects: bending of the DNA origami plate that reduces the current and separation of the DNA origami layers that increases the current. The latter is produced by the electro-osmotic flow and is reversible at the time scale of a hundred nanoseconds. The conductance of a DNA origami object is found to depend on its orientation, reaching maximum when the electric field aligns with the direction of the DNA helices. Our work demonstrates feasibility of programming the electrical properties of a self-assembled nanoscale object using DNA.

Glass transition dynamics and conductivity scaling in ionic deep eutectic solvents: The case of (acetamide + lithium nitrate/sodium thiocyanate) melts

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

Tripathy, Satya N., E-mail: satyanarayantripathy@gmail.com; Wojnarowska, Zaneta; Knapik, Justyna

2015-05-14

A detailed investigation on the molecular dynamics of ionic deep eutectic solvents (acetamide + lithium nitrate/sodium thiocyanate) is reported. The study was carried out employing dielectric relaxation spectroscopy covering seven decades in frequency (10{sup −1}-10{sup 6} Hz) and in a wide temperature range from 373 K down to 173 K, accessing the dynamic observables both in liquid and glassy state. The dielectric response of the ionic system has been presented in the dynamic window of modulus formalism to understand the conductivity relaxation and its possible connection to the origin of localized motion. Two secondary relaxation processes appear below glass transitionmore » temperature. Our findings provide suitable interpretation on the nature of secondary Johari-Goldstein process describing the ion translation and orientation of dipoles in a combined approach using Ngai’s coupling model. A nearly constant loss feature is witnessed at shorter times/lower temperatures. We also discuss the ac conductivity scaling behavior using Summerfield approach and random free energy barrier model which establish the time-temperature superposition principle. These experimental observations have fundamental importance on theoretical elucidation of the conductivity relaxation and glass transition phenomena in molten ionic conductors.« less

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

Electroosmotic flow and ionic conductance in a pH-regulated rectangular nanochannel

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Sadeghi, Arman

2017-06-01

Infinite series solutions are obtained for electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties of long pH-regulated rectangular nanochannels of low surface potential utilizing the double finite Fourier transform method. Closed form expressions are also obtained for channels of large height to width ratio for which the depthwise variations vanish. Neglecting the Stern layer impact, the effects of EDL (Electric Double Layer) overlap, multiple ionic species, and association/dissociation reactions on the surface are all taken into account. Moreover, finite-element-based numerical simulations are conducted to account for the end effects as well as to validate the analytical solutions. We show that, with the exception of the migratory ionic conductivity, all the physicochemical parameters are strong functions of the channel aspect ratio. Accordingly, a slit geometry is not a good representative of a rectangular channel when the width is comparable to the height. It is also observed that the distribution of the electrical potential is not uniform over the surface of a charge-regulated channel. In addition, unlike ordinary channels for which an increase in the background salt concentration is always accompanied by higher flow rates, quite the opposite may be true for a pH-regulated duct at higher salt concentrations.

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

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.

New Pyrazolium Salts as a Support for Ionic Liquid Crystals and Ionic Conductors

PubMed Central

Pastor, María Jesús; Sánchez, Ignacio; Schmidt, Rainer; Cano, Mercedes

2018-01-01

Ionic liquid crystals (ILCs) are a class of materials that combine the properties of liquid crystals (LCs) and ionic liquids (ILs). This type of materials is directed towards properties such as conductivity in ordered systems at different temperatures. In this work, we synthesize five new families of ILCs containing symmetrical and unsymmetrical substituted pyrazolium cations, with different alkyl long-chains, and anions such as Cl−, BF4−, ReO4−, p-CH3-6H4SO3− (PTS) and CF3SO3− (OTf). We study their thermal behavior by polarized light optical microscopy (POM) and differential scanning calorimetry (DSC). All of them, except those with OTf as counteranion, show thermotropic mesomorphism. The observations by POM reveal textures of lamellar mesophases. Those agree with the arrangement observed in the X-ray crystal structure of [H2pzR(4),R(4)][ReO4]. The nature of the mesophases is also confirmed by variable temperature powder X-ray diffraction. On the other hand, the study of the dielectric properties at variable temperature in mesomorphic (Cl− and BF4−) and non-mesomorphic (OTf) salts indicates that the supramolecular arrangement of the mesophase favors a greater ionic mobility and therefore ionic conductivity. PMID:29614030

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.].

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.

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

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

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

Geometry effect on electrokinetic flow and ionic conductance in pH-regulated nanochannels

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Moosavi, Ali; Sadeghi, Arman

2017-12-01

Semi-analytical solutions are obtained for the electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties associated with long pH-regulated nanochannels of arbitrary but constant cross-sectional area. The effects of electric double layer overlap, multiple ionic species, and surface association/dissociation reactions are all taken into account, assuming low surface potentials. The method of analysis includes series solutions which the pertinent coefficients are obtained by applying the wall boundary conditions using either of the least-squares or point matching techniques. Although the procedure is general enough to be applied to almost any arbitrary cross section, nine nanogeometries including polygonal, trapezoidal, double-trapezoidal, rectangular, elliptical, semi-elliptical, isosceles triangular, rhombic, and isotropically etched profiles are selected for presentation. For the special case of an elliptic cross section, full analytical solutions are also obtained utilizing the Mathieu functions. We show that the geometrical configuration plays a key role in determination of the ionic conductance, surface charge density, electrical potential and velocity fields, and proton enhancement. In this respect, the net electric charge and convective ionic conductance are higher for channels of larger perimeter to area ratio, whereas the opposite is true for the average surface charge density and mean velocity; the geometry impact on the two latest ones, however, vanishes if the background salt concentration is high enough. Moreover, we demonstrate that considering a constant surface potential equal to the average charge-regulated potential provides sufficiently accurate results for smooth geometries such as an ellipse at medium-high aspect ratios but leads to significant errors for geometries having narrow corners such as a triangle.

Phase behavior of 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C12MIm(FH)(n)F, n = 1.0-2.3) and their anisotropic ionic conductivity as ionic liquid crystal electrolytes.

PubMed

Xu, Fei; Matsumoto, Kazuhiko; Hagiwara, Rika

2012-08-23

The effects of the HF composition, n, in 1-dodecyl-3-methylimidazolium fluorohydrogenate salts (C(12)MIm(FH)(n)F, n = 1.0-2.3) on their physicochemical and structural properties have been investigated using infrared spectroscopy, thermal analysis, polarized optical microscopy, X-ray diffraction, and anisotropic ionic conductivity measurements. The phase diagram of C(12)MIm(FH)(n)F (n vs transition temperature) suggests that C(12)MIm(FH)(n)F is a mixed crystal system that has a boundary around n = 1.9. For all compositions, a liquid crystalline mesophase with a smectic A interdigitated bilayer structure is observed. The temperature range of the mesophase decreases with increasing n value (from 61.8 °C for C(12)MIm(FH)(1.0)F to 37.0 °C for C(12)MIm(FH)(2.3)F). The layer spacing of the smectic structure decreases with increasing n value or increasing temperature. Two structural types with different layer spacings are observed in the crystalline phase (type I, 1.0 ≤ n ≤ 1.9, and type II, 1.9 ≤ n ≤ 2.3). Ionic conductivities parallel and perpendicular to the smectic layers (σ(||) and σ([perpendicular])) increase with increasing n value, whereas the anisotropy of the ionic conductivities (σ(||)/σ([perpendicular])) is independent of the n value, since the thickness of the insulating sheet formed by the dodecyl group remains nearly unchanged.

Computational and Experimental Investigation of Li-doped Ionic Liquid Electrolytes: [pyr14][tfsi], [pyr13][fsi], and [EMIM][BF4

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Bennett, William R.; Wu, James J.; Hernandez, Dionne M.; Borodin, Oleg; Monk, Joshua D.; Bauschlicher, Charles W.; Lawson, John W.

2014-01-01

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N -methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 xLi+ 0.33) and temperature (298 K T 393 K). Structurally, Li+ is shown to be solvated by three anion neigh- bors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi+ we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi+, the contribution of Li+ to ionic conductivity increases until reach- ing a saturation doping level of xLi+ 0.10. Comparatively, the Li+ conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1-0.3 mScm. Our transport results also demonstrate the necessity of long MD simulation runs ( 200 ns) required to converge transport properties at room T. The differences in Li+ transport are reflected in the residence times of Li+ with the anions (Li), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li+ transport in each liquid, we find that while the net motion of Li+ with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange (hopping) increases at high xLi+ and in liquids with large anions.

Supramolecular ionogel lubricants with imidazolium-based ionic liquids bearing the urea group as gelator.

PubMed

Yu, Qiangliang; Wu, Yang; Li, DongMei; Cai, Meirong; Zhou, Feng; Liu, Weimin

2017-02-01

A new class of ionic liquid gels (ionogels) is prepared through the supramolecular self-assembly of imidazolium-based ionic liquids (ILs) bearing the urea group as gelators in normal ILs. The ILs gelator can self-assemble through hydrogen bonding and hydrophobic interaction to form analogous lamellar structures and solidify base ILs. The obtained ionogels exhibit superior anticorrosion and conductivity characteristics. Moreover, ionogels show fully thermoreversible and favorable thixotropic characteristics, such that they can be used as high-performance semisolid conductive lubricants. The tribological tests reveal that these ionogels lubricants can effectively reduce the friction of sliding pairs effectively and have better tribological performance than the pure ILs under harsh conditions. Ionogel lubricants not only maintain the excellent tribological properties and conductivity of ILs, but also prevent base liquids from creeping and leakage. Therefore, ionogel lubricants can be potentially used in the conductive parts of electrical equipments. Copyright © 2016 Elsevier Inc. All rights reserved.

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

PubMed

Lee, Choongyeop; Joly, Laurent; Siria, Alessandro; Biance, Anne-Laure; Fulcrand, Rémy; Bocquet, Lydéric

2012-08-08

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

Block Copolymers and Ionic Liquids: A New Class of Functional Nanocomposites

NASA Astrophysics Data System (ADS)

Lodge, Timothy

2009-03-01

Block copolymers provide a remarkably versatile platform for achieving desired nanostructures by self-assembly, with lengthscales varying from a few nanometers up to several hundred nanometers. Ionic liquids are an emerging class of solvents, with an appealing set of physical attributes. These include negligible vapor pressure, high chemical and thermal stability, tunable solvation properties, high ionic conductivity, and wide electrochemical windows. For various applications it will be necessary to solidify the ionic liquid into particular spatial arrangements, such as membranes or gels, or to partition the ionic liquid in coexisting phases, such as microemulsions and micelles. One example includes formation of spherical, cylindrical, and vesicular micelles by poly(butadiene-b-ethylene oxide) and poly(styrene-b-methylmethacrylate) in the common hydrophobic ionic liquids [BMI][PF6] and [EMI][TFSI]. This work has been extended to the formation of reversible micelle shuttles between ionic liquids and water, whereby entire micelles transfer from one phase to the other, reversibly, depending on temperature and solvent quality. Formation of ion gels has been achieved by self-assembly of poly(styrene-b-ethylene oxide-b-styrene) triblocks in ionic liquids, and by the thermoreversible system poly(N-isopropylacrylamide-b-ethylene oxide-b-N-isopropylacrylamide), using as little as 4% copolymer. Further, these gels have been shown to be remarkably effective as gate dielectrics in organic thin film transistors. The remarkably high capacitance of the ion gels (> 10 μF/cm^2) supports a very high carrier density in an organic semiconductor such as poly(3-hexylthiophene), leading to milliamp currents for low applied voltages. Furthermore, the rapid mobility of the ions enables switching speeds approaching 10 kHz, orders of magnitude higher than achievable with other polymer-based dielectrics such as PEO/LiClO4. Finally, we have shown that ordered nanostructures of block copolymers plus ionic liquids show the characteristic self-assembly properties of strongly-segregated systems. Prospects for anisotropic ionic conductivity are also being explored.

Non-crosslinked, amorphous, block copolymer electrolyte for batteries

DOEpatents

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

2006-04-11

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

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.

Effect of pressure on decoupling of ionic conductivity from structural relaxation in hydrated protic ionic liquid, lidocaine HCl.

PubMed

Swiety-Pospiech, A; Wojnarowska, Z; Hensel-Bielowka, S; Pionteck, J; Paluch, M

2013-05-28

Broadband dielectric spectroscopy and pressure-temperature-volume methods are employed to investigate the effect of hydrostatic pressure on the conductivity relaxation time (τσ), both in the supercooled and glassy states of protic ionic liquid lidocaine hydrochloride monohydrate. Due to the decoupling between the ion conductivity and structural dynamics, the characteristic change in behavior of τσ(T) dependence, i.e., from Vogel-Fulcher-Tammann-like to Arrhenius-like behavior, is observed. This crossover is a manifestation of the liquid-glass transition of lidocaine HCl. The similar pattern of behavior was also found for pressure dependent isothermal measurements. However, in this case the transition from one simple volume activated law to another was noticed. Additionally, by analyzing the changes of conductivity relaxation times during isothermal densification of the sample, it was found that compression enhances the decoupling of electrical conductivity from the structural relaxation. Herein, we propose a new parameter, dlogRτ∕dP, to quantify the pressure sensitivity of the decoupling phenomenon. Finally, the temperature and volume dependence of τσ is discussed in terms of thermodynamic scaling concept.

Anionic membrane and ionomer based on poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline membrane fuel cells

NASA Astrophysics Data System (ADS)

Ong, Ai Lien; Saad, Saeed; Lan, Rong; Goodfellow, Robert J.; Tao, Shanwen

2011-10-01

Hydroxyl-ion conductive poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membranes with different characteristics were prepared via relatively simple bromination/amination serial reactions with reduced number of involved chemicals and shorter reaction time. The effects of reactants ratio, reaction atmosphere, polymer concentration, casting solvent, and hydroxylation treatment on reaction were investigated in details. The microstructure, water uptake, swelling ratio, ion-exchange capacity and ionic conductivity of the membranes were also studied. The obtained results demonstrate that, the ionic conductivity of the membrane is dependent on casting solvent. The N-methyl-2-pyrrolidonecast membrane exhibits the highest conductivity with the thinnest film. Although the membrane was prepared via a relatively simple preparation route with least toxic chemicals, a competitive ionic conductivity value of 1.64 × 10-2 S cm-1 was achieved at 60 °C. A power density of 19.5 mW cm-2 has been demonstrated from the alkaline membrane fuel cell operated at 70 °C, assembled from the entirely homemade membrane electrode assembly without any hot-pressing.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

DTIC Science & Technology

2012-06-01

This method has been used previously with both PEM and AEM fuel cells and demonstrated its ability to accurately predict ionic conductivity [2,9,24...water. In an AMFC, the mobile species is a hydroxide ion (OH - ) and in a PEM fuel cell , the proton is solvated with a water molecule forming...membrane synthesis techniques have produced polymer electrolyte membranes that are capable of transporting anions in alkaline membrane fuel cells

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

DOE PAGES

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

2015-11-02

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

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Dynamic mechanism of equivalent conductivity minimum of electrolyte solution

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Matsuoka, T.; Koda, S.

2011-10-01

The theory on electric conductivity of electrolyte solutions we have developed [T. Yamaguchi, T. Matsuoka, and S. Koda, J. Chem. Phys. 127, 064508 (2007)] is applied to a model electrolyte solution that shows a minimum of equivalent conductivity as the function of concentration [T. Yamaguchi, T. Akatsuka, and S. Koda, J. Chem. Phys. 134, 244506 (2011)]. The theory succeeds in reproducing the equivalent conductivity minimum, whereas the mode-coupling theory (MCT) underestimates the conductivity in the low-concentration regime. The theory can also reproduce the decrease in the relaxation time of conductivity with increasing the concentration we have demonstrated with a Brownian dynamics simulation. A detailed analysis shows that the relaxation of the conductivity occurs through two processes. The faster one corresponds to the collision between a cation and an anion, and the slower one does to the polarization of the ionic atmosphere. The increase in the equivalent conductivity with concentration is attributed to the decrease in the effect of the ionic atmosphere, which is in turn explained by the fact that the counter ion cannot penetrate into the repulsive core when the Debye screening length is compatible or smaller than the ionic diameter. The same mechanism is also observed in MCT calculation with static structure factor determined by mean-spherical approximation.

Ionomers for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph

For ionic actuators and battery separators, it is vital to utilize single-ion conducting ionomers that avoid the detrimental polarization of other ions. Single-ion conducting ionomers are synthesized based on DFT calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for battery separators that conduct Li+ or Na+. Characterization by X-ray scattering, dielectric spectroscopy, FTIR, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. 7Li NMR diffusion measurements find that diffusion is faster than expected by conductivity using the Nernst-Einstein equation, which means that the majority of Li diffusion occurs by ion pairs moving with the polymer segmental motion. Segmental motion only contributes to ionic conduction in the rare event that one of these ion pairs has an extra Li (a positive triple ion). This leads us to a new metric for ion-conducting soft materials, the product of the cation number density p0 and their diffusion coefficient D; p0D is the diffusive flux of lithium ions. This new metric has a maximum at intermediate ion content that corresponds to the overlap of ion pair polarizability volumes. At higher ion contents, the ion pairs interact strongly and form larger aggregation states that retard segmental motion of both mobile ion pairs and triple ions.

3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

PubMed

Kang, Yu Jin; Yoo, Yongju; Kim, Woong

2016-06-08

State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics.

First-Principles Characterization of the Unknown Crystal Structure and Ionic Conductivity of Li7P2S8I as a Solid Electrolyte for High-Voltage Li Ion Batteries.

PubMed

Kang, Joonhee; Han, Byungchan

2016-07-21

Using first-principles density functional theory calculations and ab initio molecular dynamics (AIMD) simulations, we demonstrate the crystal structure of the Li7P2S8I (LPSI) and Li ionic conductivity at room temperature with its atomic-level mechanism. By successively applying three rigorous conceptual approaches, we identify that the LPSI has a similar symmetry class as Li10GeP2S12 (LGPS) material and estimate the Li ionic conductivity to be 0.3 mS cm(-1) with an activation energy of 0.20 eV, similar to the experimental value of 0.63 mS cm(-1). Iodine ions provide an additional path for Li ion diffusion, but a strong Li-I attractive interaction degrades the Li ionic transport. Calculated density of states (DOS) for LPSI indicate that electrochemical instability can be substantially improved by incorporating iodine at the Li metallic anode via forming a LiI compound. Our methods propose the computational design concept for a sulfide-based solid electrolyte with heteroatom doping for high-voltage Li ion batteries.

Synthesis of ionic liquids

DOEpatents

Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

2008-09-09

Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

Synthesis of ionic liquids

DOEpatents

Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

2011-11-01

Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

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.

Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

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

Harun, Fatin; Chan, Chin Han; Winie, Tan

Effect of epoxide content on the thermal and conductivity properties of epoxidized natural rubber (ENR) solid polymer nanocomposite electrolytes was investigated. Commercial available epoxidized natural rubber having 25 (ENR25) and 50 mole% (ENR50) epoxide, respectively were incorporated with lithium perchlorate (LiClO{sub 4}) salt and titanium dioxide (TiO{sub 2}) nanofiller via solution casting method. The solid polymer nanocomposite electrolytes were characterized by differential scanning calorimetry (DSC) and impedance spectroscopy (IS) for their thermal properties and conductivity, respectively. It was evident that introduction of LiClO{sub 4} causes a greater increase in glass transition temperature (T{sub g}) and ionic conductivity of ENR50 asmore » compared to ENR25. Upon addition of TiO{sub 2} in ENR/LiClO{sub 4} system, a remarkable T{sub g} elevation was observed for both ENRs where ENR50 reveals a more pronounced changes. It is interesting to note that they exhibit different phenomenon in ionic conductivity with TiO{sub 2} loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.« less

Ionic conductivity measurement in magnesium aluminate spinel and solid state galvanic cell with magnesium aluminate electrolyte

NASA Astrophysics Data System (ADS)

Lee, Myongjai

This thesis work is about the experimental measurement of electronic and ionic conductivities in the MgAl2O4 spinel at 500˜600°C range and exploring the fundamental origin of solid-state galvanic cell behavior in the cell of Al|MgAl2O4|Mg, Al|MgAl2O 4|C, and Mg|MgAl2O4|C, in which at least one metal electrode in common with the composition of the electrolyte. For the electronic conductivity measurement, we have used the ion-blocking Gold and Carbon electrodes which are inert with both Mg and Al ions to suppress the ionic conduction from the total conduction. DC polarization method was used to measure the conduction through Au|MgAl2O4|Au and C|MgAl2O4|C specimens. The measured electrical conductivity using Au|MgAl2O4|Au and C|MgAl2O4|C specimens showed 10-9.3 ˜ 10-8.4 (O·cm) -1 at 600˜720°C range following the Arrhenius-type relation. These conductivity data are in agreement with reported data obtained from Pt and Ag ion-blocking electrodes deposited on MgAl2O4 specimens. For the ionic conductivity measurement, we have used the non-blocking Al and Mg electrodes for Al and Mg ionic conductivities, respectively. Ionic conductivity measurement of Al and Mg in separate manner has not been reported yet. In both Al|MgAl2O4|Al and Mg|MgAl2O 4|Mg specimens, gradual increase of conduction was observed once at the initial period before it reaches the steady state conduction. By DC method on the range of 580˜650°C, steady state Al ionic conductivity was measured from Al|MgAl2O4|Al specimen showing 10 -7.7 ˜ 10-6.8 (O·cm)-1 with the activation energy of 1.9eV in sigma = sigma0 exp-QRT formula. There was no difference in the conductivity by the change of the atmosphere from 5%H2 + 95%N2 mixed gas to pure Ar gas. So it was confirmed that the oxygen defect chemistry did not play a role. For Mg ionic conductivity Mg|MgAl2O4|Mg specimen was used and the measured conductivity shows 10-6.7 ˜ 10-4.4 (O·cm)-1 at 400˜550°C with the activation energy of 1.44eV at Ar gas atmosphere. Higher conductivity of Mg cation than Al cation is in agreement with self-diffusion data reported in the literatures. It's also in agreement with the higher Mg ionic mobility concluded by the formation of MgO layer at the cathode as the result of reaction between Mg ions migration and surrounding oxygen decomposed by the applied voltage. To explore the fundamental origin of the emf in the Mg|MgAl2O 4|Al galvanic cell, we set-up two postulations which are able to explain by the transportation mechanism in the MgAl2O4 with the presence of two cations in the system. The possible mechanisms are (1) Only Mg ion is involved in transportation through the MgAl2O4. Thus the emf is generated from the difference in the activity of Mg between the two electrodes. (2) Both Mg2+ and Al3+ ions are participating in transportation through the MgAl2O 4. In this case, the emf is generated from the difference in the reduction-oxidation potential between Mg and Al. Based on the result that both Al|MgAl2O4|C and Mg|MgAl2O4|C have the emf with C positive polarity, the second suggested mechanism results in the spontaneous composition change inside MgAl2O4 in the both directions of Mg-rich and Al-rich according the electrode materials with fixed C electrode on the other side. Considering the spontaneous reaction involving the composition change of MgAl2O4 to lower free energy of the system, suggested mechanism one is more plausible. In order to confirm that origin of the emf is determined by the activity difference on electrodes, emf measurements were carried out using different Mg activities available by using Mg-Al alloy. OCV was dependent on the difference in the Mg activity on the electrodes of Mg|MgAl2O4|Mg-Al alloy. This result supports the emf is generated by the difference in the activity of Mg ions at the both electrodes.

A Fast and Robust Poisson-Boltzmann Solver Based on Adaptive Cartesian Grids

PubMed Central

Boschitsch, Alexander H.; Fenley, Marcia O.

2011-01-01

An adaptive Cartesian grid (ACG) concept is presented for the fast and robust numerical solution of the 3D Poisson-Boltzmann Equation (PBE) governing the electrostatic interactions of large-scale biomolecules and highly charged multi-biomolecular assemblies such as ribosomes and viruses. The ACG offers numerous advantages over competing grid topologies such as regular 3D lattices and unstructured grids. For very large biological molecules and multi-biomolecule assemblies, the total number of grid-points is several orders of magnitude less than that required in a conventional lattice grid used in the current PBE solvers thus allowing the end user to obtain accurate and stable nonlinear PBE solutions on a desktop computer. Compared to tetrahedral-based unstructured grids, ACG offers a simpler hierarchical grid structure, which is naturally suited to multigrid, relieves indirect addressing requirements and uses fewer neighboring nodes in the finite difference stencils. Construction of the ACG and determination of the dielectric/ionic maps are straightforward, fast and require minimal user intervention. Charge singularities are eliminated by reformulating the problem to produce the reaction field potential in the molecular interior and the total electrostatic potential in the exterior ionic solvent region. This approach minimizes grid-dependency and alleviates the need for fine grid spacing near atomic charge sites. The technical portion of this paper contains three parts. First, the ACG and its construction for general biomolecular geometries are described. Next, a discrete approximation to the PBE upon this mesh is derived. Finally, the overall solution procedure and multigrid implementation are summarized. Results obtained with the ACG-based PBE solver are presented for: (i) a low dielectric spherical cavity, containing interior point charges, embedded in a high dielectric ionic solvent – analytical solutions are available for this case, thus allowing rigorous assessment of the solution accuracy; (ii) a pair of low dielectric charged spheres embedded in a ionic solvent to compute electrostatic interaction free energies as a function of the distance between sphere centers; (iii) surface potentials of proteins, nucleic acids and their larger-scale assemblies such as ribosomes; and (iv) electrostatic solvation free energies and their salt sensitivities – obtained with both linear and nonlinear Poisson-Boltzmann equation – for a large set of proteins. These latter results along with timings can serve as benchmarks for comparing the performance of different PBE solvers. PMID:21984876

All-d-Enantiomer of β-Amyloid Peptide Forms Ion Channels in Lipid Bilayers

PubMed Central

2012-01-01

Alzheimer’s disease (AD) is the most common type of senile dementia in aging populations. Amyloid β (Aβ)-mediated dysregulation of ionic homeostasis is the prevailing underlying mechanism leading to synaptic degeneration and neuronal death. Aβ-dependent ionic dysregulation most likely occurs either directly via unregulated ionic transport through the membrane or indirectly via Aβ binding to cell membrane receptors and subsequent opening of existing ion channels or transporters. Receptor binding is expected to involve a high degree of stereospecificity. Here, we investigated whether an Aβ peptide enantiomer, whose entire sequence consists of d-amino acids, can form ion-conducting channels; these channels can directly mediate Aβ effects even in the absence of receptor–peptide interactions. Using complementary approaches of planar lipid bilayer (PLB) electrophysiological recordings and molecular dynamics (MD) simulations, we show that the d-Aβ isomer exhibits ion conductance behavior in the bilayer indistinguishable from that described earlier for the l-Aβ isomer. The d isomer forms channel-like pores with heterogeneous ionic conductance similar to the l-Aβ isomer channels, and the d-isomer channel conductance is blocked by Zn2+, a known blocker of l-Aβ isomer channels. MD simulations further verify formation of β-barrel-like Aβ channels with d- and l-isomers, illustrating that both d- and l-Aβ barrels can conduct cations. The calculated values of the single-channel conductance are approximately in the range of the experimental values. These findings are in agreement with amyloids forming Ca2+ leaking, unregulated channels in AD, and suggest that Aβ toxicity is mediated through a receptor-independent, nonstereoselective mechanism. PMID:22423218

Conductivity percolation in loosely compacted microcrystalline cellulose: An in situ study by dielectric spectroscopy during densification.

PubMed

Nilsson, Martin; Frenning, Göran; Gråsjö, Johan; Alderborn, Göran; Strømme, Maria

2006-10-19

The present study aims at contributing to a complete understanding of the water-induced ionic charge transport in cellulose. The behavior of this transport in loosely compacted microcrystalline cellulose (MCC) powder was investigated as a function of density utilizing a new type of measurement setup, allowing for dielectric spectroscopy measurement in situ during compaction. The ionic conductivity in MCC was found to increase with increasing density until a leveling-out was observed for densities above approximately 0.7 g/cm3. Further, it was shown that the ionic conductivity vs density followed a percolation type behavior signifying the percolation of conductive paths in a 3D conducting network. The density percolation threshold was found to be between approximately 0.2 and 0.4 g/cm3, depending strongly on the cellulose moisture content. The observed percolation behavior was attributed to the forming of interparticulate bonds in the MCC and the percolation threshold dependence on moisture was linked to the moisture dependence of particle rearrangement and plastic deformation in MCC during compaction. The obtained results add to the understanding of the density-dependent water-induced ionic transport in cellulose showing that, at given moisture content, the two major parameters determining the magnitude of the conductivity are the connectedness of the interparticluate bonds and the connectedness of pores with a diameter in the 5-20 nm size range. At densities between approximately 0.7 and 1.2 g/cm3 both the bond and the pore networks have percolated, facilitating charge transport through the MCC compact.

YSZ thin films with minimized grain boundary resistivity

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

Mills, Edmund M.; Kleine-Boymann, Matthias; Janek, Juergen

2016-03-31

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e. g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here we report that the ionic conductivity ofmore » yttria stabilized zirconia thin films with nano-­ columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500°C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film- substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

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

Criticality in charge-asymmetric hard-sphere ionic fluids.

PubMed

Aqua, Jean-Noël; Banerjee, Shubho; Fisher, Michael E

2005-10-01

Phase separation and criticality are analyzed in z:1 charge-asymmetric ionic fluids of equisized hard spheres by generalizing the Debye-Hückel approach combined with ionic association, cluster solvation by charged ions, and hard-core interactions, following lines developed by Fisher and Levin for the 1:1 case (i.e., the restricted primitive model). Explicit analytical calculations for 2:1 and 3:1 systems account for ionic association into dimers, trimers, and tetramers and subsequent multipolar cluster solvation. The reduced critical temperatures, Tc* (normalized by z), decrease with charge asymmetry, while the critical densities increase rapidly with . The results compare favorably with simulations and represent a distinct improvement over all current theories such as the mean spherical approximation, symmetric Poisson-Boltzmann theory, etc. For z not equal to 1, the interphase Galvani (or absolute electrostatic) potential difference, Deltaphi(T), between coexisting liquid and vapor phases is calculated and found to vanish as absolute value (T-Tc) beta when T-->Tc-with, since our approximations are classical, beta = (1/2). Above Tc, the compressibility maxima and so-called k-inflection loci (which aid the fast and accurate determination of the critical parameters) are found to exhibit a strong z dependence.

Amperometric glucose biosensor with remarkable acid stability based on glucose oxidase entrapped in colloidal gold-modified carbon ionic liquid electrode.

PubMed

Liu, Xiaoying; Zeng, Xiandong; Mai, Nannan; Liu, Yong; Kong, Bo; Li, Yonghong; Wei, Wanzhi; Luo, Shenglian

2010-08-15

A colloidal gold-modified carbon ionic liquid electrode was constructed by mixing colloidal gold-modified graphite powder with a solid room temperature ionic liquid n-octyl-pyridinium hexafluorophosphate (OPPF(6)). Glucose oxidase (GOD) was entrapped in this composite matrix and maintained its bioactivity well and displayed excellent stability. The effect conditions of pH, applied potential and GOD loading were examined. Especially, the glucose oxidase entrapped in this carbon ionic liquid electrode fully retained its activity upon stressing in strongly acidic conditions (pH 2.0) for over one hour. The proposed biosensor responds to glucose linearly over concentration range of 5.0x10(-6) to 1.2x10(-3) and 2.6x10(-3) to 1.3x10(-2) M, and the detection limit is 3.5x10(-6) M. The response time of the biosensor is fast (within 10s), and the life time is over two months. The effects of electroactive interferents, such as ascorbic acid, uric acid, can be significantly reduced by a Nafion film casting on the surface of resulting biosensor. Copyright 2010 Elsevier B.V. All rights reserved.

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

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

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng

In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improvedmore » ion accessibility to redox-active sites. A macroporous Ti 3C 2T x MXene film delivered up to 210 F g –1 at scan rates of 10 V s –1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm –3 reaching the previously unmatched volumetric performance of RuO 2.« less

Discrimination of lymphoma using laser-induced breakdown spectroscopy conducted on whole blood samples

PubMed Central

Chen, Xue; Li, Xiaohui; Yang, Sibo; Yu, Xin; Liu, Aichun

2018-01-01

Lymphoma is a significant cancer that affects the human lymphatic and hematopoietic systems. In this work, discrimination of lymphoma using laser-induced breakdown spectroscopy (LIBS) conducted on whole blood samples is presented. The whole blood samples collected from lymphoma patients and healthy controls are deposited onto standard quantitative filter papers and ablated with a 1064 nm Q-switched Nd:YAG laser. 16 atomic and ionic emission lines of calcium (Ca), iron (Fe), magnesium (Mg), potassium (K) and sodium (Na) are selected to discriminate the cancer disease. Chemometric methods, including principal component analysis (PCA), linear discriminant analysis (LDA) classification, and k nearest neighbor (kNN) classification are used to build the discrimination models. Both LDA and kNN models have achieved very good discrimination performances for lymphoma, with an accuracy of over 99.7%, a sensitivity of over 0.996, and a specificity of over 0.997. These results demonstrate that the whole-blood-based LIBS technique in combination with chemometric methods can serve as a fast, less invasive, and accurate method for detection and discrimination of human malignancies. PMID:29541503

Biodegradation of diesel fuel by a microbial consortium in the presence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues.

PubMed

Chrzanowski, Lukasz; Stasiewicz, Monika; Owsianiak, Mikołaj; Szulc, Alicja; Piotrowska-Cyplik, Agnieszka; Olejnik-Schmidt, Agnieszka K; Wyrwas, Bogdan

2009-09-01

Fast development of ionic liquids as gaining more and more attention valuable chemicals will undoubtedly lead to environmental pollution. New formulations and application of ionic liquids may result in contamination in the presence of hydrophobic compounds, such as petroleum mixtures. We hypothesize that in the presence of diesel fuel low-water-soluble ionic liquids may become more toxic to hydrocarbon-degrading microorganisms. In this study the influence of 1-alkoxymethyl-2-methyl-5-hydroxypyridinium chloride homologues (side-chain length from C(3) to C(18)) on biodegradation of diesel fuel by a bacterial consortium was investigated. Whereas test performed for the consortium cultivated on disodium succinate showed that toxicity of the investigated ionic liquids decreased with increase in side-chain length, only higher homologues (C(8)-C(18)) caused a decrease in diesel fuel biodegradation. As a result of exposure to toxic compounds also modification in cell surface hydrophobicity was observed (MATH). Disulphine blue active substances method was employed to determine partitioning index of ionic liquids between water and diesel fuel phase, which varied from 1.1 to 51% for C(3) and C(18) homologues, respectively. We conclude that in the presence of hydrocarbons acting as a solvent, the increased bioavailability of hydrophobic homologues is responsible for the decrease in biodegradation efficiency of diesel fuel.

Phase stability and processing of strontium and magnesium doped lanthanum gallate

NASA Astrophysics Data System (ADS)

Zheng, Feng

Fuel Cells are one of the most promising energy transformers with respect to ecological and environmental issues. Solid Oxide Fuel Cells (SOFC) are all solid-state devices. One of the challenges to improve a SOFC is to lower the operating temperature while maintaining or increasing its output voltage. Undoped LaGaO3 is an insulator, doping transforms it into an oxygen-ionic conductor. Sr and Mg doped LaGaO3 (LSGM) perovskite is a new oxygen-ionic conductor with higher conductivity than yttria-stabilized zirconia (YSZ). This material is a candidate for a wide variety of electrochemical devices. In order to realize this potential, the phase stability and processing of this material needs to be investigated in detail. In this study, a systematic investigation of the LSGM materials in terms of phase stability, phase transition, sintering, microstructure and electrical conductivity as functions of temperature, doping content and A/B cation ratio has been carried out. The generalized formula of the materials investigated is (La1--xSrx)A(Ga1--yMg y)BO3--delta. Optimized processing parameters have been obtained by investigating their impact on density change and microstructure. Consequently, a suitable compositional window of the LSGM perovskite has been identified for SOFC electrolyte applications. Based on detailed diffraction analysis, it is found that the undoped LaGaO3 takes on the orthorhombic (Pbnm) symmetry at room temperature. This structure changes to rhombohedral (R3c) at 147 +/- 2°C or changes to monoclinic (I2/a) when the doping level increases from 0.1 to 0.2 moles. We have optimized the compositional window to make the single perovskite phase with high oxygen ionic conductivity (x = 0.10 to 0.20 with A/B ratio between 0.98 to 1.02). The best processing condition, starting from glycine nitrate process (GNP) combustion synthesized ultra-fine LSGM powder, is sintering in air at 1500°C for 2 hours. The doped material has higher oxygen ionic conductivity than YSZ at all temperatures. In addition, based on the structure and phase relations, a high temperature phase diagram for this system has been proposed. Finally, a model has been proposed to account for the high ionic conductivity of this material and to explain the effect of the doping content and the stoichiometry on the ionic conductivity. (Abstract shortened by UMI.)

Structural and superionic properties of Ag+-rich ternary phases within the AgI-MI2 systems

NASA Astrophysics Data System (ADS)

Hull, S.; Keen, D. A.; Berastegui, P.

2002-12-01

The effects of temperature on the crystal structure and ionic conductivity of the compounds Ag2CdI4, Ag2ZnI4 and Ag3SnI5 have been investigated by powder diffraction and impedance spectroscopy techniques. varepsilon-Ag2CdI4 adopts a tetragonal crystal structure under ambient conditions and abrupt increases in the ionic conductivity are observed at 407(2), 447(3) and 532(4) K, consistent with the sequence of transitions varepsilon-Ag2CdI 4 rightarrow beta-Ag2CdI 4 + beta-AgI + CdI2 rightarrow alpha-AgI + CdI2 rightarrow alpha-Ag2CdI4. Hexagonal beta-Ag2CdI4 is metastable at ambient temperature. The ambient-temperature beta phase of Ag2ZnI4 is orthorhombic and the structures of beta-Ag2CdI4 and beta-Ag2ZnI4 can, respectively, be considered as ordered derivatives of the wurtzite (beta) and zincblende (gamma) phases of AgI. On heating Ag2ZnI4, there is a 12-fold increase in ionic conductivity at 481(1) K and a further eightfold increase at 542(3) K. These changes result from decomposition of beta-Ag2ZnI4 into alpha-AgI + ZnI2, followed by the appearance of superionic alpha-Ag2ZnI4 at the higher temperature. The hexagonal crystal structure of alpha-Ag2ZnI4 is a dynamically disordered counterpart to the beta modification. Ag3SnI5 is only stable at temperatures in excess of 370(3) K and possesses a relatively high ionic conductivity (sigma approx 0.19Omega-1 cm-1 at 420 K) due to dynamic disorder of the Ag+ and Sn2+ within a cubic close packed I- sublattice. The implications of these findings for the wider issue of high ionic conductivity in AgI-MI2 compounds is discussed, with reference to recently published studies of Ag4PbI6 and Ag2HgI4 and new data for the temperature dependence of the ionic conductivity of the latter compound.

Capturing the effect of [PF3(C2F5)3]-vs. [PF6]-, flexible anion vs. rigid, and scaled charge vs. unit on the transport properties of [bmim]+-based ionic liquids: a comparative MD study.

PubMed

Kowsari, Mohammad H; Ebrahimi, Soraya

2018-05-16

Comprehensive molecular dynamics simulations are performed to study the average single-particle dynamics and the transport properties of 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [bmim][FAP], ionic liquids (ILs) at 400 K. We applied one of the most widely used nonpolarizable all-atom force fields for ILs, both with the original unit (±1) charges on each ion and with the partial charges uniformly scaled to 80-85%, taking into account the average polarizability and tracing the experimentally compatible transport properties. In all simulations, [bmim]+ was considered to be flexible, while the effect of a flexible vs. rigid structure of the anions and the effect of two applied charge sets on the calculated properties were separately investigated in detail. The simulation results showed that replacing [PF6]- with [FAP]-, considering anion flexibility, and applying the charge-scaled model significantly enhanced the ionic self-diffusion, ionic conductivity, inverse viscosity, and hyper anion preference (HAP). Both of the calculated self-diffusion coefficients from the long-time linear slope of the mean-square displacement (MSD) and from the integration of the velocity autocorrelation function (VACF) for the centers of mass of the ions were used for evaluation of the ionic transference number, HAP, ideal Nernst-Einstein ionic conductivity (σNE), and the Stokes-Einstein viscosity. In addition, for quantification of the degree of complicated ionic association (known as the Nernst-Einstein deviation parameter, Δ) and ionicity phenomena in the two studied ILs, the ionic conductivity was determined more rigorously by the Green-Kubo integral of the electric-current autocorrelation function (ECACF), and then the σGK/σNE ratio was evaluated. It was found that the correlated motion of the (cationanion) neighbors in [bmim][FAP] is smaller than in [bmim][PF6]. The relaxation times of the normalized reorientational autocorrelation functions were computed to gain a deep, molecular-level insight into the rotational motion of the ions. The geometric shape of the ion is a key factor in determining its reorientational dynamics. [bmim]+ shows faster translational and slower rotational dynamics in contrast to [PF6]-.

Characterization of mixed-conducting barium cerate-based perovskites for potential fuel cell applications

NASA Astrophysics Data System (ADS)

Mukundan, R.

Chemical modifications of barium cerium gadolinium oxide through the substitution of Bi, Tb, Pr, Nb and Ta were attempted in an effort to increase the p-type or n-type conductivity, and to develop new mixed-conducting electrodes that are chemically compatible with the Ba(Cesb{1-x}Gdsb{x})Osb{3-x/2} electrolyte. The structure, oxygen non-stoichiometry, electronic and ionic-conductivity of several compositions in the doped-barium cerate systems were studied by X-ray diffraction, TGA, DC and AC conductivity, and EMF measurements. The cathodic overpotential of the mixed (electronic/ionic) conducting compositions in this system, on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte, were also studied using Current Interruption and AC impedance techniques. The substitution of Bi into Ba(Cesb{0.9}Gdsb{0.1})Osb{2.95} lead to a significant increase in the electronic conductivity, and a total conductivity of about 0.94 S/cm was obtained for Ba(Bisb{0.5}Cesb{0.4}Gdsb{0.1})Osb3 at 800sp°C in air. However, the concentration of oxygen-ion vacancies and hence the ionic conductivity decreased due to the oxidation of Bi to the 5sp{+} state. Compositions in the Ba(Bisb{0.5}Cesb{x}Gdsb{0.5-x})Osb3 system also exhibited significant oxygen non-stoichiometry depending upon the ordering of the B-site cations and the relative concentrations of Ce and Gd. However, the absence of any detectable EMF in the non-stoichiometric compositions implied that the oxygen vacancies are strongly associated with the Bisp{3+} cations. Although highly conductive, chemically stable compositions were prepared in the Ba(Bisb{x}Cesb{y}Gdsb{1-(x+y)})Osb{3-d} system, their ionic conductivities were low. The mixed-conduction properties of Ba(Cesb{1-x}Gdsb{x})Osb{3-d} were enhanced under cathode conditions (600-800sp°C in air) by the substitution of Ce by Tb and Pr. While the substitution of Tb resulted in a decrease in the total conductivity, Pr induced a significant increase in the total conductivity at high Pr levels (≥40 mole%) due to an enhancement of the electronic conductivity. The Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9} sample was found to have the best mixed-conducting properties of all the perovskites evaluated, sigmasb{T}=0.75 S/cm in air at 800sp°C, tsb{H+}=0.15 in a wet argon//dry argon gradient, and tsb{0.2-}≈ 0.05 in a dry air//dry argon gradient. The cathodic overpotentials of the mixed-conducting Pr-doped barium cerates were low, and decreased with increasing ionic and electronic conductivity of the electrode. The lowest overpotential was obtained for the Ba(Prsb{0.8}Gdsb{0.2})Osb{2.9}, cathode, and at low current densities was comparable to that of an optimized porous Pt-electrode. While the substitution of Nb and Ta for Ce lead to an enhancement in the electronic conductivity under reducing conditions associated with the increased reduction of Cesp{4+} to Cesp{3+}, the ionic-conductivity of these perovskites was low. There was no evidence for any protonic conductivity in the 15 mole% Nb and Ta substituted barium cerates. Moreover the anodic overpotential and the anode resistance of these perovskites on a Ba(Cesb{0.8}Gdsb{0.2})Osb{2.9} electrolyte were both high.

Synergistic effects of mixing sulfone and ionic liquid as safe electrolytes for lithium sulfur batteries.

PubMed

Liao, Chen; Guo, Bingkun; Sun, Xiao-Guang; Dai, Sheng

2015-01-01

A strategy of mixing both an ionic liquid and sulfone is reported to give synergistic effects of reducing viscosity, increasing ionic conductivity, reducing polysulfide dissolution, and improving safety. The mixtures of ionic liquids and sulfones also show distinctly different physicochemical properties, including thermal properties and crystallization behavior. By using these electrolytes, lithium sulfur batteries assembled with lithium and mesoporous carbon composites show a reversible specific capacity of 1265 mAh g(-1) (second cycle) by using 40 % 1.0 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in N-methyl-N-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide with 60 % 1.0 M LiTFSI in methylisopropylsulfone in the first cycle. This capacity is slightly lower than that obtained in pure 1.0 M LiTFSI as the sulfone electrolyte; however, it exhibits excellent cycling stability and remains as high as 655 mAh g(-1) even after 50 cycles. This strategy provides a method to alleviate polysulfide dissolution and redox shuttle phenomena, at the same time, with improved ionic conductivity. © 2015 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.

Ionic currents and charge movements in organ-cultured rat skeletal muscle.

PubMed

Hollingworth, S; Marshall, M W; Robson, E

1984-12-01

The middle of the fibre voltage-clamp technique was used to measure ionic currents and non-linear charge movements in intact, organ-cultured (in vitro denervated) mammalian fast-twitch (rat extensor digitorum longus) muscle fibres. Muscle fibres organ cultured for 4 days can be used as electrophysiological and morphological models for muscles in vivo denervated for the same length of time. Sodium currents in organ-cultured muscle fibres are similar to innervated fibres except that in the temperature range 0-20 degrees C (a) in the steady state, the voltage distribution of inactivation in cultured fibres is shifted negatively some 20 mV; (b) at the same temperature and membrane potential, the time constant of inactivation in cultured fibres is about twice that of innervated fibres. Potassium currents in innervated and cultured fibres at 15 degrees C can be fitted with the Hodgkin-Huxley n variable raised to the second power. Despite the large range we would estimate that the maximum value of the steady-state potassium conductance of cultured fibres is about one-half that of innervated fibres. The estimated maximum amount of charge moved in cultured fibre is about one-third that in innervated fibres. Compared to innervated fibres, culturing doubles the kinetics of the decay phase of charge movement. The possibility of a negative shift of the voltage distribution of charge movements in cultured fibres is discussed.

Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

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

Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo

2017-04-10

Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction asmore » well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.« less

Natural cellulose ionogels for soft artificial muscles.

PubMed

Nevstrueva, Daria; Murashko, Kirill; Vunder, Veiko; Aabloo, Alvo; Pihlajamäki, Arto; Mänttäri, Mika; Pyrhönen, Juha; Koiranen, Tuomas; Torop, Janno

2018-01-01

Rapid development of soft micromanipulation techniques for human friendly electronics has raised the demand for the devices to be able to carry out mechanical work on a micro- and macroscale. The natural cellulose-based ionogels (CEL-iGEL) hold a great potential for soft artificial muscle application, due to its flexibility, low driving voltage and biocompatibility. The CEL-iGEL composites undergo reversible bending already at ±500mV step-voltage values. A fast response to the voltage applied and high ionic conductivity of membranous actuator is achieved by a complete dissolution of cellulose in 1-ethyl-3-methylimidazolium acetate [EMIm][OAc]. The CEL-iGEL supported cellulose actuator films were cast out of cellulose-[EMIm][OAc] solution via phase inversion in H 2 O. The facile preparation method ensured uniform morphology along the layers and stand for the high ionic-liquid loading in a porous cellulose scaffold. During the electromechanical characterization, the CEL-iGEL actuators showed exponential dependence to the voltage applied with the max strain difference values reaching up to 0.6% at 2 V. Electrochemical analysis confirmed the good stability of CEL-iGEL actuators and determined the safe working voltage value to be below 2.5V. To predict and estimate the deformation for various step input voltages, a mathematical model was proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

Atomic Resolution Imaging of Nanoscale Chemical Expansion in PrxCe1-xO2-δ during In Situ Heating.

PubMed

Swallow, Jessica G; Lee, Ja Kyung; Defferriere, Thomas; Hughes, Gareth M; Raja, Shilpa N; Tuller, Harry L; Warner, Jamie H; Van Vliet, Krystyn J

2018-02-27

Thin film nonstoichiometric oxides enable many high-temperature applications including solid oxide fuel cells, actuators, and catalysis. Large concentrations of point defects (particularly, oxygen vacancies) enable fast ionic conductivity or gas exchange kinetics in these materials but also manifest as coupling between lattice volume and chemical composition. This chemical expansion may be either detrimental or useful, especially in thin film devices that may exhibit enhanced performance through strain engineering or decreased operating temperatures. However, thin film nonstoichiometric oxides can differ from bulk counterparts in terms of operando defect concentrations, transport properties, and mechanical properties. Here, we present an in situ investigation of atomic-scale chemical expansion in Pr x Ce 1-x O 2-δ (PCO), a mixed ionic-electronic conducting oxide relevant to electrochemical energy conversion and high-temperature actuation. Through a combination of electron energy loss spectroscopy and transmission electron microscopy with in situ heating, we characterized chemical strains and changes in oxidation state in cross sections of PCO films grown on yttria-stabilized zirconia (YSZ) at temperatures reaching 650 °C. We quantified, both statically and dynamically, the nanoscale chemical expansion induced by changes in PCO redox state as a function of position and direction relative to the film-substrate interface. Additionally, we observed dislocations at the film-substrate interface, as well as reduced cation localization to threading defects within PCO films. These results illustrate several key aspects of atomic-scale structure and mechanical deformation in nonstoichiometric oxide films that clarify distinctions between films and bulk counterparts and that hold several implications for operando chemical expansion or "breathing" of such oxide films.

A physicochemical investigation of ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02931c Click here for additional data file.

PubMed Central

Clough, Matthew T.; Crick, Colin R.; Gräsvik, John; Niedermeyer, Heiko; Whitaker, Oliver P.

2015-01-01

Ionic liquids have earned the reputation of being ‘designer solvents’ due to the wide range of accessible properties and the degree of fine-tuning afforded by varying the constituent ions. Mixtures of ionic liquids offer the opportunity for further fine-tuning of properties. A broad selection of common ionic liquid cations and anions are employed to create a sample of binary and reciprocal binary ionic liquid mixtures, which are analysed and described in this paper. Physical properties such as the conductivity, viscosity, density and phase behaviour (glass transition temperatures) are examined. In addition, thermal stabilities of the mixtures are evaluated. The physical properties examined for these formulations are found to generally adhere remarkably closely to ideal mixing laws, with a few consistent exceptions, allowing for the facile prediction and control of properties of ionic liquid mixtures. PMID:29560198

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

PubMed

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

2009-08-01

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

Ionic-liquid materials for the electrochemical challenges of the future

NASA Astrophysics Data System (ADS)

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

2009-08-01

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

Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

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

Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W., E-mail: ed.castner@rutgers.edu

2015-08-14

We report experimental results on the diffusivity of water in two ionic liquids obtained using the pulsed-gradient spin-echo NMR method. Both ionic liquids have the same cation, 1-butyl-1-methylpyrrolidinium, but different trifluoromethyl-containing anions. One has a strongly hydrophobic anion, bis(trifluoromethylsulfonyl)amide, while the second has a hydrophilic anion, trifluoromethylsulfonate. Transport of water in these ionic liquids is much faster than would be predicted from hydrodynamic laws, indicating that the neutral water molecules experience a very different friction than the anions and cations at the molecular level. Temperature-dependent viscosities, conductivities, and densities are reported as a function of water concentration to further analyzemore » the properties of the ionic liquid-water mixtures. These results on the properties of water in ionic liquids should be of interest to researchers in diverse areas ranging from separations, solubilizing biomass and energy technologies.« less

Self-assembly of three-dimensional interconnected graphene-based aerogels and its application in supercapacitors.

PubMed

Ji, Chen-Chen; Xu, Mao-Wen; Bao, Shu-Juan; Cai, Chang-Jun; Lu, Zheng-Jiang; Chai, Hui; Yang, Fan; Wei, Hua

2013-10-01

Homogeneously distributed self-assembling hybrid graphene-based aerogels with 3D interconnected pores, employing three types of carbohydrates (glucose, β-cyclodextrin, and chitosan), have been fabricated by a simple hydrothermal route. Using three types of carbohydrates as morphology oriented agents and reductants can effectively tailor the microstructures, physical properties, and electrochemical performances of the products. The effects of different carbohydrates on graphene oxide reduction to form graphene-based aerogels with different microcosmic morphologies and physical properties were also systemically discussed. The electrochemical behaviors of all graphene-based aerogel samples showed remarkably strong and stable performances, which indicated that all the 3D interpenetrating microstructure graphene-based aerogel samples with well-developed porous nanostructures and interconnected conductive networks could provide fast ionic channels for electrochemical energy storage. These results demonstrate that this strategy would offer an easy and effective way to fabricate graphene-based materials. Copyright © 2013 Elsevier Inc. All rights reserved.

Biology's built-in Faraday cages

NASA Astrophysics Data System (ADS)

Klee, Maurice M.

2014-05-01

Biological fluids are water-based, ionic conductors. As such, they have both high relative dielectric constants and substantial conductivities, meaning they are lossy dielectrics. These fluids contain charged molecules (free charges), whose movements play roles in essentially all cellular processes from metabolism to communication with other cells. Using the problem of a point source in air above a biological fluid of semi-infinite extent, the bound charges in the fluid are shown to perform the function of a fast-acting Faraday cage, which protects the interior of the fluid from external electric fields. Free charges replace bound charges in accordance with the fluid's relaxation time, thereby providing a smooth transition between the initial protection provided by the bound charges and the steady state protection provided by the free charges. The electric fields within the biological fluid are thus small for all times just as they would be inside a classical Faraday cage.

Once upon a (slow) time in the land of recurrent neuronal networks….

PubMed

Huang, Chengcheng; Doiron, Brent

2017-10-01

The brain must both react quickly to new inputs as well as store a memory of past activity. This requires biology that operates over a vast range of time scales. Fast time scales are determined by the kinetics of synaptic conductances and ionic channels; however, the mechanics of slow time scales are more complicated. In this opinion article we review two distinct network-based mechanisms that impart slow time scales in recurrently coupled neuronal networks. The first is in strongly coupled networks where the time scale of the internally generated fluctuations diverges at the transition between stable and chaotic firing rate activity. The second is in networks with finitely many members where noise-induced transitions between metastable states appear as a slow time scale in the ongoing network firing activity. We discuss these mechanisms with an emphasis on their similarities and differences. Copyright © 2017 Elsevier Ltd. All rights reserved.

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

PubMed

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking.

PubMed

De Gregorio, G L; Giannuzzi, R; Cipolla, M P; Agosta, R; Grisorio, R; Capodilupo, A; Suranna, G P; Gigli, G; Manca, M

2014-11-21

We here report the implementation of poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides as suitable polymeric hosts for a novel class of in situ cross-linkable iodine/iodide-based gel-electrolytes for dye-sensitized solar cells. The polymers are first partially quaternized and then subjected to a thermal cross-linking which allows the formation of a 3D polymeric network which is accompanied by a dramatic enhancement of the ionic conductivity.

Ionic conductivity and glass transition of phosphoric acids

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

Wang, Yangyang; Lane, Nathan A; Sun, Che-Nan

2013-01-01

Here we report the low-temperature dielectric and viscoelastic properties of phosphoric acids in the range of H2O:P2O5 1.5 5. Both dielectric and viscosity measurements allow us to determine the glass-transition temperatures of phosphoric acids. The obtained glass-transition temperatures are in good agreement with previous differential scanning calorimetric measurements. Moreover, our analysis reveals moderate decoupling of ionic conductivity from structural relaxation in the vicinity of the glass transition.

Performance of Carbon/Polytetrafluoroethylene (PTFE) Air Cathodes from pH 0 to 14 for Li-Air Batteries

DTIC Science & Technology

2007-12-01

aqueous and aqueous electrolytes are kept separate by a non-electronically conducting ceramic membrane impervious to water, but with a high ionic...thought of as being solvated by the ceramic membrane as it passes from non-aqueous to aqueous electrolyte. The half-cell reaction at the lithium...overall charge in the reaction, positive lithium ions flow through an ionically conducting ceramic membrane from the non-aqueous anode compartment to

The chemical identity of intervessel pit membranes in Acer challenges hydrogel control of xylem hydraulic conductivity

PubMed Central

Klepsch, Matthias M.; Schmitt, Marco; Paul Knox, J.; Jansen, Steven

2016-01-01

Ion-mediated enhancement of the hydraulic conductivity of xylem tissue (i.e. the ionic effect) has been reported for various angiosperm species. One explanation of the ionic effect is that it is caused by the swelling and shrinking of intervessel pit membranes due to the presence of pectins and/or other cell-wall matrix polymers such as heteroxylans or arabinogalactan–proteins (AGPs) that may contain acidic sugars. Here, we examined the ionic effect for six Acer species and their pit membrane chemistry using immunocytochemistry, including antibodies against glycoproteins. Moreover, anatomical features related to the bordered pit morphology and vessel dimensions were investigated using light and electron microscopy. The ionic effect varied from 18 % (± 9) to 32 % (± 13). Epitopes of homogalacturonan (LM18) and xylan (LM11) were not detected in intervessel pit membranes. Negative results were also obtained for glycoproteins (extensin: LM1, JIM20; AGP glycan: LM2), although AGP (JIM13)-related epitopes were detected in parenchyma cells. The mean vessel length was significantly correlated with the magnitude of the ionic effect, unlike other pit or vessel-related characteristics. Our results suggest that intervessel pit membranes of Acer are unlikely to contain pectic or other acidic polysaccharides. Therefore, alternative explanations should be tested to clarify the ionic effect. PMID:27354661

Sr- and Nb-co-doped Li7La3Zr2O12 solid electrolyte with Al2O3 addition towards high ionic conductivity

NASA Astrophysics Data System (ADS)

Lin, Changwei; Tang, Yu; Song, Jun; Han, Lei; Yu, Jingbo; Lu, Anxian

2018-06-01

In the present study, series of garnet-type Li6.75+ x La3- x Sr x Zr1.75Nb0.25O12 solid electrolytes [LLSZN with various Sr contents ( x = 0.05-0.25)] have been prepared via conventional solid-state method. The effects of Sr contents on their phase structure and ionic conductivity have been systematically investigated on the combined measurements of X-ray diffraction and scanning electron microscopy and alter current impedance spectroscopy. Our results reveal that a phase transition from tetragonal to cubic structure occurs when both Sr and Nb elements is introduced, and such a cubic structure can be stable over the whole Sr contents variation, which is suggested to provide a beneficial impact on the performance of LLSZN. Accordingly, both relative density and total ionic conductivity exhibit a favorable tendency of increasing first and then decreasing with increased Sr contents, wherein a peak value at 93.46% and 5.09 × 10-4 S cm-1, respectively, can be well achieved. Particularly, the maximum ionic conductivity is almost twice that of the compared sample (2.93 × 10-4 S cm-1), and possess the minimum activation energy 0.30 eV. Such a modification method, featured with higher efficiency and lower cost, is expected to be helpful for the development of solid electrolyte.

Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

PubMed

Oldiges, K; Diddens, D; Ebrahiminia, M; Hooper, J B; Cekic-Laskovic, I; Heuer, A; Bedrov, D; Winter, M; Brunklaus, G

2018-06-20

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

Ionic conductivity of binary fluorides of potassium and rare earth elements

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

Sorokin, N. I., E-mail: nsorokin1@yandex.ru

2016-01-15

The ionic conductivity s of KYF{sub 4} and K{sub 2}RF{sub 5} single crystals (R = Gd, Ho, Er) and KNdF{sub 4} and K{sub 2}RF{sub 5} ceramic samples (R = Dy, Er) has been studied in the temperature range of 340–500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100–150 MPa) in the R{sub 2}O{sub 3}–KF–H{sub 2}O systems. The σ values of tetraf luorides are 3 × 10{sup –5} S/cm (KYF{sub 4} single crystal) and 3 × 10{sup –6}more » S/cm (KNdF{sub 4} ceramics) at 435°C. A K{sub 2}ErF{sub 5} single crystal with σ = 1.2 × 10{sup –4} S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K{sub 2}HoF{sub 5} single crystals, σ{sub ∥c}/σ{sub ⊥c} = 2.5, where σ{sub ∥c} and σ{sub ⊥c} are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.« less

Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites

DOE PAGES

Wang, Yonggang; Wang, Qingfei; Liu, Zhenpu; ...

2015-06-10

High-performance solid electrolytes are critical for realizing all-solid-state batteries with enhance safety and cycling efficiency. However, currently available candidates (sulfides and the NASICON-typ ceramics) still suffer from drawbacks such as inflammability, high-cost and unfavorable machinability Here we present the structural manipulation approaches to improve the sodium ionic conductivity in series of affordable Na-rich antiperovskites. Experimentally, the whole solid solutions of Na 3OX (X ¼ Cl Br, I) are synthesized via a facile and timesaving route from the cheapest raw materials (Na, NaOH an NaX). The materials are nonflammable, suitable for thermoplastic processing due to low melting temperature (<300° C) withoutmore » decomposing. Notably, owing to the flexibility of perovskite-type structure it's feasible to control the local structure features by means of size-mismatch substitution an unequivalent-doping for a favorable sodium ionic diffusion pathway. Enhancement of sodium ioni conductivity by 2 magnitudes is demonstrated by these chemical tuning methods. The optimized sodiu ionic conductivity in Na 2.9Sr 0.05OBr 0.6I 0.4 bulk samples reaches 1.9 10 - 3 S/cm at 200° C and even highe at elevated temperature. Here, we believe further chemical tuning efforts on Na-rich antiperovskites wil promote their performance greatly for practical all-solid state battery applications.« less

Effects of High-pH and High-Ionic-Strength Groundwater on Iodide, Pertechnetate, and Selenate Sorption to Hanford Sediments: Final Report for Subtask 3a

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

DI Kaplan; KE Parker; RD Orr

1998-10-14

As part of the Immobilized Low-Activity Waste-Performance Assessment three experiments were conducted to evaluate the effect of the expected near-field chemistry on the sorption of iodide, selenate, and pertechnetate onto a sediment obtained from the Hanford Site. These experiments were performed in fiscal year 1998 at the Pacific Northwest National Laboratory.' During these experiments, attention was directed at the identification of the chemical mechanisms controlling the sorption processes to provide technical defensibility for the selection of the distribution coefficients (IQ to be used in the remainder of the performance assessment. It was found, during the conduct of the experiments, thatmore » selenium and technetium I&s increased as ionic strength increased. The cause for this is most likely to be that the higher ionic strength caused the double layer around the particles to decrease, thereby permitting greater interaction with the mineral surfaces. Further, the pH level had an effect on the sorption of these anions. These are the first-ever experiments conducted with Hanford Site sediment in which the IQ were measured as a function of ionic strength and pH. Overall, the observed trends were consistent with more generalized geochemical principles. One of the most important contributions of these experiments was that they quantified the & changes induced by variations in ionic strength and pH that are expected to exist in the near field.« less

Recent progress on exploring exceptionally high and anisotropic H+/OH– ion conduction in two-dimensional materials

PubMed Central

Sun, Pengzhan; Sasaki, Takayoshi

2017-01-01

Ion conducting membranes/electrolytes have been employed extensively in some important industrial and biological systems, especially in fuel cells, water electrolyzers, gas separation, sensors and biological selective ion transport, acting as one of the core components and sometimes directly determining the device performance. However, the traditional polymeric proton exchange membranes (PEMs)/anion exchange membranes (AEMs) suffer from highly toxic preparation procedures, poor thermal and chemical stabilities, and unsatisfactory ion conductivities. This has triggered researchers worldwide to explore alternative inorganic building blocks with high ion conductivities and stabilities from the new materials library, hoping to solve the above long-lasting problems. The recent burgeoning research on two-dimensional (2D) materials has unveiled exceptionally high ionic conductivities, which raises the feasibility of fabricating high-performance nanosheet-based ion conductors/membranes. In this perspective, the recent advances in measuring and understanding the exceptionally high and anisotropic H+/OH– ion conductivities of representative 2D materials, e.g. graphene oxide (GO), vermiculite and layered double hydroxide (LDH) nanosheets, are reviewed. In particular, regarding the anisotropic ionic conduction in 2D nanosheets, possible design strategies and technological innovations for fabricating macroscopic nanosheet-based ionic conductors/membranes are proposed for maximizing the high in-plane conduction, which may serve to guide future development of high-performance industrial and biological systems relying on H+/OH– conducting membranes. PMID:29629071

Recent progress on exploring exceptionally high and anisotropic H+/OH- ion conduction in two-dimensional materials.

PubMed

Sun, Pengzhan; Ma, Renzhi; Sasaki, Takayoshi

2018-01-07

Ion conducting membranes/electrolytes have been employed extensively in some important industrial and biological systems, especially in fuel cells, water electrolyzers, gas separation, sensors and biological selective ion transport, acting as one of the core components and sometimes directly determining the device performance. However, the traditional polymeric proton exchange membranes (PEMs)/anion exchange membranes (AEMs) suffer from highly toxic preparation procedures, poor thermal and chemical stabilities, and unsatisfactory ion conductivities. This has triggered researchers worldwide to explore alternative inorganic building blocks with high ion conductivities and stabilities from the new materials library, hoping to solve the above long-lasting problems. The recent burgeoning research on two-dimensional (2D) materials has unveiled exceptionally high ionic conductivities, which raises the feasibility of fabricating high-performance nanosheet-based ion conductors/membranes. In this perspective, the recent advances in measuring and understanding the exceptionally high and anisotropic H + /OH - ion conductivities of representative 2D materials, e.g. graphene oxide (GO), vermiculite and layered double hydroxide (LDH) nanosheets, are reviewed. In particular, regarding the anisotropic ionic conduction in 2D nanosheets, possible design strategies and technological innovations for fabricating macroscopic nanosheet-based ionic conductors/membranes are proposed for maximizing the high in-plane conduction, which may serve to guide future development of high-performance industrial and biological systems relying on H + /OH - conducting membranes.

Polycation induced actin bundles.

PubMed

Muhlrad, Andras; Grintsevich, Elena E; Reisler, Emil

2011-04-01

Three polycations, polylysine, the polyamine spermine and the polycationic protein lysozyme were used to study the formation, structure, ionic strength sensitivity and dissociation of polycation-induced actin bundles. Bundles form fast, simultaneously with the polymerization of MgATP-G-actins, upon the addition of polycations to solutions of actins at low ionic strength conditions. This indicates that nuclei and/or nascent filaments bundle due to attractive, electrostatic effect of polycations and the neutralization of repulsive interactions of negative charges on actin. The attractive forces between the filaments are strong, as shown by the low (in nanomolar range) critical concentration of their bundling at low ionic strength. These bundles are sensitive to ionic strength and disassemble partially in 100 mM NaCl, but both the dissociation and ionic strength sensitivity can be countered by higher polycation concentrations. Cys374 residues of actin monomers residing on neighboring filaments in the bundles can be cross-linked by the short span (5.4Å) MTS-1 (1,1-methanedyl bismethanethiosulfonate) cross-linker, which indicates a tight packing of filaments in the bundles. The interfilament cross-links, which connect monomers located on oppositely oriented filaments, prevent disassembly of bundles at high ionic strength. Cofilin and the polysaccharide polyanion heparin disassemble lysozyme induced actin bundles more effectively than the polylysine-induced bundles. The actin-lysozyme bundles are pathologically significant as both proteins are found in the pulmonary airways of cystic fibrosis patients. Their bundles contribute to the formation of viscous mucus, which is the main cause of breathing difficulties and eventual death in this disorder. Copyright © 2011 Elsevier B.V. All rights reserved.

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.

Hetero-phase fluctuations in the pre-melting region in ionic crystals

NASA Astrophysics Data System (ADS)

Matsunaga, S.; Tamaki, S.

2008-06-01

The theory of the pre-melting phenomena in ionic crystals on the basis of the concept of the hetero phase fluctuation has been applied to KCl and AgCl crystal. The large scale molecular dynamics simulations (MD) in KCl and AgCl crystals are also performed to examine the ionic configuration in premelting region in the vicinity of their melting points. The size of the liquid like clusters are estimated by the theory and MD. The structural features of liquid like clusters are discussed by MD results using the Lindemann instability condition. The ionic conductivities in the pre-melting region are also discussed on the same theoretical basis.

Static and transport properties of alkyltrimethylammonium cation-based room-temperature ionic liquids.

PubMed

Seki, Shiro; Tsuzuki, Seiji; Hayamizu, Kikuko; Serizawa, Nobuyuki; Ono, Shimpei; Takei, Katsuhito; Doi, Hiroyuki; Umebayashi, Yasuhiro

2014-05-01

We have measured physicochemical properties of five alkyltrimethylammonium cation-based room-temperature ionic liquids and compared them with those obtained from computational methods. We have found that static properties (density and refractive index) and transport properties (ionic conductivity, self-diffusion coefficient, and viscosity) of these ionic liquids show close relations with the length of the alkyl chain. In particular, static properties obtained by experimental methods exhibit a trend complementary to that by computational methods (refractive index ∝ [polarizability/molar volume]). Moreover, the self-diffusion coefficient obtained by molecular dynamics (MD) simulation was consistent with the data obtained by the pulsed-gradient spin-echo nuclear magnetic resonance technique, which suggests that computational methods can be supplemental tools to predict physicochemical properties of room-temperature ionic liquids.

IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

EPA Science Inventory

A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

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

NASA Astrophysics Data System (ADS)

Karmakar, A.; Ghosh, A.

2011-11-01

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

Embedding of polyaniline molecules on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique

NASA Astrophysics Data System (ADS)

Pamatmat, J. K.; Gillado, A. V.; Herrera, M. U.

2017-05-01

Polyaniline molecules are embedded on adhesive tape using successive ionic layer adsorption and reaction (SILAR) technique. The infrared spectrum shows the existence of molecular vibrational modes associated with the presence of polyaniline molecules on the sample. With the addition of polyaniline molecules, the conductivity of adhesive tape increases. Surface conductivity increases with number of dipping cycle until it reaches a certain value. Beyond this value, surface conductivity begins to decrease. The surface conductivity of the sample is associated with the connectivity of the embedded polyaniline molecules. The connectivity increases as the number of dipping cycle progresses. Meanwhile, the decrease in surface conductivity is attributed to the eroding of existing embedded structure at higher number of dipping cycle.

Prolonged fasting increases the response of the renin-angiotensin-aldosterone system, but not vasopressin levels, in postweaned northern elephant seal pups

NASA Technical Reports Server (NTRS)

Ortiz, R. M.; Wade, C. E.; Ortiz, C. L.

2000-01-01

The 8- to 12-week postweaning fast exhibited by northern elephant seal pups (Mirounga angustirostris) occurs without any apparent deleterious effects on fluid and electrolyte homeostasis. However, during the fast the role of vasopressin (AVP) has been shown to be inconclusive and the involvement of the renin-angiotensin-aldosterone system (RAAS) has yet to be examined. To examine the effects of prolonged fasting on these osmoregulatory hormones, 15 postweaned pups were serially blood-sampled during the first 49 days of their fast. Fasting did not induce significant changes in ionic or osmotic concentrations, suggesting electrolyte homeostasis. Total proteins were reduced by day 21 of fasting and remained depressed, suggesting a lack of dehydration. Aldosterone and plasma renin activity exhibited a correlated, linear increase over the first 49 days of the fast, suggesting an active RAAS. Aldosterone exhibited a parabolic trend over the fast with a peak at day 35, suggesting a shift in the sensitivity of the kidney to aldosterone later in the fast. AVP was elevated at day 49 only, but concentrations were relatively low. RAAS was modified during the postweaning fast in pups and appears to play a significant role in the regulation of electrolyte and, most likely, water homeostasis during this period. Copyright 2000 Academic Press.

Enhanced ionic conductivity of AgI nanowires/AAO composites fabricated by a simple approach.

PubMed

Liu, Li-Feng; Lee, Seung-Woo; Li, Jing-Bo; Alexe, Marin; Rao, Guang-Hui; Zhou, Wei-Ya; Lee, Jae-Jong; Lee, Woo; Gösele, Ulrich

2008-12-10

AgI nanowires/anodic aluminum oxide (AgI NWs/AAO) composites have been fabricated by a simple approach, which involves the thermal melting of AgI powders on the surface of the AAO membrane, followed by the infiltration of the molten AgI inside the nanochannels. As-prepared AgI nanowires have corrugated outer surfaces and are polycrystalline according to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. X-ray diffraction (XRD) shows that a considerable amount of 7H polytype AgI exists in the composites, which is supposed to arise from the interfacial interactions between the embedded AgI and the alumina. AC conductivity measurements for the AgI nanowires/AAO composites exhibit a notable conductivity enhancement by three orders of magnitude at room temperature compared with that of pristine bulk AgI. Furthermore, a large conductivity hysteresis and abnormal conductivity transitions were observed in the temperature-dependent conductivity measurements, from which an ionic conductivity as high as 8.0 × 10(2) Ω(-1) cm(-1) was obtained at around 70 °C upon cooling. The differential scanning calorimetry (DSC) result demonstrates a similar phase transition behavior as that found in the AC conductivity measurements. The enhanced ionic conductivity, as well as the abnormal phase transitions, can be explained in terms of the existence of the highly conducting 7H polytype AgI and the formation of well-defined conduction paths in the composites.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

Characterization of un-plasticized and propylene carbonate plasticized carboxymethyl cellulose doped ammonium chloride solid biopolymer electrolytes.

PubMed

Ahmad, N H; Isa, M I N

2016-02-10

Two solid biopolymer electrolytes (SBEs) systems of carboxymethyl cellulose doped ammonium chloride (CMC-AC) and propylene carbonate plasticized (CMC-AC-PC) were prepared via solution casting technique. The ionic conductivity of SBEs were analyzed using electrical impedance spectroscopy (EIS) in the frequency range of 50 Hz-1 MHz at ambient temperature (303K). The highest ionic conductivity of CMC-AC SBE is 1.43 × 10(-3)S/cm for 16 wt.% of AC while the highest conductivity of plasticized SBE system is 1.01 × 10(-2)S/cm when added with 8 wt.% of PC. TGA/DSC showed that the addition of PC had increased the decomposition temperature compared of CMC-AC SBE. Fourier transform infrared (FTIR) spectra showed the occurrence of complexation between the SBE components and it is proved successfully executed by Gaussian software. X-ray diffraction (XRD) indicated that amorphous nature of SBEs. It is believed that the PC is one of the most promising plasticizer to enhance the ionic conductivity and performance for SBE system. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

Monitoring sodium removal and delivered dialysis by conductivity.

PubMed

Locatelli, F; Di Filippo, S; Manzoni, C; Corti, M; Andrulli, S; Pontoriero, G

1995-11-01

As cardiovascular stability and the delivery of the prescribed dialysis "dose" seem to be the main factors in determining the morbidity and mortality of hemodialyzer patients today, it is of paramount importance to match hydro-sodium removal with interdialytic load and to verify the delivered dialysis at each session. A specially designed Biofeedback Module (BM--COT Hospal) allows the automatic determination of plasma water conductivity and effective ionic dialysance with no need for blood samples. Using BM, we evaluated the validity of "conductivity kinetic modelling" (CKM) and the possibility that this may substitute "sodium kinetic modelling". Moreover, we evaluated the "in vivo" relationship between ionic dialysance and effective urea clearance. Our results demonstrate that: 1) CKM makes it possible to obtain programmed end-dialysis plasma water conductivity with an error of less than +/- 0.14 mS/cm, roughly equivalent to a sodium concentration of +/- 1.4 mEq/L. 2). Ionic dialysance and effective urea clearance are not equivalent but, as the interrelationship between these is known, the BM allows the routine monitoring of delivered dialysis.

A four-diode full-wave ionic current rectifier based on bipolar membranes: overcoming the limit of electrode capacity.

PubMed

Gabrielsson, Erik O; Janson, Per; Tybrandt, Klas; Simon, Daniel T; Berggren, Magnus

2014-08-13

Full-wave rectification of ionic currents is obtained by constructing the typical four-diode bridge out of ion conducting bipolar membranes. Together with conjugated polymer electrodes addressed with alternating current, the bridge allows for generation of a controlled ionic direct current for extended periods of time without the production of toxic species or gas typically arising from electrode side-reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport Properties of Ionic Liquid Mixtures Containing Heterodications

DOE PAGES

Lall-Ramnarine, S.; Fernandez, E.; Rodriguez, C.; ...

2016-08-30

This report discusses the transport properties of ionic liquid mixtures that incorporate a series of asymmetrical dications, including heterodications. The dicationic ILs combine either triphenylphosphonium and trimethylammonium cationic sites that are bridged to methylimidazolium or methylpyrrolidinium cationic sites. Mixtures were made of the dicationic bis(trifluoromethylsulfonyl)amide ionic liquids with N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide. The IL mixtures were characterized for their transport properties (temperature dependent conductivity and viscosity) and thermal properties (melting point and glass transition point).

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

Ionic Conductivity of TlBr1-xIx(x = 0, 0.2, 1): Candidate Gamma Ray Detector

NASA Astrophysics Data System (ADS)

Bishop, S. R.; Ciampi, G.; Lee, C. D.; Kuhn, M.; Tuller, H. L.; Higgins, W.; Shah, K. S.

2012-10-01

The ionic conductivity of TlBr, TlI and their solid solutions, candidates for high energy radiation detection, was examined using impedance spectroscopy. The orthorhombic to cubic phase change in TlI was observed via a steep change in conductivity with increasing temperature, whereas the TlBr-TlI solid solution was cubic throughout the measured temperature range, in agreement with the literature. The intrinsic conductivity of the cubic phase of each material showed nearly identical behavior, indicating that I substitution for Br has little to no effect on the combined defect formation and transport parameters in the studied range. Additionally, optical transmission was correlated with I concentration.

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.

Structural and electrical characterization of tamarind seed polysaccharide (TSP) doped with NH4HCO2

NASA Astrophysics Data System (ADS)

Premalatha, M.; Mathavan, T.; Selvasekarapandian, S.; Selvalakshmi, S.

2018-04-01

In the modern era, development of electrochemical energy devices such as batteries, fuel cells and supercapacitors gain attention due to the deficiency of renewable energy resources. More specifically, proton conducting materials create prime interest in the development of electrochemical devices. In this regards, a novel proton conducting biopolymer electrolyte based on Tamarind Seed Polysaccharide (TSP) was synthesized with different concentration of ammonium formate (NH4HCO2). The amorphous nature of the polymer electrolytes has been identified by XRD technique. The observed ionic conductivity values reveal that the biopolymer containing 1 g TSP: 0.4 g NH4HCO2 has highest ionic conductivity 1.23×10-3 S cm-1.

Composite electrode/electrolyte structure

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2004-01-27

Provided is an electrode fabricated from highly electronically conductive materials such as metals, metal alloys, or electronically conductive ceramics. The electronic conductivity of the electrode substrate is maximized. Onto this electrode in the green state, a green ionic (e.g., electrolyte) film is deposited and the assembly is co-fired at a temperature suitable to fully densify the film while the substrate retains porosity. Subsequently, a catalytic material is added to the electrode structure by infiltration of a metal salt and subsequent low temperature firing. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in ionic (electrochemical) devices such as fuel cells and electrolytic gas separation systems.

Sub-nA spatially resolved conductivity profiling of surface and interface defects in ceria films

DOE PAGES

Farrow, Tim; Yang, Nan; Doria, Sandra; ...

2015-03-17

Spatial variability of conductivity in ceria is explored using scanning probe microscopy with galvanostatic control. Ionically blocking electrodes are used to probe the conductivity under opposite polarities to reveal possible differences in the defect structure across a thin film of CeO2. Data suggest the existence of a large spatial inhomogeneity that could give rise to constant phase elements during standard electrochemical characterization, potentially affecting the overall conductivity of films on the macroscale. The approach discussed here can also be utilized for other mixed ionic electronic conductor systems including memristors and electroresistors, as well as physical systems such as ferroelectric tunnelingmore » barriers« less

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

Density Optimization of Lithium Lanthanum Titanate Ceramics for Lightweight Lithium-Air Batteries

DTIC Science & Technology

2014-11-01

Thangadurai V, Weppner W. Lithium lanthanum titanates: a review. Chemistry of Materials. 2003;15:3974–3990. 4. Knauth P. Inorganic solid Li ion conductors...an overview. Solid State Ionics. 2009;180:911–916. 5. Ban CW, Choi GM. The effect of sintering on the grain boundary conductivity of lithium ...lanthanum titanates. Solid State Ionics. 2001;140:285–292. 6. Inada R, Kimura K, Kusakabe K, Tojo T, Sakurai Y. Synthesis and lithium -ion conductivity

Oxyphosphorus-containing polymers as binders for battery cathodes

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

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

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

Study of Parameters Dominating Electromechanical and Sensing Response in Ionic Electroactive Polymer (IEAP) Transducers

NASA Astrophysics Data System (ADS)

Almomani, Abdallah Mohammad

Ionic electroactive polymer (IEAP) transducers are a class of smart structures based on polymers that can be designed as soft actuators or sensors. IEAP actuators exhibit a high mechanical response to an external electrical stimulus. Conversely, they produce electrical signals when subjected to mechanical force. IEAP transducers are mainly composed of four different components: The ionomeric membrane (usually Nafion) is an ion permeable polymer that acts as the backbone of the transducer. Two conductive network composite (CNC) layer on both sides of the ionomeric membrane that enhance the surface conductivity and serve as an extra reservoir to the electrolytes. The electrolytes, (usually ionic liquids (IL)), which provides the mobile ions. And two outer electrodes on both sides of the transducer to either provide a distributed applied potential across the actuators (usually gold leaves) or to collect the generated signals from the sensors (usually copper electrodes). Any variation in any of these components or the operating conditions will directly affect the performance of the IEAP transduces. In this dissertation, we studied some of the parameters dominating the performance of the IEAP transducers by varying some of the transducers components or the transducers operating conditions in order to enhance their performance. The first study was conducted to understand the influence of ionic liquid concentration on the electromechanical performance of IEAP actuators. The IL weight percentage (wt%) was varied from 10% to 30% and both the electromechanical (induced strain) and the electrochemical (the current flow across the actuators) were studied. The results from this study showed an enhanced electrochemical performance (current flow is higher for higher IL wt%) and a maximum electromechanical strain of approximately 1.4% at 22 wt% IL content. A lower induced strain was noticed for IL wt% lower or higher than 22%. The second study was to investigate the effect of changing the morphology of the CNC on the sensing performance of IEAP stress sensors. In this study, small salt molecules were added to the CNC layers. Salt molecules directly affected the morphology of the CNC layers resulting in a thicker, more porous, and high conductive CNCs. As a result, the ionic conductivity increased through the CNC layers and sensing performance was enhanced significantly. In the third study, a non-linear angular deformation (limb-like motion) was achieved by varying the CNC layers of the IEAP actuators by adding some conjugated polymers (CP) patterns during the fabrication of the actuators. It was found that the segments with the CP layers will only expand and never contract during the actuation process. Depending on the direction of motion and the location of the CP layers, different actuation shapes such as square or triangular shapes were achieved rather than the typical circular bending. In the fourth study, the influence of temperature on the electromechanical properties of the IEAP actuators was examined. In this study, both electromechanical and electrochemical studies were conducted for actuators that were operated at temperatures ranging from 25 °C to 90 °C. The electromechanical results showed a lower cationic curvature with increasing temperature up to 70 °C. On the other hand, a maximum anionic curvature was achieved at 50 °C with a sudden decrease after 50 °C. Actuators started to lose functionality and showed unpredictable performance at temperatures higher than 70 °C. Electrochemically, an enhancement of the ionic conductivity was resulted from increasing temperature up to 80 °C. A sudden increase in current flow was recorded at 90 °C indicating a shorted circuit and actuator failure. Finally, in the fifth study, protons in Nafion membranes were exchanged with other counterions of different Van der Waals volumes. The ionic conductivity was measured for IEAP membranes with different counterions at different temperatures. The results showed higher ionic conductivities across membranes with larger Van der Waals volume counterions and higher temperatures. A different ionic conductivity behavior was also noticed for temperatures ranging from 30 °C to 55 °C than temperatures between 55 °C and 70 °C after fitting the data with the Arrhenius conductivity equation.

Computational and experimental investigation of Li-doped ionic liquid electrolytes: [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4].

PubMed

Haskins, Justin B; Bennett, William R; Wu, James J; Hernández, Dionne M; Borodin, Oleg; Monk, Joshua D; Bauschlicher, Charles W; Lawson, John W

2014-09-25

We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 ≤ xLi(+) ≤ 0.33) and temperature (298 K ≤ T ≤ 393 K). Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi(+) we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD simulations and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi(+), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi(+) = 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 and 0.3 mS/cm. Our transport results also demonstrate the necessity of long MD simulation runs (∼200 ns) to converge transport properties at room temperature. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions (τ(Li/-)), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li(+) transport in each liquid, we find that while the net motion of Li(+) with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange increases at high xLi(+) and in liquids with large anions.

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes.

PubMed

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-04-15

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1/3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given pH.

Scaling Behavior for Ionic Transport and its Fluctuations in Individual Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Secchi, Eleonora; Niguès, Antoine; Jubin, Laetitia; Siria, Alessandro; Bocquet, Lydéric

2016-04-01

In this Letter, we perform an experimental study of ionic transport and current fluctuations inside individual carbon nanotubes (CNTs). The conductance exhibits a power law behavior at low salinity, with an exponent close to 1 /3 versus the salt concentration in this regime. This behavior is rationalized in terms of a salinity dependent surface charge, which is accounted for on the basis of a model for hydroxide adsorption at the (hydrophobic) carbon surface. This is in contrast to boron nitride nanotubes which exhibit a constant surface conductance. Further, we measure the low frequency noise of the ionic current in CNTs and show that the amplitude of the noise scales with the surface charge, with data collapsing on a master curve for the various studied CNTs at a given p H .

Electrical properties of binary mixtures of amino silicone oil and methyl iso butyl ketone

NASA Astrophysics Data System (ADS)

Shah, K. N.; Rana, V. A.; Vankar, H. P.

2018-05-01

The real and imaginary parts of the dielectric function of the binary mixtures of the methyl iso butyl ketone and amino silicone oil in the frequency range 100 Hz to 2 MHz were measured using precision LCR meter at 305.15 K. The electrical properties such as electrical modulus M*(ω), electrical conductivity σ*(ω) and complex impedance Z*(ω) were calculated using the dielectric function ɛ*(ω). The ionic polarization relaxation time (Τσ) and D.C. conductivity (σdc) were also calculated using electrical properties. The ionic behavior of methyl iso butyl ketone and non-ionic behavior of amino silicone oil are also explained. The electrical parameters are used to gain information about the effect of concentration variation of components of the mixtures on the electrical properties.

Innovative Ionic Liquids: Electrolytes for Ion Power Sources

DTIC Science & Technology

2008-01-01

imide–based ILs can function not only as the electrolyte in a conventional lithium ion battery , but also as a solid nanocomposite separator when...conductivity comparable to the pure ionic liquid. Figure 6 shows the charge-discharge behavior of the micro lithium ion battery created entirely by the

The use of stable isotope to evaluate water mixing and water use by flood plain trees along the Garonne valley

USGS Publications Warehouse

Lambs, L.; Loubiat, M.; Richardson, W.

2003-01-01

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (??18O: -9.1??? to -9.0???, conductivity: 217-410??S/cm) was distinctly different from groundwater (??18O: -7.1??? to -6.6???, conductivity: 600-900??S/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (1m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Application of the compensated Arrhenius formalism to self-diffusion: implications for ionic conductivity and dielectric relaxation.

PubMed

Petrowsky, Matt; Frech, Roger

2010-07-08

Self-diffusion coefficients are measured from -5 to 80 degrees C in a series of linear alcohols using pulsed field gradient NMR. The temperature dependence of these data is studied using a compensated Arrhenius formalism that assumes an Arrhenius-like expression for the diffusion coefficient; however, this expression includes a dielectric constant dependence in the exponential prefactor. Scaling temperature-dependent diffusion coefficients to isothermal diffusion coefficients so that the exponential prefactors cancel results in calculated energies of activation E(a). The exponential prefactor is determined by dividing the temperature-dependent diffusion coefficients by the Boltzmann term exp(-E(a)/RT). Plotting the prefactors versus the dielectric constant places the data on a single master curve. This procedure is identical to that previously used to study the temperature dependence of ionic conductivities and dielectric relaxation rate constants. The energies of activation determined from self-diffusion coefficients in the series of alcohols are strikingly similar to those calculated for the same series of alcohols from both dielectric relaxation rate constants and ionic conductivities of dilute electrolytes. The experimental results are described in terms of an activated transport mechanism that is mediated by relaxation of the solution molecules. This microscopic picture of transport is postulated to be common to diffusion, dielectric relaxation, and ionic transport.

Enhancing the performance of green solid-state electric double-layer capacitor incorporated with fumed silica nanoparticles

NASA Astrophysics Data System (ADS)

Chong, Mee Yoke; Numan, Arshid; Liew, Chiam-Wen; Ng, H. M.; Ramesh, K.; Ramesh, S.

2018-06-01

Solid polymer electrolyte (SPE) based on fumed silica nanoparticles as nanofillers, hydroxylethyl cellulose (HEC) as host polymer, magnesium trifluoromethanesulfonate salt and 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid is prepared by solution casting technique. The ionic conductivity, interactions of adsorbed ions on the host polymer, structural crystallinity and thermal stability are evaluated by electrochemical impedance spectroscopy (EIS), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Ionic conductivity studies at room temperature reveals that the SPE with 2 wt. % of fumed silica nanoparticles gives the highest conductivity compared to its counterpart. The XRD and FTIR studies confirm the dissolution of salt, ionic liquid and successful incorporation of fumed silica nanoparticles with host polymer. In order to examine the performance of SPEs, electric double-layer capacitor (EDLC) are fabricated by using activated carbon electrodes. EDLC studies demonstrate that SPE incorporated with 2 wt. % fumed silica nanoparticles gives high specific capacitance (25.0 F/g) at a scan rate of 5 mV/s compared to SPE without fumed silica. Additionally, it is able to withstand 71.3% of capacitance from its initial capacitance value over 1600 cycles at a current density of 0.4 A/g.

Impedance spectroscopy of reduced monoclinic zirconia.

PubMed

Eder, Dominik; Kramer, Reinhard

2006-10-14

Zirconia doped with low-valent cations (e.g. Y3+ or Ca2+) exhibits an exceptionally high ionic conductivity, making them ideal candidates for various electrochemical applications including solid oxide fuel cells (SOFC) and oxygen sensors. It is nevertheless important to study the undoped, monoclinic ZrO2 as a model system to construct a comprehensive picture of the electrical behaviour. In pure zirconia a residual number of anion vacancies remains because of contaminants in the material as well as the thermodynamic disorder equilibrium, but electronic conduction may also contribute to the observed conductivity. Reduction of zirconia in hydrogen leads to the adsorption of hydrogen and to the formation of oxygen vacancies, with their concentration affected by various parameters (e.g. reduction temperature and time, surface area, and water vapour pressure). However, there is still little known about the reactivities of defect species and their effect on the ionic and electronic conduction. Thus, we applied electrochemical impedance spectroscopy to investigate the electric performance of pure monoclinic zirconia with different surface areas in both oxidizing and reducing atmospheres. A novel equivalent circuit model including parallel ionic and electronic conduction has previously been developed for titania and is used herein to decouple the conduction processes. The concentration of defects and their formation energies were measured using volumetric oxygen titration and temperature programmed oxidation/desorption.

Probing the bulk ionic conductivity by thin film hetero-epitaxial engineering

NASA Astrophysics Data System (ADS)

Pergolesi, Daniele; Roddatis, Vladimir; Fabbri, Emiliana; Schneider, Christof W.; Lippert, Thomas; Traversa, Enrico; Kilner, John A.

2015-02-01

Highly textured thin films with small grain boundary regions can be used as model systems to directly measure the bulk conductivity of oxygen ion conducting oxides. Ionic conducting thin films and epitaxial heterostructures are also widely used to probe the effect of strain on the oxygen ion migration in oxide materials. For the purpose of these investigations a good lattice matching between the film and the substrate is required to promote the ordered film growth. Moreover, the substrate should be a good electrical insulator at high temperature to allow a reliable electrical characterization of the deposited film. Here we report the fabrication of an epitaxial heterostructure made with a double buffer layer of BaZrO3 and SrTiO3 grown on MgO substrates that fulfills both requirements. Based on such template platform, highly ordered (001) epitaxially oriented thin films of 15% Sm-doped CeO2 and 8 mol% Y2O3 stabilized ZrO2 are grown. Bulk conductivities as well as activation energies are measured for both materials, confirming the success of the approach. The reported insulating template platform promises potential application also for the electrical characterization of other novel electrolyte materials that still need a thorough understanding of their ionic conductivity.

Rietveld refinement, electronic structure and ionic conductivity of Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics

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

Boughzala, Khaled, E-mail: khaledboughzala@gmail.com; Preparatory Institute for Engineering Studies, 5000 Monastir; Debbichi, Mourad

In this paper, we report the effect of the tunnel anions on the ionic conductivity of Strontium-Lanthanum silicate apatites. The Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics were prepared by the solid state reaction method. X-ray diffraction, NMR spectroscopy and Raman measurements were performed to investigate the crystal structure and vibrational active modes. Moreover, the electronic structures of the crystals were evaluated by the first-principles quantum mechanical calculation based on the density functional theory. Finally, the ionic conductivity was studied according to the complex impedance method. - Graphical abstract: The relaxed primitive unit cellmore » for Sr{sub 4}La{sub 6}Fap. Display Omitted.« less

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

Wang, Hui; Chen, Yan; Hood, Zachary D.

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Effects of sputtering mode on the microstructure and ionic conductivity of yttria-stabilized zirconia films

NASA Astrophysics Data System (ADS)

Yeh, Tsung-Her; Lin, Ruei-De; Cherng, Bo-Ruei; Cherng, Jyh-Shiarn

2018-05-01

The microstructure and ionic conductivity of reactively sputtered yttria-stabilized zirconia (YSZ) films are systematically studied. Those films were reactively sputtered in various sputtering modes using a closed-loop controlled system with plasma emission monitoring. A transition-mode sputtering corresponding to 45% of target poisoning produces a microstructure with ultrafine crystallites embedded in an amorphous matrix, which undergoes an abnormal grain growth upon annealing at 800 °C. At 500 °C, the measured ionic conductivity of this annealed film is higher, by about a half order of magnitude, than those of its poisoned-mode counterparts, which are in turn significantly higher than that of the YSZ bulk by about two orders of magnitude. The abnormally-grown ultra-large grain size of the film deposited in the transition mode and then annealed is believed to be responsible for the former comparison due to the suppression of the grain boundary blocking effect, while the latter comparison can be attributed to the interface effect.

Effects for rapid conversion from abalone shell to hydroxyapaptite nanosheets by ionic surfactants.

PubMed

Zhong, Shengnan; Wen, Zhenliang; Chen, Jingdi; Li, Qian; Shi, Xuetao; Ding, Shinnjyh; Zhang, Qiqing

2017-08-01

Hydroxyapatite (HAP) has been widely used for repairing or substituting human hard tissues. In this paper, two typical ionic surfactants, cation hexadecyltrimethylammonium bromide (CTAB) and anion sodium dodecyl sulfate (SDS), were used for rapid conversion of HAP from abalone shell. From field emission scanning electron microscopy (FESEM), the prepared HAP is flake-like structure. From X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal analysis, these samples contain a small amount of calcium carbonate whose content gradually increases by increasing the surfactants. The results showed that the HAP formed fast on the layer of abalone shell powder with the assistance of CTAB and SDS. Copyright © 2017 Elsevier B.V. All rights reserved.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Sorption of Lincomycin by Manure-Derived Biochars from Water

PubMed Central

Liu, Cheng-Hua; Chuang, Ya-Hui; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.; Gonzalez, Javier M.; Johnston, Cliff T.; Lehmann, Johannes; Zhang, Wei

2018-01-01

The presence of antibiotics in agroecosystems raises concerns about the proliferation of antibiotic-resistant bacteria and adverse effects to human health. Soil amendment with biochars pyrolized from manures may be a win-win strategy for novel manure management and antibiotics abatement. In this study, lincomycin sorption by manure-derived biochars was examined using batch sorption experiments. Lincomycin sorption was characterized by two-stage kinetics with fast sorption reaching quasi-equilibrium in the first 2 d, followed by slow sorption over 180 d. The fast sorption was primarily attributed to surface adsorption, whereas the long-term slow sorption was controlled by slow diffusion of lincomycin into biochar pore structures. Two-day sorption experiments were performed to explore effects of biochar particle size, solid/water ratio, solution pH, and ionic strength. Lincomycin sorption to biochars was greater at solution pH 6.0 to 7.5 below the dissociation constant of lincomycin (7.6) than at pH 9.9 to 10.4 above its dissociation constant. The enhanced lincomycin sorption at lower pH likely resulted from electrostatic attraction between the positively charged lincomycin and the negatively charged biochar surfaces. This was corroborated by the observation that lincomycin sorption decreased with increasing ionic strength at lower pH (6.7) but remained constant at higher pH (10). The long-term lincomycin sequestration by biochars was largely due to pore diffusion plausibly independent of solution pH and ionic composition. Therefore, manure-derived biochars had lasting lincomycin sequestration capacity, implying that biochar soil amendment could significantly affect the distribution, transport, and bioavailability of lincomycin in agroecosystems. PMID:27065399

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

PubMed

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-12-04

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO₂) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO₂ sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

PubMed Central

Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

2015-01-01

Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

The potential of incorporation of binary salts and ionic liquid in P(VP-co-VAc) gel polymer electrolyte in electrochemical and photovoltaic performances

PubMed Central

Ming, Ng Hon; Ramesh, S.; Ramesh, K.

2016-01-01

In this study, dye-sensitized solar cells (DSSCs) has been assembled with poly(1-vinylpyrrolidone-co-vinyl acetate) (P(VP-co-VAc)) gel polymer electrolytes (GPEs) which have been incorporated with binary salt and an ionic liquid. The potential of this combination was studied and reported. The binary salt system GPEs was having ionic conductivity and power conversion efficiency (PCE) that could reach up to 1.90 × 10−3 S cm−1 and 5.53%, respectively. Interestingly, upon the addition of the ionic liquid, MPII into the binary salt system the ionic conductivity and PCE had risen steadily up to 4.09 × 10−3 S cm−1 and 5.94%, respectively. In order to know more about this phenomenon, the electrochemical impedance studies (EIS) of the GPE samples have been done and reported. Fourier transform infrared studies (FTIR) and thermogravimetric analysis (TGA) have also been studied to understand more on the structural and thermal properties of the GPEs. The Nyquist plot and Bodes plot studies have been done in order to understand the electrochemical properties of the GPE based DSSCs and Tafel polarization studies were done to determine the electrocatalytic activity of the GPE samples. PMID:27273020

Correlation between cation conduction and ionic morphology in a PEO-based single ion conductor

NASA Astrophysics Data System (ADS)

Lin, Kan-Ju; Maranas, Janna

2011-03-01

We use molecular dynamics simulation to study ion transport and backbone mobility of a PEO-based single ion conductor. Ion mobility depends on the chemical structure and the local environment of the ions, which consequently impact ionic conductivity. We characterize the aggregation state of the ions, and assess the role of ion complexes in ionomer dynamics. In addition to solvated cations and pairs, higher order ion clusters are found. Most of the ion clusters are in string-like structure and cross-link two or more different ionomer chains through ionic binding. Ionic crosslinks decrease mobility at the ionic co-monomer; hence the mobility of the adjacent PEO segment is influenced. Na ions show slow mobility when they are inside large clusters. The hopping timescale for Na varies from 20 ns to 200. A correlation is found between Na mobility and the number of hops from one coordination site to another. Besides ether oxygens, Na ions in the ionomer also use the anion and the edge of the cluster as hopping sites. The string-like structure of clusters provide less stable sites at the two ends thus ions are more mobile in those regions. We observed Grotthus like mechanism in our ionomer, in which the positive charge migrates within the string-like cluster without the cations actually moving.

Notre Dame Geothermal Ionic Liquids Research: Ionic Liquids for Utilization of Geothermal Energy

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

Brennecke, Joan F.

The goal of this project was to develop ionic liquids for two geothermal energy related applications. The first goal was to design ionic liquids as high temperature heat transfer fluids. We identified appropriate compounds based on both experiments and molecular simulations. We synthesized the new ILs, and measured their thermal stability, measured storage density, viscosity, and thermal conductivity. We found that the most promising compounds for this application are aminopyridinium bis(trifluoromethylsulfonyl)imide based ILs. We also performed some measurements of thermal stability of IL mixtures and used molecular simulations to better understand the thermal conductivity of nanofluids (i.e., mixtures of ILsmore » and nanoparticles). We found that the mixtures do not follow ideal mixture theories and that the addition of nanoparticles to ILs may well have a beneficial influence on the thermal and transport properties of IL-based heat transfer fluids. The second goal was to use ionic liquids in geothermally driven absorption refrigeration systems. We performed copious thermodynamic measurements and modeling of ionic liquid/water systems, including modeling of the absorption refrigeration systems and the resulting coefficients of performance. We explored some IL/organic solvent mixtures as candidates for this application, both with experimentation and molecular simulations. We found that the COPs of all of the IL/water systems were higher than the conventional system – LiBr/H2O. Thus, IL/water systems appear very attractive for absorption refrigeration applications.« less

Viscoelastic Properties, Ionic Conductivity, and Materials Design Considerations for Poly(styrene-b-ethylene oxide-b-styrene)-Based Ion Gel Electrolytes

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

Zhang, Sipei; Lee, Keun Hyung; Sun, Jingru

2013-03-07

The viscoelastic properties and ionic conductivity of ion gels based on the self-assembly of a poly(styrene-b-ethylene oxide-b-styrene) (SOS) triblock copolymer (M{sub n,S} = 3 kDa, M{sub n,O} = 35 kDa) in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMI][TFSA]) were investigated over the composition range of 10-50 wt % SOS and the temperature range of 25-160 C. The poly(styrene) (PS) end-blocks associate into micelles, whereas the poly(ethylene oxide) (PEO) midblocks are well-solvated by this ionic liquid. The ion gel with 10 wt % SOS melts at 54 C, with the longest relaxation time exhibiting a similar temperature dependence to that of themore » viscosity of bulk PS. However, the actual values of the gel relaxation time are more than 4 orders of magnitude larger than the relaxation time of bulk PS. This is attributed to the thermodynamic penalty of pulling PS end-blocks through the PEO/[EMI][TFSA] matrix. Ion gels with 20-50 wt % SOS do not melt and show two plateaus in the storage modulus over the temperature and frequency ranges measured. The one at higher frequencies is that of an entangled network of PEO strands with PS cross-links; the modulus displays a quadratic dependence on polymer weight fraction and agrees with the prediction of linear viscoelastic theory assuming half of the PEO chains are elastically effective. The frequency that separates the two plateaus, {omega}{sub c}, reflects the time scale of PS end-block pull-out. The other plateau at lower frequencies is that of a congested micelle solution with PS cores and PEO coronas, which has a power law dependence on domain spacing similar to diblock melts. The ionic conductivity of the ion gels is compared to PEO homopolymer solutions at similar polymer concentrations; the conductivity is reduced by a factor of 2.1 or less, decreases with increasing PS volume fraction, and follows predictions based on a simple obstruction model. Our collective results allow the formulation of basic design considerations for optimizing the mechanical properties, thermal stability, and ionic conductivity of these gels.« less

The gelation influence on diffusion and conductivity enhancement effect in renewable ionic gels based on a LMWG.

PubMed

Bielejewski, M; Rachocki, A; Kaszyńska, J; Tritt-Goc, J

2018-02-21

This paper reports the interdisciplinary study on molecular dynamics, ionic interactions and electrical conductivity in a quaternary ammonium salt (TMABr) ionogel based on a low molecular weight gelator (LMWG) in a wide range of electrolyte molar concentrations. The thermal scanning conductometry (TSC) was used to investigate the electric properties of the ionogels. The prepared TMABr/H 2 O/LMWG ionogel exhibits better ion transport properties than the dissociated TMA + cation in solution. The enhanced ionic conductivity effect (EICE) was observed in the concentration range of the TMABr salt up to 1 M. To investigate the transport properties of the TMA + cation and solvent molecules in the gel and sol phase, the NMR diffusiometry method was used. The field-cycling relaxometry method (FFC NMR) was applied to study the local motions of the electrolyte at the surface of the gelator matrix. On the basis of the obtained data, the higher ionic conductivity observed in the gel phase has been related to the microstructure of the gel matrix. The possible explanation for the origin of this effect has been given. The investigated system is a thermally reversible physical gel, all registered data were reproducible upon transforming the sample from gel to sol and back to the gel state, confirming the enhancement effect as a permanent property of the investigated ionogels. Therefore, the EICE has been proposed to be used as an internal sensor to monitor the condition of the ionogel phase, thus making them smart materials.