Science.gov

Sample records for ionic conductivity

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Quantized ionic conductance in nanopores

    SciTech Connect

    Zwolak, Michael; Lagerqvist, Johan; Di Ventra, Massimilliano

    2009-01-01

    Ionic transport in nanopores is a fundamentally and technologically important problem in view of its ubiquitous occurrence in biological processes and its impact on DNA sequencing applications. Using microscopic calculations, we show that ion transport may exhibit strong non-liDearities as a function of the pore radius reminiscent of the conductance quantization steps as a function of the transverse cross section of quantum point contacts. In the present case, however, conductance steps originate from the break up of the hydration layers that form around ions in aqueous solution. Once in the pore, the water molecules form wavelike structures due to multiple scattering at the surface of the pore walls and interference with the radial waves around the ion. We discuss these effects as well as the conditions under which the step-like features in the ionic conductance should be experimentally observable.

  6. Ionic Conduction in Nanocrystalline Materials

    DTIC Science & Technology

    2000-02-10

    photo- largely due to oxygen desorption from particle voltaic cells and as the photocatalyst in water surfaces. The latter interpretation...and Tuller [22] prepared dense (-95%) temperature, where bulk reduction was observed. At compacts of TiO2 with the anatase phase. The lower... TiO2 , evidence preparation. is mixed. Nanocrystalline rutile appears to exhibit higher ionic conductivity than single crystal rutile while

  7. Ionic Conductivity of Nanostructured Block Copolymer and Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan L.; Virgili, Justin M.; Segalman, Rachel A.

    2010-03-01

    Block copolymer and ionic liquid mixtures are of interest for creating ionically conductive, thermally stable, and nanostructured membranes. For mixtures of poly(styrene-b-2-vinylpyridine) (S2VP) and the ionic liquid bis(trifluoromethanesulfonyl)imide ([Im][TFSI]), nanostructured ion-conducting domains are formed due to [Im][TFSI] selectively residing in the P2VP domains of the block copolymer. The dependence of ionic conductivity on temperature, ionic liquid loading, and volume fraction of PS in the neat block copolymer was investigated for membranes with the matrix phase being P2VP/[Im][TFSI]. It was determined that the temperature dependence of conductivity follows the Vogel-Tamman-Fulcher equation, with the activation energy determined by the ratio of [Im][TFSI] to 2VP monomers. The overall weight fraction of [Im][TFSI] in the mixtures, however, is the dominating factor determining conductivity, regardless of PS volume fraction. The insight gained from this work will be important for further investigation into the effect on the ion transport properties of ionic liquids when confined to minority nanostructured domains.

  8. Low frequency ionic conduction across liquid interfaces

    NASA Astrophysics Data System (ADS)

    Solis, Francisco J.; Guerrero, Guillermo Ivan; Olvera de La Cruz, Monica

    Ionic conduction in liquid media is a central component of many recently proposed technologies. As in the case of solid state systems, the presence of heterogeneous media gives rise to interesting nonlinear phenomena. We present simulations and theoretical analysis of the low frequency ionic conduction in a two-liquid system. In the case analyzed, the conduction is driven by an electric field perpendicular to the liquid-liquid interface. We show that the dielectric contrast between the liquids produces non-linear effects in the effective conductivity of the system and discuss the effects of the ion solubility in the media.

  9. High H- ionic conductivity in barium hydride

    NASA Astrophysics Data System (ADS)

    Verbraeken, Maarten C.; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T. S.

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H-) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm-1 at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  10. 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

  11. Structure, ionic conductivity and mobile carrier density in fast ionic conducting chalcogenide glasses

    SciTech Connect

    Yao, Wenlong

    2006-01-01

    This thesis consists of six sections. The first section gives the basic research background on the ionic conduction mechanism in glass, polarization in the glass, and the method of determining the mobile carrier density in glass. The proposed work is also included in this section. The second section is a paper that characterizes the structure of MI + M2S + (0.1 Ga2S3 + 0.9 GeS2) (M = Li, Na, K and Cs) glasses using Raman and IR spectroscopy. Since the ionic radius plays an important role in determining the ionic conductivity in glasses, the glass forming range for the addition of different alkalis into the basic glass forming system 0.1 Ga2S3 + 0.9 GeS2 was studied. The study found that the change of the alkali radius for the same nominal composition causes significant structure change to the glasses. The third section is a paper that investigates the ionic conductivity of MI + M2S + (0.1Ga2S3 + 0.9 GeS2) (M = Li, Na, K and Cs) glasses system. Corresponding to the compositional changes in these fast ionic conducting glasses, the ionic conductivity shows changes due to the induced structural changes. The ionic radius effect on the ionic conductivity in these glasses was investigated. The fourth section is a paper that examines the mobile carrier density based upon the measurements of space charge polarization. For the first time, the charge carrier number density in fast ionic conducting chalcogenide glasses was determined. The experimental impedance data were fitted using equivalent circuits and the obtained parameters were used to determine the mobile carrier density. The influence of mobile carrier density and mobility on the ionic conductivity was separated. The fifth section is a paper that studies the structures of low-alkali-content Na2S + B2S3 (x ≤ 0.2) glasses by neutron and synchrotron x-ray diffraction

  12. Acetonitrile boosts conductivity of imidazolium ionic liquids.

    PubMed

    Chaban, Vitaly V; Voroshylova, Iuliia V; Kalugin, Oleg N; Prezhdo, Oleg V

    2012-07-05

    We apply a new methodology in the force field generation (Phys. Chem. Chem. Phys.2011, 13, 7910) to study binary mixtures of five imidazolium-based room-temperature ionic liquids (RTILs) with acetonitrile (ACN). Each RTIL is composed of tetrafluoroborate (BF(4)) anion and dialkylimidazolium (MMIM) cations. The first alkyl group of MIM is methyl, and the other group is ethyl (EMIM), butyl (BMIM), hexyl (HMIM), octyl (OMIM), and decyl (DMIM). Upon addition of ACN, the ionic conductivity of RTILs increases by more than 50 times. It significantly exceeds an impact of most known solvents. Unexpectedly, long-tailed imidazolium cations demonstrate the sharpest conductivity boost. This finding motivates us to revisit an application of RTIL/ACN binary systems as advanced electrolyte solutions. The conductivity correlates with a composition of ion aggregates simplifying its predictability. Addition of ACN exponentially increases diffusion and decreases viscosity of the RTIL/ACN mixtures. Large amounts of ACN stabilize ion pairs, although they ruin greater ion aggregates.

  13. Anisotropic ionic conductivities in lyotropic supramolecular liquid crystals.

    PubMed

    Huang, Youju; Cong, Yuanhua; Li, Junjun; Wang, Daoliang; Zhang, Jingtuo; Xu, Lu; Li, Weili; Li, Liangbin; Pan, Guoqiang; Yang, Chuanlu

    2009-12-28

    The designed aromatic amide discotic molecule with sulfonic acid groups at its periphery exhibits a hexagonal supramolecular columnar liquid crystalline phase, which leads to the achievement of anisotropic ionic conductivity through macroscopically aligning the ionic channels.

  14. Ionic conductivity in crystalline polymer electrolytes.

    PubMed

    Gadjourova, Z; Andreev, Y G; Tunstall, D P; Bruce, P G

    2001-08-02

    Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport.

  15. Voltage charging enhances ionic conductivity in gold nanotube membranes.

    PubMed

    Gao, Peng; Martin, Charles R

    2014-08-26

    Ionically conductive membranes are used in many electrochemical processes and devices, including batteries, fuel cells, and electrolyzers. In all such applications, it is advantageous to use membranes with high ionic conductivity because membrane resistance causes a voltage loss suffered by the cell. We describe here a method for enhancing ionic conductivity in membranes containing small diameter (4 nm) gold nanotubes. This entails making the gold nanotube membrane the working electrode in an electrochemical cell and applying a voltage to the membrane. We show here that voltage charging in this way can increase membrane ionic conductivity by over an order of magnitude. When expressed in terms of the ionic conductivity of the electrolyte, κ, within an individual voltage-charged tube, the most negative applied voltage yielded a κ comparable to that of 1 M aqueous KCl, over 2 orders of magnitude higher than κ of the 0.01 M KCl solution contacting the membrane.

  16. Morphology and Ionic Conductivity of Block Copolymer--Ionic Liquid Systems

    NASA Astrophysics Data System (ADS)

    Hoarfrost, M. L.; Virgili, J. M.; Kerr, J. B.; Segalman, R. A.

    2009-03-01

    Block copolymer--ionic liquid systems are of interest for ion exchange membranes due to the ionic conductivity and thermal stability of the ionic liquid combined with the thermal stability and morphological control arising from a structural component in a block copolymer. It is anticipated that the morphology and connectivity of the resulting structural and ionic liquid-containing nanodomains will affect conduction properties. This relationship was investigated for poly(styrene-b-2-vinylpyridine) (S2VP) in ionic liquids composed of varying molar ratios of imidazole and bis(trifluoromethanesulfonyl)imide (Im:TFSI). A stoichiometrically balanced ionic liquid (1:1 Im:TFSI) swells the 2VP lamellar domains for copolymer concentrations as low as 60wt%. With 9:1 Im:TFSI the lamellar structure tolerates more swelling, forming lamellar structures with as little as 30wt% copolymer. Ionic conductivities were derived from AC impedance measurements. The S2VP-Im:TFSI systems, characterized by microphase separated domains, demonstrate ionic conductivities comparable to those of P2VP--ionic liquid systems when normalized by 2VP (monomer) to Im:TFSI ratio.

  17. Morphology-enhanced conductivity in dry ionic liquids.

    PubMed

    Erbaş, Aykut; de la Cruz, Monica Olvera

    2016-03-07

    Ionic liquids exhibit fascinating nanoscale morphological phases and are promising materials for energy storage applications. Liquid crystalline order emerges in ionic liquids with specific chemical structures. Here, we investigate the phase behaviour and related ionic conductivities of dry ionic liquids, using extensive molecular dynamics simulations. Temperature dependence, properties of polymeric tail and excluded volume symmetry of the amphiphilic ionic liquid molecules are investigated in large scale systems with both short and long-range Coulomb interactions. Our results suggest that by adjusting stiffness and steric interactions of the amphiphilic molecules, lamellar or 3D continuous phases result in these molecular salts. The resulting phases are composed of ion rich and ion pure domains. In 3D phases, ion rich clusters form ionic channels and have significant effects on the conductive properties of the observed nano-phases. If there is no excluded-volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the steric interactions become asymmetric, lamellar phases are replaced by complex 3D continuous phases. Within the temperature ranges for which morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments on ionic liquid crystals. Stiffer molecules increase the high-conductivity interval and strengthen temperature-resistance of morphological phases. Increasing the steric interactions of cation leads to higher conductivities. Moreover, at low monomeric volume fractions and at low temperatures, cavities are observed in the nano-phases of flexible ionic liquids. We also demonstrate that, in the absence of electrostatic interactions, the morphology is distorted. Our findings inspire new design principles for room temperature ionic liquids and help explain previously-reported experimental data.

  18. Morphology-induced low temperature conductivity in ionic liquids

    NASA Astrophysics Data System (ADS)

    Erbas, Aykut; Olvera de La Cruz, Monica; Olvera de la Cruz Team

    Ionic liquids exhibit nano-scale liquid crystalline order depending on the polymeric details of salt molecules. The resulting morphology and temperature behavior are key factors in determining the room temperature conductivity of ionic liquids. Here we discuss the phase behavior and related ionic conductivities of dry ionic liquids with volume fractions close to unity by using extensive molecular dynamics simulations. Temperature dependence, effective persistence length of tails, and excluded volume symmetry of amphiphilic ionic liquid molecules are investigated in large scale systems with short and long-range electrostatics. Our results suggest that by adjusting stiffness of the amphiphilic molecules and excluded volume interactions, lamellar or interconnected 3D phases can be obtained. Resulting phases have significant effects on the conductive properties. If there is no excluded volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the excluded volume interactions become asymmetric, lamellar phases are replaced by interconnected phases consist of charged groups. Within temperature ranges that morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments of ionic liquid-based liquid Center of Bio-inspried Energy Center (CBES).

  19. Structure, morphology and ionic conductivity of solid polymer electrolyte

    SciTech Connect

    Dey, Arup; Karan, S.; Dey, Ashis; De, S.K.

    2011-11-15

    Graphical abstract: Two-dimensional atomic force image of pure polyethylene oxide presents a crystallized network of regular spherulites developing spirals and branches of well distributed surface contours. Highlights: {yields} The incorporation of ceria significantly modifies the morphology of polyethylene oxide (PEO)-KI complex. {yields} The ionic conductivity increases by about two orders of magnitude by the addition of ceria nanoparticles. {yields} Ionic conductivity as a function of ceria concentration reveals two maxima. {yields} Grain boundary effect of nanofiller, strong Lewis acid-base interaction between PEO and nanosized ceria, change of conformation of PEO molecule and epitaxial effect of ceria nanoparticles control the ionic conductivity of composite polymer electrolyte. -- Abstract: Polyethylene oxide (PEO) complexed with potassium iodide (KI) is synthesized to investigate the ionic conductivity of alkaline based polymer electrolytes. The structural and morphological characterizations of the nanocomposite polymer electrolytes are performed by X-ray diffractometry (XRD), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) measurements. The ionic conductivity increases with the increase of KI concentration up to about 20 wt.%. The effect of nanosized ceria (CeO{sub 2} {approx} 10 nm) fillers on ionic conductivity in PEO-KI polymer electrolyte is also carried out, keeping PEO to KI wt.% ratio 80:20 and 85:15. The result reveals that the addition of ceria nanoparticles enhances the conductivity by two orders of magnitude. The presence of ceria at the highest concentration induces the same molecular environment within PEO chain as that of undoped PEO. Temperature dependence of ionic conductivity follows Arrhenius mechanism.

  20. Observation of highly decoupled conductivity in protic ionic conductors.

    PubMed

    Wojnarowska, Zaneta; Wang, Yangyang; Paluch, Krzysztof J; Sokolov, Alexei P; Paluch, Marian

    2014-05-21

    Ionic liquids (ILs) are key materials for the development of a wide range of emerging technologies. Protic ionic liquids, an important class of ILs, have long been envisioned as promising anhydrous electrolytes for fuel cells. It is well known that in comparison to all other cations, protons exhibit abnormally high conductivity in water. Such superprotonic dynamics was expected in protic ionic conductors as well. However, many years of extensive studies led to the disappointing conclusion that this is not the case and most protic ionic liquids display subionic behavior. Therefore, the relatively low conductivity seems to be the main obstacle for the application of protic ionic liquids in fuel cells. Using dielectric spectroscopy, herein we report the observation of highly decoupled conductivity in a newly synthesized protic ionic conductor. We show that its proton transport is strongly decoupled from the structural relaxation, in terms of both temperature dependence and characteristic rates. This finding offers a fresh look on the charge transport mechanism in PILs and also provides new ideas for design of anhydrous materials with exceptionally high proton conductivity.

  1. Ionic conduction in polymer composite electrolytes

    NASA Astrophysics Data System (ADS)

    Dam, Tapabrata; Tripathy, Satya N.; Paluch, M.; Jena, S.; Pradhan, D. K.

    2016-05-01

    Conductivity and structural relaxation has been explored from modulus and dielectric loss formalisms respectively for a series of polymer composite electrolytes with zirconia as filler. The temperature dependence of conductivity followed Vogel-Tamman-Fulcher (VTF) behavior, which suggested a close correlation between conductivity and the segmental relaxation process in polymer electrolytes. Vogel temperature (T0) plays significant role in ion conduction process in these kind of materials.

  2. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers.

    PubMed

    Liu, Wei; Liu, Nian; Sun, Jie; Hsu, Po-Chun; Li, Yuzhang; Lee, Hyun-Wook; Cui, Yi

    2015-04-08

    Solid-state electrolytes provide substantial improvements to safety and electrochemical stability in lithium-ion batteries when compared with conventional liquid electrolytes, which makes them a promising alternative technology for next-generation high-energy batteries. Currently, the low mobility of lithium ions in solid electrolytes limits their practical application. The ongoing research over the past few decades on dispersing of ceramic nanoparticles into polymer matrix has been proved effective to enhance ionic conductivity although it is challenging to form the efficiency networks of ionic conduction with nanoparticles. In this work, we first report that ceramic nanowire fillers can facilitate formation of such ionic conduction networks in polymer-based solid electrolyte to enhance its ionic conductivity by three orders of magnitude. Polyacrylonitrile-LiClO4 incorporated with 15 wt % Li0.33La0.557TiO3 nanowire composite electrolyte exhibits an unprecedented ionic conductivity of 2.4 × 10(-4) S cm(-1) at room temperature, which is attributed to the fast ion transport on the surfaces of ceramic nanowires acting as conductive network in the polymer matrix. In addition, the ceramic-nanowire filled composite polymer electrolyte shows an enlarged electrochemical stability window in comparison to the one without fillers. The discovery in the present work paves the way for the design of solid ion electrolytes with superior performance.

  3. Ionic Conductivity and Gas Permeability of Polymerized Ionic Liquid Block Copolymer Membranes

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Sanoja, Gabriel; Schneider, Yanika; Modestino, Miguel; Segalman, Rachel; Joint CenterArtificial Photosynthesis Team

    2014-03-01

    Polymer membranes for many energy applications, such as solar-to-hydrogen fuel production, require ionic conductivity while acting as gas diffusion barriers. We have synthesized a diblock copolymer consisting of poly(styrene-block-(4-(2-methacrylamidoethyl)-imidazolium trifluoroacetate) by treating poly(styrene-block-histamine methacrylamide) (PS- b-PHMA) with trifluoroacetic acid. The PS block serves as the structural support while the imidazolium derivative is an ion conducting polymerized ionic liquid (PIL). Small angle X-ray scattering and transmission electron microscopy demonstrate that the block copolymer self-assembles into well-ordered nanostructures, with lamellae and hexagonally packed cylindrical morphologies. The ionic conductivities of the PS-b-PHMA materials were as high as 2 x 10-4 S/cm while an order of magnitude increase in conductivity was observed upon conversion to PS-b-PIL. The ionic conductivity of the PS-b-PIL increased by a factor of ~ 4 up to 1.2 x 10-3 S/cm as the PIL domain size increased from 20 to 40 nm. These insights allow for the rational design of high performance ion conducting membranes with even greater conductivities via precise morphological control. Additionally, the role of thermal annealing on the ionic conductivity and gas permeability of copolymer membranes was investigated.

  4. 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.

  5. 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.

  6. Ionic conductivity on a wetting surface.

    PubMed

    Skinner, Brian; Loth, M S; Shklovksii, B I

    2009-10-01

    Recent experiments measuring the electrical conductivity of DNA molecules highlight the need for a theoretical model of ion transport along a charged surface. Here we present a simple theory based on the idea of unbinding of ion pairs. The strong humidity dependence of conductivity is explained by the decrease in the electrostatic self-energy of a separated pair when a layer of water (with high dielectric constant) is adsorbed to the surface. We compare our prediction for conductivity to experiment and discuss the limits of its applicability.

  7. Morphology and Ionic Conductivity of Humidity-Responsive Polymerized Ionic Liquid Block Copolymers

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Meek, Kelly; Ye, Yuesheng; Elabd, Yossef A.; Winey, Karen I.

    2014-03-01

    We present the ionic conductivity and morphology of humidity-responsive polymerized ionic liquid block copolymers (PIL BCPs), poly(methyl methacrylate- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-X), where X is a bromide (Br) or hydroxide (OH) anion, as a function of relative humidity (RH), temperature, and PIL composition (ϕPIL) . PIL BCPs were characterized by in situ small-angle X-ray scattering and electrochemical impedance spectroscopy. These PIL BCPs have microphase separated morphologies and long-range order increases as ϕPIL increases. Notably, ionic conductivity increases 3 to 4 orders of magnitude when RH increases from 30 to 90 percent. When ϕPIL is greater than 0.37, BCP ionic conductivity approaches or exceeds that of the homopolymer, suggesting that the dynamics in PIL microdomains mimic the homopolymer and long-range order aids ion transport. Moreover, over 60 percent of the BCP is nonconductive without a penalty in ion transport. When ϕPIL is less than 0.37, BCP conductivity is 1 to 2 orders of magnitude less than the homopolymer and non-conductive PMMA segments dominate ion transport, as expected. Ionic conductivities at 80 °C, 90 percent RH, are 7.6 mS/cm for the Br-containing BCP with ϕPIL = 0.53 and 25.0 mS/cm for the OH-containing BCP with ϕPIL = 0.50.

  8. Ion Conduction in Polymerized Ionic Liquids with Different Pendant Groups

    SciTech Connect

    Fan, Fei; Wang, Yangyang; Hong, Tao; Heres, Maximilian F.; Saito, Tomonori; Sokolov, Alexei P.

    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 deviation from the ideal line increases upon approaching the glass transition temperature (Tg). 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.

  9. 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.

  10. Defect association mediated ionic conductivity of rare earth doped nanoceria: Dependency on ionic radius

    NASA Astrophysics Data System (ADS)

    Anirban, Sk.; Sinha, A.; Bandyopadhyay, S.; Dutta, A.

    2016-05-01

    Rare earth doped nanoceria Ce0.9RE0.1O1.95 (RE = Pr, Nd, Eu and Gd) were prepared through citrate auto-ignition method. The single phase cubic fluorite structure with space group Fm3 ¯m of the compositions were confirmed from Rietveld analysis of XRD data. The particle size of the compositions were in the range 49.77 nm to 66.20 nm. An ionic radius dependent lattice parameter variation was found. The DC conductivity of each composition was evaluated using Random Barrier Model. The conductivity decreased and activation energy increased with increasing ionic radius from Gd to Pr doping due to the size mismatch with host ions and formation of stable defect associate. The formation of different defect associates and their correlation with ionic conductivity has been discussed.

  11. Thermal properties and ionic conductivity of imidazolium bis(trifluoromethanesulfonyl)imide dicationic ionic liquids.

    PubMed

    Pitawala, Jagath; Matic, Aleksandar; Martinelli, Anna; Jacobsson, Per; Koch, Victor; Croce, Fausto

    2009-08-06

    We report on the thermal and transport properties of new dicationic ionic liquids. The new ionic liquids are based on the bis(trifluoromethanesulfonyl)imide [NTf(2)](-) anion and a cation that contains two imidazolium rings, connected by either a pentane or a decane hydrocarbon chain and different side groups. We have investigated the conductivity and the thermal properties by dielectric spectroscopy and differential scanning calorimetry, respectively. Our results show that the length of the alkyl chain on the cation has no, or weak, influence on the glass transition temperature, T(g), whereas the presence of rigid aromatic side groups has a strong influence increase T(g). The highest ionic conductivity is 5.9 x 10(-4) S cm(-1) at 298 K for an ionic liquid with a decane chain and one methyl group on each imidazolium ring. The conductivity results correlate well with the glass transition temperatures. This shows that the flexibility of the geminal cations is very important for the conductivity. However, the presence of nonflexible aromatic side groups on the imidazolium ring decreases the flexibility and hence the mobility.

  12. Ordered and Disordered Polymerized Ionic Liquid Block Copolymers: Morphology and Ionic Conductivity

    NASA Astrophysics Data System (ADS)

    Wang, Sharon; Ye, Yuesheng; Elabd, Yossef; Winey, Karen

    2013-03-01

    We systematically studied the influence of temperature and relative humidity on morphology and ionic conductivity in polymerized ionic liquid block copolymers (PIL BCP). Poly(methyl methacrylate- b-1-[2-(methacryloyloxy)ethyl]-3-butylimidazolium-X-) block copolymers (X- = OH-, Br-) were characterized by SAXS, dynamical mechanical analysis, and electrochemical impedance spectroscopy. At 25 °C, weak microphase separation was observed for the PIL BCP with ϕPIL = 0.38 and X- = OH-. Upon increasing the relative humidity to 90%, this polymer exhibited an order-disorder transition (ODT). The ODT was further studied in the PIL BCPs with X- = OH- and 0.11 <ϕPIL <0.38 over a range of temperatures and %RH. In contrast, the PIL BCP with ϕPIL = 0.38 and X- = Br- formed strongly microphase separated lamellae at all investigated T and %RH. At elevated temperature and 90 %RH, ionic conductivities of 30 and 6 mS/cm were observed for ϕPIL = 0.38 and X- = OH- and Br-, respectively, surpassing the conductivities of the corresponding PIL homopolymer. By selecting the counterion and relative humidity, we significantly impact the morphology and ionic conductivity of these PIL block copolymers.

  13. High ionic conductivity in confined bismuth oxide-based heterostructures

    NASA Astrophysics Data System (ADS)

    Sanna, Simone; Esposito, Vincenzo; Christensen, Mogens; Pryds, Nini

    2016-12-01

    Bismuth trioxide in the cubic fluorite phase ( δ - Bi 2 O 3 ) exhibits the highest oxygen ionic conductivity. In this study, we were able to stabilize the pure δ - Bi 2 O 3 at low temperature with no addition of stabilizer but only by engineering the interface, using highly coherent heterostructures made of alternative layers of δ - Bi 2 O 3 and Yttria Stabilized Zirconia (YSZ), deposited by pulsed laser deposition. The resulting [ δ - Bi 2 O 3 / YSZ ] heterostructures are found to be stable over a wide temperature range (500-750 °C) and exhibits stable high ionic conductivity over a long time comparable to the value of the pure δ - Bi 2 O 3 , which is approximately two orders of magnitude higher than the conductivity of YSZ bulk.

  14. Electronic and ionic conductivities in superionic Li4C60

    NASA Astrophysics Data System (ADS)

    Quintavalle, D.; Márkus, B. G.; Jánossy, A.; Simon, F.; Klupp, G.; Győri, M. A.; Kamarás, K.; Magnani, G.; Pontiroli, D.; Riccò, M.

    2016-05-01

    The 10 GHz microwave conductivity, σ (T ) and high field, 222 GHz electron spin resonance (HF-ESR) of Li4C60 fulleride is measured in a wide temperature range. We suggest that the majority of ESR active sites and at least some of the charge carriers for σ (T ) are electrons bound to a small concentration of surplus or vacancy ions in the polymer phase. Both σ (T ) and the ESR line shape depend on ionic motion. A change of the activation energy of σ (T ) at 125 K coincides with the onset of the ionic DC conductivity. The ESR line shape is determined mainly by Li ionic motion within octahedral voids below 150 K. At higher temperatures, fluctuations due to ionic diffusion change the environment of defects from axial to effectively isotropic on the ESR time scale. σ (T ) data up to 700 K through the depolymerization transition confirm that the monomeric phase of Li4C60 is a metal.

  15. Intrinsic low thermal conductivity in weakly ionic rocksalt structures

    DOE PAGES

    Zhang, Yi; Dong, Jianjun; Kent, Paul R. C.; ...

    2015-07-06

    A fundamental challenge in thermoelectric (TE) material research is meeting the simultaneous requirements of high carrier mobility and low thermal conductivity. Simple crystal structures are ideal for maintaining high carrier mobility, but they usually have high thermal conductivity. In this paper, we show by first-principles lattice dynamics and Boltzmann transport calculations that weakly ionic rocksalt structures exhibit strong lattice anharmonicity and low acoustic-phonon group velocity, which combine to produce intrinsic low thermal conductivity. Finally, we unveil microscopic mechanisms that explain experimental observations and provide insights for TE material design and discovery.

  16. 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.

  17. Morphology and Ionic Conductivity of Oriented Block Copolymer/Ionic Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Sharick, Sharon; Winey, Karen I.

    2015-03-01

    Ion-containing block copolymers with increased continuity and long-range order of ion-containing microdomains were prepared to probe the impact of grain boundaries and microdomain orientation on ion transport. We studied poly(styrene- b-methyl methacrylate) diblock copolymers swollen with 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonylimide) (SbMMA/IL), and characterized the thermal transitions, morphologies, and ionic conductivities by differential scanning calorimetry, small-angle X-ray scattering, and electrochemical impedance spectroscopy over a range of compositions. Two glass transition temperatures (Tgs) are observed, corresponding to PS and PMMA/IL microdomains, and Tg,PMMA/IL is modeled well by the Gordon-Taylor expression. SbMMA/IL films prepared by solvent evaporation exhibit strongly microphase-separated lamellar morphology with long-range order. Slower rates of solvent evaporation produce films with lamellae preferentially oriented to be in the plane. In-plane conductivities increase with both increasing ionic liquid content and with better parallel alignment of lamellae. The Sax and Ottino model will be used to compare the conductivity of SbMMA/IL with the homopolymer/IL mixture, PMMA/IL, and to discuss the ion transport mechanism.

  18. Imidazolium-Based Poly(ionic liquid)/Ionic Liquid Ion-Gels with High Ionic Conductivity Prepared from a Curable Poly(ionic liquid).

    PubMed

    Cowan, Matthew G; Lopez, Alexander M; Masuda, Miyuki; Kohno, Yuki; McDanel, William M; Noble, Richard D; Gin, Douglas L

    2016-07-01

    Ionic liquid (IL)-based ion-gel membranes were prepared from a curable poly(IL)-based materials platform with the free ILs 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TFSI]), bis(fluorosulfonyl)imide ([EMIM][FSI]), 1-butylimidazolium bis(trifluoromethylsulfonyl)imide ([C4 IMH][TFSI]), and ethylmethylammonium nitrate [EAN][NO3 ] and evaluated for their ionic conductivity performance at ambient and elevated temperatures. The resulting cross-linked, free-standing ion-gel membranes were found to have less than 1 wt% water (with the exception of [EAN][NO3 ] which contained ≈20 wt% water). Increasing free IL content from 50 to 80 wt% produces materials with ionic conductivity values ≥10(-2) S cm(-1) at 25 °C and ≈10(-1) S cm(-1) at 110 °C. Additionally, ion-gels containing 70 wt% of the protic ILs [C4 IMH][TFSI] and [EMIM][FSI] display ionic conductivity values of ≈10(-3) to 10(-2) S cm(-1) over the temperature range of 25-110 °C.

  19. Nanostructure-thermal conductivity relationships in protic ionic liquids.

    PubMed

    Murphy, Thomas; Varela, Luis M; Webber, Grant B; Warr, Gregory G; Atkin, Rob

    2014-10-16

    The thermal conductivities of nine protic ionic liquids (ILs) have been investigated between 293 and 340 K. Within this range, the thermal conductivities are between 0.18 and 0.30 W · m(-1) · K(-1). These values are higher than those typically associated with oils and aprotic ILs, but lower than those of strongly hydrogen bonding solvents like water. Weak linear decreases in thermal conductivity with temperature are noted, with the exception of ethanolammonium nitrate (EtAN) where the thermal conductivity increases with temperature. The dependence of thermal conductivity on IL type is analyzed with use of the Bahe-Varela pseudolattice theory. This theory treats the bulk IL as an array of ordered domains with intervening domains of uncorrelated structure which enable and provide barriers to heat propagation (respectively) via allowed vibrational modes. For the protic ILs investigated, thermal conductivity depends strongly on the IL cation alkyl chain length. This is because the cation alkyl chain controls the dimensions of the IL bulk nanostructure, which consists of charged (ordered domains) and uncharged regions (disordered domains). As the cation alkyl chain controls the dimensions of the disordered domains, it thus limits the thermal conductivity. To test the generality of this interpretation, the thermal conductivities of propylammonium nitrate (PAN) and PAN-octanol mixtures were examined; water selectively swells the PAN charged domain, while octanol swells the uncharged regions. Up to a certain concentration, adding water increases thermal conduction and octanol decreases it, as expected. However, at high solute concentrations the IL nanostructure is broken. When additional solvent is added above this concentration the rate of change in thermal conductivity is greatly reduced. This is because, in the absence of nanostructure, the added solvent only serves to dilute the salt solution.

  20. Anion and Cation Ionic Conductivity of Dragon Fruit

    NASA Astrophysics Data System (ADS)

    Hajar, Nadya; Asiah, M. N.; Abdullah, S.; Rusop, M.

    2010-07-01

    The separation of all ions in a synthetic solution was achieved with an anion eluent containing 0.3392 g Na2CO3 and 0.084 g NaHCO2 and the run around 20 min. Cation eluent containing 0.60 g Tartaric acid and 0.125 g Dipicolinic acid and the run around 16 min. This method was applied to dragon fruit juice with success and has shown sensitivity. Moreover, sample preparation was a simple 1:1, 1:10, 1:100 and 1:1000 ppm with 0.20 mm filtration and direct injection without prior sample clean-up. Due to the use of eluent generator, very low conductance background conductivity can be obtained and sensitivity of dragon fruit has been greatly improved. Under the experimental condition, several inorganic anions, such as F-, NO3-, NO2-, Br- and PO43- obtained from dragon fruit. For cation, inorganic ions that occurred during the experiment were NH3+, Ca+, and Mg+. Conductivity for anion of F-, NO3-, NO2-, Br- and PO43- were approximately 20, 17, 16, 16 and 20 μS/cm, respectively. Concentration for F- is 1.57 mg/l, NO3- is 1.92 mg/l, NO2- is 0.30 mg/l, Br- is 0.45 mg/l and PO43- is 4.45 mg/l. Conductivity for cation of NH3+, Ca+, and Mg+ were approximately 537, 538 and 531 μS/cm, respectively. Concentration for cation of NH3+ is 0.93 mg/l, Ca+ is 1.15 mg/l, and Mg+ 7.285 is mg/l. The method has successfully applied to the determination of inorganic ions in dragon fruit. An ion chromatography method is described for the simultaneous determination of ionic conductivity for dragon fruit juice using a selected anion and cation eluent. The detection of ionic conductivity in dragon fruit juice has been studied.

  1. Ionic Conductivity and its Role in Oxidation Reactions

    NASA Astrophysics Data System (ADS)

    Tamimi, Mazin Abdulla

    In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

  2. Thermal Conductivity of Ionic Liquids: Measurement and Prediction

    NASA Astrophysics Data System (ADS)

    Fröba, A. P.; Rausch, M. H.; Krzeminski, K.; Assenbaum, D.; Wasserscheid, P.; Leipertz, A.

    2010-12-01

    This study reports thermal-conductivity data for a series of [EMIM] (1-ethyl-3-methylimidazolium)-based ionic liquids (ILs) having the anions [NTf2] (bis(trifluoromethylsulfonyl)imide), [OAc] (acetate), [N(CN)2] (dicyanimide), [C(CN)3] (tricyanomethide), [MeOHPO2] (methylphosphonate), [EtSO4] (ethylsulfate), or [OcSO4] (octylsulfate), and in addition for ILs with the [NTf2]-anion having the cations [HMIM] (1-hexyl-3-methylimidazolium), [OMA] (methyltrioctylammonium), or [BBIM] (1,3-dibutylimidazolium). Measurements were performed in the temperature range between (273.15 and 333.15) K by a stationary guarded parallel-plate instrument with a total measurement uncertainty of 3 % ( k = 2). For all ILs, the temperature dependence of the thermal conductivity can well be represented by a linear equation. While for the [NTf2]-based ILs, a slight increase of the thermal conductivity with increasing molar mass of the cation is found at a given temperature, the [EMIM]-based ILs show a pronounced, approximately linear decrease with increasing molar mass of the different probed anions. Based on the experimental data obtained in this study, a simple relationship between the thermal conductivity, molar mass, and density is proposed for the prediction of the thermal-conductivity data of ILs. For this, also densities were measured for [EMIM][OAc], [EMIM][C(CN)3], and [HMIM][NTf2]. The mean absolute percentage deviation of all thermal-conductivity data for ILs found in the literature from the proposed prediction is about 7 %. This result represents a convenient simplification in the acquisition of thermal conductivity information for the enormous amount of structurally different IL cation/anion combinations available.

  3. Frequency dependence of ionic conductivity of electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Chandra, Amalendu; Bagchi, Biman

    2000-01-01

    A theory for the frequency dependence of ionic conductivity of an electrolyte solution is presented. In this theory contributions to the conductivity from both the ion atmosphere relaxation and the electrophoretic effects are included in a self-consistent fashion. Mode coupling theory, combined with time-dependent density functional theory of ion atmosphere fluctuations, leads to expressions for these two contributions at finite frequencies. These expressions need to be solved self-consistently for the frequency dependence of the electrolyte friction and the ion conductivity at varying ion concentrations. In the limit of low concentration, the present theory reduces exactly to the well-known Debye-Falkenhagen (DF) expression of the frequency-dependent electrolyte friction when the non-Markovian effects in the ion atmosphere relaxation are ignored and in addition the ions are considered to be pointlike. The present theory also reproduces the expressions of the frequency-dependent conductivity derived by Chandra, Wei, and Patey when appropriate limiting situations are considered. We have carried out detailed numerical solutions of the self-consistent equations for concentrated solutions of a 1:1 electrolyte by using the expressions of pair correlation functions given by Attard. Numerical results reveal that the frequency dependence of the electrolyte friction at finite concentration can be quite different from that given by the DF expression. With the increase of ion concentration, the dispersion of the friction is found to occur at a higher frequency because of faster relaxation of the ion atmosphere. At low frequency, the real part of the conductivity shows a small increase with frequency which can be attributed to the well-known Debye-Falkenhagen effect. At high frequency, the conductivity decreases as expected. The extensions of the present theory to treat frequency-dependent diffusivities of charged colloid suspensions and conductivity of a dilute

  4. Ionic conductances of membranes in ciliated and deciliated Paramecium.

    PubMed Central

    Machemer, H; Ogura, A

    1979-01-01

    1. Paramecium caudatum was deciliated with ethanol. The ionic conductance of the membrane was investigated with constant current, voltage clamp and mechanical stimuli. 2. The resting potential was not modified by the removal of the cilia. The dependence of the resting potential on the extracellular concentrations of Ca and K was the same in deciliated and control cells. 3. The input resistance in deciliated and ciliated cells increased after the ethanol treatment. 4. The membrane capacitance decreased to 48% after deciliation, suggesting that the ciliary surface area is equal to the somatic surface area. 5. Deciliation completely removed the regenerative response (graded action potential) elicited by depolarizing current pulses or mechanical stimuli. 6. Deciliated cells retained the depolarizing and hyperpolarizing mechanoreceptor responses. 7. Voltage-clamp experiments demonstrated the loss of the early inward current in deciliated cells; it was restored during ciliary regeneration. Steady-state current-voltage relationships were unchanged by deciliation. 8. The time courses of the recovery of the membrane capacitance and of the early inward current were similar, suggesting that the number of voltage-sensitive Ca channels is proportional to the ciliary membrane area. 9. We conclude that the voltage-sensitive Ca channels reside in the ciliary membrane (in confirmation of Dunlap, 1976; Ogura & Takahashi, 1976), while mechanoreceptor channels, rectifier channels and resting conductances are localized in the somatic membrane. PMID:529122

  5. Phase Behavior and Ionic Conductivity of Concentrated Solutions of Polystyrene-Poly(ethylene oxide) Diblock Copolymers in an Ionic Liquid

    SciTech Connect

    Simone, Peter M.; Lodge, Timothy P.

    2010-03-16

    Concentrated solutions of poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymers were prepared using the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI] as the solvent. The self-assembled microstructures adopted by the copolymer solutions have been characterized using small-angle X-ray scattering. Lyotropic mesophase transitions were observed, with a progression from hexagonally packed cylinders of PEO, to lamellae, to hexagonally packed cylinders of PS upon increasing [EMI][TFSI] content. The change in lamellar domain spacing with ionic liquid concentration was found to be comparable to that reported for other block copolymers in strongly selective solvents. The ionic conductivity of the concentrated PS-PEO/[EMI][TFSI] solutions was measured via impedance spectroscopy, and ranged from 1 x 10{sup -7} to 1 x 10{sup -3} S/cm at temperatures from 25-100 C. Additionally, the ionic conductivity of the solutions was found to increase with both ionic liquid concentration and molecular weight of the PEO blocks. The ionic conductivity of PEO homopolymer/[EMI][TFSI] solutions was also measured in order to compare the conductivity of the PS-PEO solutions to the expected limit for a lamellar sample with randomly oriented microstructure grains.

  6. Ionic conductances regulating the excitability of colonic smooth muscles.

    PubMed

    Koh, Sang Don; Ward, S M; Sanders, K M

    2012-08-01

    The tunica muscularis of the gastrointestinal (GI) tract contains two layers of smooth muscle cells (SMC) oriented perpendicular to each other. SMC express a variety of voltage-dependent and voltage-independent ionic conductance(s) that develop membrane potential and control excitability. Resting membrane potentials (RMP) vary through the GI tract but generally are within the range of -80 to -40 mV. RMP sets the 'gain' of smooth muscle and regulates openings of voltage-dependent Ca(2+) channels. A variety of K(+) channels contribute to setting RMP of SMC. In most regions, RMP is considerably less negative than the K(+) equilibrium potential, due to a finely tuned balance between background K(+) channels and non-selective cation channels (NSCC). Variations in expression patterns and openings of K(+) channels and NSCC account for differences of the RMP in different regions of the GI tract. Smooth muscle excitability is also regulated by interstitial cells (interstitial cells of Cajal (ICC) and PDGFRα(+) cells) that express additional conductances and are electrically coupled to SMC. Thus, 'myogenic' activity results from the integrated behavior of the SMC/ICC/PDGFRα(+) cell (SIP) syncytium. Inputs from excitatory and inhibitory motor neurons are required to produce the complex motor patterns of the gut. Motor neurons innervate three cell types in the SIP, and receptors, second messenger pathways, and ion channels in these cells mediate postjunctional responses. Studies of isolated SIP cells have begun to unravel the mechanisms responsible for neural responses. This review discusses ion channels that set and regulate RMP of SIP cells and how neurotransmitters regulate membrane potential.

  7. Behavior of ionic conducting IPN actuators in simulated space conditions

    NASA Astrophysics Data System (ADS)

    Fannir, Adelyne; Plesse, Cédric; Nguyen, Giao T. M.; Laurent, Elisabeth; Cadiergues, Laurent; Vidal, Frédéric

    2016-04-01

    The presentation focuses on the performances of flexible all-polymer electroactive actuators under space-hazardous environmental factors in laboratory conditions. These bending actuators are based on high molecular weight nitrile butadiene rubber (NBR), poly(ethylene oxide) (PEO) derivative and poly(3,4-ethylenedioxithiophene) (PEDOT). The electroactive PEDOT is embedded within the PEO/NBR membrane which is subsequently swollen with an ionic liquid as electrolyte. Actuators have been submitted to thermal cycling test between -25 to 60°C under vacuum (2.4 10-8 mbar) and to ionizing Gamma radiations at a level of 210 rad/h during 100 h. Actuators have been characterized before and after space environmental condition ageing. In particular, the viscoelasticity properties and mechanical resistance of the materials have been determined by dynamic mechanical analysis and tensile tests. The evolution of the actuation properties as the strain and the output force have been characterized as well. The long-term vacuuming, the freezing temperature and the Gamma radiations do not affect significantly the thermomechanical properties of conducting IPNs actuators. Only a slight decrease on actuation performances has been observed.

  8. Multilayered semiconductor membranes for nanopore ionic conductance modulation.

    PubMed

    Gracheva, Maria E; Melnikov, Dmitriy V; Leburton, Jean-Pierre

    2008-11-25

    We explore the possibility of using thin layered semiconductor membranes for electrical control of the ion current flow through a nanopore, thereby operating like tunable ionic transistors. While single layer semiconductor membranes can be voltage tuned to operate as ionic filters or "switches", double layered membranes can rectify the ion current flowing through the nanopore in addition to ion filtering. Triple layer membranes exhibit enhanced functionality with characteristics similar to those of the single and double layer membranes in addition to bidirectional current blocking and switching, thereby operating similar to tunable ionic transistors.

  9. Lithium ion conductive behavior of TiO2 nanotube/ionic liquid matrices

    PubMed Central

    2014-01-01

    A series of TiO2 nanotube (TNT)/ionic liquid matrices were prepared, and their lithium ion conductive properties were studied. SEM images implied that ionic liquid was dispersed on the whole surface of TNT. Addition of TNT to ionic liquid (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMImTFSA)) resulted in significant increase of ionic conductivity. Furthermore, lithium transference number was also largely enhanced due to the interaction of anion with TNT. Vogel-Fulcher-Tammann parameter showed higher carrier ion number for TNT/BMImTFSA in comparison with BMImTFSA. PMID:25313300

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

    SciTech Connect

    He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.; Clark, Kyle; Weber, Adam Z.; Kostecki, Robert

    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 relationship 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.

  11. Programmable ionic conductance in a pH-regulated gated nanochannel.

    PubMed

    Ma, Yu; Xue, Song; Hsu, Shih-Chieh; Yeh, Li-Hsien; Qian, Shizhi; Tan, Heping

    2014-10-07

    An analytical model for the ionic conductance in a pH-regulated nanochannel gated by a field effect transistor is derived for the first time. In contrast to the existing studies, the developed model takes into account the practical effects of multiple ionic species, surface chemistry reactions, the Stern layer, and electroosmotic flow. The model is validated by the experimental data of ionic conductance available in the literature. Results show that the performance of the field effect control of the ionic conductance in the gated silica nanochannel is remarkable when the solution pH and salt concentration are low. In addition, the Stern layer effect on the ionic conductance is significant when the salt concentration is low.

  12. Ion jelly conductive properties using dicyanamide-based ionic liquids.

    PubMed

    Carvalho, Tânia; Augusto, Vera; Rocha, Ângelo; Lourenço, Nuno M T; Correia, Natália T; Barreiros, Susana; Vidinha, Pedro; Cabrita, Eurico J; Dionísio, Madalena

    2014-08-07

    The thermal behavior and transport properties of several ion jellys (IJs), a composite that results from the combination of gelatin with an ionic liquid (IL), were investigated by dielectric relaxation spectroscopy (DRS), differential scanning calorimetry (DSC), and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG NMR). Four different ILs containing the dicyanamide anion were used: 1-butyl-3-methylimidazolium dicyanamide (BMIMDCA), 1-ethyl-3-methylimidazolium dicyanamide (EMIMDCA), 1-butyl-1-methylpyrrolidinium dicyanamide (BMPyrDCA), and 1-butylpyridinium dicyanamide (BPyDCA); the bulk ILs were also investigated for comparison. A glass transition was detected by DSC for all materials, ILs and IJs, allowing them to be classified as glass formers. Additionally, an increase in the glass transition temperature upon dehydration was observed with a greater extent for IJs, attributed to a greater hindrance imposed by the gelatin matrix after water removal, rendering the IL less mobile. While crystallization is observed for some ILs with negligible water content, it was never detected for any IJ upon thermal cycling, which persist always as fully amorphous materials. From DRS measurements, conductivity and diffusion coefficients for both cations (D+) and anions (D-) were extracted. D+ values obtained by DRS reveal excellent agreement with those obtained from PFG NMR direct measurements, obeying the same VFTH equation over a large temperature range (ΔT ≈ 150 K) within which D+ varies around 10 decades. At temperatures close to room temperature, the IJs exhibit D values comparable to the most hydrated (9%) ILs. The IJ derived from EMIMDCA possesses the highest conductivity and diffusion coefficient, respectively, ∼10(-2) S·cm(-1) and ∼10(-10) m(2)·s(-1). For BMPyrDCA the relaxational behavior was analyzed through the complex permittivity and modulus formalism allowing the assignment of the detected secondary relaxation to a Johari

  13. 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

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

    NASA Astrophysics Data System (ADS)

    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

    2016-05-01

    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.

  15. Photochemical switching of ionic conductivity in composite films containing a crowned spirobenzopyran

    SciTech Connect

    Kimura, Keiichi; Yamashita, Takashi; Yokoyama, Masaaki

    1992-06-25

    Photochemical switching of ionic conductivity in vinyl chloride films with LiClO{sub 4} and a crowned spirobenzopyran revealed isomerization of the crowned spirobenzopyran to its merocyanine form proceeding under UV-irradiated or dark conditions to decrease the the film`s Li{sup +} ionic conductivity in this paper. Visible-light irradiation caused isomerization back to the spiropyran form and restoration of ionic conductivity to its original value; switching the visible light on and off caused 20-fold changes. 10 refs., 7 figs.

  16. 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

  17. The Effect of Long Range Order on Ionic Conductivity in a Solid Block Copolymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Chintapalli, Mahati; Thelen, Jacob; Teran, Alexander; Balsara, Nitash

    2014-03-01

    Poly(styrene)-block-poly(ethylene oxide) (SEO) mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt is a promising material for battery electrolytes due to its high ionic conductivity and ability to suppress lithium dendrite growth. Ion conduction has been found to depend on many aspects of the electrolyte microstructure, including the morphology and degree of ordering. The effect of long range order on ionic conductivity was investigated in a lamellar SEO/LiTFSI mixture by in situ small angle x-ray scattering and ac impedance spectroscopy during polymer annealing. The observation that increasing long range order decreases ionic conductivity indicates that disorder, due to small grain size or defects, enhances the ionic conductivity of the electrolyte.

  18. Li Ion Conducting Polymer Gel Electrolytes Based on Ionic Liquid/PVDF-HFP Blends

    PubMed Central

    Ye, Hui; Huang, Jian; Xu, Jun John; Khalfan, Amish; Greenbaum, Steve G.

    2009-01-01

    Ionic liquids thermodynamically compatible with Li metal are very promising for applications to rechargeable lithium batteries. 1-methyl-3-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13TFSI) is screened out as a particularly promising ionic liquid in this study. Dimensionally stable, elastic, flexible, nonvolatile polymer gel electrolytes (PGEs) with high electrochemical stabilities, high ionic conductivities and other desirable properties have been synthesized by dissolving Li imide salt (LiTFSI) in P13TFSI ionic liquid and then mixing the electrolyte solution with poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP) copolymer. Adding small amounts of ethylene carbonate to the polymer gel electrolytes dramatically improves the ionic conductivity, net Li ion transport concentration, and Li ion transport kinetics of these electrolytes. They are thus favorable and offer good prospects in the application to rechargeable Li batteries including open systems like Li/air batteries, as well as more “conventional” rechargeable lithium and lithium ion batteries. PMID:20354587

  19. Engineered Ionic Gates for Ion Conduction Based on Sodium and Potassium Activated Nanochannels.

    PubMed

    Liu, Qian; Xiao, Kai; Wen, Liping; Lu, Heng; Liu, Yahui; Kong, Xiang-Yu; Xie, Ganhua; Zhang, Zhen; Bo, Zhishan; Jiang, Lei

    2015-09-23

    In living systems, ion conduction plays a major role in numerous cellular processes and can be controlled by biological ion channels in response to specific environmental stimuli. This article describes biomimetic ionic gates for ion conduction based on sodium and potassium activated nanochannels. The Na(+) activated ionic gate and K(+) activated ionic gate were developed by immobilizing the alkali metal cation-responsive functional molecules, 4'-aminobenzo-15-crown-5 and 4'-aminobenzo-18-crown-6, respectively, onto the conical polyimide nanochannels. When the ionic gate was in the presence of the specific alkali metal cation, positively charged complexes formed between the crown ether and the alkali metal cation. On the basis of the resulting changes in surface charge, wettability and effective pore size, the nanochannel can achieve reversible switching. The switching behaviors of the two complexes differed due to the differences in binding strength between the two complexes. The Na(+) activated ionic gate is able to open and close to control the ion conduction through the nanochannel, and the K(+) activated ionic gate enables selective cation and anion conduction through the nanochannel. The Na(+) and K(+) activated ionic gates show great promise for use in clinical medicine, biosensors and drug delivery based on their high sensitivity and selectivity of being activated, and good stability.

  20. Study on Ion-Conducting Properties of Ionic Liquid Containing Carbonate Electrolytes Against Carbon Electrode.

    PubMed

    Choi, Bo-Ra; Park, Soo-Jin; Kim, Seok

    2016-03-01

    The ionic performances for the mixture of ethylene carbonate (EC) and dimethylcarbonate (DMC) were investigated for supercapacitor electrolyte. The usage of ethylene carbonate (EC) and dimethylcarbonate (DMC) as organic solvent could solve some problems of acetonitrile (AN). The general aim of present paper is compare to properties of electrochemical properties based on two mixed organic electrolytes. The ionic conductivity, viscosity, and electrochemical performances of EC/DMC+0.1 M TEABF4 mixtures were determined. The ionic conductivity of the electrolytes was measured by AC impedance, and the capacitative performances of the electrolytes were evaluated by using cyclic voltammetry.

  1. Defect Physics and Ionic conduction in Solid Electrolyte Interphase for Lithium Ion Batteries

    NASA Astrophysics Data System (ADS)

    Pan, Jie; Cheng, Yang-Tse; Qi, Yue

    The ionic conduction through the solid electrolyte interphase (SEI) is important to the rate capability of the battery. The origin of ionic conduction in the SEI is defect formation and transport. In this study, we developed a theoretical method based on density functional theory to calculate the ionic conductivity in LiF, an important SEI component, in contact with electrode materials. Seventeen native defects with their relevant charge states were investigated to determine the dominant defects on various electrodes. The contacted electrode serves as a Li reservoir with adjustable Li chemical potential (μLi) for defect formation. The formation energy and diffusion barrier of defects were mapped to ionic conductivity by the Nernst-Einstein relationship. The main defect is Schottky pair in the intrinsic region and Li ion vacancy in the p-type region. The ionic conductivity is calculated to be approximately 10-31 S/cm when LiF is in contact with an anode but it can increase to 10-12 S/cm on a cathode. Comparing with other SEI components, the ionic conductivity is very low in LiF if it is coated on an anode surface. However, due to the low concentration of electronic carriers, LiF can act as a good passivation layer on the electrode and prevent further electrolyte decomposition. This work is supported by Department of Energy and National Science Foundation.

  2. UV cross-linked, lithium-conducting ternary polymer electrolytes containing ionic liquids

    NASA Astrophysics Data System (ADS)

    Kim, G. T.; Appetecchi, G. B.; Carewska, M.; Joost, M.; Balducci, A.; Winter, M.; Passerini, S.

    In this manuscript is reported an attempt to prepare high ionic conductivity lithium polymer electrolytes by UV cross-linking the poly(ethyleneoxide) (briefly called PEO) polymer matrix in presence of the plasticizing lithium salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and an ionic liquid of the pyrrolidinium family (N-alkyl- N-methylpyrrolidinium TFSI) having a common anion with the lithium salt. It is demonstrated that polymer electrolytes with room temperature ionic conductivities of nearly 10 -3 S cm -1 could be obtained as a result of the reduced crystallinity of the ternary electrolytes. The results clearly indicate that the cross-linked ternary electrolyte shows superior mechanical properties with respect to the non-cross-linked electrolytes and higher conductivities with respect to polymer electrolytes containing none or less ionic liquid.

  3. High Pressure as a Key Factor to Identify the Conductivity Mechanism in Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Wojnarowska, Z.; Wang, Y.; Pionteck, J.; Grzybowska, K.; Sokolov, A. P.; Paluch, M.

    2013-11-01

    In this Letter we report the relation between ionic conductivity and structural relaxation in supercooled protic ionic liquids (PILs) under high pressure. The results of high-pressure dielectric and volumetric measurements, combined with rheological and temperature-modulated differential scanning calorimetry experiments, have revealed a fundamental difference between the conducting properties under isothermal and isobaric conditions for three PILs with different charge transport mechanisms (Grotthuss vs vehicle). Our findings indicate a breakdown of the fractional Stokes-Einstein relation and Walden rule when the ionic transport is controlled by fast proton hopping. Consequently, we demonstrate that the studied PILs exhibit significantly higher conductivity than one would expect taking into account that they are in fact a mixture of ionic and neutral species. Thus, the examined herein samples represent a new class of “superionic” materials desired for many advanced applications.

  4. Fast dynamic holographic recording based on conductive ionic metal-alkanoate liquid crystals and smectic glasses.

    PubMed

    Klimusheva, G; Bugaychuk, S; Garbovskiy, Yu; Kolesnyk, O; Mirnaya, T; Ishchenko, A

    2006-01-15

    Recordings of dynamic holograms with microsecond relaxation times under the action of nanosecond laser pulses are obtained in composites on the base of a novel class of liquid crystals (LCs) in ionic metal-alkanoates. Holographic parameters and relaxation characteristics are measured for doped lyotropic ionic LC, for sandwichlike cells (consisting of a dye layer and a layer of the lyotropic ionic LC), and for colored ionic smectic glasses. The structure of the materials is investigated by use of the small-angle x-ray technique. The mechanism of resonance nonlinearity in photosensitive centers and mechanisms of the grating erasure connected with a charge transport in the ionic conductive LC matrix are discussed.

  5. Ionic conductivity and thermoelectric power of pure and Al2O3-dispersed AgI

    NASA Technical Reports Server (NTRS)

    Shahi, K.; Wagner, J. B., Jr.

    1981-01-01

    Ionic and electronic conductivities, and thermoelectric power have been measured for AgI and AgI containing a dispersion of submicron size Al2O3 particles. While the dispersion of Al2O3 enhances the ionic conductivity significantly, it does not affect the electronic properties of the matrix. The enhancement is a strong function of the size and concentration of the dispersoid. Various models have been tested to account for the enhanced conduction. However, the complex behavior of the present results points out the need for more sophisticated theoretical models. Ionic conduction and thermoelectric power data suggest that the dispersed Al2O3 generates an excess of cation vacancies and thereby enhances the conductivity and suppresses the thermoelectric power of the matrix. The individual heats of transport of cation interstitials and vacancies have been estimated and compared to their respective migration energies.

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

    SciTech Connect

    Seol, Daehee; Seo, Hosung; Jesse, Stephen; Kim, Yunseok

    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.

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

    SciTech Connect

    Seol, Daehee; Seo, Hosung; Kim, Yunseok; Jesse, Stephen

    2015-08-21

    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.

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

    SciTech Connect

    Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; Assary, Rajeev S.; Woodford, William H.; Curtiss, Larry A.; Carter, W. Craig; Chiang, Yet -Ming

    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 current 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 Li2S8 and Li2S4).

  9. 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 Li2S8 and Li2S4).« less

  10. Effects of plasticization on ionic conductivity enhancement of crosslinked polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Kyu, Thein; Kyu's Team, Dr.

    Glass transition temperatures (Tg) of solid polymer electrolyte membranes (PEM), comprised of polyethylene glycol diacrylate (PEGDA) prepolymer, lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt, and succinonitrile (SCN) plasticizer, were systematically examined before and after crosslinking in the isotropic region guided by their ternary phase diagram. With increasing LiTFSI concentration, the Tg of uncured binary PEGDA/LiTFSI mixture increases drastically due to molecular complexation between lithium cation and ether oxygen, but ionic conductivity is very low (<10-6 S cm-1). Upon curing, this Tg increases and further reduces ionic conductivity. Upon adding SCN plasticizer, the Tg of PEM has significantly decreased to -60 oC and ionic conductivity also increased to the superionic conductor level of 10-3 S cm-1. The analysis of ionic conductivity vs. Tg behavior by Vogel-Tamman-Fulcher(VTF) equation revealed that this ionic conductivity enhancement is due to SCN plasticization resulting in lowering the network Tg as well as lowering the activation energy. Supported by NSF-DMR 1161070.

  11. 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.

  12. Suppressed phase transition and giant ionic conductivity in La2Mo2O9 nanowires

    PubMed Central

    Liu, Wei; Pan, Wei; Luo, Jian; Godfrey, Andy; Ou, Gang; Wu, Hui; Zhang, Wei

    2015-01-01

    Improving the ionic conductivity of solid electrolytes at low temperatures represents a major challenge and an opportunity for enabling a variety of solid-state ionic devices for energy conversion and storage, as well as for environmental protection. Here we report a giant ionic conductivity of 0.20 Scm−1, achieved at 500 °C, in the La2Mo2O9 nanowires with a bamboo-wire morphology, corresponding to a 1000-fold enhancement in conductivity over conventional bulk material. Stabilization of the high-temperature phase is observed to account for about a 10-fold increase in the conductivity. We further demonstrate that fast surface conduction in ∼3 nm thick, partially ordered, surface ‘amorphous' films, under strain on the curved surfaces of the nanowires (as a non-autonomous surface phase or complexion), contributes to an enhancement of the conductivity by another two orders of magnitude. Exemplified here by the study of the La2Mo2O9 nanowires, new possibilities for improvement of conductivity and for miniaturization of solid-state ionic devices by the careful use of one-dimensional nanomaterials can be envisioned. PMID:26380943

  13. Suppressed phase transition and giant ionic conductivity in La2Mo2O9 nanowires.

    PubMed

    Liu, Wei; Pan, Wei; Luo, Jian; Godfrey, Andy; Ou, Gang; Wu, Hui; Zhang, Wei

    2015-09-18

    Improving the ionic conductivity of solid electrolytes at low temperatures represents a major challenge and an opportunity for enabling a variety of solid-state ionic devices for energy conversion and storage, as well as for environmental protection. Here we report a giant ionic conductivity of 0.20 Scm(-1), achieved at 500 °C, in the La2Mo2O9 nanowires with a bamboo-wire morphology, corresponding to a 1000-fold enhancement in conductivity over conventional bulk material. Stabilization of the high-temperature phase is observed to account for about a 10-fold increase in the conductivity. We further demonstrate that fast surface conduction in ∼3 nm thick, partially ordered, surface 'amorphous' films, under strain on the curved surfaces of the nanowires (as a non-autonomous surface phase or complexion), contributes to an enhancement of the conductivity by another two orders of magnitude. Exemplified here by the study of the La2Mo2O9 nanowires, new possibilities for improvement of conductivity and for miniaturization of solid-state ionic devices by the careful use of one-dimensional nanomaterials can be envisioned.

  14. Morphology and Ionic Conductivity of Block Copolymer Electrolytes Containing Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Park, Moon Jeong

    2015-03-01

    The global energy crisis and an increase in environmental pollution in the recent years have drawn the attention of the scientific community towards the development of efficient electrochemical devices. Polymers containing charged species have the potential to serve as electrolytes in next-generation devices and achieving high ion transport properties in these electrolytes is the key to improving their efficiency. Although the synthesis and characterization of a wide variety of ion-containing polymers have been extensively reported over the last decade, quantitative understanding of the factors governing the ion transport properties of these materials is in its infancy. In this talk, I will present the current understanding of the diverse factors affecting the thermodynamics, morphologies and ion transport of ion-containing polymers by focusing on the use of ionic liquids (ILs). Various strategies for accessing improved transport properties of IL-containing polymers are elucidated by focusing on the role of IL-polymer interactions. The major accomplishment of obtaining well-defined morphologies for these IL-containing polymers by the use of block copolymer is particularly emphasized as a novel means of controlling the transport properties. The application of IL-incorporated polymer electrolytes in high temperature fuel cells and electro-active actuators is also enclosed.

  15. Conductivity and electrophoretic mobility of dilute ionic solutions.

    PubMed

    Allison, Stuart; Wu, Hengfu; Twahir, Umar; Pei, Hongxia

    2010-12-01

    Two complementary continuum theories of electrokinetic transport are examined with particular emphasis on the equivalent conductance of binary electrolytes. The "small ion" model [R.M. Fuoss, L. Onsager, J. Phys. Chem. 61 (1957) 668] and "large ion" model [R.W. O'Brien, L.R. White, J. Chem. Soc. Faraday Trans. 2 (74) (1978) 1607] are both discussed and the "large ion" model is generalized to include an ion exclusion distance and to account in a simple but approximate way for the Brownian motion of all ions present. In addition, the "large ion" model is modified to treat "slip" hydrodynamic boundary conditions in addition to the standard "stick" boundary condition. Both models are applied to the equivalent conductance of dilute KCl, MgCl(2), and LaCl(3) solutions and both are able to reproduce experimental conductances to within an accuracy of several tenths of a percent. Despite fundamental differences in the "small ion" and "large ion" theories, they both work equally well in this application. In addition, both "stick-large ion" and "slip-large ion" models are equally capable of accounting for the equivalent conductances of the three electrolyte solutions.

  16. 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.

  17. Ion beam irradiation as a tool to improve the ionic conductivity in solid polymer electrolyte systems

    NASA Astrophysics Data System (ADS)

    Manjunatha, H.; Damle, R.; Kumaraswamy, G. N.

    2016-05-01

    Solid polymer electrolytes (SPEs) have potential applications in solid state electronic and energy devices. The optimum conductivity of SPEs required for such applications is about 10-1 - 10-3 Scm-1, which is hard to achieve in these systems. It is observed that ionic conductivity of SPEs continuously increase with increasing concentration of inorganic salt in the host polymer. However, there is a critical concentration of the salt beyond which the conductivity of SPEs decreases due to the formation of ion pairs. In the present study, solid polymer thin films based on poly (ethylene oxide) (PEO) complexed with NaBr salt with different concentrations have been prepared and the concentration at which ion pair formation occurs in PEOxNaBr is identified. The microstructure of the SPE with highest ionic conductivity is modified by irradiating it with low energy O+1 ion (100 keV) of different fluencies. It is observed that the ionic conductivity of irradiated SPEs increases by one order in magnitude. The increase in ionic conductivity may be attributed to the enhanced segmental motion of the polymer chains due to radiation induced micro structural modification.

  18. 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.

  19. Control of ionic conductivity of ionic liquid/photoresponsive poly(amide acid) gels by photoirradiation.

    PubMed

    Tamada, Masahiro; Watanabe, Toshiyuki; Horie, Kazuyuki; Ohno, Hiroyuki

    2007-10-21

    1,3-Dibutylimidazolium bromide was soaked into a polymer network prepared by condensation of 4-4'-diaminoazobenzene, pyromellitic dianhydride and 1,3,5-tri(4-aminophenyl)benzene to form photoresponsive ion conductive gels.

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

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    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.

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

    DOEpatents

    Lin, YuPo J.; Henry, Michael P.; Snyder, Seth W.

    2008-11-18

    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.

  2. Ionic Conductivity And Structural Relaxation Studies on Lithium Niobophosphate Glass

    SciTech Connect

    Dabas, Prashant; Hariharan, K.

    2011-07-15

    Niobium pentoxide (Nb{sub 2}O{sub 5}) increases the chemical and thermal stability of otherwise hygroscopic alkali phosphate glasses and also enhances the conduction characteristics. Ion dynamics and structural relaxation have been investigated for mol%50Li{sub 2}0-45P{sub 2}0{sub 5}-5Nb{sub 2}O{sub 5}. The non-linearity parameter 'x' in the Tool-Narayanaswamy model is evaluated using the dependence of fictive and glass transition temperatures on the cooling and heating rates.

  3. Thermomorphic phase separation in ionic liquid-organic liquid systems--conductivity and spectroscopic characterization.

    PubMed

    Riisager, Anders; Fehrmann, Rasmus; Berg, Rolf W; van Hal, Roy; Wasserscheid, Peter

    2005-08-21

    Electrical conductivity, FT-Raman and NMR measurements are demonstrated as useful tools to probe and determine phase behavior of thermomorphic ionic liquid-organic liquid systems. To illustrate the methods, consecutive conductivity measurements of a thermomorphic methoxyethoxyethyl-imidazolium ionic liquid/1-hexanol system are performed in the temperature interval 25-80 degrees C using a specially constructed double-electrode cell. In addition, FT-Raman and 1H-NMR spectroscopic studies performed on the phase-separable system in the same temperature interval confirm the mutual solubility of the components in the system, the liquid-liquid equilibrium phase diagram of the binary mixture, and signify the importance of hydrogen bonding between the ionic liquid and the hydroxyl group of the alcohol.

  4. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Boehm, L.; Volin, K.J.; Delbecq, C.J.

    1982-05-06

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS/sub 2/, B/sub 2/S/sub 2/ and SiS/sub 2/ in mixture with a glass modifier such as Na/sub 2/S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1 - X) Na/sub 2/O:XB/sub 2/S/sub 3/ is disclosed.

  5. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, S.; Delbecq, C.J.; Volin, K.J.; Boehm, L.

    1984-02-21

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS[sub 2], B[sub 2]S[sub 3] and SiS[sub 2] in mixture with a glass modifier such as Na[sub 2]S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na[sub 2]O:XB[sub 2]S[sub 3] is disclosed. 4 figs.

  6. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Boehm, Leah; Volin, Kenneth J.; Delbacq, Charles J.

    1985-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  7. Glass capable of ionic conduction and method of preparation

    DOEpatents

    Susman, Sherman; Delbecq, Charles J.; Volin, Kenneth J.; Boehm, Leah

    1984-01-01

    Sulfide glasses capable of conducting alkali metal ions are prepared from a nonmetal glass former such as GeS.sub.2, B.sub.2 S.sub.3 and SiS.sub.2 in mixture with a glass modifier such as Na.sub.2 S or another alkali metal sulfide. A molten mixture of the constituents is rapidly quenched to below the glass transition temperature by contact with a metal mold. The rapid quench is sufficient to prevent crystallization and permit solidification as an amorphous solid mixture. An oxygen-free atmosphere is maintained over the mixture to prevent oxidation. A new glass system of (1-X) Na.sub.2 O:XB.sub.2 S.sub.3 is disclosed.

  8. Morphology and Proton Conductivity of Ionic Liquid Containing Sulfonated Block Copolymers

    NASA Astrophysics Data System (ADS)

    Kim, Sung Yeon; Park, Moon Jeong

    2011-03-01

    Proton exchange membrane fuel cells (PEMFC) offer the prospect of supplying clean electrical power for a wide variety of systems such as portable electronic devices and vehicles. Although, significant effort has been devoted to improvement of the transport properties of PEMs which is operated relatively lower temperature below 80circ; C, it suffers from a CO poisoning at Pt catalysis, complexity of water and heat management in the system. Herein, we report unique block copolymer electrolyte membrane systems containing ionic liquid. Due to the nonvolatile property of ionic liquid the systems exhibit effective proton transport above 100circ; C without humidification. In present study, sulfonated block copolymers, i.e., poly(styrenesulfonate-b-methylbuthylene) (SnMBm), are utilized for matrix materials by varying the ion contents and molecular weight. Imidazolium based ionic liquids are selectively incorporated into polystyrenesulfonate phases, which results in various morphological transitions as a function of the amount of the ionic liquid. The effect of counter ions on the observed morphologies is significant yielding concurrently different values of conductivity. Small angle x-ray scattering and transmission electron microscopy have been employed to determine various morphologies of the ionic liquid containing sulfonated block copolymer membranes and impedance spectroscopy is used for the conductivity measurements.

  9. Structure and ionic conductivity of block copolymer electrolytes over a wide salt concentration range

    NASA Astrophysics Data System (ADS)

    Chintapalli, Mahati; Le, Thao; Venkatesan, Naveen; Thelen, Jacob; Rojas, Adriana; Balsara, Nitash

    Block copolymer electrolytes are promising materials for safe, long-lasting lithium batteries because of their favorable mechanical and ion transport properties. The morphology, phase behavior, and ionic conductivity of a block copolymer electrolyte, SEO mixed with LiTFSI was studied over a wide, previously unexplored salt concentration range using small angle X-ray scattering, differential scanning calorimetry and ac impedance spectroscopy, respectively. SEO exhibits a maximum in ionic conductivity at twice the salt concentration that PEO, the homopolymer analog of the ion-containing block, does. This finding is contrary to prior studies that examined a more limited range of salt concentrations. In SEO, the phase behavior of the PEO block and LiTFSI closely resembles the phase behavior of homopolymer PEO and LiTFSI. The grain size of the block copolymer morphology was found to decrease with increasing salt concentration, and the ionic conductivity of SEO correlates with decreasing grain size. Structural effects impact the ionic conductivity-salt concentration relationship in block copolymer electrolytes. SEO: polystyrene-block-poly(ethylene oxide); also PS-PEO LiTFSI: lithium bis(trifluoromethanesulfonyl imide

  10. Conductivity Scaling Relationships in Nanostructured Membranes based on Protic Polymerized Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Lynd, Nathaniel; Segalman, Rachel

    2015-03-01

    Nanostructured membranes based on protic polymerized ionic liquids are of great interest for a variety of electrochemical applications. Understanding the relationship between composition, structure, and ionic conductivity for these materials is essential for designing novel membranes with improved properties. In this work, we explore the effect of volume fraction of ionic liquid on conductivity, σ using a model system composed of poly[isoprene-block-(ethylene oxide-stat-histamine glycidyl ether) diblock copolymers [PI- b - P(EO-stat-HGE)] and the resulting [PI- b - P(EO-stat-IL)] obtained after treatment with trifluoroacetic acid. These materials self-assemble into lamellar structures with volume fractions of ionic liquid ranging from 0.50 to 0.90 as demonstrated by SAXS. PI- b - P(EO-stat-IL) membranes exhibit conductivities up to 4 x 10-3 S/cm at room temperature. In addition, PI- b - P(EO-stat-IL) based membranes have lower water uptake (λ = 8-10) in comparison with most proton conducting membranes reported elsewhere. The low λ in these membranes might translate into a stronger effect of morphology on transport properties. Joint Center for Artificial Photosynthesis.

  11. Molecular modeling of diffusion coefficient and ionic conductivity of CO2 in aqueous ionic solutions.

    PubMed

    Garcia-Ratés, Miquel; de Hemptinne, Jean-Charles; Bonet Avalos, Josep; Nieto-Draghi, Carlos

    2012-03-08

    Mass diffusion coefficients of CO(2)/brine mixtures under thermodynamic conditions of deep saline aquifers have been investigated by molecular simulation. The objective of this work is to provide estimates of the diffusion coefficient of CO(2) in salty water to compensate the lack of experimental data on this property. We analyzed the influence of temperature, CO(2) concentration,and salinity on the diffusion coefficient, the rotational diffusion, as well as the electrical conductivity. We observe an increase of the mass diffusion coefficient with the temperature, but no clear dependence is identified with the salinity or with the CO(2) mole fraction, if the system is overall dilute. In this case, we notice an important dispersion on the values of the diffusion coefficient which impairs any conclusive statement about the effect of the gas concentration on the mobility of CO(2) molecules. Rotational relaxation times for water and CO(2) increase by decreasing temperature or increasing the salt concentration. We propose a correlation for the self-diffusion coefficient of CO(2) in terms of the rotational relaxation time which can ultimately be used to estimate the mutual diffusion coefficient of CO(2) in brine. The electrical conductivity of the CO(2)-brine mixtures was also calculated under different thermodynamic conditions. Electrical conductivity tends to increase with the temperature and salt concentration. However, we do not observe any influence of this property with the CO(2) concentration at the studied regimes. Our results give a first evaluation of the variation of the CO(2)-brine mass diffusion coefficient, rotational relaxation times, and electrical conductivity under the thermodynamic conditions typically encountered in deep saline aquifers.

  12. Ionic conductivity and battery characteristic studies of a new PAN-based Na+ ion conducting gel polymer electrolyte system

    NASA Astrophysics Data System (ADS)

    Krishna Jyothi, N.; Vijaya Kumar, K.; Sunita Sundari, G.; Narayana Murthy, P.

    2016-03-01

    Sodium ion conducting gel polymer electrolytes based on polyacrylonitrile (PAN) with ethylene carbonate and dimethyl formamide as plasticizing solvents are prepared by the solution cast technique. These electrolyte films are free standing, transparent and dimensionally stable. Na+ ions are derived from NaI. The structural properties of pure and complex formations have been examined by X-ray diffraction, Fourier transform infrared spectroscopic studies and differential scanning calorimetric studies. The variation of the conductivity with salt concentration ranging from 10 to 40 wt% is studied. The sample containing 30 wt% of NaI exhibits the highest conductivity of 2.35 × 10-4 S cm-1 at room temperature (303 K) and 1 × 10-3 S cm-1 at 373 K. The conductivity-temperature dependence of polymer electrolyte films obeys Arrhenius behavior with activation energy in the range of 0.25-0.46 eV. The transport numbers both electronic ( t e) and ionic ( t i) are evaluated using Wagner's polarization technique. It is revealed that the conducting species are predominantly due to ions. The ionic transport number of highest conducting film is found to be 0.991. Solid-state battery with configuration Na/(PAN + NaI)/(I2 + C + electrolyte) is developed using the highest conducting gel polymer electrolyte system and the discharge characteristics of the cell are evaluated over the load of 100 KΩ.

  13. Enhancing ionic conductivity of bulk single-crystal yttria-stabilized zirconia by tailoring dopant distribution

    SciTech Connect

    Lee, E.; Prinz, F. B.; Cai, W.

    2011-02-11

    We present an ab initio–based kinetic Monte Carlo model for ionic conductivity in single-crystal yttria-stabilized zirconia. Ionic interactions are taken into account by combining density functional theory calculations and the cluster expansion method and are found to be essential in reproducing the effective activation energy observed in experiments. The model predicts that the effective energy barrier can be reduced by 0.15–0.25 eV by arranging the dopant ions into a superlattice.

  14. Proton Conducting Polymer Membrane Using The Ionic Liquid 2-Hydroxyethylammonium Lactate For Ethanol Fuel Cells

    NASA Astrophysics Data System (ADS)

    Oliveira, L.; José, N. M.; Boaventura, J.; Iglesias, M.; Mattedi, S.

    2011-12-01

    In this work, there were developed a proton conducting polymer membrane using an ammonium based protic ionic liquid: 2-hydroxyethylamominum lactate for use in proton exchange fuel cells (PEMFC). This kind of ionic liquid has been proven to be biodegradable and they have potentially low toxicity besides low cost of preparation, simple synthesis and purification. The prepared membranes are hybrid organic-inorganic materials. The polymeric matrix is prepared with polydimethylsiloxane (PDMS) mixed with tetraethoxysilane (TEOS) in a ratio of 70/30% in weight. Then, the eletrolytical mixture containing sodium monododecylsulfate (SDS) and the ionic liquid was introduced in the lattice near the gel point, there were used different proportions of the eletrolyte from 5 to 30% in weight. The prepared membranes were characterized using infrared spectroscopy (FTIR), X-ray diffraction (DRX), termogravimetric analysis (TGA), scanning electronic microscopy (SEM) and conductivity and impedance measurements. The prepared materials are flexible, with good thermal and mechanical stability and with a great potential to be used as conducting membranes of fuel cells. The used mixture minimizes the lixiviation lost of the ionic liquid from the polymeric membrane and enhances the cell efficiency if compared with traditional synthetic membranes.

  15. Li+ ionic conductivities and diffusion mechanisms in Li-based imides and lithium amide.

    PubMed

    Li, Wen; Wu, Guotao; Xiong, Zhitao; Feng, Yuan Ping; Chen, Ping

    2012-02-07

    In this study, both experimental ionic conductivity measurements and the first-principles simulations are employed to investigate the Li(+) ionic diffusion properties in lithium-based imides (Li(2)NH, Li(2)Mg(NH)(2) and Li(2)Ca(NH)(2)) and lithium amide (LiNH(2)). The experimental results show that Li(+) ions present superionic conductivity in Li(2)NH (2.54 × 10(-4) S cm(-1)) and moderate ionic conductivity in Li(2)Ca(NH)(2) (6.40 × 10(-6) S cm(-1)) at room temperature; while conduction of Li(+) ions is hardly detectable in Li(2)Mg(NH)(2) and LiNH(2) at room temperature. The simulation results indicate that Li(+) ion diffusion in Li(2)NH may be mediated by Frenkel pair defects or charged vacancies, and the diffusion pathway is more likely via a series of intermediate jumps between octahedral and tetrahedral sites along the [001] direction. The calculated activation energy and pre-exponential factor for Li(+) ion conduction in Li(2)NH are well comparable with the experimentally determined values, showing the consistency of experimental and theoretical investigations. The calculation of the defect formation energy in LiNH(2) reveals that Li defects are difficult to create to mediate the Li(+) ion diffusion, resulting in the poor Li(+) ion conduction in LiNH(2) at room temperature.

  16. Electrochemical deposition of conducting polymer coatings on magnesium surfaces in ionic liquid

    PubMed Central

    Luo, Xiliang; Cui, Xinyan Tracy

    2012-01-01

    A conducting polymer based smart coating for magnesium (Mg) implants that can both improve the corrosion resistance of Mg and release drug in a controllable way is reported. As the ionic liquid is a highly conductive and stable solvent with a very wide electrochemical window, the conducting polymer coatings can be directly electrodeposited on the active metal Mg in ionic liquid at mild conditions, and Mg is considerably stable during the electrodeposition. The electrodeposited Poly(3,4-ethylenedioxythiophene) (PEDOT) coatings on Mg are uniform and can significantly improve the corrosion resistance of Mg. In addition, the PEDOT coatings can load the anti-inflammatory drug dexamethasone during the electrodeposition which can be subsequently released upon electric stimulation. PMID:20832505

  17. 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.

  18. 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.

  19. Lithium-Ion-Conducting Electrolytes: From an Ionic Liquid to the Polymer Membrane

    PubMed Central

    Fernicola, A.; Weise, F. C.; Greenbaum, S. G.; Kagimoto, J.; Scrosati, B.; Soleto, A.

    2009-01-01

    This work concerns the design, the synthesis, and the characterization of the N-butyl-N-ethylpiperidinium N,N-bis(trifluoromethane)sulfonimide (PP24TFSI) ionic liquid (IL). To impart Li-ion transport, a suitable amount of lithium N,N-bis-(trifluoromethane)sulfonimide (LiTFSI) is added to the IL. The Li–IL mixture displays ionic conductivity values on the order of 10−4 S cm−1 and an electrochemical stability window in the range of 1.8–4.5 V vs Li+/Li. The voltammetric analysis demonstrates that the cathodic decomposition gives rise to a passivating layer on the surface of the working electrode, which kinetically extends the stability of the Li/IL interface as confirmed by electrochemical impedance spectroscopy measurements. The LiTFSI–PP24TFSI mixture is incorporated in a poly(vinylidene fluoride-co-hexafluoropropylene) matrix to form various electrolyte membranes with different LiTFSI–PP24TFSI contents. The ionic conductivity of all the membranes resembles that of the LiTFSI–IL mixture, suggesting an ionic transport mechanism similar to that of the liquid component. NMR measurements demonstrate a reduction in the mobility of all ions following the addition of LiTFSI to the PP24TFSI IL and when incorporating the mixture into the membrane. Finally, an unexpected but potentially significant enhancement in Li transference number is observed in passing from the liquid to the membrane electrolyte system. PMID:20354582

  20. Advanced two-photon photolithography for patterning of transparent, electrically conductive ionic liquid-polymer nanostructures

    NASA Astrophysics Data System (ADS)

    Bakhtina, Natalia A.; MacKinnon, Neil; Korvink, Jan G.

    2016-04-01

    A key challenge in micro- and nanotechnology is the direct patterning of functional structures. For example, it is highly desirable to possess the ability to create three-dimensional (3D), conductive, and optically transparent structures. Efforts in this direction have, to date, yielded less than optimal results since the polymer composites had low optical transparency over the visible range, were only slightly conductive, or incompatible with high resolution structuring. We have previously presented the novel cross-linkable, conductive, highly transparent composite material based on a photoresist (IP-L 780, OrmoComp, or SU-8) and the ionic liquid 1-butyl-3-methylimidazolium dicyanamide. Material patterning by conventional and two-photon photolithography has been demonstrated as proof-of-concept. Aiming to increase the resolution and to extend the spectrum of exciting applications we continued our research into identifying new ionic liquid - polymer composites. In this paper, we report the precise 3D single-step structuring of optically transparent and electrically conductive ionic liquid - polymer nanostructures with the highest spatial resolution (down to 150 nm) achieved to date. This was achieved via the development of novel cross-linkable composite based on the photoresist IP-G 780 and the ionic liquid 1-butyl-3-methylimidazolium dicyanamide. The successful combination of the developed material with the advanced direct laser writing technique enabled the time- and cost-saving direct manufacturing of transparent, electrically conductive components. We believe that the excellent characteristics of the structured material will open a wider range of exciting applications.

  1. 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.

  2. Structural control of mixed ionic and electronic transport in conducting polymers

    SciTech Connect

    Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; Sessolo, Michele; Stavrinidou, Eleni; Strakosas, Xenofon; Tassone, Christopher; Delongchamp, Dean M.; Malliaras, George G.

    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. We 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.

  3. Structural control of mixed ionic and electronic transport in conducting polymers

    NASA Astrophysics Data System (ADS)

    Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; Sessolo, Michele; Stavrinidou, Eleni; Strakosas, Xenofon; Tassone, Christopher; Delongchamp, Dean M.; Malliaras, George G.

    2016-04-01

    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. We 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. These findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction.

  4. Structural control of mixed ionic and electronic transport in conducting polymers

    PubMed Central

    Rivnay, Jonathan; Inal, Sahika; Collins, Brian A.; Sessolo, Michele; Stavrinidou, Eleni; Strakosas, Xenofon; Tassone, Christopher; Delongchamp, Dean M.; Malliaras, George G.

    2016-01-01

    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. We 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. These findings may pave the way for the rational design of polymeric materials and processing routes to enhance devices reliant on mixed conduction. PMID:27090156

  5. A mixed ionic and electronic conducting dual-phase membrane with high oxygen permeability.

    PubMed

    Fang, Wei; Liang, Fangyi; Cao, Zhengwen; Steinbach, Frank; Feldhoff, Armin

    2015-04-13

    To combine good chemical stability and high oxygen permeability, a mixed ionic-electronic conducting (MIEC) 75 wt% Ce(0.85)Gd(0.1)Cu(0.05)O(2-δ)-25 wt% La(0.6)Ca(0.4)FeO(3-δ)(CGCO-LCF) dual-phase membrane based on a MIEC-MIEC composite has been developed. Copper doping into Ce(0.9)Gd(0.1)O(2-δ) (CGO) oxide enhances both ionic and electronic conductivity, which then leads to a change from ionic conduction to mixed conduction at elevated temperatures. For the first time we demonstrate that an intergranular film with 2-10 nm thickness containing Ce, Ca, Gd, La, and Fe has been formed between the CGCO grains in the CGCO-LCF one-pot dual-phase membrane. A high oxygen permeation flux of 0.70 mL min(-1) cm(-2) is obtained by the CGCO-LCF one-pot dual-phase membrane with 0.5 mm thickness at 950 °C using pure CO2 as the sweep gas, and the membrane shows excellent stability in the presence of CO2 even at lower temperatures (800 °C) during long-term operation.

  6. 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

  7. Correlating crystallization and ionic conductivity of PEO/graphene oxide nanocomposite

    NASA Astrophysics Data System (ADS)

    Cheng, Shan; Smith, Derrick; Hsuan, Grace; Li, Christopher

    2012-02-01

    Polyethylene oxide (PEO) is one of the best candidates for solid state electrolyte due to its chemical stability and strong ability to form complex with lithium salts. Crystallization behavior of PEO directly affects the lithium ion transport, and in turn the ionic conductivity of the electrolyte. By adding two dimensional graphene oxide nanosheets into PEO matrix, mechanical property of the latter is significantly strengthened, while the crystallization behavior of PEO is also altered by the graphene oxide sheets. The crystallization of PEO/graphene oxide nanocomposites was studied by differential scanning calorimetry (DSC) and the orientations of graphene oxide and PEO crystal were studied by small angle X-ray scattering and wide angle X-ray diffraction. PEO/graphene oxide nanocomposite doped with lithium salt was further fabricated and characterized by electrochemical impedance spectroscopy. Anisotropic ionic conductivity was observed for the nanocomposite electrolyte due to the orientation of graphene oxide and directional growth of PEO crystals.

  8. Aerospace Power Scholarly Research Program. Delivery Order 0011: Single Ionic Conducting Polymer Electrolyte

    DTIC Science & Technology

    2005-12-01

    crystalline forms were modeled at 300 K and lithium ion self- diffusion coefficients and ionic conductivities were calculated . These calculated ...assembled and used to demonstrate charging and discharging behavior by way of slow scan cyclic voltammetry . Although proof of concept has been shown, the...However, these calculated results reflect ion movement via self- diffusion as determined by the field created by the self-assembly of Li2Pc molecules

  9. Li-rich anti-perovskite Li3OCl films with enhanced ionic conductivity

    SciTech Connect

    Lu, XJ; Wu, G; Howard, JW; Chen, AP; Zhao, YS; Daemen, LL; Jia, QX

    2014-08-13

    Anti-perovskite solid electrolyte films were prepared by pulsed laser deposition, and their room-temperature ionic conductivity can be improved by more than an order of magnitude in comparison with its bulk counterpart. The cyclability of Li3OCl films in contact with lithium was evaluated using a Li/Li3OCl/Li symmetric cell, showing self-stabilization during cycling test.

  10. Simultaneous electronic and ionic conduction in a block copolymer: application in lithium battery electrodes.

    PubMed

    Javier, Anna E; Patel, Shrayesh N; Hallinan, Daniel T; Srinivasan, Venkat; Balsara, Nitash P

    2011-10-10

    Charging ahead: separate values for the simultaneous electronic and ionic conductivity of a conjugated polymer containing poly(3-hexylthiophene) and poly(ethylene oxide) (P3HT-PEO) were determined by using ac impedance and dc techniques. P3HT-PEO was used as binder, and transporter of electronic charge and Li(+) ions in a LiFePO(4) cathode, which was incorporated into solid-state lithium batteries.

  11. Doping, Ionic Conductivity and Photothermal Stability of Functionalized DNA for Solar Energy Conversion and Electrochromic Applications

    DTIC Science & Technology

    2011-06-01

    to 85 0C and the optical absorption spectra were monitored as function of time. Similar experiments were done using the UV light to degrade the...Rh590 – rhodamine 590 Rh610 – rhodamine 610 SHG – second harmonic generation THZ – Tetra Hertz UV – ultraviolet light VIS – visible light ...AFRL-AFOSR-UK-TR-2011-0025 DOPING , IONIC CONDUCTIVITY AND PHOTOTHERMAL STABILITY OF FUNCTIONALIZED DNA FOR SOLAR ENERGY CONVERSION

  12. Ionic conductivity of binary fluorides of potassium and rare earth elements

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.

    2016-01-01

    The ionic conductivity s of KYF4 and K2 RF5 single crystals ( R = Gd, Ho, Er) and KNdF4 and K2 RF5 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 2O3-KF-H2O systems. The σ values of tetraf luorides are 3 × 10-5 S/cm (KYF4 single crystal) and 3 × 10-6 S/cm (KNdF4 ceramics) at 435°C. A K2ErF5 single crystal with σ = 1.2 × 10-4 S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K2HoF5 single crystals, σ∥ c /σ⊥ c = 2.5, where σ∥ c and σ⊥ c are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.

  13. 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 Na3OX (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) without decomposing.more » 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 Na2.9Sr0.05OBr0.6I0.4 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

  14. Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites

    SciTech Connect

    Wang, Yonggang; Wang, Qingfei; Liu, Zhenpu; Zhou, Zhengyang; Li, Shuai; Zhu, Jinlong; Zou, Ruqiang; Wang, Yingxia; Lin, Jianhua; Zhao, Yusheng

    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 Na3OX (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) without 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 Na2.9Sr0.05OBr0.6I0.4 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.

  15. Ionic conductivity of binary fluorides of potassium and rare earth elements

    SciTech Connect

    Sorokin, N. I.

    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} 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.

  16. Nonaqueous CE using contactless conductivity detection and ionic liquids as BGEs in ACN.

    PubMed

    Borissova, Maria; Gorbatsova, Jelena; Ebber, Arkadi; Kaljurand, Mihkel; Koel, Mihkel; Vaher, Merike

    2007-10-01

    N,N'-Alkylmethylimidazolium cations have been separated in NACE when one of the N,N'-dialkylimidazolium salts (ionic liquids (ILs)) was used as an electrolyte additive to the organic solvent separation medium. The separated species were 1-methyl-, 1-ethyl-, 1-butyl-, 1-octyl-, 1-decyl-3-methylimidazolium and N-butyl-3-methylpyridinium cations and BGE composed of 1-ethyl-3-methylimidazolium ethylsulfate or 1-butyl-3-methylimidazolium trifluoroacetate [BMIm][FAcO] (A6; B2) diluted in ACN. It was demonstrated that contactless conductivity detection (CCD) may be applied to monitoring the separation process in nonaqueous separation media, allowing to use the UV light-absorbing imidazolium-based electrolyte additives. There could be marked three concentration regions of added ILs; at first ionic strength of BGE below 1-2 mM, and then the actual electrophoretic mobility of analytes rises from 0. At concentrations above 1-2 mM, the added IL facilitated separation. In concentration region of 1-20 mM, the actual electrophoretic mobility of analyzed imidazolium cations was increasing with decrease in separation medium ionic strength. At higher concentrations of BGE (above 30 mM), the conductivity of the separation media became too high for this detector. Some organic dyes were also successfully separated and detected by contactless conductivity detector in a 20 mM A6 separation electrolyte in ACN.

  17. Copper and silver selenide crystal growth rate measurements as a method for determination of ionic conductivity

    NASA Astrophysics Data System (ADS)

    Vučić, Zlatko; Lovrić, Davorin; Gladić, Jadranko; Etlinger, Božidar

    2004-03-01

    The motivation behind this work is the discrepancy between the measured and calculated growth rates of copper selenide spherical single crystals between 740 and 800 K. The growth of cylindrical polycrystalline samples of copper selenide at high temperatures was monitored in experiments that enabled full control of the geometry of growth. Together with the calculations based on Yokota's transport equation, these measurements eliminated ionic conductivity data as a possible reason behind too high values of the calculated growth rates. The equivalent growth experiments on polycrystalline silver selenide samples were performed as a test of the method, yielding excellent agreement with the results obtained by extrapolation of existing data. On the basis of these measurements and associated analysis, this method is proposed as a method for determination of ionic conductivity of mixed superionic conductors on temperatures up to the temperatures of melting, i.e. in the range in which other methods of ionic conductivity measurements either do not work or are not accurate enough.

  18. Interfacial interactions in aprotic ionic liquid based protonic membrane and its correlation with high temperature conductivity and thermal properties.

    PubMed

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

    2009-08-18

    Novel supported liquid membranes (SLMs) have been developed by impregnating Nafion and Hyflon membranes with ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI). These supported liquid membranes were characterized in terms of their ionic liquid uptake behavior, leaching of ionic liquid by water, thermal stability, mechanical properties, glass transition temperature, ion exchange capacity, and proton conductivity. In general, modified membranes are more flexible than unmodified samples due to the plasticization effects of the ionic liquid. However, these supported liquid membranes exhibit a significant increase in their operational stability and proton conductivity over unmodified membranes. We also demonstrate that proton conductivity of these supported liquid membranes allows conduction of protons in anhydrous conditions with conductivity increasing with temperature. Conductivity of up to 3.58 mS cm(-1) has been achieved at 160 degrees C in dry conditions, making these materials promising for various electrochemical applications.

  19. 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.

  20. 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

  1. Sensitive and Fast Humidity Sensor Based on A Redox Conducting Supramolecular Ionic Material for Respiration Monitoring.

    PubMed

    Yan, Hailong; Zhang, Li; Yu, Ping; Mao, Lanqun

    2017-01-03

    Real-time monitoring of respiratory rate (RR) is highly important for human health, clinical diagnosis, and fundamental scientific research. Exhaled humidity-based RR monitoring has recently attracted increased attention because of its accuracy and portability. Here, we report a new design of an exhaled humidity sensor for the real-time monitoring of the RR based on a synthetic redox conducting supramolecular ionic material (SIM). The humidity-dependent conducting SIM is prepared by ionic self-assembly in aqueous solutions of electroactive 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 1,10-bis(3-methylimidazolium-1-yl) decane (C10(mim)2). By taking full advantage of the high hygroscopicity and water stability arising from the ionic and hydrophobic interactions between two building blocks (i.e., ABTS and C10(mim)2), the SIM-based humidity sensor exhibits both high sensitivity (less than 0.1% relative humidity) and fast response time (∼37 ms). These excellent properties allow this humidity sensor to noninvasively monitor the RRs of not only humans but also rats that have a much faster RR and much smaller tidal volume than humans. Moreover, this sensor could also be efficiently used for the real-time monitoring of the recovery process of rats from anesthesia.

  2. 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 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 vacanciesmore » 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. 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

  3. 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

  4. Enhancing grain boundary ionic conductivity in mixed ionic–electronic conductors

    SciTech Connect

    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. 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.

  5. Correlation between the glass-rubber transition and ionic conductivity in poly(3-hexylthiophene)

    NASA Astrophysics Data System (ADS)

    Lada, M.

    2008-10-01

    Using impedance spectroscopy and metal-insulator-semiconductor structures, the small-signal bulk conductivity of annealed poly(3-hexylthiophene) (P3HT) has been extracted in the temperature range of 150-420K. A faster-than-Arrhenius increase in the conductivity of P3HT observed near and above room temperature is shown to be a result of the glass-rubber transition and is closely related to the amorphous phase of the polymer. The super-Arrhenius conductivity can be modeled and interpreted as ionic, arising from the thermal motion of the polymer segments. In addition, a percolative conduction mechanism induced by the glass transition can phenomenologically model the conductivity increase.

  6. Altered ion channel conductance and ionic selectivity induced by large imposed membrane potential pulse.

    PubMed Central

    Chen, W; Lee, R C

    1994-01-01

    The effects of large magnitude transmembrane potential pulses on voltage-gated Na and K channel behavior in frog skeletal muscle membrane were studied using a modified double vaseline-gap voltage clamp. The effects of electroconformational damage to ionic channels were separated from damage to lipid bilayer (electroporation). A 4 ms transmembrane potential pulse of -600 mV resulted in a reduction of both Na and K channel conductivities. The supraphysiologic pulses also reduced ionic selectivity of the K channels against Na+ ions, resulting in a depolarization of the membrane resting potential. However, TTX and TEA binding effects were unaltered. The kinetics of spontaneous reversal of the electroconformational damage of channel proteins was found to be dependent on the magnitude of imposed membrane potential pulse. These results suggest that muscle and nerve dysfunction after electrical shock may be in part caused by electroconformational damage to voltage-gated ion channels. PMID:7948676

  7. Enhanced ionic conductivity of AgI nanowires/AAO composites fabricated by a simple approach

    NASA Astrophysics Data System (ADS)

    Liu, Li-Feng; Lee, Seung-Woo; Li, Jing-Bo; Alexe, Marin; Rao, Guang-Hui; Zhou, Wei-Ya; Lee, Jae-Jong; Lee, Woo; Gösele, Ulrich

    2008-12-01

    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 × 102 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.

  8. Effect of ionic conductivity of zirconia electrolytes on polarization properties of various electrodes in SOFC

    SciTech Connect

    Watanabe, Masahiro; Uchida, Hiroyuki; Yoshida, Manabu

    1996-12-31

    Solid oxide fuel cells (SOFCs) have been intensively investigated because, in principle, their energy conversion efficiency is fairly high. Lowering the operating temperature of SOFCs from 1000{degrees}C to around 800{degrees}C is desirable for reducing serious problems such as physical and chemical degradation of the constructing materials. The object of a series of the studies is to find a clue for achieving higher electrode performances at a low operating temperature than those of the present level. Although the polarization loss at electrodes can be reduced by using mixed-conducting ceria electrolytes, or introducing the mixed-conducting (reduced zirconia or ceria) laver on the conventional zirconia electrolyte surface, no reports are available on the effect of such an ionic conductivity of electrolytes on electrode polarizations. High ionic conductivity of the electrolyte, of course, reduces the ohmic loss. However, we have found that the IR-free polarization of a platinum anode attached to zirconia electrolytes is greatly influenced by the ionic conductivity, {sigma}{sub ion}, of the electrolytes used. The higher the {sigma}{sub ion}, the higher the exchange current density, j{sub 0}, for the Pt anode in H{sub 2} at 800 {approximately} 1000{degrees}C. It was indicated that the H{sub 2} oxidation reaction rate was controlled by the supply rate of oxide ions through the Pt/zirconia interface which is proportional to the {sigma}{sub ion}. Recently, we have proposed a new concept of the catalyzed-reaction layers which realizes both high-performances of anodes and cathodes for medium-temperature operating SOFCs. We present the interesting dependence of the polarization properties of various electrodes (the SDC anodes with and without Ru microcatalysts, Pt cathode, La(Sr)MnO{sub 3} cathodes with and without Pt microcatalysts) on the {sigma}{sub ion} of various zirconia electrolytes at 800 {approximately} 1000{degrees}C.

  9. Conductivity dispersion in supercooled calcium potassium nitrate: caged ionic motion viewed as part of standard behaviour.

    PubMed

    Funke, Klaus; Singh, Prabhakar; Banhatti, Radha Dilip

    2007-11-07

    Conductivity spectra of ionic materials with disordered structures are usually thought to consist of several parts, i.e., the DC conductivity, a power-law component, a nearly-constant-loss feature (if identified) and the (far-)infrared conductivity caused by vibrational motion. Such a decomposition may, however, easily lead to a misinterpretation of the underlying dynamics. Here, we discuss broad-band conductivity data of the supercooled glass-forming melt calcium potassium nitrate, of composition 0.4 Ca(NO(3))(2).0.6 KNO(3), often abbreviated as CKN. Data have been taken at frequencies up to the far infrared. We show that the frequency-dependent conductivity is very well reproduced by a superposition of only two components. One of them is due to vibrations, the other is caused by displacements of the mobile ions. The latter component, which does not follow a power law, is described in terms of a physical model called the MIGRATION concept. This model treatment has been found to apply in many solid electrolytes as well and is, therefore, considered to provide a "standard" formulation of the ion dynamics. The gradual transition from a correlated forward-backward ("caged") ionic motion to a stepwise translational motion may be regarded as the main feature of the MIGRATION concept.

  10. Noncovalent approach to one-dimensional ion conductors: enhancement of ionic conductivities in nanostructured columnar liquid crystals.

    PubMed

    Shimura, Harutoki; Yoshio, Masafumi; Hoshino, Koji; Mukai, Tomohiro; Ohno, Hiroyuki; Kato, Takashi

    2008-02-06

    Noncovalent design of new liquid-crystalline (LC) columnar assemblies based on an ionic liquid has shown to be useful to achieve anisotropic high ionic conductivities. An equimolar mixture of an ionic liquid, 1-butyl-3-methylimidazolium bromide, and 3-[3,4,5-tri(octyloxy)benzoyloxy]propane-1,2-diol, which is partially miscible with the ionic liquid, exhibits an LC hexagonal columnar phase from -4 to 63 degrees C. This columnar supramolecular assembly forming the nanostructures shows the one-dimensional (1D) ionic conductivity of 3.9 x 10(-3) S cm(-1) at 50 degrees C along the column, which is more than 700 times higher than that of the corresponding covalent-type columnar ionic liquid, 1-methyl-3-[3,4,5-tri(octyloxy)benzyl]imidazolium bromide, which is 5.3 x 10(-6) S cm(-1) at 50 degrees C. This significant enhancement of the ionic conductivity is attributed to the increase of the mobility of the ionic part.

  11. Liquid crystal self-assembly of halloysite nanotubes in ionic liquids: a novel soft nanocomposite ionogel electrolyte with high anisotropic ionic conductivity and thermal stability

    NASA Astrophysics Data System (ADS)

    Zhao, Ningning; Liu, Yulin; Zhao, Xiaomeng; Song, Hongzan

    2016-01-01

    We report a novel class of liquid crystalline (LC) nanohybrid ionogels fabricated via self-assembly of natural halloysite nanotubes (HNTs) in ionic liquids (ILs). The obtained ionogels are very stable and nonvolatile and show LC phases over a wide temperature range. Remarkably, the nanocomposite ionogels exhibit high anisotropic ionic conductivity after shear, and their room temperature ionic conductivity can reach 3.8 × 10-3 S cm-1 for aligned nanotubes perpendicular to the electrode even when the HNTs content increases to 40 wt%, which is 380 times higher than that obtained for aligned nanotubes parallel to the electrode, which is 1.0 × 10-5 S cm-1. Crucially, the obtained LC nanocomposite ionogels have very high thermal stability, which can sustain 400 °C thermal treatment. The findings will promote the development of novel nanocomposite ionogel electrolytes with faster ion transport and larger anisotropic conductivity.We report a novel class of liquid crystalline (LC) nanohybrid ionogels fabricated via self-assembly of natural halloysite nanotubes (HNTs) in ionic liquids (ILs). The obtained ionogels are very stable and nonvolatile and show LC phases over a wide temperature range. Remarkably, the nanocomposite ionogels exhibit high anisotropic ionic conductivity after shear, and their room temperature ionic conductivity can reach 3.8 × 10-3 S cm-1 for aligned nanotubes perpendicular to the electrode even when the HNTs content increases to 40 wt%, which is 380 times higher than that obtained for aligned nanotubes parallel to the electrode, which is 1.0 × 10-5 S cm-1. Crucially, the obtained LC nanocomposite ionogels have very high thermal stability, which can sustain 400 °C thermal treatment. The findings will promote the development of novel nanocomposite ionogel electrolytes with faster ion transport and larger anisotropic conductivity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06888f

  12. Influence of anionic vacancies on the ionic conductivity of silicated rare earth apatites

    SciTech Connect

    Panteix, P.J. Bechade, E.; Julien, I.; Abelard, P.; Bernache-Assollant, D.

    2008-05-06

    Oxyapatites are very promising materials in terms of ionic conductivity. They can be considered as a potential electrolyte for Solid Oxide Fuel Cells (SOFC). Doped silicated rare earth apatites with formula La{sub 9.33-x}Ca{sub x}(SiO{sub 4}){sub 6}O{sub 2-x/2} (0 {<=} x {<=} 1) have been prepared by solid state reaction at high temperature in order to determine the influence of anionic vacancies on the electrical properties of the material. The incorporation of calcium in the structure has been checked by characterizations of the powders (X-ray diffraction, helium pycnometry). The cell parameters of the hexagonal apatite were refined. Samples were sintered at 1550 deg. C. Electrical properties of each composition have been studied between 280 and 620 deg. C by the complex impedance method. The evolution of the bulk conductivity and of the activation energy with the substituting ratio gives information on the conductivity mechanism in these materials. An improvement of ionic conductivity about one order of magnitude has been observed for low calcium substitution ratios.

  13. Ionic conductivity and dielectric permittivity of PEO-LiClO{sub 4} solid polymer electrolyte plasticized with propylene carbonate

    SciTech Connect

    Das, S.; Ghosh, A.

    2015-02-15

    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 free 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.

  14. Ionic charge transport between blockages: Sodium cation conduction in freshly excised bulk brain tissue

    SciTech Connect

    Emin, David; Akhtari, Massoud; Ellingson, B. M.; Mathern, G. W.

    2015-08-15

    We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

  15. Electrical conductivity study on micelle formation of long-chain imidazolium ionic liquids in aqueous solution.

    PubMed

    Inoue, Tohru; Ebina, Hayato; Dong, Bin; Zheng, Liqiang

    2007-10-01

    Electrical conductivity was measured for aqueous solutions of long-chain imidazolium ionic liquids (IL), 1-alkyl-3-methylimidazolium bromides with C(12)-C(16) alkyl chains. The break points appeared in specific conductivity (kappa) vs concentration (c) plot indicates that the molecular aggregates, i.e., micelles, are formed in aqueous solutions of these IL species. The critical micelle concentration (cmc) determined from the kappa vs c plot is somewhat lower than those for typical cationic surfactants, alkyltrimethylammonium bromides with the same hydrocarbon chain length. The electrical conductivity data were analyzed according to the mixed electrolyte model of micellar solution, and the aggregation number, n, and the degree of counter ion binding, beta, were estimated. The n values of the present ILs are somewhat smaller than those reported for alkyltrimethylammonium bromides, which may be attributed to bulkiness of the cationic head group of the IL species. The thermodynamic parameters for micelle formation of the present ILs were estimated using the values of cmc and beta as a function of temperature. The contribution of entropy term to the micelle formation is superior to that of enthalpy term below about 30 degrees C, and it becomes opposite at higher temperature. This coincides with the picture drawn for the micelle formation of conventional ionic surfactants.

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

    PubMed

    Ramesh, S; Shanti, R; Morris, Ezra

    2013-01-02

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

  17. Ionic Conductance Changes in Lobster Axon Membrane When Lanthanum Is Substituted for Calcium

    PubMed Central

    Takata, M.; Pickard, W. F.; Lettvin, J. Y.; Moore, J. W.

    1966-01-01

    The trivalent rare earth lanthanum was substituted for calcium in the sea water bathing the exterior of an "artificial node" of a lobster axon in a sucrose gap. It caused a progressive rise in threshold, and a decrease in the height of the action potential as well as in its rates of rise and fall. Prolonged application produced an excitation block. Voltage-clamp studies of the ionic currents showed that the time courses of the ionic conductance changes for both sodium and potassium were increased. Concurrently, the potentials at which the conductance increases occurred were shifted to more positive inside values for the La+++ sea water. These effects resemble changes resulting from a high external calcium concentration. Over and above this, La+++ also causes a marked reduction in the maximum amount of conductance increase following a depolarizing potential step. Membrane action potentials similar to those observed experimentally in the La+++ solution have been computed with appropriate parameter changes in the Hodgkin-Huxley equations. PMID:11526840

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

    SciTech Connect

    Duan, QJ; Ge, SH; Wang, CY

    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. (C) 2013 Elsevier B.V. All rights reserved.

  19. Ionic conductivity of nanocrystalline yttria-stabilized zirconia: Grain boundary and size effects

    NASA Astrophysics Data System (ADS)

    Durá, O. J.; López de La Torre, M. A.; Vázquez, L.; Chaboy, J.; Boada, R.; Rivera-Calzada, A.; Santamaria, J.; Leon, C.

    2010-05-01

    We report on the effect of grain size on the ionic conductivity of yttria-stabilized zirconia samples synthesized by ball milling. Complex impedance measurements, as a function of temperature and frequency are performed on 10mol% yttria-stabilized zirconia nanocrystalline samples with grain sizes ranging from 900 to 17 nm. Bulk ionic conductivity decreases dramatically for grain sizes below 100 nm, although its activation energy is essentially independent of grain size. The results are interpreted in terms of a space-charge layer resulting from segregation of mobile oxygen vacancies to the grain-boundary core. The thickness of this space-charge layer formed at the grain boundaries is on the order of 1 nm for large micron-sized grains but extends up to 7 nm when decreasing the grain size down to 17 nm. This gives rise to oxygen vacancies depletion over a large volume fraction of the grain and consequently to a significant decrease in oxide-ion conductivity.

  20. Ionic conductance changes in lobster axon membrane when lanthanum is substituted for calcium.

    PubMed

    Takata, M; Pickard, W F; Lettvin, J Y; Moore, J W

    1966-11-01

    The trivalent rare earth lanthanum was substituted for calcium in the sea water bathing the exterior of an "artificial node" of a lobster axon in a sucrose gap. It caused a progressive rise in threshold, and a decrease in the height of the action potential as well as in its rates of rise and fall. Prolonged application produced an excitation block. Voltage-clamp studies of the ionic currents showed that the time courses of the ionic conductance changes for both sodium and potassium were increased. Concurrently, the potentials at which the conductance increases occurred were shifted to more positive inside values for the La+++ sea water. These effects resemble changes resulting from a high external calcium concentration. Over and above this, La+++ also causes a marked reduction in the maximum amount of conductance increase following a depolarizing potential step. Membrane action potentials similar to those observed experimentally in the La+++ solution have been computed with appropriate parameter changes in the Hodgkin-Huxley equations.

  1. Influence of Ionic Conductances on Spike Timing Reliability of Cortical Neurons for Suprathreshold Rhythmic Inputs

    PubMed Central

    Schreiber, Susanne; Fellous, Jean-Marc; Tiesinga, Paul; Sejnowski, Terrence J.

    2010-01-01

    Spike timing reliability of neuronal responses depends on the frequency content of the input. We investigate how intrinsic properties of cortical neurons affect spike timing reliability in response to rhythmic inputs of suprathreshold mean. Analyzing reliability of conductance-based cortical model neurons on the basis of a correlation measure, we show two aspects of how ionic conductances influence spike timing reliability. First, they set the preferred frequency for spike timing reliability, which in accordance with the resonance effect of spike timing reliability is well approximated by the firing rate of a neuron in response to the DC component in the input. We demonstrate that a slow potassium current can modulate the spike timing frequency preference over a broad range of frequencies. This result is confirmed experimentally by dynamic-clamp recordings from rat prefrontal cortical neurons in vitro. Second, we provide evidence that ionic conductances also influence spike timing beyond changes in preferred frequency. Cells with the same DC firing rate exhibit more reliable spike timing at the preferred frequency and its harmonics if the slow potassium current is larger and its kinetics are faster, whereas a larger persistent sodium current impairs reliability. We predict that potassium channels are an efficient target for neuromodulators that can tune spike timing reliability to a given rhythmic input. PMID:14507985

  2. Phase behavior and ionic conductivity in lithium bis(trifluoromethanesulfonyl)imide-doped ionic liquids of the pyrrolidinium cation and Bis(trifluoromethanesulfonyl)imide anion.

    PubMed

    Martinelli, Anna; Matic, Aleksandar; Jacobsson, Per; Börjesson, Lars; Fernicola, Alessandra; Scrosati, Bruno

    2009-08-13

    The phase behavior and the ionic conductivity of ionic liquids (ILs) of the N-alkyl-N-alkylpyrrolidinium (PYR(xy)) cation and the bis(trifluoromethanesulfonyl)imide (TFSI) anion are investigated upon addition of LiTFSI salt. We compare the case of two new ILs of the PYR(2y) cation (where 2 is ethyl and y is butyl or propyl) with that of the PYR(14) (where 1 is methyl and 4 is butyl). We find that the addition of LiTFSI increases the glass transition temperature, decreases the melting temperature and the heat of fusion and, in the ILs of the PYR(2y) family, suppresses crystallization. In the solid state, significant ionic conductivities are found, being as high as 10(-5) S cm(-1), strongly increasing with Li(+) concentration. The opposite trend is found in the liquid state, where the conductivity is on the order of 10(-3)-10(-2) S cm(-1) at room temperature. A T(g)-scaled Arrhenius plot shows that the liquid-state ionic conductivity in these systems is mainly governed by viscosity and that the fragility of the liquids is slightly influenced by the structural modifications on the cation.

  3. Interface proximity effects on ionic conductivity in nanoscale oxide-ion conducting yttria stabilized zirconia: an atomistic simulation study.

    PubMed

    Sankaranarayanan, Subramanian K R S; Ramanathan, Shriram

    2011-02-14

    We present an atomistic simulation study on the size dependence of dopant distribution and the influence of nanoscale film thickness on carrier transport properties of the model oxide-ion conductor yttria stabilized zirconia (YSZ). Simulated amorphization and recrystallization approach was utilized to generate YSZ films with varying thicknesses (3-9 nm) on insulating MgO substrates. The atomic trajectories generated in the molecular dynamics simulations are used to study the structural evolution of the YSZ thin films and correlate the resulting microstructure with ionic transport properties at the nanoscale. The interfacial conductivity increases by 2 orders of magnitude as the YSZ film size decreases from 9 to 3 nm owing to a decrease in activation energy barrier from 0.54 to 0.35 eV in the 1200-2000 K temperature range. Analysis of dopant distribution indicates surface enrichment, the extent of which depends on the film thickness. The mechanisms of oxygen conductivity for the various film thicknesses at the nanoscale are discussed in detail and comparisons with experimental and other modeling studies are presented where possible. The study offers insights into mesoscopic ion conduction mechanisms in low-dimensional solid oxide electrolytes.

  4. Bombardment induced ion transport - part IV: ionic conductivity of ultra-thin polyelectrolyte multilayer films.

    PubMed

    Wesp, Veronika; Hermann, Matthias; Schäfer, Martin; Hühn, Jonas; Parak, Wolfgang J; Weitzel, Karl-Michael

    2016-02-14

    The dependence of the ionic conductance of ultra-thin polyelectrolyte multilayer (PEM) films on the temperature and the number of bilayers has been investigated by the recently developed low energy bombardment induced ion transport (BIIT) method. To this end multilayers of alternating poly(sodium 4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) layers were deposited on a metal electrode and subsequently bombarded by a low energy potassium ion beam. Ions are transported through the film according to the laws of electro-diffusion towards a grounded backside electrode. They are neutralized at the interface between the polymer film and the metal electrode. The detected neutralization current scales linearly with the acceleration potential of the ion beam indicating Ohmic behavior for the (PAH/PSS)x multilayer, where x denotes the number of bilayers. The conductance exhibits a non-monotonic dependence on the number of bilayers, x. For 2 ≤ x ≤ 8 the conductance increases non-linearly with the number of bilayers. For x ≥ 8 the conductance decreases with increasing number of bilayers. The variation of the conductance is rationalized by a model accounting for the structure dependence of the conductivity. The thinnest sample for which the conductance has been measured is the single bilayer reflecting properties dominated by the interface. The activation energy for the ion transport is 0.49 eV.

  5. Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

    PubMed

    Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

    2013-07-23

    Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

  6. Anomalous Electrical Conductivity Behavior at Elevated Pressure in the Protic Ionic Liquid Procainamide Hydrochloride

    NASA Astrophysics Data System (ADS)

    Wojnarowska, Z.; Roland, C. M.; Swiety-Pospiech, A.; Grzybowska, K.; Paluch, M.

    2012-01-01

    Using broadband dielectric spectroscopy, we investigated the effect of hydrostatic pressure on the conductivity relaxation time τσ of the supercooled protic ionic liquid, procainamide hydrochloride, a common pharmaceutical. The pressure dependence of τσ exhibited anomalous behavior in the vicinity of the glass transition Tg, manifested by abrupt changes in activation volume. This peculiar behavior, paralleling the change in temperature dependence of τσ near Tg, is a manifestation of the decoupling between electrical conductivity and structural relaxation. Although the latter effectively ceases in the glassy state, free ions retain their mobility but with a reduced sensitivity to thermodynamic changes. This is the first observation of decoupling of ion migration from structural relaxation in a glassy conductor by isothermal densification.

  7. Enhanced ionic conduction and disproportionation in pure CuCl at high pressure

    NASA Astrophysics Data System (ADS)

    Batlogg, B.; Remeika, J. P.; Maines, R. G.

    1981-04-01

    The optical and electrical properties of pure cuprous chloride (CuCl) single crystals have been studied under pressure up to 12 GPa. The transition pressures for the three crystallographic phases have been determined as 5.1 ± 0.1 GPa (ZnS → tetragonal) and 8.8 ± 0.4 GPa (tetrag.-NaCl). During the transition at 5.1 GPa, where the coordination number changes, the formation of cupric ions is observed. This is interpreted as a result of a partial, transient, and reversible disproportionation. In the ZnS and NaCl phase, an enhanced ionic conductivity is found following the first transformation into the tetragonal structure. The concentration of the mobile ions is typically 10 18 cm -3 and their diffusivity is ˜ 4×10 -7 cm 2s -1. An applied voltage in excess of 0.7 V causes anodic oxidation of Cu + which mimics much higher conductivity.

  8. Investigation of ionic conductivity of lanthanum cerium oxide nano crystalline powder synthesized by co precipitation method

    NASA Astrophysics Data System (ADS)

    Tinwala, Hozefa; Shah, Patij; Siddhapara, Kirit; Shah, Dimple; Menghani, Jyoti

    2016-10-01

    Lanthanum (La) doped Ceria (CeO2) electrolyte has attracted considerable interest, as a candidate material for solid oxide fuel cells (SOFCs). The ionic conductivity of La doped CeO2 system (La2Ce2O7) nano-particles synthesized by the co-precipitation method has been investigated. The cubic fluorite structure was observed from the structural analysis of the material. Morphology of the sintered pellets are observed by scanning electron microscope (SEM), respectively. From the results of impedance spectroscopy from temperature range of room temperature to 400 °C, the oxide ion conductivity due to proton charge carrier was observed. Thermogravimetric analysis (TGA) was performed on the material to check stability of phase at high temperature.

  9. Protein Kinase C Regulates Ionic Conductance in Hippocampal Pyramidal Neurons: Electrophysiological Effects of Phorbol Esters

    NASA Astrophysics Data System (ADS)

    Baraban, Jay M.; Snyder, Solomon H.; Alger, Bradley E.

    1985-04-01

    The vertebrate central nervous system contains very high concentrations of protein kinase C, a calcium-and phospholipid-stimulated phosphorylating enzyme. Phorbol esters, compounds with inflammatory and tumor-promoting properties, bind to and activate this enzyme. To clarify the role of protein kinase C in neuronal function, we have localized phorbol ester receptors in the rat hippocampus by autoradiography and examined the electrophysiological effects of phorbol esters on hippocampal pyramidal neurons in vitro. Phorbol esters blocked a calcium-dependent potassium conductance. In addition, phorbol esters blocked the late hyperpolarization elicited by synaptic stimulation even though other synaptic potentials were not affected. The potencies of several phorbol esters in exerting these actions paralleled their affinities for protein kinase C, suggesting that protein kinase C regulates membrane ionic conductance.

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

    SciTech Connect

    Dietrich, Christian; Sadowski, Marcel; Sicolo, Sabrina; Weber, Dominik A.; Sedlmaier, Stefan J.; Weldert, Kai S.; Indris, Sylvio; Albe, Karsten; Janek, Jürgen; Zeier, Wolfgang G.

    2016-12-13

    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 PS43–, P2S64–, and P2S74– 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 Li4P2S6. In this work, we show that the material crystallizes in a planar structural arrangement as 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.

  11. Parasitic Currents Caused by Different Ionic and Electronic Conductivities in Fuel Cell Anodes.

    PubMed

    Schalenbach, Maximilian; Zillgitt, Marcel; Maier, Wiebke; Stolten, Detlef

    2015-07-29

    The electrodes in fuel cells simultaneously realize electric and ionic conductivity. In the case of acidic polymer electrolytes, the electrodes are typically made of composites of carbon-supported catalyst and Nafion polymer electrolyte binder. In this study, the interaction of the proton conduction, the electron conduction, and the electrochemical hydrogen conversion in such composite electrode materials was examined. Exposed to a hydrogen atmosphere, these composites displayed up to 10-fold smaller resistivities for the proton conduction than that of Nafion membranes. This effect was ascribed to the simultaneously occurring electrochemical hydrogen oxidation and evolution inside the composite samples, which are driven by different proton and electron resistivities. The parasitic electrochemical currents resulting were postulated to occur in the anode of fuel cells with polymer, solid oxide, or liquid alkaline electrolytes, when the ohmic drop of the ion conduction in the anode is higher with the anodic kinetic overvoltage (as illustrated in the graphical abstract). In this case, the parasitic electrochemical currents increase the anodic kinetic overpotential and the ohmic drop in the anode. Thinner fuel cell anodes with smaller ohmic drops for the ion conduction may reduce the parasitic electrochemical currents.

  12. Syntheses, structures, and ionic conductivities of perovskite-structured lithium–strontium–aluminum/gallium–tantalum-oxides

    SciTech Connect

    Phraewphiphat, Thanya; Iqbal, Muhammad; Suzuki, Kota; Matsuda, Yasuaki; Yonemura, Masao; Hirayama, Masaaki; Kanno, Ryoji

    2015-05-15

    The ionic conductivities of new perovskite-structured lithium–strontium–aluminum/gallium–tantalum oxides were investigated. Solid solutions of the new perovskite oxides, (Li{sub x}Sr{sub 1−x})(Al{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3} and (Li{sub x}Sr{sub 1−x})(Ga{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3}, were synthesized using a ball-milled-assisted solid-state method. The partial substitution of the smaller Ga{sup +3} for Ta{sup +5} resulted in new compositions, the structures of which were determined by neutron diffraction measurements using a cubic perovskite structural model with the Pm−3m space group. Vacancies were introduced into the Sr(Li) sites by the formation of solid solutions with compositions (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}, where the composition range of 0≤y≤0.20 was examined for x=0.2 and 0.25. The highest conductivity, 1.85×10{sup −3} S cm{sup −1} at 250 °C, was obtained for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125). Enhanced ionic conductivities were achieved by the introduction of vacancies at the A-sites. - Graphical abstract: Novel lithium-conducting oxides with the cubic perovskite structure (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3} provide a specific solid-solution region with various x and y values, exhibiting the highest ionic conductivity (1.85 S cm{sup −1} at 250 °C) for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125 in (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}). The vacancies (☐) introduced into the A-sites contribute to the enhancement of lithium diffusion in the perovskite structure because of the enlargement of the bottleneck size and suppression of the interaction between lithium and oxygen. - Highlights: • The perovskite-structured novel Li

  13. AC and DC conductivity of ionic liquid containing polyvinylidene fluoride thin films

    NASA Astrophysics Data System (ADS)

    Frübing, Peter; Wang, Feipeng; Kühle, Till-Friedrich; Gerhard, Reimund

    2016-01-01

    Polarisation processes and charge transport in polyvinylidene fluoride (PVDF) with a small amount (0.01-10 wt%) of the ionic liquid (IL) 1-ethyl-3-methylimidazolium nitrate ({[EMIM]}^+[{NO}_3]^-) are investigated by means of dielectric spectroscopy. The response of PVDF that contains more than 0.01 wt% IL is dominated by a low-frequency relaxation which shows typical signatures of electrode polarisation. Furthermore, the α a relaxation, related to the glass transition, disappears for IL contents of more than 1 wt%, which indicates that the amorphous phase loses its glass-forming properties and undergoes structural changes. The DC conductivity is determined from the low-frequency limit of the AC conductivity and from the dielectric loss peak related to the electrode polarisation. DC conductivities of 10^{-10} to 10^{-2} {S}/{m} are obtained—increasing with IL content and temperature. The dependence of the DC conductivity on the IL content follows a power law with an exponent greater than one, indicating an increase in the ion mobility. The temperature dependence of the DC conductivity shows Vogel-Fulcher-Tammann behaviour, which implies that charge transport is coupled to polymer chain motion. Mobile ion densities and ion mobilities are calculated from the DC conductivity and the dielectric loss related to electrode polarisation, with the results that less than one per cent of the total ion concentration contributes to the conductivity and that the strong increase in conductivity with temperature is mainly caused by a strong increase in ion mobility. This leads to the conclusion that in particular the ion mobility must be reduced in order to decrease the DC conductivity.

  14. Tunable ionic-conductivity of collapsed Sandia octahedral molecular sieves (SOMS).

    SciTech Connect

    Pless, Jason; Nenoff, Tina Maria; Garino, Terry J.; Axness, Marlene

    2006-11-01

    This proposal focuses on the synthesis and characterization of ''tunable'' perovskite ceramics with resulting controlled strength and temperature of dielectric constants and/or with ionic conductivity. Traditional methods of synthesis involve high temperature oxide mixing and baking. We developed a new methodology of synthesis involving the (1) low temperature hydrothermal synthesis of metastable porous phases with ''tuned'' stoichiometry, and element types, and then (2) low temperature heat treatment to build exact stoichiometry perovskites, with the desired vacancy concentrations. This flexible pathway can lead to compositions and structures not attainable by conventional methods. During the course of this program, a series of Na-Nb perovskites were synthesized by calcining and collapsing microporous Sandia Octahedral Molecular Sieve (SOMS) phases. These materials were studied by various characterization techniques and conductivity measurements to better delineate stability and stoichiometry/bulk conductivity relationships. The conductivity can be altered by changing the concentration and type of the substituting framework cation(s) or by ion exchange of sodium. To date, the Na{sub 0.9}Mg{sub 0.1}Nb{sub 0.8}Ti{sub 0.2}O{sub 3-{delta}} shows the best conductivity.

  15. Phase Behavior and Conductivity of Phosphonated Block Copolymers Containing Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Jung, Ha Young; Kim, Sung Yeon; Park, Moon Jeong

    2015-03-01

    As the focus on proton exchange fuel cells continues to escalate in the era of alternative energy systems, the rational design of sulfonated polymers has emerged as a key technique for enhancing device efficiency. While the sulfonic acid group guarantees high proton conductivity of membranes under humidified conditions, the growing need for high temperature operation has discouraged their practical uses in fuel cells. In this respect, phosphonated polymers have drawn intensive attention in recent years owing to their self-dissociation ability. In this study, we have synthesized a set of phosphonated block copolymers, poly(styrenephosphonate-methylbutylene) (PSP- b - PMB), by varying phosphonation level (PL). A wide variety of self-assembled morphologies, i.e., disordered, lamellar, hexagonally perforated lamellae and hexagonally packed cylindrical phases, were observed with PL. Remarkably, upon comparing the morphology of PSP- b-PMB and that of sulfonated analog, we found distinctly dissimilar domain sizes at the same molecular weight and composition. A range of ionic liquids (ILs) were incorporated into the PSP- b-PMB block copolymers and their ion transport properties were examined. It has been revealed that the degree of confinement of ionic phases (domain size) impacts the ion mobility and proton dissociation efficiency of IL-containing polymers.

  16. Ammonium based ionic liquids immobilized in large pore zeolites: Encapsulation procedures and proton conduction performance

    NASA Astrophysics Data System (ADS)

    Eguizábal, A.; Lemus, J.; Urbiztondo, M.; Moschovi, A. M.; Ntais, S.; Soler, J.; Pina, M. P.

    Ammonium based ionic liquids immobilized in Y (FAU framework code) and beta (BEA framework code) type zeolites by different solution methods have been comprehensively characterized for their potential applications as hydrophilic-conducting fillers for PEM. In particular (2-hydroxymethyl) trimethylammonium dimethyl phosphate (IL1) and N,N-dimethyl-N-(2-hydroxyethyl) ammonium bis(trifluoromethanesulfonyl) imide (IL2) encapsulated into commercial NaY (Si/Al = 1.5) and NH 4-BEA (Si/Al = 12.5) type zeolites have been investigated. X-ray diffraction, N 2 physisorption, TGA analysis, ATR-FTIR and Raman spectroscopy techniques have been used to assess about the goodness of the encapsulation procedures. Finally, A.C. impedance spectroscopy measurements of tablets prepared from PVDF/composite (1:9 wt. ratio) were performed in order to evaluate their conduction properties. The conduction properties of the composites as a function of temperature and water partial pressure have been finally chosen as analytical tool to define the best encapsulation procedure and IL/Z composite for PEMFCs applications. A possible conduction mechanism, where synergic-inhibition effects between ILs and H 2O molecules coupled to IL dragging by water desorption take place, is also presented.

  17. Thermally conductive of nanofluid from surfactant doped polyaniline nanoparticle and deep eutectic ionic liquid

    NASA Astrophysics Data System (ADS)

    Siong, Chew Tze; Daik, Rusli; Hamid, Muhammad Azmi Abdul

    2014-09-01

    Nanofluid is a colloidal suspension of nano-size particles in a fluid. Spherical shape dodecylbenzenesulfonic acid doped polyaniline (DBSA-PANI) nanoparticles were synthesized via reverse micellar polymerization in isooctane with average size of 50 nm- 60 nm. The aim of study is to explore the possibility of using deep eutectic ionic liquid (DES) as a new base fluid in heat transfer application. DES was prepared by heating up choline chloride and urea with stirring. DES based nanofluids containing DBSA-PANI nanoparticles were prepared using two-step method. Thermal conductivity of nanofluids was measured using KD2 Pro Thermal Properties Analyzer. When incorporated with DBSA-PANI nanoparticles, DES with water was found to exhibit a bigger increase in thermal conductivity compared to that of the pure DES. The thermal conductivity of DES with water was increased by 4.67% when incorporated with 0.2 wt% of DBSA-PANI nanoparticles at 50°C. The enhancement in thermal conductivity of DES based nanofluids is possibly related to Brownian motion of nanoparticles as well as micro-convection of base fluids and also interaction between dopants and DES ions.

  18. Block copolymer with simultaneous electric and ionic conduction for use in lithium ion batteries

    DOEpatents

    Javier, Anna Esmeralda K; Balsara, Nitash Pervez; Patel, Shrayesh Naran; Hallinan, Jr., Daniel T

    2013-10-08

    Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.

  19. Conductive Hybrid Crystal Composed from Polyoxomolybdate and Deprotonatable Ionic-Liquid Surfactant.

    PubMed

    Kobayashi, Jun; Kawahara, Ryosuke; Uchida, Sayaka; Koguchi, Shinichi; Ito, Takeru

    2016-06-23

    A polyoxomolybdate inorganic-organic hybrid crystal was synthesized with deprotonatable ionic-liquid surfactant. 1-dodecylimidazolium cation was employed for its synthesis. The hybrid crystal contained δ-type octamolybdate (Mo₈) isomer, and possessed alternate stacking of Mo₈ monolayers and interdigitated surfactant bilayers. The crystal structure was compared with polyoxomolybdate hybrid crystals comprising 1-dodecyl-3-methylimidazolium surfactant, which preferred β-type Mo₈ isomer. The less bulky hydrophilic moiety of the 1-dodecylimidazolium interacted with the δ-Mo₈ anion by N-H···O hydrogen bonds, which presumably induced the formation of the δ-Mo₈ anion. Anhydrous conductivity of the hybrid crystal was estimated to be 5.5 × 10(-6) S·cm(-1) at 443 K by alternating current (AC) impedance spectroscopy.

  20. Conductive Hybrid Crystal Composed from Polyoxomolybdate and Deprotonatable Ionic-Liquid Surfactant

    PubMed Central

    Kobayashi, Jun; Kawahara, Ryosuke; Uchida, Sayaka; Koguchi, Shinichi; Ito, Takeru

    2016-01-01

    A polyoxomolybdate inorganic-organic hybrid crystal was synthesized with deprotonatable ionic-liquid surfactant. 1-dodecylimidazolium cation was employed for its synthesis. The hybrid crystal contained δ-type octamolybdate (Mo8) isomer, and possessed alternate stacking of Mo8 monolayers and interdigitated surfactant bilayers. The crystal structure was compared with polyoxomolybdate hybrid crystals comprising 1-dodecyl-3-methylimidazolium surfactant, which preferred β-type Mo8 isomer. The less bulky hydrophilic moiety of the 1-dodecylimidazolium interacted with the δ-Mo8 anion by N–H···O hydrogen bonds, which presumably induced the formation of the δ-Mo8 anion. Anhydrous conductivity of the hybrid crystal was estimated to be 5.5 × 10−6 S·cm−1 at 443 K by alternating current (AC) impedance spectroscopy. PMID:27347926

  1. Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties

    DOEpatents

    Mackay, Richard; Sammells, Anthony F.

    2000-01-01

    Ceramics of the composition: Ln.sub.x Sr.sub.2-x-y Ca.sub.y B.sub.z M.sub.2-z O.sub.5+.delta. where Ln is an element selected from the fblock lanthanide elements and yttrium or mixtures thereof; B is an element selected from Al, Ga, In or mixtures thereof; M is a d-block transition element of mixtures thereof; 0.01.ltoreq.x.ltoreq.1.0; 0.01.ltoreq.y.ltoreq.0.7; 0.01.ltoreq.z.ltoreq.1.0 and .delta. is a number that varies to maintain charge neutrality are provided. These ceramics are useful in ceramic membranes and exhibit high ionic conductivity, high chemical stability under catalytic membrane reactor conditions and low coefficients of expansion. The materials of the invention are particularly useful in producing synthesis gas.

  2. Three-dimensional ionic conduction in the strained electrolytes of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Han, Yupei; Zou, Minda; Lv, Weiqiang; Mao, Yiwu; Wang, Wei; He, Weidong

    2016-05-01

    Flexible power sources including fuel cells and batteries are the key to realizing flexible electronic devices with pronounced foldability. To understand the bending effects in these devices, theoretical analysis on three-dimensional (3-D) lattice bending is necessary. In this report, we derive a 3-D analytical model to analyze the effects of electrolyte crystal bending on ionic conductivity in flexible solid-state batteries/fuel cells. By employing solid oxide fuel cells as a materials' platform, the intrinsic parameters of bent electrolyte materials, including lattice constant, Young's modulus, and Poisson ratio, are evaluated. Our work facilitates the rational design of highly efficient flexible electrolytes for high-performance flexible device applications.

  3. Relationships between resting conductances, excitability, and t-system ionic homeostasis in skeletal muscle.

    PubMed

    Fraser, James A; Huang, Christopher L-H; Pedersen, Thomas H

    2011-07-01

    Activation of skeletal muscle fibers requires rapid sarcolemmal action potential (AP) conduction to ensure uniform excitation along the fiber length, as well as successful tubular excitation to initiate excitation-contraction coupling. In our companion paper in this issue, Pedersen et al. (2011. J. Gen. Physiol. doi:10.1085/jgp.201010510) quantify, for subthreshold stimuli, the influence upon both surface conduction velocity and tubular (t)-system excitation of the large changes in resting membrane conductance (G(M)) that occur during repetitive AP firing. The present work extends the analysis by developing a multi-compartment modification of the charge-difference model of Fraser and Huang to provide a quantitative description of the conduction velocity of actively propagated APs; the influence of voltage-gated ion channels within the t-system; the influence of t-system APs on ionic homeostasis within the t-system; the influence of t-system ion concentration changes on membrane potentials; and the influence of Phase I and Phase II G(M) changes on these relationships. Passive conduction properties of the novel model agreed with established linear circuit analysis and previous experimental results, while key simulations of AP firing were tested against focused experimental microelectrode measurements of membrane potential. This study thereby first quantified the effects of the t-system luminal resistance and voltage-gated Na(+) channel density on surface AP propagation and the resultant electrical response of the t-system. Second, it demonstrated the influence of G(M) changes during repetitive AP firing upon surface and t-system excitability. Third, it showed that significant K(+) accumulation occurs within the t-system during repetitive AP firing and produces a baseline depolarization of the surface membrane potential. Finally, it indicated that G(M) changes during repetitive AP firing significantly influence both t-system K(+) accumulation and its influence on the

  4. Enhancing oxygen transport through Mixed-Ionic-and-Electronic-Conducting ceramic membranes

    NASA Astrophysics Data System (ADS)

    Yu, Anthony S.

    Ceramic membranes based on Mixed-Ionic-and-Electronic-Conducting (MIEC) oxides are capable of separating oxygen from air in the presence of an oxygen partial-pressure gradient. These MIEC membranes show great promise for oxygen consuming industrial processes, such as the production of syngas from steam reforming of natural gas (SRM), as well as for electricity generation in Solid Oxide Fuel Cells (SOFC). For both applications, the overall performance is dictated by the rate of oxygen transport across the membrane. Oxygen transport across MIEC membranes is composed of a bulk oxygen-ion diffusion process and surface processes, such as surface reactions and adsorption/desorption of gaseous reactants/products. The main goal of this thesis was to determine which process is rate-limiting in order to significantly enhance the overall rate of oxygen transport in MIEC membrane systems. The rate-limiting step was determined by evaluating the total resistance to oxygen transfer, Rtot. Rtot is the sum of a bulk diffusion resistance in the membrane itself, Rb, and interfacial loss components, Rs. Rb is a function of the membrane's ionic conductivity and thickness, while Rs arises primarily from slow surface-exchange kinetics that cause the P(O2) at the surfaces of the membrane to differ from the P(O 2) in the adjacent gas phases. Rtot can be calculated from the Nernst potential across the membrane and the measured oxygen flux. The rate-limiting process can be determined by evaluating the relative contributions of the various losses, Rs and Rb, to Rtot. Using this method, this thesis demonstrates that for most membrane systems, Rs is the dominating factor. In the development of membrane systems with high oxygen transport rates, thin membranes with high ionic conductivities are required to achieve fast bulk oxygen-ion diffusion. However, as membrane thickness is decreased, surface reaction kinetics become more important in determining the overall transport rate. The two

  5. Tunable Mixed Ionic/Electronic Conductivity and Permittivity of Graphene Oxide Paper for Electrochemical Energy Conversion.

    PubMed

    Bayer, Thomas; Bishop, Sean R; Perry, Nicola H; Sasaki, Kazunari; Lyth, Stephen M

    2016-05-11

    Graphene oxide (GO) is a two-dimensional graphitic carbon material functionalized with oxygen-containing surface functional groups. The material is of interest in energy conversion, sensing, chemical processing, gas barrier, and electronics applications. Multilayer GO paper has recently been applied as a new proton conducting membrane in low temperature fuel cells. However, a detailed understanding of the electrical/dielectric properties, including separation of the ionic vs electronic contributions under relevant operating conditions, has so far been lacking. Here, the electrical conductivity and dielectric permittivity of GO paper are investigated in situ from 30 to 120 °C, and from 0 to 100% relative humidity (RH) using impedance spectroscopy. These are related to the water content, measured by thermogravimetric analysis. With the aid of electron blocking measurements, GO is demonstrated to be a mixed electronic-protonic conductor, and the ion transference number is derived for the first time. For RH > 40%, conductivity is dominated by proton transport (with a maximum of 0.5 mS/cm at 90 °C and 100% RH). For RH < 40%, electronic conductivity dominates (with a maximum of 7.4 mS/cm at ∼80 °C and 0% RH). The relative permittivity of GO paper increases with decreasing humidity, from ∼10 at 100% RH to several 1000 at 10% RH. These results underline the potential of GO for application not only as a proton conducting electrolyte but also as a mixed conducting electrode material under appropriate conditions. Such materials are highly applicable in electrochemical energy conversion and storage devices such as fuel cells and electrolyzers.

  6. Ionic Conductivity of Poly(ethylene oxide)-Containing Block Copolymers at Order-Disorder and Order-Order Transitions

    NASA Astrophysics Data System (ADS)

    Wanakule, Nisita; Panday, Ashoutosh; Mullin, Scott; Balsara, Nitash

    2009-03-01

    The order-disorder transition (ODT) and order-order transition (OOT) of block copolymers with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salts are measured with a combination of small-angle x-ray scattering (SAXS) and birefringence. The block copolymers comprise of polyethylene oxide (PEO), a polymer with a higher dielectric constant that dissolves LiTFSI, and polystyrene (PS), a polymer with a lower dielectric constant that does not dissolve LiTFSI. Ionic conductivity of the block copolymers are measured through the observed ODT and OOT. The effect of morphology on the ionic conductivity will be presented and compared with literature results.

  7. Ionic conductivity of dual-phase polymer electrolytes comprised of NBR/SBR latex films swollen with lithium salt solutions

    SciTech Connect

    Matsumoto, Morihiko; Ichino, Toshihiro; Rutt, J.S.; Nishi, Shiro . NTT Interdisciplinary Research Lab.)

    1994-08-01

    Dual-phase polymer electrolytes (DPE) with high ionic conductivity and good mechanical strength were prepared by swelling poly(acrylonitrile-co-butadiene) rubber (NBR) and poly(styrene-co-butadiene) rubber (SBR) mixed latex films with lithium salt solutions (e.g., 1M LiClO[sub 4]/[gamma]-butyrolactone). The latex films retain particle morphology in the solid state. The NBR phase (formed from fused NBR latex particles) is polar and is impregnated selectively with polar lithium salt solutions, yielding ion-conductive channels, whereas the SBR phase (formed from fused SBR latex particles) is nonpolar and is not impregnated, providing a mechanically supportive matrix. The ionic conductivity of the DPE increased dramatically with increasing content of lithium salt solution, and higher amounts of solution were imbibed with increasing content of NBR relative to SBR. Several factors which affect the ionic conductivity of this system were examined, and the highest ionic conductivity (>10[sup [minus]3] S/cm) was obtained when either an NBR/SBR 70/30 (w/w) or a 50/50 (w/w) latex film was saturated with 1M LiClO[sub 4]/[gamma]-BL solution or 1M LiClO[sub 4]/[gamma]-BL/DME solution. Ion-conductive behavior changed critically with increasing lithium salt solution uptake. At low levels of lithium salt solution uptake, evidence suggested that ionic conductivity of the absorbed lithium salt solution was strongly influenced by the presence of the NBR in the ion-conductive channel, but at higher levels, the effects of the NBR were reduced and free'' lithium salt solution was present.

  8. Structure and ionic conductivity of well-aligned polycrystalline sodium titanogallate grown by reactive diffusion

    SciTech Connect

    Hasegawa, Ryo; Okabe, Momoko; Asaka, Toru; Ishizawa, Nobuo; Fukuda, Koichiro

    2015-09-15

    We prepared the b-axis-oriented polycrystalline Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} (NTGO) embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix using the reactive diffusion technique. When the sandwich-type Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5} diffusion couple was heated at 1323 K for 24 h, the NTGO polycrystal was readily formed in the presence of a liquid phase. The resulting polycrystalline material was characterized by X-ray diffractometry, electron microscopy and impedance spectroscopy. We mechanically processed the annealed diffusion couple and obtained the thin-plate electrolyte consisting mostly of the grain-aligned NTGO polycrystal. The ionic conductivity (σ) of the electrolyte along the common b-axis direction steadily increased from 1.3×10{sup −4} to 7.3×10{sup −3} S/cm as the temperature increased from 573 to 1073 K. There was a slope change at ca. 792 K for the Arrhenius plot of σ; the activation energies were 0.39 eV above this temperature and 0.57 eV below it. The NTGO showed the crystal structure (space group C2/m) with substantial positional disordering of one of the two Ga sites. The Na{sup +} ions occupied ca. 43% of the Wyckoff position 4i site, the deficiency of which would contribute to the relatively high ionic conductivity along the b-axis. The reactive diffusion could be widely applicable as the novel technique to the preparation of grain-aligned ceramics of multi-component systems. - Graphical abstract: We have prepared the b-axis-oriented Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} polycrystal embedded in Ga{sub 2}O{sub 3}-doped Na{sub 2}Ti{sub 4}O{sub 9} matrix by the heat treatment of sandwich-type diffusion couple of Ga{sub 2}TiO{sub 5}/NaGaO{sub 2}/Ga{sub 2}TiO{sub 5}. The resulting Na{sub 0.85}Ti{sub 0.51}Ga{sub 4.37}O{sub 8} electrolyte showed the ionic conductivity ranging from 1.3×10{sup −4} S/cm at 573 K to 7.3×10{sup −3} S/cm at 1073 K. - Highlights: • The b

  9. Mixed-Salt Effects on the Ionic Conductivity of Lithium-Doped PEO-Containing Block Copolymers

    SciTech Connect

    Young, Wen-Shiue; Albert, Julie N.L.; Schantz, A. Benjamin; Epps, III, Thomas H.

    2012-10-10

    We demonstrate a simple, yet effective, mixed-salt method to increase the room temperature ionic conductivity of lithium-doped block copolymer electrolyte membranes by suppressing the crystalline phases in the conducting block. We examined a mixed-salt system of LiClO{sub 4} and LiN(SO{sub 2}CF{sub 3}){sub 2} (LiTFSI) doped into a lamellae-forming poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymer. The domain spacings, morphologies, thermal behavior, and crystalline phases of salt-doped PS-PEO samples were characterized, and the ionic conductivities of block copolymer electrolytes were obtained through ac impedance measurements. Comparing the ionic conductivity profiles of salt-doped PS-PEO samples at different mixed-salt ratios and total salt concentrations, we found that the ionic conductivity at room temperature can be improved by more than an order of magnitude when coinhibition of crystallite growth is promoted by the concerted behavior of the PEO:LiClO{sub 4} and PEO:LiTFSI phases. Additionally, we examined the influence of mixed-salt ratio and total salt concentration on copolymer energetics, and we found that the slope of the effective interaction parameter ({chi}{sub eff}) vs salt concentration in our lamellae-forming PS-PEO system was lower than that reported for a cylinder-forming PS-PEO system due to the balance between chain stretching and salt segregation in the PEO domains.

  10. Mixed-salt Effects on the Ionic Conductivity of Lithium-doped PEO-containing Block Copolymers

    SciTech Connect

    W Young; J Albert; A Schantz; T Epps

    2011-12-31

    We demonstrate a simple, yet effective, mixed-salt method to increase the room temperature ionic conductivity of lithium-doped block copolymer electrolyte membranes by suppressing the crystalline phases in the conducting block. We examined a mixed-salt system of LiClO{sub 4} and LiN(SO{sub 2}CF{sub 3}){sub 2} (LiTFSI) doped into a lamellae-forming poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymer. The domain spacings, morphologies, thermal behavior, and crystalline phases of salt-doped PS-PEO samples were characterized, and the ionic conductivities of block copolymer electrolytes were obtained through ac impedance measurements. Comparing the ionic conductivity profiles of salt-doped PS-PEO samples at different mixed-salt ratios and total salt concentrations, we found that the ionic conductivity at room temperature can be improved by more than an order of magnitude when coinhibition of crystallite growth is promoted by the concerted behavior of the PEO:LiClO{sub 4} and PEO:LiTFSI phases. Additionally, we examined the influence of mixed-salt ratio and total salt concentration on copolymer energetics, and we found that the slope of the effective interaction parameter (x{sub eff}) vs salt concentration in our lamellae-forming PS-PEO system was lower than that reported for a cylinder-forming PS-PEO system due to the balance between chain stretching and salt segregation in the PEO domains.

  11. Enhanced ionic conductivity of apatite-type lanthanum silicate electrolyte for IT-SOFCs through copper doping

    NASA Astrophysics Data System (ADS)

    Ding, Xifeng; Hua, Guixiang; Ding, Dong; Zhu, Wenliang; Wang, Hongjin

    2016-02-01

    Apatite-type Lanthanum silicate (LSO) is among the most promising electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs) owing to the high conductivity and low activation energy at lower temperature than traditional doped-zirconia electrolyte. The ionic conductivity as well as the sintering density of lanthanum silicate oxy-apatite, La10Si6-xCuxO27-δ (LSCO, 0 ≤ x ≤ 2), was effectively enhanced through a small amount of doped copper. The phase composition, relative density, ionic conductivity and thermal expansion behavior of La10Si6-xCuxO27-δ was systematically investigated by X-ray diffraction (XRD), Archimedes' drainage method, scanning electron microscope (SEM), electrochemical impedance spectra (EIS) and thermal dilatometer techniques. With increasing copper doping content, the ionic conductivity of La10Si6-xCuxO27-δincreased, reaching a maximum of 4.8 × 10-2 S cm-1 at 800 °C for x = 1.5. The improved ionic conductivity could be primarily associated with the enhanced grain conductivity. The power output performance of NiO-LSCO/LSCO/LSCF single cell was superior to that obtained on NiO-LSO/LSO/LSCF at different temperatures using hydrogen as fuel and oxygen as oxidant, which could be attributed to the enhanced oxygen ionic conductivity as well as the sintering density for the copped doped lanthanum silicate. In conclusion, the apatite La10Si4.5Cu1.5O25.5 is a promising candidate electrolyte for IT-SOFCs.

  12. Defect Physics, Delithiation Mechanism, and Electronic and Ionic Conduction in Layered Lithium Manganese Oxide Cathode Materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang

    2015-02-01

    Layered Li Mn O2 and Li2Mn O3 are of great interest for lithium-ion battery cathodes because of their high theoretical capacities. The practical application of these materials is, however, limited due to poor electrochemical performance. We herein report a comprehensive first-principles study of defect physics in Li Mn O2 and Li2Mn O3 using hybrid density-functional calculations. We find that manganese antisites have low formation energies in Li Mn O2 and may act as nucleation sites for the formation of impurity phases. The antisites can also occur with high concentrations in Li2Mn O3 ; however, unlike in Li Mn O2 , they can be eliminated by tuning the experimental conditions during preparation. Other intrinsic point defects may also occur and have an impact on the materials' properties and functioning. An analysis of the formation of lithium vacancies indicates that lithium extraction from Li Mn O2 is associated with oxidation at the manganese site, resulting in the formation of manganese small hole polarons; whereas in Li2Mn O3 the intrinsic delithiation mechanism involves oxidation at the oxygen site, leading to the formation of bound oxygen hole polarons ηO+ . The layered oxides are found to have no or negligible bandlike carriers, and they cannot be doped n or p type. The electronic conduction proceeds through hopping of hole and/or electron polarons; the ionic conduction occurs through lithium monovacancy and/or divacancy migration mechanisms. Since ηO+ is not stable in the absence of negatively charged lithium vacancies in bulk Li2Mn O3 , the electronic conduction near the start of delithiation is likely to be poor. We suggest that the electronic conduction associated with ηO+ and, hence, the electrochemical performance of Li2Mn O3 can be improved through nanostructuring and/or ion substitution.

  13. Ionic-liquid-based proton conducting membranes for anhydrous H2/Cl2 fuel-cell applications.

    PubMed

    Liu, Sa; Zhou, Li; Wang, Pengjie; Zhang, Fangfang; Yu, Shuchun; Shao, Zhigang; Yi, Baolian

    2014-03-12

    An ionic-liquid-doped poly(benzimidazole) (PBI) proton-conducting membrane for an anhydrous H2/Cl2 fuel cell has been proposed. Compared with other ionic liquids, such as imidazole-type ionic liquids, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) showed better electrode reaction kinetics (H2 oxidation and Cl2 reduction reaction at platinum) and was more suitable for a H2/Cl2 fuel cell. PBI polymer and [dema][TfO] were compatible with each other, and the hybrid membranes exhibited high stability and good ionic conductivity, reaching 20.73 mS cm(-1) at 160 °C. We also analyzed the proton-transfer mechanism in this ionic-liquid-based membrane and considered that both proton-hopping and diffusion mechanisms existed. In addition, this composite electrolyte worked well in a H2/Cl2 fuel cell under non-water conditions. This work would give a good path to study the novel membranes for anhydrous H2/Cl2 fuel-cell application.

  14. 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.

  15. Elucidating interactions and conductivity of newly synthesised low bandgap polymer with protic and aprotic ionic liquids.

    PubMed

    Attri, Pankaj; Lee, Seung-Hyun; Hwang, Sun Woo; Kim, Joong I L; Lee, Sang Woo; Kwon, Gi-Chung; Choi, Eun Ha; Kim, In Tae

    2013-01-01

    In this paper, we have examined the conductivity and interaction studies of ammonium and imidazolium based ionic liquids (ILs) with the newly synthesised low bandgap polymer (Poly(2-heptadecyl-4-vinylthieno[3,4-d]thiazole) (PHVTT)). Use of low bandgap polymers is the most suitable way to harvest a broader spectrum of solar radiations for solar cells. But, still there is lack of most efficient low bandgap polymer. In order to solve this problem, we have synthesised a new low bandgap polymer and investigated its interaction with the ILs to enhance its conductivity. ILs may undergo almost unlimited structural variations; these structural variations have attracted extensive attention in polymer studies. The aim of present work is to illustrate the state of art progress of implementing the interaction of ILs (protic and aprotic ILs) with newly synthesised low bandgap polymer. In addition to this, our UV-Vis spectroscopy, confocal Raman spectroscopy and FT-IR spectroscopy results have revealed that all studied ILs (tributylmethylammonium methyl sulfate ([N1444][MeSO4] from ammonium family) and 1-methylimidazolium chloride ([Mim]Cl, and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl from imidazolium family) have potential to interact with polymer. Our semi empirical calculation with help of Hyperchem 7 shows that protic IL ([Mim]Cl) interacts strongly with the low bandgap polymer through the H-bonding. Further, protic ILs shows enhanced conductivity than aprotic ILs in association with low bandgap polymer. This study provides the combined effect of low bandgap polymer and ILs that may generate many theoretical and experimental opportunities.

  16. Mixed ionic and electronic conducting electrode studies for an alkali metal thermal to electric converter

    NASA Astrophysics Data System (ADS)

    Guo, Yuyan

    This research focuses on preparation, kinetics, and performance studies of mixed ionic and electronic conducting electrodes (MIEE) applied in an alkali metal thermal to electric converter (AMTEC). Two types of MIEE, metal/sodium titanate and metal/beta″-alumina were investigated, using Ni, Cu, Co and W as the metal components. Pure metal electrodes (PME) were also studied, including Ta, Ni, Nb, Ir, W and MoRe electrodes. The stability of MIEE/beta″-alumina solid electrolyte (BASE) interface was studied in terms of the chemical potential of Na-Al-Ti-O system at 1100K (typical AMTEC operating temperature). Ni metal was compatible with sodium titanate and BASE and displayed the best initial performance among all tested PMEs. Ni/sodium titanate electrodes with 4/1 mass ratios of metal/ceramic performed best among all tested electrodes. Scanning Electron Microscope (SEM) observations showed that grain agglomeration, which is the main mechanism for electrode degradation, occurred in all tested electrodes. Ceramic components were able to effectively limit the growth of metal grains and resulted in a long lifetime for MIEEs. Ni particles in the MIEE formed a network microstructure that was close to the theoretical morphology of the ideal electrode. A model based on percolation theory was constructed to interpret and predict the performance of MIEEs. The electrode kinetics was studied and a theoretical expression for the interface impedance was derived for both PME and MIEE, using electrochemical impedance spectroscopy (EIS). The conductivity of the Na2Ti 3O7 and Na2Ti6O13 mixture was measured. The average activation energy for the bulk conductivity was 0.87ev. Finally, theoretical analysis clarified that the transfer coefficient alpha value change would cause at most a few percent change in the electrode performance parameter B.

  17. Elucidating Interactions and Conductivity of Newly Synthesised Low Bandgap Polymer with Protic and Aprotic Ionic Liquids

    PubMed Central

    Attri, Pankaj; Lee, Seung-Hyun; Hwang, Sun Woo; Kim, Joong I. L.; Lee, Sang Woo; Kwon, Gi-Chung; Choi, Eun Ha; Kim, In Tae

    2013-01-01

    In this paper, we have examined the conductivity and interaction studies of ammonium and imidazolium based ionic liquids (ILs) with the newly synthesised low bandgap polymer (Poly(2-heptadecyl-4-vinylthieno[3,4-d]thiazole) (PHVTT)). Use of low bandgap polymers is the most suitable way to harvest a broader spectrum of solar radiations for solar cells. But, still there is lack of most efficient low bandgap polymer. In order to solve this problem, we have synthesised a new low bandgap polymer and investigated its interaction with the ILs to enhance its conductivity. ILs may undergo almost unlimited structural variations; these structural variations have attracted extensive attention in polymer studies. The aim of present work is to illustrate the state of art progress of implementing the interaction of ILs (protic and aprotic ILs) with newly synthesised low bandgap polymer. In addition to this, our UV-Vis spectroscopy, confocal Raman spectroscopy and FT-IR spectroscopy results have revealed that all studied ILs (tributylmethylammonium methyl sulfate ([N1444][MeSO4] from ammonium family) and 1-methylimidazolium chloride ([Mim]Cl, and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl from imidazolium family) have potential to interact with polymer. Our semi empirical calculation with help of Hyperchem 7 shows that protic IL ([Mim]Cl) interacts strongly with the low bandgap polymer through the H-bonding. Further, protic ILs shows enhanced conductivity than aprotic ILs in association with low bandgap polymer. This study provides the combined effect of low bandgap polymer and ILs that may generate many theoretical and experimental opportunities. PMID:23874829

  18. Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction.

    PubMed

    Young, Joshua A; Zhang, Cheng; Devasurendra, Amila M; Tillekeratne, L M Viranga; Anderson, Jared L; Kirchhoff, Jon R

    2016-03-03

    Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-)) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C6MIm][NTf2]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME.

  19. Microscopic derivation of the Hubbard-Onsager-Zwanzig expression of limiting ionic conductivity

    NASA Astrophysics Data System (ADS)

    Bagchi, Biman

    1998-09-01

    An outstanding problem in the theory of ionic conductivity is a derivation of the well-known Hubbard-Onsager-Zwanzig expression for the dielectric friction on an ion from first principles. In fact, microscopic theories have repeatedly failed to reproduce the Hubbard-Onsager-Zwanzig expression under any limiting conditions. We show in this article that the existing molecular theories and the continuum model treatments calculate two entirely different contributions to the friction on the ion. While the former calculates the contribution from the solvent density mode alone, the latter includes only the contribution from the current mode. Thus the existing molecular theories can never be reduced to the Hubbard-Onsager (H-O) theory. In addition, we show that the existing molecular theories become inconsistent for larger ions where the H-O theory is accurate. The reverse is true for smaller ions. An expression is derived here which is valid at both the limits and for all ion sizes and its consequences discussed.

  20. Electrochemical fields within 3D reconstructed microstructures of mixed ionic and electronic conducting devices

    NASA Astrophysics Data System (ADS)

    Zhang, Yanxiang; Chen, Yu; Lin, Ye; Yan, Mufu; Harris, William M.; Chiu, Wilson K. S.; Ni, Meng; Chen, Fanglin

    2016-11-01

    The performance and stability of the mixed ionic and electronic conducting (MIEC) membrane devices, such as solid oxide cells (SOCs) and oxygen separation membranes (OSMs) interplay tightly with the transport properties and the three-dimensional (3D) microstructure of the membrane. However, development of the MIEC devices is hindered by the limited knowledge about the distribution of electrochemical fields within the 3D local microstructures, especially at surface and interface. In this work, a generic model conforming to local thermodynamic equilibrium is developed to calculate the electrochemical fields, such as electric potential and oxygen chemical potential, within the 3D microstructure of the MIEC membrane. Stability of the MIEC membrane is evaluated by the distribution of oxygen partial pressure. The cell-level performance such as polarization resistance and voltage vs. current curve can be further calculated. Case studies are performed to demonstrate the capability of the framework by using X-ray computed tomography reconstructed 3D microstructures of a SOC and an OSM. The calculation method demonstrates high computational efficiency for large size 3D tomographic microstructures, and permits parallel calculation. The framework can serve as a powerful tool for correlating the transport properties and the 3D microstructure to the performance and the stability of MIEC devices.

  1. Electrical conductivity and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

    NASA Astrophysics Data System (ADS)

    Sangoro, J.; Iacob, C.; Serghei, A.; Naumov, S.; Galvosas, P.; Kärger, J.; Wespe, C.; Bordusa, F.; Stoppa, A.; Hunger, J.; Buchner, R.; Kremer, F.

    2008-06-01

    Broadband dielectric and terahertz spectroscopy (10-2-10+12 Hz) are combined with pulsed field gradient nuclear magnetic resonance (PFG-NMR) to explore charge transport and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. The dielectric spectra are interpreted as superposition of high-frequency relaxation processes associated with dipolar librations and a conductivity contribution. The latter originates from hopping of charge carriers on a random spatially varying potential landscape and quantitatively fits the observed frequency and temperature dependence of the spectra. A further analysis delivers the hopping rate and enables one to deduce-using the Einstein-Smoluchowski equation-the translational diffusion coefficient of the charge carriers in quantitative agreement with PFG-NMR measurements. By that, the mobility is determined and separated from the charge carrier density; for the former, a Vogel-Fulcher-Tammann and for the latter, an Arrhenius temperature dependence is obtained. There is no indication of a mode arising from the reorientation of stable ion pairs.

  2. 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.

  3. Mixed ionic and electronic conducting membranes for hydrogen generation and separation

    NASA Astrophysics Data System (ADS)

    Cui, Hengdong

    Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process

  4. Structural and Ionic Transport Properties of Protonic Conducting Solid Biopolymer Electrolytes Based on Carboxymethyl Cellulose Doped with Ammonium Fluoride.

    PubMed

    Ramlli, M A; Isa, M I N

    2016-11-10

    Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and transference number measurement (TNM) techniques were applied to investigate the complexation, structural, and ionic transport properties of and the dominant charge-carrier species in a solid biopolymer electrolyte (SBE) system based on carboxymethyl cellulose (CMC) doped with ammonium fluoride (NH4F), which was prepared via a solution casting technique. The SBEs were partially opaque in appearance, with no phase separation. The presence of interactions between the host polymer (CMC) and the ionic dopant (NH4F) was proven by FT-IR analysis at the C-O band. XRD spectra analyzed using Origin 8 software disclose that the degree of crystallinity (χc%) of the SBEs decreased with the addition of NH4F, indicating an increase in the amorphous nature of the SBEs. Analysis of the ionic transport properties reveals that the ionic conductivity of the SBEs is dependent on the ionic mobility (μ) and diffusion of ions (D). TNM analysis confirms that the SBEs are proton conductors.

  5. Gold-ionic liquid nanofluids with preferably tribological properties and thermal conductivity

    NASA Astrophysics Data System (ADS)

    Wang, Baogang; Wang, Xiaobo; Lou, Wenjing; Hao, Jingcheng

    2011-12-01

    Gold/1-butyl-3-methylimidazolium hexafluorophosphate (Au/[Bmim][PF6]) nanofluids containing different stabilizing agents were fabricated by a facile one-step chemical reduction method, of which the nanofluids stabilized by cetyltrimethylammonium bromide (CTABr) exhibited ultrahighly thermodynamic stability. The transmission electron microscopy, UV-visible absorption, Fourier transform infrared, and X-ray photoelectron characterizations were conducted to reveal the stable mechanism. Then, the tribological properties of these ionic liquid (IL)-based gold nanofluids were first investigated in more detail. In comparison with pure [Bmim][PF6] and the nanofluids possessing poor stability, the nanofluids with high stability exhibited much better friction-reduction and anti-wear properties. For instance, the friction coefficient and wear volume lubricated by the nanofluid with rather low volumetric concentration (1.02 × 10-3%) stabilized by CTABr under 800 N are 13.8 and 45.4% lower than that of pure [Bmim][PF6], confirming that soft Au nanoparticles (Au NPs) also can be excellent additives for high performance lubricants especially under high loads. Moreover, the thermal conductivity (TC) of the stable nanofluids with three volumetric fraction (2.55 × 10-4, 5.1 × 10-4, and 1.02 × 10-3%) was also measured by a transient hot wire method as a function of temperature (33 to 81°C). The results indicate that the TC of the nanofluid (1.02 × 10-3%) is 13.1% higher than that of [Bmim][PF6] at 81°C but no obvious variation at 33°C. The conspicuously temperature-dependent and greatly enhanced TC of Au/[Bmim][PF6] nanofluids stabilized by CTABr could be attributed to micro-convection caused by the Brownian motion of Au NPs. Our results should open new avenues to utilize Au NPs and ILs in tribology and the high-temperature heat transfer field.

  6. Gold-ionic liquid nanofluids with preferably tribological properties and thermal conductivity.

    PubMed

    Wang, Baogang; Wang, Xiaobo; Lou, Wenjing; Hao, Jingcheng

    2011-03-28

    Gold/1-butyl-3-methylimidazolium hexafluorophosphate (Au/[Bmim][PF6]) nanofluids containing different stabilizing agents were fabricated by a facile one-step chemical reduction method, of which the nanofluids stabilized by cetyltrimethylammonium bromide (CTABr) exhibited ultrahighly thermodynamic stability. The transmission electron microscopy, UV-visible absorption, Fourier transform infrared, and X-ray photoelectron characterizations were conducted to reveal the stable mechanism. Then, the tribological properties of these ionic liquid (IL)-based gold nanofluids were first investigated in more detail. In comparison with pure [Bmim][PF6] and the nanofluids possessing poor stability, the nanofluids with high stability exhibited much better friction-reduction and anti-wear properties. For instance, the friction coefficient and wear volume lubricated by the nanofluid with rather low volumetric concentration (1.02 × 10-3%) stabilized by CTABr under 800 N are 13.8 and 45.4% lower than that of pure [Bmim][PF6], confirming that soft Au nanoparticles (Au NPs) also can be excellent additives for high performance lubricants especially under high loads. Moreover, the thermal conductivity (TC) of the stable nanofluids with three volumetric fraction (2.55 × 10-4, 5.1 × 10-4, and 1.02 × 10-3%) was also measured by a transient hot wire method as a function of temperature (33 to 81°C). The results indicate that the TC of the nanofluid (1.02 × 10-3%) is 13.1% higher than that of [Bmim][PF6] at 81°C but no obvious variation at 33°C. The conspicuously temperature-dependent and greatly enhanced TC of Au/[Bmim][PF6] nanofluids stabilized by CTABr could be attributed to micro-convection caused by the Brownian motion of Au NPs. Our results should open new avenues to utilize Au NPs and ILs in tribology and the high-temperature heat transfer field.

  7. Imaging alpha-hemolysin with molecular dynamics: ionic conductance, osmotic permeability, and the electrostatic potential map.

    PubMed

    Aksimentiev, Aleksij; Schulten, Klaus

    2005-06-01

    alpha-Hemolysin of Staphylococcus aureus is a self-assembling toxin that forms a water-filled transmembrane channel upon oligomerization in a lipid membrane. Apart from being one of the best-studied toxins of bacterial origin, alpha-hemolysin is the principal component in several biotechnological applications, including systems for controlled delivery of small solutes across lipid membranes, stochastic sensors for small solutes, and an alternative to conventional technology for DNA sequencing. Through large-scale molecular dynamics simulations, we studied the permeability of the alpha-hemolysin/lipid bilayer complex for water and ions. The studied system, composed of approximately 300,000 atoms, included one copy of the protein, a patch of a DPPC lipid bilayer, and a 1 M water solution of KCl. Monitoring the fluctuations of the pore structure revealed an asymmetric, on average, cross section of the alpha-hemolysin stem. Applying external electrostatic fields produced a transmembrane ionic current; repeating simulations at several voltage biases yielded a current/voltage curve of alpha-hemolysin and a set of electrostatic potential maps. The selectivity of alpha-hemolysin to Cl(-) was found to depend on the direction and the magnitude of the applied voltage bias. The results of our simulations are in excellent quantitative agreement with available experimental data. Analyzing trajectories of all water molecule, we computed the alpha-hemolysin's osmotic permeability for water as well as its electroosmotic effect, and characterized the permeability of its seven side channels. The side channels were found to connect seven His-144 residues surrounding the stem of the protein to the bulk solution; the protonation of these residues was observed to affect the ion conductance, suggesting the seven His-144 to comprise the pH sensor that gates conductance of the alpha-hemolysin channel.

  8. Electronic and ionic co-conductive coating on the separator towards high-performance lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Wang, Qingsong; Wen, Zhaoyin; Yang, Jianhua; Jin, Jun; Huang, Xiao; Wu, Xiangwei; Han, Jinduo

    2016-02-01

    A thin coating layer composed of the mixture of the electronic conductive carbon and lithium ionic conductive inorganic solid electrolyte was introduced on one side of the routine Celgard separator. This functional coated separator is designed to localize the polysulfides on the cathode side and act as an upper current collector for further utilization of sulfur while alleviating the ion conductivity decrease induced by the dissolved polysulfides in the discharge and charge process. Moreover, catalytic conversion of polysulfides by the solid state highly ionic conductor is observed. This brings significant improvement in battery specific capacity and cycling stability, with an initial discharge capacity of 1247 mA h g-1 and a reversible capacity of 830 mA h g-1 after 150 extended cycles at 0.5 C rate. Rest-testing proves a low self-discharge and excellent capacity retention of the modified cells.

  9. Molecular mechanics of DNA bricks: in situ structure, mechanical properties and ionic conductivity

    NASA Astrophysics Data System (ADS)

    Slone, Scott Michael; Li, Chen-Yu; Yoo, Jejoong; Aksimentiev, Aleksei

    2016-05-01

    The DNA bricks method exploits self-assembly of short DNA fragments to produce custom three-dimensional objects with subnanometer precision. In contrast to DNA origami, the DNA brick method permits a variety of different structures to be realized using the same library of DNA strands. As a consequence of their design, however, assembled DNA brick structures have fewer interhelical connections in comparison to equivalent DNA origami structures. Although the overall shape of the DNA brick objects has been characterized and found to conform to the features of the target designs, the microscopic properties of DNA brick objects remain yet to be determined. Here, we use the all-atom molecular dynamics method to directly compare the structure, mechanical properties and ionic conductivity of DNA brick and DNA origami structures different only by internal connectivity of their consistituent DNA strands. In comparison to equivalent DNA origami structures, the DNA brick structures are found to be less rigid and less dense and have a larger cross-section area normal to the DNA helix direction. At the microscopic level, the junction in the DNA brick structures are found to be right-handed, similar to the structure of individual Holliday junctions (HJ) in solution, which contrasts with the left-handed structure of HJ in DNA origami. Subject to external electric field, a DNA brick plate is more leaky to ions than an equivalent DNA origami plate because of its lower density and larger cross-section area. Overall, our results indicate that the structures produced by the DNA brick method are fairly similar in their overall appearance to those created by the DNA origami method but are more compliant when subject to external forces, which likely is a consequence of their single crossover design.

  10. Reusable electrochemical sensor for bisphenol A based on ionic liquid functionalized conducting polymer platform.

    PubMed

    Wang, Jhe-Yi; Su, Ya-Ling; Wu, Bo-Hao; Cheng, Shu-Hua

    2016-01-15

    The toxicity of bisphenol A (BPA) has attracted considerable attention, and the reported electrochemical sensors for BPA need further improvement in reusability due to serious surface fouling. In this study, a composite film is designed aiming to provide both an accurate and repeatable platform for BPA determination. The conducting poly(3,4-ethylenedioxythiophene) film (PEDOT) and ionic liquid 1-butyl-3-methylimidazolium bromide (BMIMBr) were modified onto screen-printed carbon electrodes (SPCE) by electropolymerization and drop/spin methods, respectively. The surface characteristics of the composite film were characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and surface water contact angle experiments. The composite film-modified electrodes exhibited a linear response to BPA in the range of 0.1-500µM in pH 7.0 phosphate buffer solution (PBS) under optimized flow-injection amperometry. The method sensitivity and detection limit (S/N=3) were 0.2661μA μM(-1) (2.419μA μM(-1)cm(-2)) and 0.02µM, respectively. A relative standard deviation of 1.95% was obtained for 77 successive measurements of 10µM BPA, and the repeatability outperformed previously reported work. The proposed method was applied to detect BPA released from plastic water bottles using the standard addition method, and satisfactory recoveries were obtained. The electrochemical assay was validated by comparison with the chromatographic method, and the results showed good agreement between the two methods.

  11. Structure and ionic conductivity of the solid electrolyte interphase layer on tin anodes in Na-ion batteries

    NASA Astrophysics Data System (ADS)

    Kuo, Liang-Yin; Moradabadi, Ashkan; Huang, Hsin-Fu; Hwang, Bing-Joe; Kaghazchi, Payam

    2017-02-01

    Structure, stability, and ionic conductivity of the SEI layer on Sn anodes in Na-ion batteries (NIBs) are studied using experimental and theoretical methods. Raman spectra show that the SEI layer consists of Na2O and Na2CO3, the latter becoming more dominant close to the discharged state (at 0.3 V). According to our theoretical phase diagrams, Na2O can be stable in the whole voltage range of charge/discharge (from 0.0 V to 1.90 V), but Na2CO3 can decompose under carbon and/or oxygen poor conditions, leading to the formation of Na2O. These findings are in agreement with our experimental cyclic voltammetry and Raman spectra as function of voltage. Both compounds of the SEI layer have very low ionic conductivity close to the discharge state (0.2-0.3 V), but the ionic conductivity of Na2O is much larger than that of Na2CO3 for a wide range of voltages from 0.4 V to the charge state (∼1.5 V). This work suggests that engineered artificial SEI with Na2O or naturally formed SEI in a carbon and/or oxygen poor environment can improve the conductivity of the SEI layer in NIBs.

  12. Gold-ionic liquid nanofluids with preferably tribological properties and thermal conductivity

    PubMed Central

    2011-01-01

    Gold/1-butyl-3-methylimidazolium hexafluorophosphate (Au/[Bmim][PF6]) nanofluids containing different stabilizing agents were fabricated by a facile one-step chemical reduction method, of which the nanofluids stabilized by cetyltrimethylammonium bromide (CTABr) exhibited ultrahighly thermodynamic stability. The transmission electron microscopy, UV-visible absorption, Fourier transform infrared, and X-ray photoelectron characterizations were conducted to reveal the stable mechanism. Then, the tribological properties of these ionic liquid (IL)-based gold nanofluids were first investigated in more detail. In comparison with pure [Bmim][PF6] and the nanofluids possessing poor stability, the nanofluids with high stability exhibited much better friction-reduction and anti-wear properties. For instance, the friction coefficient and wear volume lubricated by the nanofluid with rather low volumetric concentration (1.02 × 10-3%) stabilized by CTABr under 800 N are 13.8 and 45.4% lower than that of pure [Bmim][PF6], confirming that soft Au nanoparticles (Au NPs) also can be excellent additives for high performance lubricants especially under high loads. Moreover, the thermal conductivity (TC) of the stable nanofluids with three volumetric fraction (2.55 × 10-4, 5.1 × 10-4, and 1.02 × 10-3%) was also measured by a transient hot wire method as a function of temperature (33 to 81°C). The results indicate that the TC of the nanofluid (1.02 × 10-3%) is 13.1% higher than that of [Bmim][PF6] at 81°C but no obvious variation at 33°C. The conspicuously temperature-dependent and greatly enhanced TC of Au/[Bmim][PF6] nanofluids stabilized by CTABr could be attributed to micro-convection caused by the Brownian motion of Au NPs. Our results should open new avenues to utilize Au NPs and ILs in tribology and the high-temperature heat transfer field. PMID:21711789

  13. Ionic conductivity of single crystals of sodium aluminium germanate Na8Al6Ge6O24(OH)2

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.

    2015-09-01

    The electrical conductivity of single crystals of sodium aluminium germanate Na8Al6Ge6O24(OH)2 (cubic system, sp. gr. ), which is a germanium analog of sodalite, has been studied in the temperature range of 468‒758 K. Na8Al6Ge6O24(OH)2 crystals are obtained by hydrothermal synthesis (temperature in the dissolution zone 573‒673 K, temperature gradient ~1.5 K/cm). NaAlO2 and GeO2В oxides are used as starting reagents; NaOH hydroxide serves as a solvent. The ionic conductivity of Na8Al6Ge6O24(OH)2 crystals is 2 × 10-4 S/cm (at 758 K); the activation energy of ionic transfer is 0.46 ± 0.03 eV.

  14. Effects of ionic conduction on hydrothermal hydrolysis of corn starch and crystalline cellulose induced by microwave irradiation.

    PubMed

    Tsubaki, Shuntaro; Oono, Kiriyo; Onda, Ayumu; Yanagisawa, Kazumichi; Mitani, Tomohiko; Azuma, Jun-ichi

    2016-02-10

    This study investigated the effects of ionic conduction of electrolytes under microwave field to facilitate hydrothermal hydrolysis of corn starch and crystalline cellulose (Avicel), typical model biomass substrates. Addition of 0.1M NaCl was effective to improve reducing sugar yield by 1.61-fold at unit energy (kJ) level. Although Avicel cellulose was highly recalcitrant to hydrothermal hydrolysis, addition of 0.1M MgCl2 improved reducing sugar yield by 6.94-fold at unit energy (kJ). Dielectric measurement of the mixture of corn starch/water/electrolyte revealed that ionic conduction of electrolytes were strongly involved in facilitating hydrothermal hydrolysis of polysaccharides.

  15. Multilayered YSZ/GZO films with greatly enhanced ionic conduction for low temperature solid oxide fuel cells.

    PubMed

    Li, Bin; Zhang, Jiaming; Kaspar, Tiffany; Shutthanandan, Vaithiyalingam; Ewing, Rodney C; Lian, Jie

    2013-01-28

    Strain confinement in heterostructured films significantly affects ionic conductivity of the electrolytes for solid oxide fuel cells based on a multi-layered design strategy. Nearly ideal tensile strain can be achieved by a dedicated manipulation of the lattice mismatch between adjacent layers and fine control of the layer thicknesses to minimize the formation of dislocations and thus to achieve optimized ionic conduction. This strategy was demonstrated by a model system of multilayered 8 mol%Y(2)O(3) stabilized ZrO(2) (YSZ) with Gd(2)Zr(2)O(7) (GZO) films, which were epitaxially grown on Al(2)O(3) (0001) substrates by pulsed laser deposition (PLD) with the {111} planes of YSZ/GZO along the Al(2)O(3) [0 1 -1 0] direction. The tensile strain (3%) resulting from the lattice mismatch can be confined in individual YSZ layers with the formation of a coherent, dislocation-free interface upon the manipulation of the layer thickness below a critical value, e.g., down to 5 nm. The strained heterostructure displays a two order-of-magnitude increase in oxide-ion conductivity as compared with bulk YSZ, and a high ionic conductivity of 0.01 S cm(-1) at 475 °C can be achieved, five times greater than that of Gd-doped ceria/zirconia. The approach of strain confinement by fine control of lattice mismatch and layer thickness represents a promising strategy in developing advanced electrolytes enabling the miniaturization of solid-state ionic devices that can be operated at low temperatures below 500 °C.

  16. Influence of ionic strength and polyelectrolyte concentration on the electrical conductivity of suspensions of soft colloidal polysaccharides.

    PubMed

    Sagou, Jean-Pierre S; Ahualli, Silvia; Thomas, Fabien; Duval, Jérôme

    2015-12-01

    The electrokinetic properties of carboxymethyldextran, a soft and anionic polysaccharide, were analysed in aqueous NaNO3 solutions through measurements of the electrical conductivity of the suspensions. The results, which furnish new experimental support for the structure of soft polysaccharides in electrolyte solution show that the polyion concentration governs the conductance behavior of the suspension as the ionic strength decreases. This is particularly evident for large polymer concentrations, for which electrical double layer overlap is more likely. In contrast, the electrical conductivity of the suspension at high ionic strength reduces to the contribution of the ions in solution, as screening of the polyion charges is more efficient in such conditions. The applicability of Ohshima's general conductivity expression to these electrical conductivity measurements was examined, and a major discrepancy against the theory was observed. The calculated values of the electrical conductivity deduced on the basis of this theory were found to be lower than the experimental ones. Possible reasons for this discrepancy are discussed and a numerical model, based on the use of a cell approach to account for hydrodynamic and electrical interactions between particles, has shown to be a good description of the experimental electrokinetic data.

  17. 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

  18. Ionic conductivity and dielectric studies of LiClO4 doped poly(vinylalcohol)(PVA)/chitosan(CS) composites

    NASA Astrophysics Data System (ADS)

    Rathod, Sunil G.; Bhajantri, R. F.; Ravindrachary, V.; Pujari, P. K.; Sheela, T.

    2014-12-01

    This paper focuses on the dielectric constant (ɛ‧), dielectric loss factor (ɛ″) and frequency dependent conductivity (σac) properties of newly prepared poly(vinylalcohol) (PVA) chitosan (CS) composite films incorporated with different concentrations of LiClO4. The composite films were prepared using solution casting technique. The complexation between salt and polymer host is confirmed by FT Raman and UV-Vis studies. The sample containing 20 wt.% LiClO4 exhibits a highest ionic conductivity of 3 × 10-6 S/cm at room temperature. The dielectric properties of the composites follow non-Debye behavior.

  19. Ionic conductivity of mesoporous block copolymer membranes in liquid electrolyte as a function of copolymer and homopolymer molecular weight

    NASA Astrophysics Data System (ADS)

    Wong, David; Mullin, Scott; Stone, Greg; Battaglia, Vincent; Balsara, Nitash

    2011-03-01

    Mesoporous block copolymer membranes have been synthesized using poly(styrene-block-ethylene-block-polystyrene) (SES). A series of symmetric SES copolymers and PS homopolymers have been studied at different blending fractions. Ionic conductivities of the porous films in a liquid electrolyte, 1.0 M Li PF6 in ethylene carbonate/diethyl carbonate, compare favorably to conventional battery separators and generally increase with internal surface area, as measured by nitrogen adsorption. Characterization of the effects of pore structure and SES morphology on conductivity will be presented. Support from the U.S. Department of Energy Office of Vehicles Technologies (FCVT) under the Batteries for Advanced Transportation Technologies (BATT) Program.

  20. Elastic strain at interfaces and its influence on ionic conductivity in nanoscaled solid electrolyte thin films--theoretical considerations and experimental studies.

    PubMed

    Schichtel, N; Korte, C; Hesse, D; Janek, J

    2009-05-07

    Ionic transport in solids parallel to grain or phase boundaries is usually strongly enhanced compared to the bulk. Transport perpendicular to an interface (across an interface) is often much slower. Therefore in modern micro- and nanoscaled devices, a severe influence on the ionic/atomic transport properties can be expected due to the high density of interfaces.Transport processes in boundaries of ionic materials are still not understood on an atomic scale. In most of the studies on ionic materials the interfacial transport properties are explained by the influence of space charge regions. Here we discuss the influence of interfacial strain at semicoherent or coherent heterophase boundaries on ionic transport along these interfaces in ionic materials. A qualitative model is introduced for (untilted and untwisted) hetero phase boundaries. For experimental verification, the interfacial oxygen ionic conductivity of different multilayer systems consisting of cubic ZrO(2) stabilised by aliovalent dopands (YSZ, CSZ) and an insulating oxide is investigated as a function of structural mismatch. Recent results on extremely fast ionic conduction in YSZ/SrTiO(3) thin film systems ("colossal ionic concuctivity at interfaces") is discussed from the viewpoint of strain effects.

  1. Cellulose acetate-lithium bis(trifluoromethanesulfonyl)imide solid polymer electrolyte: ATR-FTIR and ionic conductivity behavior

    NASA Astrophysics Data System (ADS)

    Mohd Razalli, Siti Masyitah; Sheikh Mohd Saaid, Siti Irma Yuana; Marwan Ali, Ab Malik; Hassan, Oskar Hasdinor; Yahya, Muhd Zu Azhan

    2015-05-01

    Solid polymer electrolytes (SPEs) based on cellulose acetate (CA) doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt are prepared by solution cast technique. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy of the polymer salt complexes are recorded in the frequency range between 400 cm-1 and 4000 cm-1. The shifting of carbonyl band (C=O) at 1737 cm-1 to a lower wavenumber confirms the occurrence of complexation between the polymer and the salt. The electrochemical impedance spectroscopy (EIS) analysis discovered that the film with 25 wt.% of salt shows the highest ionic conductivity at room temperature. The change in real dielectric permittivity (ɛr) as a function of frequency at different salt concentrations which exhibits a dispersive behavior at low frequencies and decays at higher frequencies, shows the electrode polarization and space charge effect. The real modulus formalism (Mr) analysis shows that the polymer electrolytes in this work are ionic conductors.

  2. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    NASA Astrophysics Data System (ADS)

    Harun, Fatin; Chan, Chin Han; Sim, Lai Har; Winie, Tan; Zainal, Nurul Fatahah Asyqin

    2015-08-01

    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 (LiClO4) salt and titanium dioxide (TiO2) 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 LiClO4 causes a greater increase in glass transition temperature (Tg) and ionic conductivity of ENR50 as compared to ENR25. Upon addition of TiO2 in ENR/LiClO4 system, a remarkable Tg 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 TiO2 loading where ENR25 shows enhancement of conductivity while ENR50 shows declination.

  3. Effect of epoxidation level on thermal properties and ionic conductivity of epoxidized natural rubber solid polymer nanocomposite electrolytes

    SciTech Connect

    Harun, Fatin; Chan, Chin Han; Winie, Tan; Sim, Lai Har; Zainal, Nurul Fatahah Asyqin

    2015-08-28

    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 as 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.

  4. Effect of Adding Plasticizer on Ionic Conductivity and Glass Transition Temperature of PMMA+Lithium Iodide Complexes

    NASA Astrophysics Data System (ADS)

    Zulkepely, N. R.; Majid, S. R.; Osman, Z.

    2010-07-01

    Polymer electrolyte films based on poly-methylmethacrylate (PMMA) have been prepared using the solution casting technique. Ethylene carbonate (EC) was used as a plasticizer and lithium iodide (LiI) as a doping salt. The ionic conductivity of the films was analyzed using ac impedance spectroscopy. It can be observed that the ionic conductivity of PMMA+LiI film increased when the plasticizer was added. The conductivity-temperature dependence studies were carried out in the temperature range between 303 and 393 K. The results indicate that the conductivity is increased when the temperature is increased. The glass transition temperature, Tg of the polymer electrolyte films was measured using Differential Scanning Calorimetry (DSC). The Tg of the pure PMMA film is ˜125 °C. On addition of plasticizer, it can be observed that the Tg of PMMA+LiI film is decreased. This reveals that the plasticizer, EC has reduced the Tg of the polymer electrolyte film by increasing segmental motion of the polymer resulting in conductivity enhancement.

  5. An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

    NASA Astrophysics Data System (ADS)

    Zeng, Pingying

    In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and

  6. Monitoring the ionic content of exhaled breath condensate in various respiratory diseases by capillary electrophoresis with contactless conductivity detection.

    PubMed

    Greguš, Michal; Foret, František; Kindlová, Dagmar; Pokojová, Eva; Plutinský, Marek; Doubková, Martina; Merta, Zdeněk; Binková, Ilona; Skřičková, Jana; Kubáň, Petr

    2015-05-06

    The analysis of an ionic profile of exhaled breath condensate (EBC) by capillary electrophoresis with contactless conductivity detection and double opposite end injection, is demonstrated. A miniature sampler made from a 2 ml syringe and an aluminium cooling cylinder was used for the fast collection of EBC (under one minute). Analysis of the collected EBC was performed in a 60 mM 2-(N-morpholino)ethanesulfonic acid, 60 mM L-histidine background electrolyte with 30 µM cetyltrimethylammonium bromide and 2 mM 18-crown-6 at pH 6, and excellent repeatability of migration times (RSD  <1.3% (n = 7)) and peak areas (RSD  <  7% (n = 7)) of 14 ions (inorganic anions, cations and organic acids) was obtained. It is demonstrated that the analysis of EBC samples obtained from patients with various respiratory diseases (chronic obstructive pulmonary disease, asthma, pulmonary fibrosis, sarcoidosis, cystic fibrosis) is possible in less than five minutes and the ionic profile can be compared with the group of healthy individuals. The analysis of the ionic profile of EBC samples provides a set of data in which statistically significant differences among the groups of patients could be observed for several clinically relevant anions (nitrite, nitrate, acetate, lactate). The developed collection system and method provides a highly reproducible and fast way of collecting and analyzing EBC, with future applicability in point-of-care diagnostics.

  7. Electrochemical activity and high ionic conductivity of lithium copper pyroborate Li6CuB4O10.

    PubMed

    Strauss, Florian; Rousse, Gwenaëlle; Alves Dalla Corte, Daniel; Ben Hassine, Mohamed; Saubanère, Matthieu; Tang, Mingxue; Vezin, Hervé; Courty, Matthieu; Dominko, Robert; Tarascon, Jean-Marie

    2016-06-01

    In the search for new cathode materials for Li-ion batteries, borate (BO3(3-)) based compounds have gained much interest during the last two decades due to the low molecular weight of the borate polyanions which leads to active materials with increased theoretical capacities. In this context we herein report the electrochemical activity versus lithium and the ionic conductivity of a diborate or pyroborate B2O5(4-) based compound, Li6CuB4O10. By combining various electrochemical techniques with in situ X-ray diffraction, we show that this material can reversibly insert/deinsert limited amounts of lithium (∼0.3 Li(+)) in a potential window ranging from 2.5 to 4.5 V vs. Li(+)/Li(0). We demonstrate, via electron paramagnetic resonance (EPR), that such an electrochemical activity centered near 4.25 V vs. Li(+)/Li(0) is associated with the Cu(3+)/Cu(2+) redox couple, confirmed by density functional theory (DFT) calculations. Another specificity of this compound lies in its different electrochemical behavior when cycled down to 1 V vs. Li(+)/Li(0) which leads to the extrusion of elemental copper via a conversion type reaction as deduced by transmission electron microscopy (TEM). Lastly, we probe the ionic conductivity by means of AC and DC impedance measurements as a function of temperature and show that Li6CuB4O10 undergoes a reversible structural transition around 350 °C, leading to a surprisingly high ionic conductivity of ∼1.4 mS cm(-1) at 500 °C.

  8. A correlation between the ionic conductivities and the formation enthalpies of trivalent-doped ceria at relatively low temperatures.

    PubMed

    Avila-Paredes, Hugo J; Shvareva, Tatiana; Chen, Weiqun; Navrotsky, Alexandra; Kim, Sangtae

    2009-10-14

    We report a correlation between oxygen ionic conductivity and the enthalpy of formation of trivalent-doped ceria from the component binary oxides observed at relatively low temperatures (150-275 degrees C). The bulk conductivities of La-doped ceria samples identical to those previously examined by thermochemical studies were measured as a function of La content for a direct comparison. The conductivity showed a maximum at a La concentration of 5 mol%, implying that the number of freely mobile oxygen vacancies reaches a maximum near that doping level in the temperature range of interest. The formation enthalpies previously reported by Chen and Navrotsky also show a maximum, indicating destabilization near that composition. Additional measurements show that this maximum is very pronounced and sharply peaked near that composition. These enthalpies suggest that the energetically favorable long-range interactions between the charged defects that trap the oxygen vacancies become dominant above 5 mol% doping in the CeO2-LaO1.5 solid solution. In addition, the conductivities measured from independently prepared Gd-doped ceria samples show a maximum at around 10 mol% doping below 450 degrees C as anticipated from a pronounced maximum in the formation enthalpies of the CeO2-GdO1.5 solid solution. These empirical findings confirm that the ionic conductivity of trivalent-doped ceria is strongly enough correlated with its formation enthalpy at relatively low temperatures so that information about the critical dopant concentration associated with the conductivity maximum may be gained from the formation enthalpies of the solid solutions, and vice versa. We have no direct information about this correlation at higher temperatures; both thermodynamics and conductivity maximum might change if the defect clusters dissociate to any significant extent.

  9. Consistent prediction of streaming potential in non-Newtonian fluids: the effect of solvent rheology and confinement on ionic conductivity.

    PubMed

    Bandopadhyay, Aditya; Chakraborty, Suman

    2015-03-21

    By considering an ion moving inside an imaginary sphere filled with a power-law fluid, we bring out the implications of the fluid rheology and the influence of the proximity of the other ions towards evaluating the conduction current in an ionic solution. We show that the variation of the conductivity as a function of the ionic concentration is both qualitatively and quantitatively similar to that predicted by the Kohlrausch law. We then utilize this consideration for estimating streaming potentials developed across narrow fluidic confinements as a consequence of the transport of ions in a convective medium constituting a power-law fluid. These estimates turn out to be in sharp contrast to the classical estimates of streaming potential for non-Newtonian fluids, in which the effect of rheology of the solvent is merely considered to affect the advection current, disregarding its contributions to the conduction current. Our results have potential implications of devising a new paradigm of consistent estimation of streaming potentials for non-Newtonian fluids, with combined considerations of the confinement effect and fluid rheology in the theoretical calculations.

  10. Investigation of Ionic Conductivity of Nanocomposite Polymer Electrolytes Based On PVDF-HFP/PVC Blend, LiClO4 and TiO2 Nanofiller

    NASA Astrophysics Data System (ADS)

    Basri, N. H.; Mohamed, N. S.

    2010-07-01

    The effects of nanosized TiO2 on the conductivity of PVDF-HFP/PVC-LiClO4 was studied by means of impedance spectroscopy and x-ray diffraction (XRD). The addition of TiO2 nanofiller increases the crystalline phase fraction but slightly increases the conductivity of the PVDF-HFP/PVC-LiClO4 complex. The increase in conductivity is attributed to the formation of highly conducting layer at the electrolyte/filler interface. The temperature dependence of conductivity obeys the VTF type behaviour while the transference number confirms that the electrolyte containing 6 wt.% TiO2 is an ionic conductor are ionic conductors.

  11. Influence of Al2O3 on the ionic conductivity of plasticized PVC-PEG blend polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Ravindran, D.; Vickraman, P.

    2016-05-01

    Polymer electrolytes with PVC-PEG blend as host matrix and LiClO4 as dopant salt was prepared through conventional solution casting method. To enhance the conductivity propylene carbonate (PC) was used as plasticizer. The influence of ceramic filler Al2O3 on the conductivity of the electrolyte films were studied by varying the (PVC: Al2O3) ratio. The films were subjected to XRD, complex impedance analysis and SEM analysis. The XRD studies reveal a marginal increase in the amorphous phase of the electrolyte films due to the incorporation of filler. The AC impedance analysis shows the dependency of ionic conductivity on the content (wt %) of filler and exhibit a maximum at 4 wt% filler. The SEM analysis depicts the occurrence of phase separation in electrolyte which is attributed to the poor solubility of polymer PVC in the liquid electrolyte.

  12. Lithium ionic conduction and relaxation dynamics of spark plasma sintered Li5La3Ta2O12 garnet nanoceramics.

    PubMed

    Ahmad, Mohamad M

    2015-01-01

    In the present work, nanoceramics of Li5La3Ta2O12 (LLT) lithium ion conductors with the garnet-like structure are fabricated by spark plasma sintering (SPS) technique at different temperatures of 850°C, 875°C, and 900°C (SPS-850, SPS-875, and SPS-900). The grain size of the SPS nanoceramics is in the 50 to 100 nm range, indicating minimal grain growth during the SPS experiments. The ionic conduction and relaxation properties of the current garnets are studied by impedance spectroscopy (IS) measurements. The SPS-875 garnets exhibit the highest total Li ionic conductivity of 1.25 × 10(-6) S/cm at RT, which is in the same range as the LLT garnets prepared by conventional sintering technique. The high conductivity of SPS-875 sample is due to the enhanced mobility of Li ions by one order of magnitude compared to SPS-850 and SPS-900 ceramics. The concentration of mobile Li(+) ions, n c, and their mobility are estimated from the analysis of the conductivity spectra at different temperatures. n c is found to be independent of temperature for the SPS nanoceramics, which implies that the conduction process is controlled by the Li(+) mobility. Interestingly, we found that only a small fraction of lithium ions of 3.9% out of the total lithium content are mobile and contribute to the conduction process. Moreover, the relaxation dynamics in the investigated materials have been studied through the electric modulus formalism.

  13. Electro-osmotic pumping and ionic conductance measurements in porous membranes

    NASA Astrophysics Data System (ADS)

    Vajandar, Saumitra K.

    fabricated out of heavily doped silicon wafers using microfabrication techniques. The pores have a 15 mum x 40 mum cross sectional area with a thin layer of SiNx coated conformally over the pores by low-pressure chemical vapor deposition (LPCVD). The range of gate voltages applied was from -45 V to + 40 V. For Vg < 0, current leakage through the SiNx film was observed whereas negligible leaking current was detected for Vg > 0. This current rectification effect is known as electrolytic rectification, as a result of which a greater EO flow control, nearly 70% reduction in flow velocity, was observed for positive gate bias and 15% flow velocity enhancement under negative gate bias of similar magnitude. Ionic current is closely related to EO flow and the last part of the dissertation is devoted to ionic current measurements through commercially made nanoporous glass membranes (4 nm average pore diameter). This study was motivated by a molecular dynamics (MD) simulation highlighting an unusual ionic current trend in a 3 nm diameter pore having high surface charge density at high electrolyte concentrations. The ionic current was measured with two kinds of electrolytes---NaCl and KCl. The experimental results, however, indicated an expected linear trend of ionic current for electrolyte concentrations beyond 1 M, contrary to the results of the MD simulation study, which was attributed to a low surface charge density measured for the porous glass membranes.

  14. Polyethylene separator activated by hybrid coating improving Li+ ion transference number and ionic conductivity for Li-metal battery

    NASA Astrophysics Data System (ADS)

    Mao, Xufeng; Shi, Liyi; Zhang, Haijiao; Wang, Zhuyi; Zhu, Jiefang; Qiu, Zhengfu; Zhao, Yin; Zhang, Meihong; Yuan, Shuai

    2017-02-01

    Low Li+ ion transference number is one fatal defect of the liquid LiPF6 electrolyte for Li-metal anode based batteries. This work aims to improve Li+ ion transference number and ionic conductivity polyethylene (PE) separators. By a simple dip-coating method, the water-borne nanosized molecular sieve with 3D porous structure (ZSM-5) can be coated on PE separators. Especially, the Li+ ion transference number is greatly enhanced from 0.28 to 0.44, which should be attributed to the specific pore structure and channel environment of ZSM-5 as well as the interaction between ZSM-5 and electrolyte. Compared with the pristine PE separator, the ionic conductivity of modified separators is remarkably improved from 0.30 to 0.54 mS cm-1. As results, the C-rate capability and cycling stability are both improved. The Li-metal battery using the ZSM-5-modified PE separator keeps 94.2% capacity after 100 cycles. In contrast, the discharge capacity retention of the battery using pristine PE is only 74.7%.

  15. Monte Carlo simulation of diffusion and ionic conductivity in a simple cubic random alloy via the interstitialcy mechanism

    NASA Astrophysics Data System (ADS)

    Wilangowski, F.; Stolwijk, N. A.

    2015-12-01

    This Monte Carlo study deals with mass and charge transport in binary ionic alloys governed by interstitialcy defects acting as diffusion vehicles. In particular, we calculate tracer correlation factors {{f}\\text{A}} and {{f}\\text{B}} in a simple cubic random alloy AB for diffusion via the collinear interstitialcy mechanism as a function of composition and jump frequency ratio {{w}\\text{A}}\\ll {{w}\\text{B}} . Interstitialcy correlation factors {{f}\\text{I}} , which play a crucial role in the interpretation of ion-conductivity data, are also determined. The evaluation of partial correlation factors provides insight into the types of jumps that mostly contribute to the different transport processes under consideration. Examination of the percolation behaviour yields the site-percolation threshold of the mobile component B for {{w}\\text{A}}=0 . Surprisingly, a unique second-order threshold composition is found, which relates to the abundance of different interstitialcy jump types when {{w}\\text{A}}/{{w}\\text{B}} . Both numerically obtained threshold values are accurately reproduced by estimated analytical expressions based on simple arguments. Practical implications of the simulation results are explored by calculating tracer diffusivity ratios D\\text{A}*/D\\text{B}* and by comparing self-diffusion with ionic conductivity using the Nernst-Einstein equation.

  16. Enhanced ionic conductivity with Li7O2Br3 phase in Li3OBr anti-perovskite solid electrolyte

    NASA Astrophysics Data System (ADS)

    Zhu, Jinlong; Li, Shuai; Zhang, Yi; Howard, John W.; Lü, Xujie; Li, Yutao; Wang, Yonggang; Kumar, Ravhi S.; Wang, Liping; Zhao, Yusheng

    2016-09-01

    Cubic anti-perovskites with general formula Li3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li3OBr and layered Li7O2Br3, by solid state reaction routes. The results indicate that with the phase fraction of Li7O2Br3 increasing to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li3OBr. Formation energy calculations revealed the meta-stable nature of Li7O2Br3, which supports the great difficulty in producing phase-pure Li7O2Br3 at ambient pressure. Methods of obtaining phase-pure Li7O2Br3 will continue to be explored, including both high pressure and metathesis techniques.

  17. Enhanced ionic conductivity with Li7O2Br3 phase in Li3OBr anti-perovskite solid electrolyte

    DOE PAGES

    Zhu, Jinlong; Li, Shuai; Zhang, Yi; ...

    2016-09-07

    Cubic anti-perovskites with general formula Li3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li3OBr and layered Li7O2Br3, by solid state reaction routes. The results indicate that with the phase fraction of Li7O2Br3 increasing to 44 wt. %, the ionic conductivity increasedmore » by more than one order of magnitude compared with pure phase Li3OBr. Formation energy calculations revealed the meta-stable nature of Li7O2Br3, which supports the great difficulty in producing phase-pure Li7O2Br3 at ambient pressure. Here, methods of obtaining phase-pure Li7O2Br3 will continue to be explored, including both high pressure and metathesis techniques.« less

  18. Monte Carlo simulation of diffusion and ionic conductivity in a simple cubic random alloy via the interstitialcy mechanism.

    PubMed

    Wilangowski, F; Stolwijk, N A

    2015-12-23

    This Monte Carlo study deals with mass and charge transport in binary ionic alloys governed by interstitialcy defects acting as diffusion vehicles. In particular, we calculate tracer correlation factors f(A) and f(B) in a simple cubic random alloy AB for diffusion via the collinear interstitialcy mechanism as a function of composition and jump frequency ratio wA/wB. [corrected]. Interstitialcy correlation factors f(I), which play a crucial role in the interpretation of ion-conductivity data, are also determined. The evaluation of partial correlation factors provides insight into the types of jumps that mostly contribute to the different transport processes under consideration. Examination of the percolation behaviour yields the site-percolation threshold of the mobile component B for w(A) = 0. Surprisingly, a unique second-order threshold composition is found, which relates to the abundance of different interstitialcy jump types when wA < wB [corrected]. Both numerically obtained threshold values are accurately reproduced by estimated analytical expressions based on simple arguments. Practical implications of the simulation results are explored by calculating tracer diffusivity ratios D*(A)/D*(B) and by comparing self-diffusion with ionic conductivity using the Nernst-Einstein equation.

  19. Irreversible change of electric conduction in ionic-liquid-gated (La,Sr)MnO3 thin films

    NASA Astrophysics Data System (ADS)

    Lee, Tae Kwon; Jung, Jong Hoon

    2016-10-01

    We have investigated the ionic-liquid-gating effect on electric conduction in (La0.8Sr0.2)MnO3(LSMO) thin films. The gating effect is significant for the LSMO thin films grown at low oxygen partial pressures. We observed that the channel resistance of LSMO was altered only for a positive gating voltage, not for a negative one, mainly through the changes of mobility rather than the carrier density. The increased sheet resistance at positive voltage does not return to the original value even after the removal of gating voltage as well as the application of a negative voltage. Through the Mn 2 p X-ray absorption, the increased resistance of LSMO after a positive voltage is found to be associated with the increase of the Mn3+ ions over Mn4+ ones. We proposed that oxygen vacancy and electrochemical reactions should play a role for the irreversible electric conduction in ionic-liquid-gated (La,Sr)MnO3 thin films.

  20. Surfactant-free ionic liquid-based nanofluids with remarkable thermal conductivity enhancement at very low loading of graphene

    PubMed Central

    2012-01-01

    We report for the first time the preparation of highly stable graphene (GE)-based nanofluids with ionic liquid as base fluids (ionic liquid-based nanofluids (Ionanofluids)) without any surfactant and the subsequent investigations on their thermal conductivity, specific heat, and viscosity. The microstructure of the GE and MWCNTs are observed by transmission electron microscope. Thermal conductivity (TC), specific heat, and viscosity of these Ionanofluids were measured for different weight fractions and at varying temperatures, demonstrating that the Ionanofluids exhibit considerably higher TC and lower viscosity than that of their base fluids without significant specific heat decrease. An enhancement in TC by about 15.5% and 18.6% has been achieved at 25 °C and 65 °C respectively for the GE-based nanofluid at mass fraction of as low as 0.06%, which is larger than that of the MWCNT-dispersed nanofluid at the same loading. When the temperature rises, the TC and specific heat of the Ionanofluid increase clearly, while the viscosity decreases sharply. Moreover, the viscosity of the prepared Ionanofluids is lower than that of the base fluid. All these advantages of this new kind of Ionanofluid make it an ideal fluid for heat transfer and thermal storage. PMID:22713249

  1. Fast ionic conduction in tetravalent metal pyrophosphate-alkali carbonate composites: New potential electrolytes for intermediate-temperature fuel cells

    NASA Astrophysics Data System (ADS)

    Singh, Bhupendra; Bhardwaj, Aman; Gautam, Sandeep K.; Kumar, Devendra; Parkash, Om; Kim, In-Ho; Song, Sun-Ju

    2017-03-01

    Here we present a report on synthesis and characterization of tetravalent metal pyrophosphate (TMP) and alkali carbonate (A2CO3; A = Li and/or Na) composites. The TMP-carbonate composites are prepared by mixing indium-doped tin pyrophosphate or yttrium-doped zirconium pyrophosphate with Li2CO3 or an eutectic mixture of Li2CO3-Na2CO3 in different wt.% ratios. The phase composition, microstructure and electrical conductivity of the sintered specimen are analyzed. In addition, the effect of different TMP and A2CO3 phases is investigated. A maximum ionic conductivity of 5.5 × 10-2 S cm-1 at 630 °C is observed in this study with a Sn0.9In0.1P2O7-Li2CO3 composite. Based on the literature data, TMP-carbonate composites can be considered to be primarily a proton and oxygen-ion co-ionic conductor and, therefore, have strong potential as electrolytes in fuel cells in 500-700 °C range.

  2. Analysis of cationic structure in some room-temperature molten fluorides and dependence of their ionic conductivity and viscosity on hydrofluoric acid concentration.

    PubMed

    Isogai, Tomohiro; Nakai, Takaaki; Inoue, Hidemi; Nakanishi, Kenta; Kohara, Shinji; Saito, Morihiro; Inaba, Minoru; Tasaka, Akimasa

    2011-08-11

    To understand the ionic and nonionic species in (CH(3))(4)NF·mHF, (CH(3))(3)N·mHF, (C(2)H(5))(4)NF·mHF, and (C(2)H(5))(3)N·mHF melts, the structures of these melts were investigated by infrared spectroscopy, NMR, and high-energy X-ray diffraction. Infrared spectra revealed that three kinds of fluorohydrogenate anions, (FH)(n)F(-) (n = 1, 2, and 3), and molecular hydrofluoric acid (HF) are present in every melt. Ionic conductivity and viscosity of these melts were measured and correlated with their cationic structure. The ionic conductivity of the R(4)N(+)-systems was higher than that of corresponding R(3)NH(+)-systems because a strong N-H···F(HF)(n) interaction prevents the motion of R(3)NH(+) cations in the R(3)N·mHF melts. (CH(3))(4)N(+) and (CH(3))(3)NH(+) cations gave higher ionic conductivity than (C(2)H(5))(4)N(+) and (C(2)H(5))(3)NH(+) cations, respectively, because the ionic radii of former cations were smaller than those of latter. It was concluded that these effects on ionic conductivity can be explained by the cationic structure and the concentration of molecular HF in the melts.

  3. Phase stability and ionic conductivity in substituted La{sub 2}W{sub 2}O{sub 9}

    SciTech Connect

    Marrero-Lopez, D.

    2008-02-15

    Different substitutions, i.e. Sr{sup 2+}, Ba{sup 2+}, K{sup +}, Nb{sup 5+} and V{sup 5+}, have been performed in the triclinic {alpha}-La{sub 2}W{sub 2}O{sub 9} structure in order to stabilise the high temperature and better ionic conductor cubic {beta}-phase. This approach has been used to try to obtain a new series of ionic conductors with LAMOX-type structure without molybdenum and presumably better redox stability compared to {beta}-La{sub 2}Mo{sub 2}O{sub 9}. Nanocrystalline materials obtained by a freeze-drying precursor method at 600 deg. C exhibit mainly the {beta}-La{sub 2}W{sub 2}O{sub 9} structure, however, the triclinic {alpha}-form is stabilised as the firing temperature increases and the crystallite size grows. Only high levels of Ba{sup 2+} and V{sup 5+} substitutions retained the cubic form at room temperature after firing above 1100 deg. C. However, these phases are metastable above 700 deg. C, exhibiting an irreversible transformation to the low temperature triclinic {alpha}-phase. The synthesis, structure, phase stability, kinetic of phase transformation and electrical conductivity of these materials have been studied in the present report. - Graphical abstract: Several substitutions have been tested in order to investigate the stabilisation of the high temperature cubic {beta}-La{sub 2}W{sub 2}O{sub 9} and to obtain new ionic conductors with LAMOX structure without molybdenum composition.

  4. Effect of Temperature and Pressure on Ionic Conductivity of PAN-Based Polymer Electrolytes Containing Inorganic Salts

    NASA Astrophysics Data System (ADS)

    Ahmad, A.; Isa, K. B. Md.; Osman, Z.

    2010-07-01

    The conducting polymer electrolyte films consisting polyacrylonitrile (PAN) as the host polymer, ethylene carbonate (EC) as a plasticizer, lithium triflate (LiCF3SO3) and sodium triflate (NaCF3SO3) as inorganic salts were prepared by the solution cast technique. The pure PAN film was prepared as a reference. The ionic conductivity for the films is characterized using impedance spectroscopy. The room temperature conductivity for the PAN+24 wt.%EC film, PAN+26 wt.%LiCF3SO3 film, the PAN+24 wt.%NaCF3SO3 film is 3.43×10-11 S cm-1, 3.04×10-4 S cm-1, and 7.13×10-4 S cm-1, respectively. On addition of plasticizer, the room temperature of PAN+LiCF3SO3 and PAN+NaCF3SO3 films increases by one order of magnitude. The conductivity-temperature and conductivity-pressure dependence studies are then performed on the highest conducting film from the unplasticized and plasticized systems in the temperature and pressure range between 303 K and 373 K and 0.01 MPa and 0.09 MPa, respectively. The conductivity-temperature studies indicate the activation energy, Ea for all system decrease with the increase of the conductivity. The activation volume, ΔV* for each system can be determined from the plot of ln σ versus pressure. It can be observed that the ΔV* is decreased as the conductivity increased. This result can be explained in term of free volume.

  5. Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

    SciTech Connect

    Brombosz, Scott M.; Lee, Sungwon; Firestone, Millicent A.

    2014-11-04

    We describe post-polymerization radical bromination of a nanostructured poly(ionic liquid) that selectively introduces a reactive bromo-group onto the polyalkylthiophene backbone. Raman and FT-IR spectroscopy proves that the bromine is successfully introduced at the 3-methyl position of the thiophene and that the molecular structure of the polymer remains largely intact with only minimal chain scission detected. FT-IR and Vis-NIR spectroscopy indicates that incorporation of the bromine induces twisting (loss of co-planarity) of the polythiophene backbone. WAXS confirms retention of an ordered lamellar structure with minor lattice spacing contraction. Cyclic voltammetry confirms spectroscopic findings that the bromination reaction yields a stable p-doped polymer. The installed bromine is susceptible to nucleophilic displacement permitting the covalent attachment of other functional molecules, such as a dialkylphosphonate. Elemental analysis of such a transformation established that 100 % functionalization can be achieved. These results collectively demonstrate that post-modification of a π-conjugated polymer can be used to both tune electronic and photonic properties, as well as install a chemoselective attachment point for the covalent wiring of other molecules.

  6. DEVELOPMENT AND SELECTION OF IONIC LIQUID ELECTROLYTES FOR HYDROXIDE CONDUCTING POLYBENZIMIDAZOLE MEMBRANES IN ALKALINE FUEL CELLS

    SciTech Connect

    Fox, E.

    2012-05-01

    Alkaline fuel cell (AFC) operation is currently limited to specialty applications such as low temperatures and pure HO due to the corrosive nature of the electrolyte and formation of carbonates. AFCs are the cheapest and potentially most efficient (approaching 70%) fuel cells. The fact that non-Pt catalysts can be used, makes them an ideal low cost alternative for power production. The anode and cathode are separated by and solid electrolyte or alkaline porous media saturated with KOH. However, CO from the atmosphere or fuel feed severely poisons the electrolyte by forming insoluble carbonates. The corrosivity of KOH (electrolyte) limits operating temperatures to no more than 80°C. This chapter examines the development of ionic liquids electrolytes that are less corrosive, have higher operating temperatures, do not chemically bond to CO and enable alternative fuels. Work is detailed on the IL selection and characterization as well as casting methods within the polybenzimidazole based solid membrane. This approach is novel as it targets the root of the problem (the electrolyte) unlike other current work in alkaline fuel cells which focus on making the fuel cell components more durable.

  7. Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

    DOE PAGES

    Brombosz, Scott M.; Lee, Sungwon; Firestone, Millicent A.

    2014-11-04

    We describe post-polymerization radical bromination of a nanostructured poly(ionic liquid) that selectively introduces a reactive bromo-group onto the polyalkylthiophene backbone. Raman and FT-IR spectroscopy proves that the bromine is successfully introduced at the 3-methyl position of the thiophene and that the molecular structure of the polymer remains largely intact with only minimal chain scission detected. FT-IR and Vis-NIR spectroscopy indicates that incorporation of the bromine induces twisting (loss of co-planarity) of the polythiophene backbone. WAXS confirms retention of an ordered lamellar structure with minor lattice spacing contraction. Cyclic voltammetry confirms spectroscopic findings that the bromination reaction yields a stable p-dopedmore » polymer. The installed bromine is susceptible to nucleophilic displacement permitting the covalent attachment of other functional molecules, such as a dialkylphosphonate. Elemental analysis of such a transformation established that 100 % functionalization can be achieved. These results collectively demonstrate that post-modification of a π-conjugated polymer can be used to both tune electronic and photonic properties, as well as install a chemoselective attachment point for the covalent wiring of other molecules.« less

  8. Conductive polymer as a controlled microenvironment for the potentiometric high-throughput evaluation of ionic liquid cell toxicity.

    PubMed

    Qiu, Weilian; Zeng, Xiangqun

    2008-09-01

    This paper presents both biological and potentiometric evaluations of the cell toxicity of a widely used ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF(4)), to Chinese hamster lung fibroblast cells (V79 cell line). The innovative potentiometric study takes advantage of the unique properties of conductive polymer polypyrrole (PPY) for the potentiometric evaluation of cell toxicity of [bmim]BF(4) to the V79 cells in a real-time, noninvasive and high-throughput manner. The conductive polymer PPY provides a controlled microenvironment that allows the quantitative release of the anions of the ionic liquids into the cells being monitored in real time and noninvasively. Parallel biological assay results showed that V79 cells exposed to [bmim]BF(4) usually grew in clusters, and that many small vacuoles could be seen in the cytoplasm. At the 24th hour after the V79 cells had been exposed to the ionic liquid (IL), the half inhibition concentration (EC(50)) of [bmim]BF(4) was around 5 mM. From a cell cycle study performed using a FACScan flow cytometer, it was found that the V79 cells could be partially locked to the G(1) phase by [bmim]BF(4), which extended the doubling time for cell growth. Comparing with the EC(50) values of cadmium chloride and mercury chloride, [bmim]BF(4) is not very toxic, but it may have a long-term toxic effect on mammalian cells. Compared to traditional biological in vitro assays, the use of a conductive polymer substrate in combination with a potentiometric sensor array is much more sensitive, faster, and enables a simpler evaluation of chemical cell toxicity. Additionally, it simplifies the study of the reversibility of cell toxicity, i.e., cell recovery, because there is no need to refresh the culture medium since a finite amount of chemicals can be doped and released. We found that the cytotoxicity of [bmim]BF(4) at a concentration of less than 6 mM was reversible for the V79 cell line, because cell morphology and

  9. One-dimensional ion-conductive polymer films: alignment and fixation of ionic channels formed by self-organization of polymerizable columnar liquid crystals.

    PubMed

    Yoshio, Masafumi; Kagata, Takayoshi; Hoshino, Koji; Mukai, Tomohiro; Ohno, Hiroyuki; Kato, Takashi

    2006-04-26

    We have prepared two types of one-dimensional ion-conductive polymer films containing ion nanochannels that are both perpendicular and parallel to the film surface. These films have been obtained by photopolymerization of aligned columnar liquid crystals of a fan-shaped imidazolium salt having acrylate groups at the periphery. In the columnar structure, the ionic part self-assembles into the inner part of the column. The column is oriented macroscopically in two directions by different methods: orientation perpendicular to the modified surfaces of glass and indium tin oxide with 3-(aminopropyl)triethoxysilane and orientation parallel to a glass surface by mechanical shearing. Ionic conductivities have been measured for the films with columnar orientation vertical and parallel to the surface. Anisotropic ionic conductivities are observed for the oriented films fixed by photopolymerization. The ionic conductivities parallel to the columnar axis are higher than those perpendicular to the columnar axis because the lipophilic part functions as an ion-insulating part. The film with the columns oriented vertically to the surface shows an anisotropy of ionic conductivities higher than that of the film with the columns aligned parallel to the surface.

  10. Correlation between ionic radii of metal azodye complexes and electrical conductivity.

    PubMed

    El-Ghamaz, N A; El-Sonbati, A Z; Diab, M A; El-Bindary, A A; Mohamed, G G; Morgan, Sh M

    2015-08-05

    5-(2,3-Dimethyl-1-phenylpyrazol-5-one azo)-2-thioxo-4-thiazolidinone (HL) and its metal complexes with copper(II) (1), cobalt(II) (2) and nickel(II) (3) are synthesized and characterized by physico-chemical techniques. The thermal properties of the ligand (HL) and its metal complexes (1-3) are discussed. The thermal activation energies of decomposition (Ea) of HL and its metal complexes with Cu(II), Co(II) and Ni(II) are found to be 48.76, 36.83, 30.59 and 40.45 kJ/mol, respectively. The frequency and temperature dependence of ac conductivity, dielectric constants for HL and its complexes (1-3) are investigated in the temperature range 300-356 K and frequency range 0.1-100 kHz. Both of the ac conductivity and the values of the thermal activation energy for conduction, as well as the dielectric properties of the complexes of HL are found to depend on the nature of the metallic ions. The values of the thermal activation energies of electrical conductivity decrease with increasing the value of test frequency. The small polarons tunneling (SPT) is the dominant conduction mechanism for the ligand (HL), while for complex (2) the overlapping large tunneling model (OLPT) is the dominant conduction mechanism. The correlated barrier hopping (CBH) is the dominant conduction mechanism for both of the complexes (1) and (3).

  11. Ionic conductivity in poly(propylene glycol) complexed with lithium and sodium triflate

    NASA Astrophysics Data System (ADS)

    Albinsson, I.; Mellander, B.-E.; Stevens, J. R.

    1992-01-01

    Conductivity and viscosity measurements have been made for poly(propylene glycol)-MCF3SO3 (M=Li, Na) complexes in order to examine more closely the Vogel-Tammann-Fulcher (VTF) empirical relationship which has been found in previous reports to provide a good fit to the experimental data. Further, a dynamic bond percolation model of ion conduction in polymer electrolytes has predicted VTF behavior and an inverse relationship between molar conductivity and viscosity or Walden ``rule'' behavior. We find that deviations occur from both the VTF and Walden empirical relationships and propose a modest alteration in the form of the dynamic percolation model for ions moving in polyether systems.

  12. Impact of segregation energetics on oxygen conductivity at ionic grain boundaries

    SciTech Connect

    Aidhy, Dilpuneet S; Zhang, Yanwen; Weber, William J

    2014-01-01

    In pursuit of whether nanocrystallinity could lead to higher anion conductivity, research has revealed contradicting results exposing the limited understanding of point defect energetics at grain boundaries (GBs)/interfaces. By disentangling and addressing key GB energetics issues, i.e., segregation, migration and binding energies of oxygen vacancies in the presence and absence of dopants at the GBs, and the segregation energetics of dopants, we elucidate, using atomic simulations of doped ceria, that dopant segregation is the key factor leading to degradation of oxygen conductivity in nanocrystalline materials. A framework for designing enhanced conducting nanocrystalline materials is proposed where the focus of doping strategies shifts from bulk to segregation at GBs.

  13. 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.

  14. Sparse Cyclic Excitations Explain the Low Ionic Conductivity of Stoichiometric Li_{7}La_{3}Zr_{2}O_{12}.

    PubMed

    Burbano, Mario; Carlier, Dany; Boucher, Florent; Morgan, Benjamin J; Salanne, Mathieu

    2016-04-01

    We have performed long time scale molecular dynamics simulations of the cubic and tetragonal phases of the solid lithium-ion electrolyte Li_{7}La_{3}Zr_{2}O_{12} (LLZO), using a first-principles parametrized interatomic potential. Collective lithium transport was analyzed by identifying dynamical excitations: persistent ion displacements over distances comparable to the separation between lithium sites, and stringlike clusters of ions that undergo cooperative motion. We find that dynamical excitations in c-LLZO (cubic) are frequent, with participating lithium numbers following an exponential distribution, mirroring the dynamics of fragile glasses. In contrast, excitations in t-LLZO (tetragonal) are both temporally and spatially sparse, consisting preferentially of highly concerted lithium motion around closed loops. This qualitative difference is explained as a consequence of lithium ordering in t-LLZO and provides a mechanistic basis for the much lower ionic conductivity of t-LLZO compared to c-LLZO.

  15. Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

    PubMed

    Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

    2015-12-15

    The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days.

  16. Effect of Al concentration on the holographic grating efficiency and ionic conductivity in sodium magnesium aluminosilicate glasses

    NASA Astrophysics Data System (ADS)

    Hamad, Abdulatif Y.; Wicksted, James P.; Hogsed, Michael R.; Martin, Joel J.; Hunt, Charles A.; Dixon, George S.

    2002-02-01

    A systematic study of grating formation, erasure, and decay in 15Na2O.12MgO.xAl2O3.(73-x)SiO2 glasses doped with 1.26 mol% Eu2O3 is reported as a function of Al2O3 concentration for x=0 to 15. The permanent change in the index of refraction was a linearly increasing function of Al2O3 concentration. The grating buildup and erasure rates also increased with Al2O3 concentrations. This is attributed to the reduced activation energy for forced diffusion of small modifiers bound to AlO-4 clusters rather than to nonbridging oxygens. Ionic conductivities were also measured to confirm the reduction of the activation energies. The results of this study support the model for grating kinetics in rare-earth sensitized glasses proposed recently by Dixon, Hamad, and Wicksted.

  17. Structure and properties of Li-ion conducting polymer gel electrolytes based on ionic liquids of the pyrrolidinium cation and the bis(trifluoromethanesulfonyl)imide anion

    NASA Astrophysics Data System (ADS)

    Pitawala, Jagath; Navarra, Maria Assunta; Scrosati, Bruno; Jacobsson, Per; Matic, Aleksandar

    2014-01-01

    We have investigated the structure and physical properties of Li-ion conducting polymer gel electrolytes functionalized with ionic liquid/lithium salt mixtures. The membranes are based on poly(vinylidene fluoride-co-hexafluoropropylene) copolymer, PVdF-HFP, and two ionic liquids: pyrrolidinium cations, N-butyl-N-methylpyrrolidinium (PyR14+), N-butyl-N-ethylpyrrolidinium (PyR24+), and bis(trifluoromethanesulfonyl)imide anion (TFSI). The ionic liquids where doped with 0.2 mol kg-1 LiTFSI. The resulting membranes are freestanding, flexible, and nonvolatile. The structure of the polymer and the interactions between the polymer and the ionic liquid electrolyte have been studied using Raman spectroscopy. The ionic conductivity of the membranes has been studied using dielectric spectroscopy whereas the thermal properties were investigated using differential scanning caloriometry (DSC). These results show that there is a weak, but noticeable, influence on the physical properties of the ionic liquid by the confinement in the membrane. We observe a change in the Li-ion coordination, conformation of the anion, the fragility and a slight increase of the glass transition temperatures for IL/LiTFSI mixtures in the membranes compared to the neat mixtures. The effect can be related to the confinement of the liquid in the membrane and/or to interactions with the PVdF-HFP polymer matrix where the crystallinity is decreased compared to the starting polymer powder.

  18. Local structure and ionic conductivity in the Zr2Y2O7-Y3NbO7 system

    NASA Astrophysics Data System (ADS)

    Norberg, Stefan T.; Ahmed, Istaq; Hull, Stephen; Marrocchelli, Dario; Madden, Paul A.

    2009-05-01

    The Zr0.5-0.5xY0.5+0.25xNb0.25xO1.75 solid solution possesses an anion-deficient fluorite structure across the entire 0<=x<=1 range. The relationship between the disorder within the crystalline lattice and the preferred anion diffusion mechanism has been studied as a function of x, using impedance spectroscopy measurements of the ionic conductivity (σ), powder neutron diffraction studies, including analysis of the 'total' scattering to probe the nature of the short-range correlations between ions using reverse Monte Carlo (RMC) modelling, and molecular dynamics (MD) simulations using potentials derived with a strong ab initio basis. The highest total ionic conductivity (σ = 2.66 × 10-2 Ω-1 cm-1 at 1473 K) is measured for the Zr2Y2O7 (x = 0) end member, with a decrease in σ with increasing x, whilst the neutron diffraction studies show an increase in lattice disorder with x. This apparent contradiction can be understood by considering the local structural distortions around the various cation species, as determined from the RMC modelling and MD simulations. The addition of Nb5+ and its stronger Coulomb interaction generates a more disordered local structure and enhances the mobility of some anions. However, the influence of these pentavalent cations is outweighed by the effect of the additional Y3+ cations introduced as x increases, which effectively trap many anions and reduce the overall concentration of the mobile O2- species.

  19. AC impedance analysis of ionic and electronic conductivities in electrode mixture layers for an all-solid-state lithium-ion battery

    NASA Astrophysics Data System (ADS)

    Siroma, Zyun; Sato, Tomohiro; Takeuchi, Tomonari; Nagai, Ryo; Ota, Akira; Ioroi, Tsutomu

    2016-06-01

    The ionic and electronic effective conductivities of an electrode mixture layers for all-solid-state lithium-ion batteries containing Li2Ssbnd P2S5 as a solid electrolyte were investigated by AC impedance measurements and analysis using a transmission-line model (TLM). Samples containing graphite (graphite electrodes) or LiNi0.5Co0.2Mn0.3O2 (NCM electrodes) as the active material were measured under a "substrate | sample | bulk electrolyte | sample | substrate" configuration (ion-electron connection) and a "substrate | sample | substrate" configuration (electron-electron connection). Theoretically, if the electronic resistance is negligibly small, which is the case with our graphite electrodes, measurement with the ion-electron connection should be effective for evaluating ionic conductivity. However, if the electronic resistance is comparable to the ionic resistance, which is the case with our NCM electrodes, the results with the ion-electron connection may contain some inherent inaccuracy. In this report, we theoretically and practically demonstrate the advantage of analyzing the results with the electron-electron connection, which gives both the ionic and electronic conductivities. The similarity of the behavior of ionic conductivity with the graphite and NCM electrodes confirms the reliability of this analysis.

  20. Electrical and ionic conductivity effects on magic-angle spinning nuclear magnetic resonance parameters of CuI.

    PubMed

    Yesinowski, James P; Ladouceur, Harold D; Purdy, Andrew P; Miller, Joel B

    2010-12-21

    We investigate experimentally and theoretically the effects of two different types of conductivity, electrical and ionic, upon magic-angle spinning NMR spectra. The experimental demonstration of these effects involves (63)Cu, (65)Cu, and (127)I variable temperature MAS-NMR experiments on samples of γ-CuI, a Cu(+)-ion conductor at elevated temperatures as well as a wide bandgap semiconductor. We extend previous observations that the chemical shifts depend very strongly upon the square of the spinning-speed as well as the particular sample studied and the magnetic field strength. By using the (207)Pb resonance of lead nitrate mixed with the γ-CuI as an internal chemical shift thermometer we show that frictional heating effects of the rotor do not account for the observations. Instead, we find that spinning bulk CuI, a p-type semiconductor due to Cu(+) vacancies in nonstoichiometric samples, in a magnetic field generates induced AC electric currents from the Lorentz force that can resistively heat the sample by over 200 °C. These induced currents oscillate along the rotor spinning axis at the spinning speed. Their associated heating effects are disrupted in samples containing inert filler material, indicating the existence of macroscopic current pathways between micron-sized crystallites. Accurate measurements of the temperature-dependence of the (63)Cu and (127)I chemical shifts in such diluted samples reveal that they are of similar magnitude (ca. 0.27 ppm/K) but opposite sign (being negative for (63)Cu), and appear to depend slightly upon the particular sample. This relationship is identical to the corresponding slopes of the chemical shifts versus square of the spinning speed, again consistent with sample heating as the source of the observed large shift changes. Higher drive-gas pressures are required to spin samples that have higher effective electrical conductivities, indicating the presence of a braking effect arising from the induced currents produced by

  1. Study on phase stability and ionic conductivity in TiIV-substituted bismuth vanadate

    NASA Astrophysics Data System (ADS)

    Beg, Saba; Haneef, Sadaf

    2014-09-01

    The solid solutions Bi4TixV2-xO11-(x/2)-δ in the composition range 0.05 ≤ x ≤ 0.30 were obtained by solid state reaction according to the substitution equation: ? The sample characterization and the study of phase transition were performed by using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), alternating current (AC) impedance and electrical conductivity measurements. The solid solutions with composition 0.05 ≤ x ≤ 0.17 are isostructural with the orthorhombic β-phase, and those with x ≥ 0.20 represent tetragonal γ‧-phase as confirmed by the XRD and DSC results. Arrhenius plots of conductivity show that with increase in Ti concentration, the conductivity of solid solutions increase and reaches a maximum value of 4.38 × 10-5 Scm-1 for x = 0.17 at 340 °C. It is seen that the highly conducting tetragonal γ‧-phase is effectively stabilized to room temperature for the composition x ≥ 0.20. AC impedance plots show that the conductivity is mainly due to the grain and the grain boundary contribution which is confirmed by the existence of two semicircles along with an inclined spike.

  2. Effect of pressure on the ionic conductivity of Li+ and Cl- ions in water

    NASA Astrophysics Data System (ADS)

    Varanasi, Srinivasa R.; Kumar, Parveen; Subramanian, Yashonath

    2012-10-01

    A molecular dynamics simulation study of aqueous solution of LiCl is reported as a function of pressure. Experimental measurements of conductivity of Li+ ion as a function of pressure shows an increase in conductivity with pressure. Our simulations are able to reproduce the observed trend in conductivity. A number of relevant properties have been computed in order to understand the reasons for the increase in conductivity with pressure. These include radial distribution function, void and neck distributions, hydration or coordination numbers, diffusivity, velocity autocorrelation functions, angles between ion-oxygen and dipole of water as well as OH vector, mean residence time for water in the hydration shell, etc. These show that the increase in pressure acts as a structure breaker. The decay of the self part of the intermediate scattering function at small wave number k shows a bi-exponential decay at 1 bar which changes to single exponential decay at higher pressures. The k dependence of the ratio of the self part of the full width at half maximum of the dynamic structure factor to 2Dk2 exhibits trends which suggest that the void structure of water is playing a role. These support the view that the changes in void and neck distributions in water can account for changes in conductivity or diffusivity of Li+ with pressure. These results can be understood in terms of the levitation effect.

  3. Conductivity Modulation of Gold Thin Film at Room Temperature via All-Solid-State Electric-Double-Layer Gating Accelerated by Nonlinear Ionic Transport.

    PubMed

    Asano, Tetsuya; Kaneko, Yukihiro; Omote, Atsushi; Adachi, Hideaki; Fujii, Eiji

    2017-02-15

    We demonstrated the field-effect conductivity modulation of a gold thin film by all-solid-state electric-double-layer (EDL) gating at room temperature using an epitaxially grown oxide fast lithium conductor, La2/3-xLi3xTiO3 (LLT), as a solid electrolyte. The linearly increasing gold conductivity with increasing gate bias demonstrates that the conductivity modulation is indeed due to carrier injection by EDL gating. The response time becomes exponentially faster with increasing gate bias, a result of the onset of nonlinear ionic transportation. This nonlinear dynamic response indicates that the ionic motion-driven device can be much faster than would be estimated from a linear ionic transport model.

  4. Toward Higher Energy Conversion Efficiency for Solid Polymer Electrolyte Dye-Sensitized Solar Cells: Ionic Conductivity and TiO2 Pore-Filling.

    PubMed

    Song, Donghoon; Cho, Woohyung; Lee, Jung Hyun; Kang, Yong Soo

    2014-04-03

    Even though the solid polymer electrolyte has many intrinsic advantages over the liquid electrolyte, its ionic conductivity and mesopore-filling are much poorer than those of the liquid electrolyte, limiting its practical application to electrochemical devices such as dye-sensitized solar cells (DSCs). Two major shortcomings associated with utilizing solid polymer electrolytes in DSCs are first discussed, low ionic conductivity and poor pore-filling in mesoporous photoanodes for DSCs. In addition, future directions for the successful utilization of solid polymer electrolytes toward improving the performance of DSCs are proposed. For instance, the facilitated mass-transport concept could be applied to increase the ionic conductivity. Modified biphasic and triple-phasic structures for the photoanode are suggested to take advantage of both the liquid- and solid-state properties of electrolytes.

  5. Ion diffusion coefficients model and molar conductivities of ionic salts in aprotic solvents.

    PubMed

    Garrido, Leoncio; Mejía, Alberto; García, Nuria; Tiemblo, Pilar; Guzmán, Julio

    2015-02-19

    In the study of the electric properties of electrolytes, the determination of the diffusion coefficients of the species that intervene in the charge transport process is of great importance, particularly that of the free ions (D(+) and D(-)), the only species that contribute to the conductivity. In this work we propose a model that allows, with reasonable assumptions, determination of D(+) and D(-), and the degree of dissociation of the salt, α, at different concentrations, using the diffusion coefficients experimentally obtained with NMR. Also, it is shown that the NMR data suffice to estimate the conductivity of the electrolytes. The model was checked by means of experimental results of conductivity and NMR diffusion coefficients obtained with solutions of lithium triflate in ethylene and propylene carbonates, as well as with other results taken from the literature.

  6. Pressure dependence of ionic conductivity of hydrated and dehydrated zeolites A

    NASA Astrophysics Data System (ADS)

    Goryainov, S. V.; Secco, R. A.; Huang, Y.; Liu, H.

    2007-03-01

    Hydrated and dehydrated zeolites MA (where M=Li, Na and K) with LTA structure have been studied by impedance spectroscopy with scanning frequency from 1 Hz to 1 MHz at high pressure up to 4.5 GPa and high temperature up to 250 °C. Anomalous increase in electrical AC conductivity at about 1.5-2 GPa observed in hydrated zeolites is associated with changes in crystalline structure leading to the formation of high-diffusion state of cation and water stuffing of the channels. In dehydrated zeolites, electrical conductivity is controlled by diffusion of cations (Li +, Na + and K +), which is determined by cation sites and aluminosilicate ring windows. LiA and NaA zeolites show normal decrease of conductivity with pressure, whereas KA zeolite exhibits the anomalous dependence with considerable increase and then fast decrease of conductivity. The behaviour of KA zeolite is associated with nearly central location of cation site in 8-membered ring, different from that in LiA and NaA zeolites.

  7. Structural origin of the enhanced ionic conductivity upon Nb doping in Sr11Mo4O23 defective double perovskite.

    PubMed

    Miranda, C D; López, C A; Pedregosa, J C; Alonso, J A

    2017-03-21

    We report a substantial enhancement of the oxide-ion conductivity in Sr11Mo4O23 achieved by Nb doping the Mo sites. This series responds to the formula: Sr11Mo4-xNbxO23-δ (with x = 0.0, 0.5 and 1.0). The original structure can be related to the conventional double perovskite; however, it presents a broken corner sharing connectivity of the octahedral framework, hence leading to a complex and highly defective network. The samples were prepared via citrate precursor method, followed by thermal treatments at 1300 °C for 12 hours in air. The crystal structures were refined from X-ray and neutron powder diffraction (NPD) data. A phase transition from tetragonal to cubic symmetry is identified in a temperature-dependent NPD study, driven by an oxygen delocalization effect. The ionic conductivity measured by impedance spectroscopy is enhanced upon Nb-doping; the x = 1 doped phase exhibits a threefold increase compared to the pristine Sr11Mo4O23 oxide, with conductivity values of 7.6 × 10(-3) and 2.7 × 10(-2) S·cm(-1) at 650 and 800 °C, which are even greater than for YSZ in the 650-800 °C temperature range, and close to those reported for other state-of-the art solid-oxide electrolytes.

  8. Microscopic signature of insulator-to-metal transition in highly doped semicrystalline conducting polymers in ionic-liquid-gated transistors

    SciTech Connect

    Tanaka, Hisaaki Nishio, Satoshi; Ito, Hiroshi; Kuroda, Shin-ichi

    2015-12-14

    Electronic state of charge carriers, in particular, in highly doped regions, in thin-film transistors of a semicrystalline conducting polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), has been studied by using field-induced electron spin resonance (ESR) spectroscopy. By adopting an ionic-liquid gate insulator, a gate-controlled reversible electrochemical hole-doping of the polymer backbone is achieved, as confirmed from the change of the optical absorption spectra. The edge-on molecular orientation in the pristine film is maintained even after the electrochemical doping, which is clarified from the angular dependence of the g value. As the doping level increases, spin 1/2 polarons transform into spinless bipolarons, which is demonstrated from the spin-charge relation showing a spin concentration peak around 1%, contrasting to the monotonic increase in the charge concentration. At high doping levels, a drastic change in the linewidth anisotropy due to the generation of conduction electrons is observed, indicating the onset of metallic state, which is also supported by the temperature dependence of the spin susceptibility and the ESR linewidth. Our results suggest that semicrystalline conducting polymers become metallic with retaining their molecular orientational order, when appropriate doping methods are chosen.

  9. 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.

  10. Design and synthesis of guest-host nanostructures to enhance ionic conductivity across nanocomposite membranes

    DOEpatents

    Hu, Michael Z [Knoxville, TN; Kosacki, Igor [Oak Ridge, TN

    2010-01-05

    An ion conducting membrane has a matrix including an ordered array of hollow channels and a nanocrystalline electrolyte contained within at least some or all of the channels. The channels have opposed open ends, and a channel width of 1000 nanometers or less, preferably 60 nanometers or less, and most preferably 10 nanometers or less. The channels may be aligned perpendicular to the matrix surface, and the length of the channels may be 10 nanometers to 1000 micrometers. The electrolyte has grain sizes of 100 nanometers or less, and preferably grain sizes of 1 to 50 nanometers. The electrolyte may include grains with a part of the grain boundaries aligned with inner walls of the channels to form a straight oriented grain-wall interface or the electrolyte may be a single crystal. In one form, the electrolyte conducts oxygen ions, the matrix is silica, and the electrolyte is yttrium doped zirconia.

  11. 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.

  12. Filler effect of ionic liquid attached titanium oxide on conducting property of poly(ethylene oxide)/poly(methyl methacrylate) composite electrolytes.

    PubMed

    Lee, Lyungyu; Kim, Ick-Jun; Yang, Sunhye; Kim, Seok

    2014-10-01

    Composite polymer electrolytes (CPEs) were prepared by containing blend of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) as a host polymer, propylene carbonate as a plasticizer, and LiClO4 as a salt. By an addition of a various content of ionic liquid attached TiO2 (IL-TiO2) to above electrolytes, the effects were studied. As a result, by increasing the IL-TiO2 content, the crystallinity of PEO was decreased and the ionic conductivity was increased. The ionic conductivity of CPEs was dependent on the content of IL-TiO2 and showed the highest value of 1.05 x 10(-4) S/cm at 9 wt.%. However, when IL-TiO2 content exceeds 9 wt.%, the ionic conductivity was decreased due to the slow ionic transport due to immiscibility or aggregation of the IL-TiO2 filler within the polymer film matrix.

  13. Application for continuation of mixed ionic and electronic conductivity in polymers

    SciTech Connect

    Shiver, D.F.; Ratner, M.A.

    1990-01-01

    The aim in this portion of the research is to prepare new electroactive films with high ion mobility, and to characterize the transport properties of these materials. The classic conducting polymers, polyacetylene, polythiophene, and polypyrrole have dense structures that prevent rapid redox switching because of the low diffusivity of ions. The objective is to modify the last two polymers with pendant polyethers, which should greatly improve ion transport.

  14. Slopes, nearly constant loss, universality, and hopping rates for dispersive ionic conduction

    NASA Astrophysics Data System (ADS)

    Macdonald, J. Ross; Ahmad, Mohamad M.

    2007-01-01

    The title topics are investigated, discussed, and new insights provided by considering isothermal frequency response data for seven different materials having quite different conductivity spans and involving different electrode polarization effects and temperatures. These data sets were fitted using several different models, including the Kohlrausch-related K0 and K1 ones derived from stretched-exponential response in the temporal domain. The quasi-universal UN model, the K1 with its shape parameter, β1, fixed at 1/3, fitted most of the data very well, and its fits of such data were used to compare its predictions for hopping rate with those derived from fitting with the conventional 'universal dynamic response' Almond-West real-part-of-conductivity model. The K1-model theoretical hopping rate, involving the mean waiting time for a hop and derived from microscopic stochastic analysis, was roughly twice as large as the empirical Almond-West rate for most of the materials considered and should be used in place of it. Its use in a generalized Nernst-Einstein equation led to comparison of estimates of the concentration of fully dissociated mobile charge carriers in superionic PbSnF4 with earlier estimates of Ahmad using an Almond-West hopping rate value. Agreement with an independent structure-derived value was relatively poor. Fitting results obtained using the K0 model, for Na2SO4 data sets for two different polycrystalline material phases, and involving severely limited conductivity variation, were far superior to those obtained using the K1 model. The estimated values of the K0 shape parameter, β0, were close to 1/3 for both phases, strongly suggesting that the charge motion was one dimensional for each phase, even though they involved different crystalline structures.

  15. Enhanced ionic conductivity and optical studies of plasticized (PEO-KCl) solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Chapi, Sharanappa; H, Devendrappa

    2015-06-01

    Solid polymer electrolytes (SPEs) based on Polyethylene oxide (PEO) doped with potassium chloride (KCl) were prepared by the solution cast technique. The conductivity increases from 10-10 to 10-6 Scm-1 at 303K with dopant. Optical absorption study shows that the direct & indirect optical band gaps were found decreased from 5.45-4.46eV and 4.96-3.86eV respectively with increasing the KCl. The XRD patterns reveal increasing the amorphous with increasing the dopent. The obtained results suggest that, these polymer systems are suitable candidates for solid state battery, electro chromic devices & optoelectronics display etc.

  16. Pressure-induced increase of ionic conduction of water-treated NaA zeolite

    NASA Astrophysics Data System (ADS)

    Secco, Richard A.; Goryainov, Sergei V.; Huang, Yining

    2005-07-01

    Dehydrated, hydrated and superhydrated NaA zeolites have been studied by impedance spectroscopy with scanning frequency from 1 Hz to 1 MHz at high pressure up to 4.5 GPa. A considerable anomalous increase in electrical conductivity in the range of 0.5-1.1 GPa was observed in superhydrated NaA zeolite containing additional water in the channels. A very high mobility of ions in superhydrated zeolite may be associated with the liquid-like state of the water-cation stuffing of zeolite channels.

  17. Charged local anesthetics block ionic conduction in the sheep cardiac sarcoplasmic reticulum calcium release channel.

    PubMed Central

    Tinker, A; Williams, A J

    1993-01-01

    We have examined the effect of the charged local anesthetics QX314, QX222, and Procaine on monovalent cation conduction in the Ca2+ release channel of the sheep cardiac sarcoplasmic reticulum. All three blockers only affect cation conductance when present at the cytoplasmic face of the channel. QX222 and Procaine act as voltage-dependent blockers. With 500 Hz filtering, this is manifest as a relatively smooth reduction in single-channel current amplitude most prominent at positive holding potentials. Quantitative analysis gives an effective valence of approximately 0.9 for both ions and Kb(0)s of 9.2 and 15.8 mM for QX222 and Procaine, respectively. Analysis of the concentration dependence of block suggests that QX222 is binding to a single site with a Km of 491 microM at a holding potential of 60 mV. The use of amplitude distribution analysis, with the data filtered at 1 to 2 kHz, reveals that the voltage and concentration dependence of QX222 block occurs largely because of changes in the blocker on rate. The addition of QX314 has a different effect, leading to the production of a substate with an amplitude of approximately one-third that of the control. The substate's occurrence is dependent on holding potential and QX314 concentration. Quantitative analysis reveals that the effect is highly voltage dependent, with a valence of approximately 1.5 caused by approximately equal changes in the on and off rates. Kinetic analysis of the concentration dependence of the substate occurrence reveals positive cooperativity with at least two QX314s binding to the conduction pathway, and this is largely accounted for by changes in the on rate. A paradoxical increase in the off rate at high positive holding potentials and with increasing QX314 concentration at 80 mV suggests the existence of a further QX314-dependent reaction that is both voltage and concentration dependent. The substate block is interpreted physically as a form of partial occlusion in the vestibule of the

  18. Lead titanate/cyclic carbonate dependence on ionic conductivity of ferro/acrylate blend polymer composites

    NASA Astrophysics Data System (ADS)

    Jayaraman, R.; Vickraman, P.; Subramanian, N. M. V.; Justin, A. Simon

    2016-05-01

    Impedance, XRD, DSC and FTIR studies had been carried out for PVdF-co-HFP/LIBETI based system for three plasticizer (EC/DMC) - filler (PbTiO3) weight ratios. The enhanced conductivity 4.18 × 10-5 Scm-1 was noted for 57.5 wt% -7.5 wt% plasticizer - filler. while blending PEMA to PVdF-co-HFP respectively 7.5: 22.5 wt % (3/7), 15 wt%: 15 wt % (5/5) and 22.5wt %: 7.5 wt % (7/3), the improved conductivity was noted for 3/7 ratio 1.22 × 10-5 S cm-1 and its temperature dependence abide Arrhenius behavior. The intensity of peaks in XRD diffractogram registered dominance of lead titanate, from 2θ = 10° to 80° and absence of VdF crystallites (α+β phase) was noted. In DSC studies, the presence of the exotherm events, filler effect was distinctively seen exhibiting recrystallization of VdF crystallites. In blending PEMA, however, no trace of exotherms was found suggestive of PEMA better inhibiting recrystallization. FTIR study confirmed molecular interactions of various constituents in the vibrational band 500 - 1000 cm-1 both in pristine PVdF-co-HFP and PEMA blended composites with reference to C-F stretching, C-H stretching and C=O carbonyl bands.

  19. Porous polymer electrolytes with high ionic conductivity and good mechanical property for rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Liang, Bo; Jiang, Qingbai; Tang, Siqi; Li, Shengliang; Chen, Xu

    2016-03-01

    Porous polymer electrolytes (PPEs) are attractive for developing lithium-ion batteries because of the combined advantages of liquid and solid polymer electrolytes. In the present study, a new porous polymer membrane doped with phytic acid (PA) is prepared, which is used as a crosslinker in polymer electrolyte matrix and can also plasticize porous polymer electrolyte membranes, changing them into soft tough flexible materials. A PEO-PMMA-LiClO4-x wt.% PA (x = weight of PA/weight of polymer, PEO: poly(ethylene oxide); PMMA: poly(methyl methacrylate)) polymer membrane is prepared by a simple evaporation method. The effects of the ratio of PA to PEO-PMMA on the properties of the porous membrane, including morphology, porous structure, and mechanical property, are systematically studied. PA improves the porous structure and mechanical properties of polymer membrane. The maximum tensile strength and elongation of the porous polymer membranes are 20.71 MPa and 45.7% at 15 wt.% PA, respectively. Moreover, the PPEs with 15 wt.% PA has a conductivity of 1.59 × 10-5 S/cm at 20 °C, a good electrochemical window (>5 V), and a low interfacial resistance. The results demonstrate the compatibility of the mechanical properties and conductivity of the PPEs, indicating that PPEs have good application prospects for lithium-ion batteries.

  20. Ionic ac and dc conductivities of NaCrP2O7 compound

    NASA Astrophysics Data System (ADS)

    Sassi, M.; Oueslati, A.; Gargouri, M.

    2015-05-01

    The NaCrP2O7 compound was prepared by the solid-state reaction method. The formation of a single-phase material was confirmed by the X-ray diffraction studies and found to be a monoclinic system. The electrical properties of this compound have been measured in the temperature range from 523 to 673 K and the frequency range from 209 Hz to 5 MHz. The Nyquist plots are well fitted to an equivalent circuit consisting of a series of combination of grains and grain boundary elements. The ac conductivity of NaCrP2O7 has been analyzed as a function of temperature and frequency. The scaling behavior of the imaginary part of the complex modulus suggests that the relaxation describes the same mechanism at various temperatures. The conductivity and modulus formalisms provide nearly the same activation energies for electrical relaxation of mobile ions suggesting that the ion transport is probably due to a hopping mechanism dominated by the motion of the monovalent ions Na+ along tunnels presented in the structure of the investigated material.

  1. Conductance, a contrivance to explore ion association and solvation behavior of an ionic liquid (tetrabutylphosphonium tetrafluoroborate) in acetonitrile, tetrahydrofuran, 1,3-dioxolane, and their binaries.

    PubMed

    Ekka, Deepak; Roy, Mahendra Nath

    2012-09-27

    Precise measurements on electrical conductance (Λ) of solutions of an ionic liquid (IL) tetrabutylphosphonium tetrafluoroborate in acetonitrile (ACN), tetrahydrofuran (THF), and 1,3-dioxolane (1,3-DO) and their binary mixtures have been reported at 298.15 K. The conductance data have been analyzed by the Fuoss conductance equation (1978) in terms of the limiting molar conductance (Λ(o)), the association constant (K(A)), and the association diameter (R) for ion-pair formation. The Walden product is obtained and discussed. However, the deviation of the conductometric curves (Λ versus √c) from linearity for the electrolyte in THF and 1,3-DO and their binary mixtures indicated triple-ion formation and therefore the corresponding conductance data have been analyzed by the Fuoss–Kraus theory of triple ions. The limiting ionic conductances (λ(o)(±)) have been estimated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu(4)NBPh(4)] as the “reference electrolyte” method along with a numerical evaluation of ion-pair and triple-ion formation constants (K(P) ≈ K(A) and K(T)). The results have been discussed in terms of solvent properties and configurational theory. Ionic association in the limiting molar conductances as well as the single-ion conductivity values have been determined for the electrolyte in the solvent media.

  2. Atomistic simulations of ammonium-based protic ionic liquids: steric effects on structure, low frequency vibrational modes and electrical conductivity.

    PubMed

    Sunda, Anurag Prakash; Mondal, Anirban; Balasubramanian, Sundaram

    2015-02-14

    Protic ionic liquids (PILs) are of great interest as electrolytes in various energy applications. Molecular dynamics simulations of trialkylammonium (with varying alkyl group such as methyl, ethyl, and n-propyl) triflate PILs are performed to characterize the influence of the alkyl group on the acidic site (N-H) of the ammonium cation. Spatial distribution function of anions over this site on the cation reveals significant influence of the length of alkyl tail on intermolecular structure. Vibrational density of states and normal modes are calculated for bulk liquids to probe atomic displacements in the far infrared region. The observed N-H···O hydrogen bond stretching vibration in 155-165 cm(-1) frequency region agrees well with experiments. Trends in electrical conductivity calculated using Nernst-Einstein and Green-Kubo relation are in qualitative agreement with experiments. The self-diffusion coefficient and the electrical conductivity is highest for N,N-dimethyl-N-ethylammonium triflate ([N112][TfO]) and is lowest for N,N-di-n-propyl-N-methylammonium triflate ([N133][TfO]) IL.

  3. Study of Mast Cells and Granules from Primo Nodes Using Scanning Ionic Conductance Microscopy.

    PubMed

    Yoo, Yeong-Yung; Jung, Goo-Eun; Kwon, Hee-Min; Bae, Kyoung-Hee; Cho, Sang-Joon; Soh, Kwang-Sup

    2015-12-01

    Acupuncture points have a notable characteristic in that they have a higher density of mast cells (MCs) compared with nonacupoints in the skin, which is consistent with the augmentation of the immune function by acupuncture treatment. The primo vascular system, which was proposed as the anatomical structure of the acupuncture points and meridians, also has a high density of MCs. We isolated the primo nodes from the surfaces of internal abdominal organs, and the harvested primo nodes were stained with toluidine blue. The MCs were easily recognized by their stained color and their characteristic granules. The MCs were classified into four stages according to the degranulation of histamine granules in the MCs. Using conventional optical microscopes details of the degranulation state of MCs in each stage were not observable. However, we were able to investigate the distribution of the granules on the surfaces of the MCs in each stage, and to demonstrate the height profiles and three-dimensional structures of the MCs without disturbance of the cell membrane by using the scanning ion conductance microscopy.

  4. Thermal, mechanical and ionic conductive behaviour of gamma-radiation induced PEO/PVDF(SIN)-LiClO 4 polymer electrolyte system

    NASA Astrophysics Data System (ADS)

    Song, Yongxian; Wu, Shuyun; Jing, Xiabing; Sun, Jiazhen; Chen, Donglin

    1997-05-01

    An effort has been made to modify the mechanical behaviour of our previously reported gel-type gamma-radiation crosslinked polyethylene oxide (PEO)-LiClO 4 polymer electrolyte. A highly polar and gamma-radiation crosslinkable crystalline polymer, polyvinylidene fluoride (PVDF), was selected to blend with PEO and then subjected to gamma-irradiation in order to make an simultaneous interpenetrating network (SIN), which was used as a polymer host to impart stiffness to the plasticized system. Experimental results have shown that the presence of PVDF in the system, through gamma-radiation induced SIN formation, could not only give a rather high mechanical modulus of 10 7 Pa at ambient temperature, but also maintain the room temperature ionic conductivity at a high level (greater than 10 -4 S/cm). DSC, DMA and conductivity measurement techniques were used to examine the effects of blending, gamma-irradiation and plasticization on the variations of glass transition and melting endotherm, on the appearance of high elastic plateau and on the temperature dependence of ionic conductivity. In addition, it was found that, in contrast with the unplasticized system, the ionic conductivity mechanism of this gel-type electrolyte seems to conform to the Arrhenius model, suggesting that, as a result of the high degree of plasticization, the polymer chains act mainly as the skeleton of the networks or polymer cages to immobilize the liquid electrolyte solution, whereas the ionic species migrate as if they were in a liquid medium.

  5. Enhanced Ionic Conductivity and Power Generation Using Ion-Exchange Resin Beads in a Reverse-Electrodialysis Stack.

    PubMed

    Zhang, Bopeng; Gao, Haiping; Chen, Yongsheng

    2015-12-15

    Reverse electrodialysis (RED) is a promising technique for harvesting energy by mixing seawater with river water. The energy production is usually limited by ionic conductivity in dilute compartments of a RED system. Novel tests were conducted in this research, which used ion-exchange resin beads (IERB) to replace nonconductive spacer fabrics in RED compartments with dilute NaCl solution in a modified stack containing Fumasep FKS and Fumasep FAS membranes. We compared the conductivity of an IERB packed bed with that of an inert glass-beads-packed bed as a control to confirm IERB's effectiveness. When applied in a RED system, IERB decreased the stack resistance by up to 40%. The maximum gross power density improved by 83% in the RED stack compared to that in a regular RED stack at 1.3 cm/s average linear flow velocity. IERB-filled stack resistance was modeled. The model results fit well with experimental data, thereby confirming the effectiveness of the new approach presented here. The net power density is also estimated based on the measured pressure drop and pumping energy model. Both gross and net power density was improved by over 75% at higher flow rate. A net power density of 0.44 W/m(2) was achieved at a cell thickness of 500 μm. To the best of our knowledge, this research is the first to study the impact of IERB on power generation and establishes a new approach to improving the power performance of a RED system.

  6. Ionic conductivity studies of solid oxide fuel cell electrolytes and theoretical modeling of an entire solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pornprasertsuk, Rojana

    Because of the steep increase in oil prices, the global warming effect and the drive for energy independence, alternative energy research has been encouraged worldwide. The sustainable fuels such as hydrogen, biofuel, natural gas, and solar energy have attracted the attention of researchers. To convert these fuels into a useful energy source, an energy conversion device is required. Fuel cells are one of the energy conversion devices which convert chemical potentials into electricity. Due to their high efficiency, the ease to scale from 1 W range to megawatts range, no recharging requirement and the lack of CO2 and NOx emission (if H2 and air/O 2 are used), fuel cells have become a potential candidate for both stationary power generators and portable applications. This thesis has been focused primarily on solid oxide fuel cell (SOFC) studies due to its high efficiency, varieties of fuel choices, and no water management problem. At the present, however, practical applications of SOFCs are limited by high operating temperatures that are needed to create the necessary oxide-ion vacancy mobility in the electrolyte and to create sufficient electrode reactivities. This thesis introduces several experimental and theoretical approaches to lower losses both in the electrolyte and the electrodes. Yttria stabilized zirconia (YSZ) is commonly used as a solid electrolyte for SOFCs due to its high oxygen-ion conductivity. To improve the ionic conductivity for low temperature applications, an approach that involves dilating the structure by irradiation and introducing edge dislocations into the electrolyte was studied. Secondly, to understand the activation loss in SOFC, the kinetic Monte Carlo (KMC) technique was implemented to model the SOFC operation to determining the rate-limiting step due to the electrodes on different sizes of Pt catalysts. The isotope exchange depth profiling technique was employed to investigate the irradiation effect on the ionic transport in different

  7. Dielectric α-relaxation and ionic conductivity in propylene glycol and its oligomers measured at elevated pressure

    NASA Astrophysics Data System (ADS)

    Casalini, Riccardo; Roland, C. Michael

    2003-12-01

    Structural dynamics and volume were measured as a function of both temperature and pressure for a propylene glycol and its oligomers (PPG), and the results compared with previous data on higher molecular weight polypropylene glycols. PPG is of special interest because the terminal groups form hydrogen bonds; thus, by studying different molecular weights, the manner in which hydrogen bonding influences the dynamics in the supercooled regime can be systematically investigated. The fragility (Tg-normalized temperature dependence) of the dimer and trimer of PPG increases with pressure, similar to results for other H-bonded liquids, but different from van der Waals glass formers. This behavior is believed to be due to the effect of pressure in decreasing the extent of hydrogen bonding. From the combined temperature and volume dependences of the relaxation times, the relative degree to which thermal energy and volume govern the dynamics was quantified. With decreasing molecular weight, the relative contribution of thermal energy to the dynamics was found to strongly increase, reflecting the role of hydrogen bonding. By comparing the ionic conductivity and the dielectric relaxation times, a decoupling between rotational and translational motions was observed. Interestingly, this decoupling was independent of both pressure and molecular weight, indicating that hydrogen bonds have a negligible effect on the phenomenon.

  8. Effect of the structural evolution on the ionic conductivity of Li-N-H system during the dehydrogenation

    NASA Astrophysics Data System (ADS)

    Paik, Biswajit; Matsuo, Motoaki; Sato, Toyoto; Qu, Liyuan; Wolczyk, Anna Roza; Orimo, Shin-ichi

    2016-05-01

    On the way to transform lithium amide (LiNH2) into lithium imide (Li2NH) by releasing H2, the 1:1 molar mixture of LiNH2-LiH forms cubic ( F m 3 ¯ m ) non-stoichiometric complex hydride phases (Li1+xNH2-x; 0 < x < 1) that co-exist with the tetragonal ( I 4 ¯ ) LiNH2 and with the cubic ( F d 3 ¯ m ) Li2NH, respectively, at the early and at the advanced stage of the dehydrogenation. The change in LiNH2 → Li2NH may be viewed as a mechanism which continuously fills up the vacant Li sites of the tetragonal structure and, in a parallel process, transforms the anions [NH2]- → [NH]2-. The Li-N-H system, thus formed, by releasing >6 wt. % H2 can offer high Li-ionic conductivity (>10-4 S.cm-1 at room temperature) having an electrochemical stability window >5 V. The study suggests that the Li-N-H system may be a prospective electrolyte in the all-solid-state Li-ion battery, in addition to its use as a reversible hydrogen storage material.

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

    SciTech Connect

    Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; Wang, Haiyan; Jia, Quanxi; MacManus-Driscoll, Judith L.

    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 ZrO2 (YSZ) nanocolumns, strain coupled to a SrTiO3 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 of the YSZ nanocolumns to the SrTiO3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO2 nanocolumns within the SrTiO3 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.

  10. 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 ZrO2 (YSZ) nanocolumns, strain coupled to a SrTiO3 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 of the YSZmore » nanocolumns to the SrTiO3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO2 nanocolumns within the SrTiO3 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

  11. 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.

  12. A Metal-Organic Framework Impregnated with a Binary Ionic Liquid for Safe Proton Conduction above 100 °C.

    PubMed

    Sun, Xiao-Li; Deng, Wei-Hua; Chen, Hui; Han, Hong-Liang; Taylor, Jared M; Wan, Chong-Qing; Xu, Gang

    2017-01-26

    To develop proton-conducting materials under low-humidity conditions and at moderate working temperature still remains challenging for fuel-cell technology. Here, a new type of proton-conducting material, EIMS-HTFSA@MIL, which was prepared by impregnating the binary ionic liquid, EIMS-HTFSA (EIMS=1-(1-ethyl-3-imidazolium)propane-3-sulfonate; HTFSA=N,N-bis(trifluoromethanesulfonyl)amide), into a mesoporous metal-organic framework, MIL-101 ([Cr3 F(H2 O)2 O(BDC)3 ⋅n H2 O] (n≈0.25, BDC=1,4-benzenedicarboxylate)) is reported. By taking advantage of the ionic-liquid properties, such as high thermal stability, non-volatility, non-flammability, and low corrosivity, EIMS-HTFSA@MIL shows potential application as a safe electrolyte in proton conduction above 100 °C.

  13. Crystal Structure and Ionic Conductivity of Three Polymorphic Phases of Rubidium Trefluoromethyl Sulfonate, RbSO3CF3

    SciTech Connect

    Hildebrandt,L.; Dinnebier, R.; Jansen, M.

    2006-01-01

    The crystal structures of three polymorphic phases of rubidium trifluoromethyl sulfonate (RbSO{sub 3}CF{sub 3}, rubidium 'triflate') were solved from X-ray powder diffraction data. At room temperature, rubidium triflate crystallizes in the monoclinic space group Cm with lattice parameters of a = 19.9611(5) Angstroms, b = 23.4913(7) Angstroms, c = 5.1514(2) Angstroms, = 102.758(2); Z = 16. At T = 321 K, a first-order phase transition occurs toward a monoclinic phase in space group P2{sub 1} with lattice parameters at T = 344 K of a = 10.3434(5) Angstroms, b = 5.8283(3) Angstroms, c = 5.1982(3) Angstroms, = 104.278(6); Z = (2). At T = 461 K, another phase transition, this time of second order, occurs toward an orthorhombic phase in space group Cmcm with lattice parameters at T = 510 K of a = 5.3069(2) Angstroms, b = 20.2423(10) Angstroms, c = 5.9479(2) Angstroms; Z = 4. As a common feature within all three crystal structures of rubidium triflate, the triflate anions are arranged in double layers with the lipophilic CF{sub 3} groups facing each other. The rubidium ions are located between the SO{sub 3} groups. The general packing is similar to the packing in cesium triflate. Rubidium triflate can be classified as a solid electrolyte with a specific ionic conductivity of = 9.89 x 10{sup -9} S/cm at T = 384 K and = 3.84 x 10{sup -6} S/cm at T = 481 K.

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

    SciTech Connect

    Suthirakun, Suwit; Xiao, Guoliang; Ammal, Salai Cheettu; Chen, Fanglin; zur Loye, Hans-Conrad; Heyden, Andreas

    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- 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.

  15. Ionic conductivity of Bi12(V,Bi)O20 + δ single crystal (δ = 0.27) with a sillenite-type structure

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.

    2012-11-01

    The ionic conductivity of nonstoichiometric Bi12(V0.89Bi0.03)O20.27 single crystal with a sillenite-type structure has been investigated by impedance spectroscopy; its conductivity at 673 K is 2 × 10-3 S/cm, which is about two orders of magnitude higher than the conductivity of oxide superionic conductor single crystal Zr0.88Y0.12O1.94. As follows from crystallochemical analysis, ion transport in Bi12(V0.89Bi0.03)O20.27 is due to additional O2- ions, which arise due to oxygen nonstoichiometry.

  16. EFFECT OF (Bi2O3)0.75(Y2O3)0.25 ADDITION ON MICROSTRUCTURES AND IONIC CONDUCTIVITIES OF CODOPED ZIRCONIA

    NASA Astrophysics Data System (ADS)

    Chou, Chen Chia; Huang, Chun Feng; Yeh, Tsung Her

    2012-09-01

    Variation of microstructures and ionic conductivities in (Bi2O3)0.75(Y2O3)0.25 (YSB) modified electrolyte of 8 mol% Y2O3 stabilized zirconia (8YSZ) and YSB modified codoped zirconia (ZrO2)0.92(Y2O3)0.075(MgO)0.005 (YSZM) is investigated in this work. The results demonstrated that a small amount of δ-YSB addition is effective in reducing the sintering temperature of 8YSZ from 1500 to 1200°C and promoting the densification rate of ceramics. Compared to 8YSZ electrolyte, it is interesting that a very limited amount of monoclinic ZrO2 was observed due to the MgO stabilizer in YSB modified codoped zirconia electrolyte. Besides, enhancement of ionic conductivity in δ-YSB modified codoped zirconia is evidently increased by 67% in comparison to the specimen of 8YSZ electrolyte.

  17. Strain tuning and strong enhancement of ionic conductivity in SrZrO3-RE2O3 (RE = Sm, Eu, Gd, Dy, and Er) nanocomposite films

    DOE PAGES

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

    2015-06-05

    Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO3–RE2O3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE2O3. With increasing lattice constant of RE2O3 from Er2O3 to Sm2O3, it is found that the tensile strain in the SrZrO3 increases proportionately, and the ionic conductivity ofmore » the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    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 (10-1-106 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.

  19. 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.

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

    SciTech Connect

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

    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 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.

  1. 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

  2. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    DOE PAGES

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; ...

    2016-04-29

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, themore » electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.« less

  3. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    SciTech Connect

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

    2016-04-29

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, the electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.

  4. Rigid-flexible coupling high ionic conductivity polymer electrolyte for an enhanced performance of LiMn2O4/graphite battery at elevated temperature.

    PubMed

    Hu, Pu; Duan, Yulong; Hu, Deping; Qin, Bingsheng; Zhang, Jianjun; Wang, Qingfu; Liu, Zhihong; Cui, Guanglei; Chen, Liquan

    2015-03-04

    LiMn2O4-based batteries exhibit severe capacity fading during cycling or storage in LiPF6-based liquid electrolytes, especially at elevated temperatures. Herein, a novel rigid-flexible gel polymer electrolyte is introduced to enhance the cyclability of LiMn2O4/graphite battery at elevated temperature. The polymer electrolyte consists of a robust natural cellulose skeletal incorporated with soft segment poly(ethyl α-cyanoacrylate). The introduction of the cellulose effectively overcomes the drawback of poor mechanical integrity of the gel polymer electrolyte. Density functional theory (DFT) calculation demonstrates that the poly(ethyl α-cyanoacrylate) matrices effectively dissociate the lithium salt to facilitate ionic transport and thus has a higher ionic conductivity at room temperature. Ionic conductivity of the gel polymer electrolyte is 3.3 × 10(-3) S cm(-1) at room temperature. The gel polymer electrolyte remarkably improves the cycling performance of LiMn2O4-based batteries, especially at elevated temperatures. The capacity retention after the 100th cycle is 82% at 55 °C, which is much higher than that of liquid electrolyte (1 M LiPF6 in carbonate solvents). The polymer electrolyte can significantly suppress the dissolution of Mn(2+) from surface of LiMn2O4 because of strong interaction energy of Mn(2+) with PECA, which was investigated by DFT calculation.

  5. Graphene with Electrochemical Ionic-Liquid Assistance Synthesis to Explore the Metal Adsorption Ability and the High Electrical Conductivity in Graphene/Epoxy Composite

    NASA Astrophysics Data System (ADS)

    Chang, Chia-Feng; Chiang, Yi-Fang; Chen, Jiann-Ruey

    2012-10-01

    A simple and one-step method of producing graphenes was investigated in this work. We have modified the Hummer electrolysis method and combined it with ionic liquid for productions. The results showed that the graphenes could absorb Cu2+ at 202.2 mg/g. Additionally, the mechanism of how graphenes absorb metal and the effects of acidity are described. We have proved that the synthesized graphenes successfully based on transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray powder diffraction (XRD), Raman spectroscopy (Raman), and Fourier transform infrared (FTIR) analysis. This investigation also showed that the graphenes' highest adsorption of Cu(II) at pH 8 mainly resulted from the ionic-like charge and no-defect surface. We found that the highest conductivity of 10-2 S/m was achieved as the binary graphene/epoxy composite (0.3%).

  6. NMR, surface tension and conductance study to investigate host-guest inclusion complexes of three sequential ionic liquids with β-cyclodextrin in aqueous media

    NASA Astrophysics Data System (ADS)

    Barman, Siti; Ekka, Deepak; Saha, Subhadeep; Roy, Mahendra Nath

    2016-08-01

    Host-guest inclusion complexes of three sequential cationic room temperature surface active ionic liquids, benzyltrialkylammonium chloride [(C6H5CH2)N(CnH2n+1)3Cl; where n = 1, 2, 4] with β-cyclodextrin in aqueous media have been studied using surface tension, conductance and NMR spectroscopy. All the studies have suggested that the hydrophobic benzyl group of ionic liquids is encapsulated inside into the cavity of β-cyclodextrin and played a crucial role in supporting the formation of inclusion complexes. The variation of the thermodynamic parameters with guest size, shape is used to draw inferences about contributions to the overall binding by means of the driving forces, viz., hydrophobic effect, steric hindrance, van der Waal force, and electrostatic force.

  7. Viscoelastic Properties, Ionic Conductivity, and Materials Design Considerations for Poly(styrene-b-ethylene oxide-b-styrene)-Based Ion Gel Electrolytes

    SciTech Connect

    Zhang, Sipei; Lee, Keun Hyung; Sun, Jingru; Frisbie, C. Daniel; Lodge, Timothy P.

    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 the 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

  8. Obtaining Mixed Ionic/Electronic Conductivity in Perovskite Oxides in a Reducing Environment: A Computational Prediction for Doped SrTiO3

    SciTech Connect

    Suthirakun, Suwit; Ammal, Salai Cheettu; Xiao, Guoliang; Chen, Fanglin; Huang, Kevin; zur Loye, Hans-Conrad; Heyden, Andreas

    2012-11-30

    The electronic conductivity and thermodynamic stability of mixed p- and n-doped SrTiO3 perovskites have been investigated under anodic solid oxide fuel cell conditions using density functional theory (DFT). In particular, constrained ab initio thermodynamic calculations have been performed to evaluate the phase stability of various Ga- and La-doped SrTiO3 at synthesized and anodic SOFC conditions. The density of states (DOS) of these materials was analyzed to determine the number of charge carriers and the degree of electronic conductivity. We find that a mixed ionic/electronic conductor can be obtained when doping SrTiO3 perovskite oxide with both p-type and n-type dopants. Calculations show that 10% Ga- and 20% La-doped SrTiO3 exhibit mixed ionic/electronic conductivity at high temperature and low oxygen partial pressure whereas doping with higher concentrations of Ga, e.g., 20%, diminishes the electronic conductivity of the material. Furthermore, changing the n-dopant from La (A-site) to Nb (B-site) does not significantly affect the reducibility and number of charge carriers in p- and n-doped SrTiO3. However, a higher degree of oxygen vacancy clustering is observed for the La-doped material which reduces the oxygen ion diffusion rate and traps electrons. Nevertheless, our findings suggest that independent of doping site, mixed ionic/ electronic conductivity can be obtained in SrTiO3 perovskite oxides under reducing conditions and high temperatures when using a mixed p- and n-type doping strategy that uses a p-dopant concentration smaller than the n-dopant concentration.

  9. Fundamental Studies on Confinement Effects in Ionic Conduction and Inversion Layers in 2-D Single Crystal Free Standing Oxide Membranes

    DTIC Science & Technology

    2014-02-14

    hysteresis in a model system vanadium dioxide. Electric double layer transistors are then fabricated with the membranes and compared to thin film devices... vanadium dioxide. Electric double layer transistors are then fabricated with the membranes and compared to thin film devices. The ionic liquid...02/14/2014 Received Paper 1.00 2.00 4.00 J. Sim, Y. Zhou, S. Ramanathan. Suspended sub-50 nm vanadium dioxide membrane transistors: fabricationand

  10. 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.

  11. Study of reversible electrode reaction and mixed ionic and electronic conduction of lithium phosphate electrolyte for an electrochemical CO2 gas sensor

    NASA Astrophysics Data System (ADS)

    Lee, Chong-Hoon

    An electrochemical CO2 gas sensor with lithium ion conductor was developed and characterized in order to examine the potential for real-life applications and understand its sensing mechanism. Li2CO3 and Li2TiO3 + TiO2 mixture were used as a sensing and a reference auxiliary phase, respectively. This electrochemical cell with a solid state Li3PO4 electrolyte has shown good selectivity, sensitivity and linear response in laboratory and automobile exhaust tests. However, the sensor response to CO2 gas showed a systematic deviation from the Nernst equation. Measured EMF did not agree with that calculated from the Nernst equation, even though it followed logarithmic behavior. Moreover, high sensitivity was observed for high CO2 concentrations (5˜50%), compared to that for concentrations (500˜5000 ppm). Two possible reasons for this deviation are: (1) reversibility of electrode reaction and (2) mixed ionic and electronic conduction of the electrolyte. Unless electrode reaction is fast enough, electrode polarization can easily induce overpotential. Pure ionic conduction of electrolyte is also necessary to avoid EMF loss during open circuit potential measurement. EIS (Electrochemical Impedance Spectroscopy) was used to study electrode kinetics. We found that Li2TiO3 + TiO2 mixture reference electrode reaction is sluggish showing large electrode impedance. This impedance, however, was not affected by gas concentration change. On the other hand, that at the Li2CO3 sensing electrode is relatively small and it increased with decreased CO2 and O 2 concentration. It was also observed that these electrode impedances induced the overpotential when the current flowed through the sensor. This electrode overpotential problem was minimized by mixing gold powder or porous sputtered gold electrode increasing effective reaction sites of the electrode. New electrode design improved the sensor EMF closer to the Nernstian values, however, the discrepancy still remained. Moreover, at

  12. Ionic liquid containing microemulsions: probe by conductance, dynamic light scattering, diffusion-ordered spectroscopy NMR measurements, and study of solvent relaxation dynamics.

    PubMed

    Pramanik, Rajib; Sarkar, Souravi; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

    2011-03-17

    Room-temperature ionic liquid (RTIL), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([P(13)][Tf(2)N]), was substituted for polar water and formed nonaqueous microemulsions with benzene by the aid of nonionic surfactant TX-100. The phase behavior of the ternary system was investigated, and microregions of [P(13)][Tf(2)N]-in-benzene (IL/O), bicontinuous, and benzene-in-[P(13)][Tf(2)N] (O/IL) were identified by traditional electrical conductivity measurements. Dynamic light scattering (DLS) revealed the formation of these IL microemulsions because with gradual increase of RTIL contents the droplet sizes of the microemulsions are also gradually increasing. Pulsed-field gradient spin-echo NMR have been studied to measure the diffusion coefficients of neat [P(13)][Tf(2)N] and [P(13)][Tf(2)N] in microemulsions which indicate ionic liquid containing microemulsions is formed. Moreover, the dynamics of solvent relaxation have been investigated in [P(13)][Tf(2)N]/TX100/benzene microemulsions using steady-state and time-resolved fluorescence spectroscopy using coumarin 153 (C-153) and coumarin 480 (C-480) fluorescence probe with variation of RTIL contents in microemulsions. For both of the probes with increasing amount of ionic liquids in microemulsions the relative contribution of the fast components increases and the slow components contribution decreases; therefore the average solvation time decreases.

  13. Effect of water on the transport properties of protic and aprotic imidazolium ionic liquids - an analysis of self-diffusivity, conductivity, and proton exchange mechanism.

    PubMed

    Yaghini, N; Nordstierna, L; Martinelli, A

    2014-05-28

    In this paper we report on the transport properties of protic and aprotic ionic liquids of the imidazolium cation (C2C1Im(+) or C2HIm(+)) and the TFSI(-) or TfO(-) anion as a function of added water. We observe that the self-diffusion coefficient of the ionic species increases upon addition of water, and that the cation diffuses faster than the anion in the entire water concentration range investigated. We also observe that the overall increase of anionic and cationic diffusion coefficients is significant for C2HImTfO while it is rather weak for C2C1ImTFSI, the former being more hydrophilic. Moreover, the difference between cationic and anionic self-diffusivity specifically depends on the structure of the ionic liquid's ions. The degree of ion-ion association has been investigated by comparing the molar conductivity obtained by impedance measurements with the molar conductivity calculated from NMR data using the Nernst-Einstein equation. Our data indicate that the ions are partly dissociated (Λimp/ΛNMR in the range 0.45-0.75) but also that the degree of association decreases in the order C2HImTfO > C2HImTFSI ≈ C2C1ImTfO > C2C1ImTFSI. From these results, it seems that water finds different sites of interaction in the protic and aprotic ionic liquids, with a strong preference for hydrogen bonding to the -NH group (when available) and a stronger affinity to the TfO anion as compared to the TFSI. For the protic ionic liquids, the analysis of (1)H NMR chemical shifts (upon addition of H2O and D2O, respectively) indicates a water-cation interaction of hydrogen bonding nature. In addition, we could probe proton exchange between the -NH group and deuterated water for the protic cation, which occurs at a significantly faster rate if associated with the TfO anion as compared to the TFSI.

  14. Electrical conductivity of seven binary systems containing 1-ethyl-3-methyl imidazolium alkyl sulfate ionic liquids with water or ethanol at four temperatures.

    PubMed

    Rilo, E; Vila, J; García-Garabal, S; Varela, L M; Cabeza, O

    2013-02-07

    We present experimental measurements of specific electrical (or ionic) conductivity of seven binary systems of 1-ethyl-3-methyl imidazolium alkyl sulfate (EMIM-C(n)S) with water or ethanol. Electrical conductivity was measured at 298.15 K in all ranges of concentrations and selected mixtures also at 288.15, 308.15, and 318.15 K. The alkyl chains of the anions used are ethyl (EMIM-ES), butyl (EMIM-BS), hexyl (EMIM-HS), and, only for mixtures with ethanol, octyl (EMIM-OS). Let us note that the four ionic liquids (ILs) measured are miscible in water and ethanol at those temperatures and atmospheric pressure in all ranges of concentrations, but EMIM-OS jellifies for a given range of concentration with water. We compare the measured data in terms of the alkyl chain length and solvent nature. Data are compared with previously scarce results for these same systems and also for other aqueous and ethanol mixtures with ILs. In addition, we verify that our data fit the universal theoretical expression with no fitting parameters given by the pseudolattice-based Bahe-Varela model, except for IL concentrated mixtures. To fit well all ranges of concentrations, we add to the original equation two phenomenological terms with one fitting parameter each. Finally, we calculate the molar conductivity and fit it successfully with an expression derived from Onsager theory.

  15. Conductivity and spectroscopic investigation of bis(trifluoromethanesulfonyl)imide solution in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

    PubMed

    Yu, Lei; Pizio, Benjamin S; Vaden, Timothy D

    2012-06-07

    Protic ionic liquids (PILs) are promising alternatives to water for swelling Nafion as a fuel cell proton exchange membrane (PEM). PILs can significantly improve the high-temperature performance of a PEM. The proton dissociation and solvation mechanisms in a PIL, which are keys to understanding the proton transportation and conductivity, have not been fully explored. In this paper, we used FTIR, Raman, and electronic spectroscopy with computational simulation techniques to explore the spectroscopic properties of bis(trifluoromethanesulfonyl)imide (HTFSI) solutions in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) ionic liquid at concentrations from ∼0.1 to as high as ∼1.0 M. Solution conductivities were measured at room temperature and elevated temperatures up to ∼65 °C. The solution structure and properties depend on the concentration of HTFSI. At lower concentration, around 0.1 M, the HTFSI solution has higher conductivity than pure BMITFSI. However, the conductivity decreases when the concentration increases from 0.1 to 1.0 M. Temperature-dependent conductivities followed the Vogel-Fulcher-Tamman equation at all concentrations. Conductivity and spectroscopy results elucidate the complicated ionization and solvation mechanism of HTFSI in BMITFSI solutions. Raman spectroscopy and density functional theory (DFT) calculations are consistent with the complete ionization of HTFSI to generate solvated H(+) at low concentrations. FTIR, Raman, and electronic spectroscopic results as well as DFT computational simulation indicated that when the concentration is as high as 1.0 M, a significant amount of TFSI(-) is protonated, most likely at the imide nitrogen.

  16. Effect of Ionic Conductivity on Response Speed of SrTiO3-Based All-Solid-State Electric-Double-Layer Transistor.

    PubMed

    Tsuchiya, Takashi; Ochi, Masanori; Higuchi, Tohru; Terabe, Kazuya; Aono, Masakazu

    2015-06-10

    An all-solid-state electric-double-layer transistor (EDLT) with a Y-stabilized ZrO₂ (YSZ) proton conductor/SrTiO₃ (STO) single crystal has been fabricated to investigate ionic conductivity effect on the response speed, which should be a key parameter for development of next-generation EDLTs. The drain current exhibited a 4-order-of-magnitude increment by electrostatic carrier doping at the YSZ/STO interface due to ion migration, and the behavior strongly depended on the operation temperature. An Arrhenius-type plot of the ionic conductivity (σ(i)) in the YSZ and t(c)⁻¹, which is a current-rise time needed for charge accumulation at the YSZ/STO interface, shows a synchronized variation, indicating a proportional relationship between the two parameters. Analysis of the σ(i)-t(c) diagram shows that, in contrast to conventional EDLTs, the response speed should reach picosecond order at room temperature by using extreme miniaturization and superionic conductors. Furthermore, the diagram indicates that plenty of solid electrolytes, which have not been used due to the lack of criteria for evaluation, can be a candidate for all-solid-state EDLTs exceeding the carrier density of conventional EDLTs, even though the response speed becomes comparably lower than those of FETs.

  17. Proton conducting sulfonated poly (imide-benzimidazole) with tunable density of covalent/ionic cross-linking for fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Yue, Zhouying; Cai, Yang-Ben; Xu, Shiai

    2015-07-01

    Ionic cross-linked sulfonated polyimides containing bis-benzimidazole rings have been prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 6,6‧-bis[2-(4-aminophenyl)benzimidazole] (BAPBI) and 3,3‧-bis(4-sulfophenoxy)- benzidine (BSPOB). A new cross-linker, 4,4‧-bibromomethenyl diphenyl ether, is used to induce covalent cross-linking between halogen and imidazole groups in SPIBI chains via a facile thermally activated reaction. The resulted covalent and ionic cross-linked membranes show an improved resistance to hydrolytic attack in deionized water at 80 °C (more than two months) and free radical attack in Fenton's solution (more than 690 min) as compared to non-cross-linked SPIBIs (less than two days and 270 min, respectively). Cross-linking also results in a reduction in proton conductivity due to the blockage of a hydrophilic channel. However, all the prepared CBr-ySPIBI-x membranes show a proton conductivity higher than 10-2 S cm-1 under hydrous condition. This could be attributed to the fact that more cross-linking sites are contained in each repeating unit, which ensures enough cross-linking degree at high sulfonation level. All these results suggest that CBr-ySPIBI-x membranes have a great potential for applications in the proton exchange membrane fuel cells.

  18. Scroll-wave dynamics in the presence of ionic and conduction inhomogeneities in an anatomically realistic mathematical model for the pig heart

    NASA Astrophysics Data System (ADS)

    Majumder, R.; Pandit, R.; Panfilov, A. V.

    2016-12-01

    Nonlinear waves of the reaction-diffusion (RD) type occur in many biophysical systems, including the heart, where they initiate cardiac contraction. Such waves can form vortices called scroll waves, which result in the onset of life-threatening cardiac arrhythmias. The dynamics of scroll waves is affected by the presence of inhomogeneities, which, in a very general way, can be of ionic type, i.e., they affect the reaction part, or conduction type, i.e., they affect the diffusion part of an RD-equation. We demostrate, for the first time, by using a state-of-the-art, anatomically realistic model of the pig heart, how differences in the geometrical and biophysical nature of such inhomogeneities can influence scroll-wave dynamics in different ways. Our study reveals that conduction-type inhomogeneities become increasingly important at small length scales, i.e., in the case of multiple, randomly distributed, obstacles in space at the cellular scale (0.2-0.4mm). Such configurations can lead to scroll-wave break up. In contrast, ionic inhomogeneities, affect scroll-wave dynamics significantly at large length scales, when these inhomogeneities are localized in space at the tissue level (5-10mm). In such configurations, these inhomogeneities can attract scroll waves, by pinning them to the heterogeneity, or lead to scroll-wave breakup.

  19. Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature

    NASA Astrophysics Data System (ADS)

    Yang, Chih-Ping; Chen, Hsiao-Chien; Wang, Ching-Chiung; Tsai, Po-Wei; Ho, Chia-Wen; Liu, Yu-Chuan

    2015-12-01

    Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water’s tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water’s fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte’s concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4’-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water’s fundamental activities via effective energy transfer.

  20. Effective Energy Transfer via Plasmon-Activated High-Energy Water Promotes Its Fundamental Activities of Solubility, Ionic Conductivity, and Extraction at Room Temperature

    PubMed Central

    Yang, Chih-Ping; Chen, Hsiao-Chien; Wang, Ching-Chiung; Tsai, Po-Wei; Ho, Chia-Wen; Liu, Yu-Chuan

    2015-01-01

    Water is a ubiquitous solvent in biological, physical, and chemical processes. Unique properties of water result from water’s tetrahedral hydrogen-bonded (HB) network (THBN). The original THBN is destroyed when water is confined in a nanosized environment or localized at interfaces, resulting in corresponding changes in HB-dependent properties. In this work, we present an innovative idea to validate the reserve energy of high-energy water and applications of high-energy water to promote water’s fundamental activities of solubility, ionic conductivity, and extraction at room temperature. High-energy water with reduced HBs was created by utilizing hot electrons with energies from the decay of surface plasmon excited at gold (Au) nanoparticles (NPs). Compared to conventional deionized (DI) water, solubilities of alkali metal-chloride salts in high-energy water were significantly increased, especially for salts that release heat when dissolved. The ionic conductivity of NaCl in high-energy water was also markedly higher, especially when the electrolyte’s concentration was extremely low. In addition, antioxidative components, such as polyphenols and 2,3,5,4’-tetrahydroxystilbene-2-O-beta-d-glucoside (THSG) from teas, and Polygonum multiflorum (PM), could more effectively be extracted using high-energy water. These results demonstrate that high-energy water has emerged as a promising innovative solvent for promoting water’s fundamental activities via effective energy transfer. PMID:26658304

  1. Investigation of ionic conductivity and long-term stability of a LiI and KI coupled diphenylamine quasi-solid-state dye-sensitized solar cell.

    PubMed

    Agarwala, S; Peh, C K N; Ho, G W

    2011-07-01

    In this work, enhancement of ionic conductivity and long-term stability through the addition of diphenylamine (DPA) in poly(ethylene oxide) (PEO) is demonstrated. Potassium iodide (KI) is adopted as the crystal growth inhibitor, and DPA is used as a charge transport enhancer in the electrolyte. The modified electrolyte is used with titanium dioxide (TiO2) nanoparticles, which is systematically tuned to obtain high surface area. The dye-sensitized solar cell (DSSC) showed a photocurrent of 14 mAcm2 with a total conversion efficiency of 5.8% under one sun irradiation. DPA enhances the interaction of the TiO2 nanoparticle film and the I-/I3- electrolyte leading to high ionic conductivity (3.5 × 10-3 Scm-1), without compromising on the electrochemical and mechanical stability. Electrochemical impedance spectroscopy (EIS) studies show that electron transport and electron lifetime are enhanced in the DPA added electrolyte due to reduced sublimation of iodine. The most promising feature of the electrolyte is increased device stability with 89% of the overall efficiency preserved even after 40 days.

  2. Ionic Intercalation in Two-Dimensional van der Waals Materials: In Situ Characterization and Electrochemical Control of the Anisotropic Thermal Conductivity of Black Phosphorus.

    PubMed

    Kang, Joon Sang; Ke, Ming; Hu, Yongjie

    2017-03-08

    Two-dimensional van der Waals materials have shown novel fundamental properties and promise for wide applications. Here, we report for the first time an experimental demonstration of the in situ characterization and highly reversible control of the anisotropic thermal conductivity of black phosphorus. We develop a novel platform based on lithium ion batteries that integrates ultrafast optical spectroscopy and electrochemical control to investigate the interactions between lithium ions and the lattices of the black phosphorus electrode. We discover a strong dependence of the thermal conductivity on battery charge states (lithium concentrations) during the discharge/charge process. The thermal conductivity of black phosphorus is reversibly tunable over a wide range of 2.45-3.86, 62.67-85.80, and 21.66-27.58 W·m(-1)·K(-1) in the cross-plan, zigzag, and armchair directions, respectively. The modulation in thermal conductivity is attributed to phonon scattering introduced by the ionic intercalation in between the interspacing layers and shows anisotropic phonon scattering mechanism based on semiclassical model. At the fully discharged state (x ∼ 3 in LixP), a dramatic reduction of thermal conductivity by up to 6 times from that of the pristine crystal has been observed. This study provides a unique approach to explore the fundamental energy transport involving lattices and ions in the layered structures and may open up new opportunities in controlling energy transport based on novel operation mechanisms and the rational design of nanostructures.

  3. An evaluation of in-situ measurements of water temperature, specific conductance, and pH in low ionic strength streams

    USGS Publications Warehouse

    Ranalli, A.J.

    1998-01-01

    Survey for continuous measurement of water temperature, specific conductance, and pH in four low ionic strength streams in the Catskill Mountains of New York was evaluated through a calculation of their bias, precision, and accuracy and by comparison with laboratory measurements of specific conductance and pH on samples collected concurrently. Results indicate that the mini-monitor measurements of specific conductance and pH in an acidic stream (acid-neutralizing capacity always less than 0) agreed with laboratory measurements well enough that the minimonitors can be used to supplement laboratory measurements (mean difference in pH was 0.02 pH unit and mean difference in specific conductance was 0.72 ??S cm-1. This mean difference was 0.32 ??S cm-1 if the minimonitor data were adjusted by the bias). In less acidic streams (two streams in which the acid-neutralizing capacity was always greater than 0 and one in which the acid-neutralizing capacity was greater than 0 except during high flows), there was poor agreement between laboratory and minimonitor measurements of specific conductance at high flows and pH at all flows. The water-temperature probes measured with sufficiently small bias (-0.1 ??C) and adequate precision (??0.70 ??C) for use with most applications.

  4. Thiophosphates Containing Ag(+) and Lone-Pair Cations with Interchiral Double Helix Show Both Ionic Conductivity and Phase Transition.

    PubMed

    Fan, Yu-Hang; Zeng, Hui-Yi; Jiang, Xiao-Ming; Zhang, Ming-Jian; Liu, Bin-Wen; Guo, Guo-Cong; Huang, Jin-Shun

    2017-01-17

    Quaternary metal thiophosphates containing second-order Jahn-Teller distorted d(10) Ag(+) and lone-pair cations, Ag3Bi(PS4)2 (1), Ag7Sn(PS4)3 (2), and Ag7Pb(PS4)3 (3), were obtained by solid-state synthesis. The structural frameworks of 2 and 3 feature an infinite 1-D interchiral double helix ∞(1)(Ag3P2S11), which is rare in inorganic compounds. Compound 3 undergoes a significant first-order structural phase transition from monoclinic to hexagonal at ∼204 °C. This can be ascribed to the significant mismatch in the expansion coefficients between Pb-S (Ag-S) and P-S bonds evaluated by bond valence theory. The three compounds are Ag(+) ionic conductors, and Ag(+) ion migration pathways are proposed by calculating maps of low bond valence mismatch. Moreover, the optical properties of the three compounds were studied, and electronic structure calculations were performed. The combination of second-order Jahn-Teller distorted d(10) cation and lone-pair cation provides a new strategy to explore new metal thiophosphates with interesting structures and promising properties.

  5. Exploration on effects of 15 nm SiO2 filler on miscibility, thermal stability and ionic conductivity of PMMA/ENR 50 electrolytes

    NASA Astrophysics Data System (ADS)

    Zamri, S. F. M.; Latif, F. A.; Ali, A. M. M.; Ibrahim, R.; Azuan, S. I. H. M.; Kamaluddin, N.; Hadip, F.

    2017-02-01

    The effects of silicon dioxide (SiO2) (15 nm) filler on miscibility, thermal stability and ionic conductivity of polymethyl methacrylate/50% epoxidized narural rubber (PMMA/ENR 50) electrolytes were successfully explored. Samples were prepared by solvent casting method with tetrahydrofuran (THF) as solvent and doped with lithium tetrafluoroborate (LiBF4). Fourier transform infrared spectroscopy (FTIR) confirmed the present of hydrogen bond between PMMA and ENR 50. However, the hydrogen bond was reduced when SiO2 was added. Differential scanning calorimeter (DSC) analysis shows that PMMA/ENR 50 blends exhibit two glass transition temperatures (Tgs) recorded at -35 and 89 °C corresponding to the Tg of ENR 50 rich phase (Tg1) and PMMA rich phase (Tg2), respectively. However, the two Tgs almost merging and reduced when SiO2 was added. Tg1 was found increases as SiO2 weight percent increased. Thermogravimetric analysis (TGA) revealed that thermal degradation temperatures (Tds) of SiO2 filled PMMA/ENR 50 was similar as PMMA/ENR 50. Interestingly, thermal degradation temperatures of the loss of impurities (Td1) and thermal degradation temperatures of PMMA side chain (Td2) were increased when SiO2 was added. Meanwhile thermal degradation temperatures of main PMMA and ENR 50 main chain (Td3) was decreased as SiO2 was added. There was no significant change in Td1, Td2 and Td3 as SiO2 weight percent was varied. Electrochemical impedence spectroscopy (EIS) analysis shows that room temperature ionic conductivity of SiO2 filled PMMA/ENR 50 electrolytes were higher compaed PMMA/ENR 50 electrolyte with two conductivity maxima.

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

    PubMed

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

    2005-12-29

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

  7. Ion distribution in quaternary-ammonium-functionalized aromatic polymers: effects on the ionic clustering and conductivity of anion-exchange membranes.

    PubMed

    Weiber, E Annika; Jannasch, Patric

    2014-09-01

    A series of copoly(arylene ether sulfone)s that have precisely two, three, or four quaternary ammonium (QA) groups clustered directly on single phenylene rings along the backbone are studied as anion-exchange membranes. The copolymers are synthesized by condensation polymerizations that involve either di-, tri-, or tetramethylhydroquinone followed by virtually complete benzylic bromination using N-bromosuccinimide and quaternization with trimethylamine. This synthetic strategy allows excellent control and systematic variation of the local density and distribution of QA groups along the backbone. Small-angle X-ray scattering of these copolymers shows extensive ionic clustering, promoted by an increasing density of QA on the single phenylene rings. At an ion-exchange capacity (IEC) of 2.1 meq g(-1), the water uptake decreases with the increasing local density of QA groups. Moreover, at moderate IECs at 20 °C, the Br(-) conductivity of the densely functionalized copolymers is higher than a corresponding randomly functionalized polymer, despite the significantly higher water uptake of the latter. Thus, the location of multiple cations on single aromatic rings in the polymers facilitates the formation of a distinct percolating hydrophilic phase domain with a high ionic concentration to promote efficient anion transport, despite probable limitations by reduced ion dissociation. These findings imply a viable strategy to improve the performance of alkaline membrane fuel cells.

  8. Chloride conductance across toad skin: effects of ionic acclimations and cyclic AMP and relationship to mitochondria-rich cell density.

    PubMed

    Rozman, A; Gabbay, S; Katz, U

    2000-07-01

    The anionic conductance across toad (Bufo viridis) skin was studied using the voltage-clamp technique following long-term (more than 10 days) acclimation to NaCl and KCl solutions. The non-specific baseline conductance was approximately 0.6 mS cm(-)(2) and was similar in skins from all acclimation conditions. The voltage-activated Cl(-) conductance (G(Cl)) was maximal in skins from distilled-water- and KCl-acclimated toads (>3 mS cm(-)(2)) and was greatly reduced following acclimation to NaCl solutions. Cyclic AMP (EC(50)=13 micromol l(-)(1)) and isobutylmethyl xanthine (IBMX) (EC(50)=69 micromol l(-)(1)) exerted different effects on the activated conductance. IBMX only sensitized the activated conductance, whereas cyclic AMP (CPTcAMP) at high concentrations induced an increase in anionic conductance that was insensitive to electrical potential. Furthermore, external Cl(-) was not required for the stimulatory effect of cyclic AMP, and the conductive pathway had low selectivity. The effects of the two agonists were reversible and depended on the acclimation conditions. Following electrical measurements, the skin of the toads was removed and stained with silver to measure mitochondria-rich cell density (D(mrc)). There was no correlation between D(mrc) and Cl(-) conductance in the present study.

  9. Effect of Li{sub 2}SO{sub 4} addition on structure and ionic conductivity of lithium borosilicotitanate glasses

    SciTech Connect

    Satpute, N. S.; Deshpande, A. V.

    2014-04-24

    Lithium borosilicotitanate glasses containing Li{sub 2}SO{sub 4} were prepared by melt quenching technique. Electrical conductivity, density, molar volume and glass transition temperature T{sub g} for all the glass samples were measured. IR spectroscopy was used for structural studies of these glasses in the range from 400 to 2000 cm{sub −1}. The conductivity of the Li{sub 2}SO{sub 4} containing glasses was found to be half an order higher than the base glass. The electrical conductivity was interpreted from the point of view of glass structure which suggests that an enhancement in conductivity is due to the incorporation of Li{sub 2}SO{sub 4} in the macromolecular network. The molar volume and glass transition temperature T{sub g} results are found to be in good correlation with conductivity results.

  10. Liquid-like ionic conduction in solid lithium and sodium monocarba-closo-decaborates near or at room temperature

    DOE PAGES

    Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; ...

    2016-02-05

    Both LiCB9H10 and NaCB9H10 exhibit liquid-like cationic conductivities (≥0.03 S cm–1) in their disordered hexagonal phases near or at room temperature. Furthermore, these unprecedented conductivities and favorable stabilities enabled by the large pseudoaromatic polyhedral anions render these materials in their pristine or further modified forms as promising solid electrolytes in next-generation, power devices.

  11. Ionic Conductivity of Mesostructured Yttria-Stabilized Zirconia Thin Films with Cubic Pore Symmetry—On the Influence of Water on the Surface Oxygen Ion Transport.

    PubMed

    Elm, Matthias T; Hofmann, Jonas D; Suchomski, Christian; Janek, Jürgen; Brezesinski, Torsten

    2015-06-10

    Thermally stable, ordered mesoporous thin films of 8 mol % yttria-stabilized zirconia (YSZ) were prepared by solution-phase coassembly of chloride salt precursors with an amphiphilic diblock copolymer using an evaporation-induced self-assembly process. The resulting material is of high quality and exhibits a well-defined three-dimensional network of pores averaging 24 nm in diameter after annealing at 600 °C for several hours. The wall structure is polycrystalline, with grains in the size range of 7 to 10 nm. Using impedance spectroscopy, the total electrical conductivity was measured between 200 and 500 °C under ambient atmosphere as well as in dry atmosphere for oxygen partial pressures ranging from 1 to 10(-4) bar. Similar to bulk YSZ, a constant ionic conductivity is observed over the whole oxygen partial pressure range investigated. In dry atmosphere, the sol-gel derived films have a much higher conductivity, with different activation energies for low and high temperatures. Overall, the results indicate a strong influence of the surface on the transport properties in cubic fluorite-type YSZ with high surface-to-volume ratio. A qualitative defect model which includes surface effects (annihilation of oxygen vacancies as a result of water adsorption) is proposed to explain the behavior and sensitivity of the conductivity to variations in the surrounding atmosphere.

  12. Ionic-to-electronic conductivity of glasses in the P2O5-V2O5-ZnO-Li2O system

    NASA Astrophysics Data System (ADS)

    Langar, A.; Sdiri, N.; Elhouichet, H.; Ferid, M.

    2016-12-01

    Glasses having a composition 15V2O5-5ZnO-(80- x P2O5- xLi2O ( x = 5 , 10, 15 mol%) were prepared by the conventional melt quenching. Conduction and relaxation mechanisms in these glasses were studied using impedance spectroscopy in a frequency range from 10 Hz to 10 MHz and in a temperature range from 513 K to 566 K. The structure of the amorphous synthetic product was corroborated by X-ray diffraction (disappearance of nacrite peaks). The DC conductivity follows the Arrhenius law and the activation energy determined by regression analysis varies with the content of Li2O. Frequency-dependent AC conductivity was analyzed by Jonscher's universal power law, which is varying as ωn, and the temperature-dependent power parameter supported by the Correlated Barrier Hopping (CBH) model. For x = 15 mol%, the values of n ≤ 0.5 confirm the dominance of ionic conductivity. The analysis of the modulus formalism with a distribution of relaxation times was carried out using the Kohlrausch-Williams-Watts (KWW) stretched exponential function. The stretching exponent, β, is dependent on temperature. The analysis of the temperature variation of the M" peak indicates that the relaxation process is thermally activated. Modulus study reveals the temperature-dependent non-Debye-type relaxation phenomenon.

  13. Effect of poly(ethylene oxide) on ionic conductivity and electrochemical properties of poly(vinylidenefluoride) based polymer gel electrolytes prepared by electrospinning for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Prasanth, Raghavan; Shubha, Nageswaran; Hng, Huey Hoon; Srinivasan, Madhavi

    2014-01-01

    Effect of poly(ethylene oxide) on the electrochemical properties of polymer electrolyte based on electrospun, non-woven membrane of PVdF is demonstrated. Electrospinning process parameters are controlled to get a fibrous membrane consisting of bead-free, uniformly dispersed thin fibers with diameter in the range of 1.5-1.9 μm. The membrane with good mechanical strength and porosity exhibits high uptake when activated with the liquid electrolyte of lithium salt in a mixture of organic solvents. The polymer gel electrolyte shows ionic conductivity of 4.9 × 10-3 S cm-1 at room temperature. Electrochemical performance of the polymer gel electrolyte is evaluated in Li/polymer electrolyte/LiFePO4 coin cell. Good performance with low capacity fading on charge-discharge cycling is demonstrated.

  14. A high performance flexible all solid state supercapacitor based on the MnO2 sphere coated macro/mesoporous Ni/C electrode and ionic conducting electrolyte

    NASA Astrophysics Data System (ADS)

    Zhi, Jian; Reiser, Oliver; Wang, Youfu; Hu, Aiguo

    2016-06-01

    A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating

  15. Ionic conductivity and dielectric relaxation in Y doped La2Mo2O9 oxide-ion conductors

    NASA Astrophysics Data System (ADS)

    Paul, T.; Ghosh, A.

    2014-10-01

    In this work, we have studied electrical conductivity and dielectric properties of polycrystalline La2-xYxMo2O9 (0.05 ≤ x ≤ 0.3) compounds in the temperature range from 358 K to 1088 K and the frequency range from 10 Hz to 3 GHz. The bulk and grain boundary contributions to the overall conductivity of these compounds show Arrhenius type behavior at low temperatures. The random free-energy barrier model has been used to analyze the frequency dependence of the conductivity. The charge carrier relaxation time and its activation energy have been determined from the analysis of the conductivity spectra using this model. The results obtained from the random free-energy barrier model satisfy Barton-Nakajima-Namikawa relation. The conduction mechanism has been also predicted using random free-energy barrier model and the scaling formalism. We have observed that the dielectric relaxation peaks arise from the diffusion of oxygen ions via vacancies.

  16. Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries.

    PubMed

    Wu, Jian-Fang; Pang, Wei Kong; Peterson, Vanessa K; Wei, Lu; Guo, Xin

    2017-04-12

    All-solid-state Li-ion batteries with metallic Li anodes and solid electrolytes could offer superior energy density and safety over conventional Li-ion batteries. However, compared with organic liquid electrolytes, the low conductivity of solid electrolytes and large electrolyte/electrode interfacial resistance impede their practical application. Garnet-type Li-ion conducting oxides are among the most promising electrolytes for all-solid-state Li-ion batteries. In this work, the large-radius Rb is doped at the La site of cubic Li6.10Ga0.30La3Zr2O12 to enhance the Li-ion conductivity for the first time. The Li6.20Ga0.30La2.95Rb0.05Zr2O12 electrolyte exhibits a Li-ion conductivity of 1.62 mS cm(-1) at room temperature, which is the highest conductivity reported until now. All-solid-state Li-ion batteries are constructed from the electrolyte, metallic Li anode, and LiFePO4 active cathode. The addition of Li(CF3SO2)2N electrolytic salt in the cathode effectively reduces the interfacial resistance, allowing for a high initial discharge capacity of 152 mAh g(-1) and good cycling stability with 110 mAh g(-1) retained after 20 cycles at a charge/discharge rate of 0.05 C at 60 °C.

  17. Ionic conductivity of crystallization products of Ba1- x Yb x F2 + x melts ( x = 0.1, 0.2, 0.25)

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.; Sul'yanova, E. A.; Sobolev, B. P.

    2016-05-01

    The ionic conductivity σ of the crystallization products of Ba1 - x Yb x F2 + x melts with 10, 20 and 25 mol % YbF3 has been studied. A Ba0.9Yb0.1F2.1 sample is a solid solution with the CaF2 structure type, sp. gr. Fmoverline 3 m. A Ba0.8Yb0.2F2.2 sample contains two cubic forms with sp. gr. Fmoverline 3 m and Pmoverline 3 m. The σ values for Ba0.9Yb0.1F2.1 and Ba0.8Yb0.2F2.2 coincide and are equal to 3 × 10-5 S/cm at 500 K. A Ba0.75Yb0.25F2.25 sample is heterogeneous, despite its monolithic nature and transparency. A greater part of its volume has a cubic lattice with sp. gr. Pmoverline 3 m, while the smaller part is a phase crystallizing in the orthorhombic system. A change of composition from x = 0.2 to 0.25 leads to a change in the symmetry group and type of the cluster defects in the Ba1 - x Yb x F2 + x phase. The sp. gr. Fmoverline 3 m is replaced by the sp. gr. Pmoverline 3 m, and octahedral‒cubic {Ba8Yb6F69} clusters are transformed into "inverse" octahedral‒cubic {Yb8Ba6F71} clusters. These changes in the defect structure lead to an increase in conductivity by a factor of about 100. The fluorine-ionic conductivity of Ba0.75Yb0.25F2.25 is 2.5 × 10-3 S/cm at 500 K. This value exceeds the conductivity of Ba0.69La0.31F2.31 crystal by a factor of 15 (Ba0.69La0.31F2.31 has the best conducting properties among the fluorite phases of the Ba1 - x R x F2 + x family, for which σ was found to increase with a decrease in the atomic number of rare earth element (REE)).

  18. Ionic conduction in non-uniform nanopores and DNA translocation: a Nernst-Planck-Jacobs one-dimensional description

    NASA Astrophysics Data System (ADS)

    Marini Bettolo Marconi, Umberto; Melchionna, Simone

    2013-12-01

    The conduction of an electrolyte solution in the presence of a DNA intruder in a synthetic charged pore is studied by theoretical means. The pore conductivity is controlled by two competing mechanisms: the steric effect of the DNA decreases the current and the extra-surface charges determine an increase in the number of charge carriers that increase the current. By using a Nernst-Planck description of the electrolyte and a one-dimensional advection-diffusion equation similar to the Jacobs-Zwanzig method, we obtain the characteristic curve within the local electroneutrality approximation. Such an information allows predicting the variation of the conductance caused by the DNA intruder and determining the current blockage/enhancement phase diagram.

  19. Hierarchical Nanostructured WO3 with Biomimetic Proton Channels and Mixed Ionic-Electronic Conductivity for Electrochemical Energy Storage.

    PubMed

    Chen, Zheng; Peng, Yiting; Liu, Fang; Le, Zaiyuan; Zhu, Jian; Shen, Gurong; Zhang, Dieqing; Wen, Meicheng; Xiao, Shuning; Liu, Chi-Ping; Lu, Yunfeng; Li, Hexing

    2015-10-14

    Protein channels in biologic systems can effectively transport ions such as proton (H(+)), sodium (Na(+)), and calcium (Ca(+)) ions. However, none of such channels is able to conduct electrons. Inspired by the biologic proton channels, we report a novel hierarchical nanostructured hydrous hexagonal WO3 (h-WO3) which can conduct both protons and electrons. This mixed protonic-electronic conductor (MPEC) can be synthesized by a facile single-step hydrothermal reaction at low temperature, which results in a three-dimensional nanostructure self-assembled from h-WO3 nanorods. Such a unique h-WO3 contains biomimetic proton channels where single-file water chains embedded within the electron-conducting matrix, which is critical for fast electrokinetics. The mixed conductivities, high redox capacitance, and structural robustness afford the h-WO3 with unprecedented electrochemical performance, including high capacitance, fast charge/discharge capability, and very long cycling life (>50,000 cycles without capacitance decay), thus providing a new platform for a broad range of applications.

  20. Ionic conductivity and electrical relaxation of nanocrystalline scandia-stabilized c-zirconia using complex impedance analysis

    NASA Astrophysics Data System (ADS)

    Kumar, Ashok; Manna, I.

    2008-07-01

    A solid solution of 8 mol% of scandia-stabilized cubic-zirconia (8ScSZ) has been prepared by co-precipitation technique. The synthesized powder has an average crystallite size ∼40 nm, surface area of 8.49 m 2/g, and agglomerated particle size of 150 nm. The activation energy of 8ScSZ has been calculated from impedance loss spectra; electrical modulus spectra are in the range of 0.90-1.30 eV. The frequency and temperature-dependent conductivities and impedance were measured in range of 50 Hz-1 MHz and 300-900 K, respectively. Complex impedance spectra, complex modulus formalism and complex conductivity spectra have been carefully analyzed in order to separate the grain, grain boundary and electrode-electrolyte effects. Analysis of ac impedance data using complex impedance indicates a typical negative temperature coefficient of resistance (NTCR) behavior of the materials. The intrinsic conductivity is mainly due to hopping of mobile ions among the available localized site. Relaxation time obtained from complex conductivity spectra are matched well with the impedance loss and modulus loss spectra. Impedance analysis suggests the presence of temperature-dependent electrical relaxation process in the material.

  1. Ionic conductivity, structural and thermal properties of pure and Sr 2+ doped Y 2Ti 2O 7 pyrochlores for SOFC

    NASA Astrophysics Data System (ADS)

    Gill, Jasmeet Kaur; Pandey, O. P.; Singh, K.

    2011-11-01

    In the present study, SrO doped Yttrium titanate pyrochlore was synthesized using solid state reaction technique. The sintering characteristics, crystal structure, thermal and conductivity behavior of doped and undoped pyrochlores have been studied to find their suitability in solid oxide fuel cells (SOFC). The as-prepared samples were characterized using X-ray diffraction (XRD), Fourier-Transform-Infrared spectroscopy (FT-IR), thermal-gravimetric analysis (TGA) and ac conductivity up to 900 °C. The results are discussed in light of oxygen vacancy formation and structural disordering. Undoped and doped yttrium titanate with SrO ( x = 0.1) exhibits single Y 2Ti 2O 7 phase with relative density of 94%. It was observed that further doping of SrO ( x = 0.2-0.4) leads to formation of Y 2Ti 2O 7 phase along with SrTiO 3 phase. Excessive SrO ( x = 0.4) results in increase in ionic conductivity to 1.50 × 10 -1 S cm -1 whereas it impedes the densification process with relative density of 85%.

  2. Rietveld refinement, electronic structure and ionic conductivity of Sr4La6(SiO4)6F2 and Sr4La6(SiO4)6O ceramics

    NASA Astrophysics Data System (ADS)

    Boughzala, Khaled; Debbichi, Mourad; Njema, Hela; Bouzouita, Khaled

    2016-07-01

    In this paper, we report the effect of the tunnel anions on the ionic conductivity of Strontium-Lanthanum silicate apatites. The Sr4La6(SiO4)6F2 and Sr4La6(SiO4)6O 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.

  3. Structural and ionic conductivity behavior in hydroxypropylmethylcellulose (HPMC) polymer films complexed with sodium iodide (NaI)

    NASA Astrophysics Data System (ADS)

    Rani, N. Sandhya; Sannappa, J.; Demappa, T.; Mahadevaiah

    2013-02-01

    Solid polymer electrolyte films based on Hydroxypropylmethylcellulose (HPMC) complexed with Sodium Iodide (NaI) were prepared using solution cast method. The dissolution of the salt into the polymer host and the micro structural properties of pure and NaI complexed HPMC polymer electrolyte films were confirmed by X - Ray diffraction (XRD) studies. The XRD results revealed that the amorphous domains of HPMC polymer matrix was increased with increase in the NaI salt concentration. The degree of crystallanity and crystallite size is high for pure HPMC samples. Direct current (dc) conductivity was measured in the temperature range of 313-383k. Temperature dependence of dc electrical conductivity and activation energy regions data indicated the dominance of ion type charge transport in these polymer electrolyte films.

  4. Strong tendency of homeotropic alignment and anisotropic lithium ion conductivity of sulfonate functionalized zwitterionic imidazolium ionic liquid crystals.

    PubMed

    Rondla, Rohini; Lin, Joseph C Y; Yang, C T; Lin, Ivan J B

    2013-09-17

    Here, we report the first attempt to investigate the liquid crystal (LC) behavior of SO3(-) functionalized imidazolium zwitterionic (SO3(-)ImZI) salts, which display homeotropic alignment on a glass slide without the aid of any aligning approach. Doping lithium salt to ImZI salts lowers the melting temperatures and raises the clearing temperatures substantially to form room temperature ImZILCs. Excellent anisotropic lithium ion conductivity is achieved; which is strengthened by their tendency for homeotropic alignment.

  5. Effects of TiO2 addition on ionic conductivity of PVC/PEMA blend based composite polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Subban, R. H. Y.; Sukri, Nursyazwani

    2015-08-01

    PVC/PEMA blend based polymer electrolytes with lithium bistrifluoromethane sulfonimide (LiN(CF3SO2)2) and PVC/PEMA/(LiN(CF3SO2)2-TiO2 films were prepared by solution cast technique. The sample containing 35 wt. % LiN(CF3SO2)2 exhibited the highest conductivity of 1.75 × 10-5 Scm-1. The conductivity of the sample increased to 2.12 × 10-5 Scm-1 and 4.61 × 10-5 Scm-1 when 4 wt. % and 10 wt. % of titanium dioxide (TiO2) was added to the sample at 65 wt. % PVC/PEMA-35 wt. % LiN(CF3SO2)2 composition respectively. The low increase in conductivity is attributed to two competing factors: increase in crystallinity as accounted by X-Ray diffraction (XRD) and decrease in glass transition temperature as accounted by differential scanning calorimetry (DSC).

  6. Effects of TiO{sub 2} addition on ionic conductivity of PVC/PEMA blend based composite polymer electrolyte

    SciTech Connect

    Subban, R. H. Y.; Sukri, Nursyazwani

    2015-08-28

    PVC/PEMA blend based polymer electrolytes with lithium bistrifluoromethane sulfonimide (LiN(CF{sub 3}SO{sub 2}){sub 2}) and PVC/PEMA/(LiN(CF{sub 3}SO{sub 2}){sub 2}-TiO{sub 2} films were prepared by solution cast technique. The sample containing 35 wt. % LiN(CF{sub 3}SO{sub 2}){sub 2} exhibited the highest conductivity of 1.75 × 10{sup −5} Scm{sup −1}. The conductivity of the sample increased to 2.12 × 10{sup −5} Scm{sup −1} and 4.61 × 10{sup −5} Scm{sup −1} when 4 wt. % and 10 wt. % of titanium dioxide (TiO{sub 2}) was added to the sample at 65 wt. % PVC/PEMA-35 wt. % LiN(CF{sub 3}SO{sub 2}){sub 2} composition respectively. The low increase in conductivity is attributed to two competing factors: increase in crystallinity as accounted by X-Ray diffraction (XRD) and decrease in glass transition temperature as accounted by differential scanning calorimetry (DSC)

  7. 12-crown-4 ether-assisted enhancement of ionic conductivity and interfacial kinetics in polyethylene oxide electrolytes

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    The electrical and electrochemical properties of thin films of polyethylene oxide electrolytes with and without 12-crown-4 ether (12Cr4) are studied as a function of temperature and in the frequency regime from 100 kHz to 0.1 Hz. These measurements were made on electrolytes containing LiCF3SO3, LiBF4, or LiClO4 salts. At a given temperature, the bulk conductivity for a particular salt depends on the 12Cr4 concentration, reaching a maximum for a ratio of 12Cr4 to Li of 0.003.

  8. Correlation of the properties of ionic conductivity-structure for the RbGaO2 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Proskurnina, N. V.; Voronin, V. I.; Berger, I. F.; Shekhtman, G. Sh.

    2016-12-01

    The crystal structure of rubidium gallate RbGaO2 in the temperature range of 300-853 K has been investigated using high-temperature neutron diffraction. The channels available for the motion of rubidium cations in the low-temperature and high-temperature modifications of RbGaO2 have been determined using the computer simulation with the TOPOS program. A correlation between the radius of the migration channel cross section and the rubidium cation conductivity has been established.

  9. Silver diffusion and ionic conduction in Ag/sub 6/I/sub 4/WO/sub 4/ solid electrolyte

    SciTech Connect

    Vlasov, Yu.G.; Ermolenko, Yu.E.; Glazunov, S.V.; Kolodnikov, V.V.

    1987-08-01

    This paper studies the diffusion of silver (Ag/sup 110m/) and the Haven ratio found for the first time at temperatures between 110 and 190/sup 0/C. A mixture of the salts AgI and Ag/sub 2/WO/sub 4/ (molar ratio) was obtained by joint precipitation with silver nitrate from solutions containing stoichiometric amounts of sodium iodide and tungstate. The conductivity and diffusion of the silver radiotracer Ag/sup 110m/ in solid electrolytes of the alpha-AgI type are measured. The activity distributions in the samples after homogenizing and the temperature dependence of the diffusion coefficients are shown.

  10. Synthesis and characterization of cancrinite-type zeolite, and its ionic conductivity study by AC impedance analysis

    NASA Astrophysics Data System (ADS)

    Kriaa, A.; Ben Saad, K.; Hamzaoui, A. H.

    2012-12-01

    The synthesis of cancrinite in the system NaOH-SiO2-Al2O3-NaHCO3-H2O was performed, according to methods described in the literature, in an autoclave under hydrothermal conditions at T = 473 K. The electrical properties of cancrinite-type zeolite pellets were investigated by complex impedance spectroscopy in the temperature range 465-800°C. The effect of temperature on impedance parameters was studied using an impedance analyzer in a wide frequency range (1 Hz to 13 MHz). The real and imaginary parts of complex impedance trace semicircles in the complex plane are plotted. The bulk resistance of the material decreases with rise in temperature. This exhibits a typical negative temperature coefficient of resistance (NTCR) behavior of the material. The results of bulk electrical conductivity and its activation energy are presented. The modulus analysis suggests that the electrical transport processes in the material are very likely to be of electronic nature. Relaxation frequencies follow an Arrhenius behavior with activation energy values not comparable to those found for the electrical conductivity.

  11. Effects of 12-Crown-4 ether on the ionic conductivity and electrode kinetics of electrolytes in polyethylene oxide

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Di Stefano, S.

    1990-01-01

    Results are described of investigations of the electrical and electrochemical properties of thin films of polyethylene oxide (PEO) electrolytes with and without 12-Crown-4 ether (12Cr4) as a function of temperature and in the frequency regime 100 kHz-0.1 Hz. These measurements were made for LiCF3SO3, LiBF4, and LiClO4 salts. At a given temperature, the bulk conductivity, sigma, (S/cm), for a particular salt, depends on the 12Cr4 concentration with sigma reaching a maximum at about 3 mM 12Cr4. Of the three salts studied, the sigma is the highest for PEO/LiBF4 with 3 mM 12Cr4. The ac and dc measurements yield a lower charge transfer resistance for 12Cr4-incorporated samples than for samples without. Plating/stripping of Li occurs at a potential closer to Li(+)/Li for 12Cr4 samples than those without. The conductivities of a thin (about 100 microns) and a thick (400 microns) films are similar.

  12. 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

    SciTech Connect

    El Moudane, M.; El Maniani, M.; Sabbar, A.; Ghanimi, A.; Tabyaoui, M.; Bellaouchou, A.; Guenbour, 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 have 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.

  13. 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.

  14. Ionic conductivity measurements of H2O ice at high pressure and temperature and superionic ice in the mantle of ice giants

    NASA Astrophysics Data System (ADS)

    Sugimura, E.; Komabayashi, T.; Ohta, K.; Hirose, K.; Sata, N.; Ohishi, Y.; Shimizu, K.; Dubrovinsky, L. S.

    2011-12-01

    The experimental evidence for the superionic conduction in H2O ice at high pressure (P) and temperature (T) has been long-searched since its theoretical prediction. Melting experiments reported a steep rise of the melting curve at P-T range of 35-43 GP and 1000-1600 K, which could be due to a first-order phase transition in the solid phases, namely the presence of the triple point of water, ice VII, and a high-T phase which was assumed superionic. Nonetheless, there has still been no report on direct experimental evidence for superionic conduction (ca. 0.1 S/cm) in ice at high pressure. Here we examined ionic conductivity and isothermal molar volume of ice at high-P-T based on impedance spectroscopy (IS) and x-ray diffraction measurements in an externally-resistive heated diamond anvil cell. In situ IS measurements up to 62 GPa and 920 K demonstrated that ice exhibits superionic conduction (> 0.1 S/cm) above 580-720 K at 20-60 GPa. This suggests that superionic conduction occurs at sufficiently lower P-T than the triple point. Isothermal P-V data collected at P = 33-101 GPa and T = 873 K revealed that an anomalous volume reduction occurs at P = 50-53 GPa. This compression manner corresponds to the previously reported highly compressible regime at P = 40-60 GPa, T = 300 K, which were attributed to hydrogen bond symmetrization. There is no volume discontinuity in the isothermal compression, which contradicts the proposed first order P-T boundary between ice VII and superionic ice. Furthermore, all the conductivity data is expressed by a single Arrhenius equation so that the superionic conduction occurs regardless of the ongoing hydrogen bond symmetrization upon compression. We suggests that the previously reported steep rise of the melting temperature of ice above 35-43 GPa is independent of superionic transition, and is a consequence of the hydrogen bond symmetrization. Combining above results with the existing planetary isentropes, superionic conduction in H2O ice

  15. Concentration dependence of ionic conductance measured with ion-selective sub-micro pipette probes in aqueous sodium and potassium chloride solutions

    NASA Astrophysics Data System (ADS)

    Son, J. W.; Takami, T.; Lee, J.-K.; Kawai, T.; Park, B. H.

    2011-07-01

    Selective ionic currents in aqueous sodium and potassium chloride solutions with concentrations from 0.01 M to 1.0 M were measured using sub-micro pipette probes in which a poly(vinyl chloride) film containing crown ethers selectively filtered sodium or potassium ions. The selective ionic currents were monitored with a sub-picoampere current measurement system developed from the techniques of TΩ-gap impedance scanning tunneling microscopy. The ionic currents increased with the concentration of the corresponding solution, and thus these sub-micro pipette probes can be applied to detect local ionic concentration of a specific ion in living cells with ionic concentration higher than 0.1 M.

  16. Conductive Polymeric Ionic Liquid/Fe3O4 Nanocomposite as an Efficient Catalyst for the Voltammetric Determination of Amlodipine Besylate.

    PubMed

    Fathirad, Fariba; Mostafavi, Ali; Afzali, Daryoush

    2017-03-01

    A novel conductive polymeric ionic liquid (IL)-Fe3O4 nanocomposite (represented as PIL-Fe3O4) based on inorganic-organic hybrid material was synthesized using two different methods. Nuclear magnetic resonance, Fourier transform infrared, X-ray diffraction, and field emission scanning electron microscopy characterized the structures of IL, Fe3O4 nanoparticles, and PIL-Fe3O4. The electrochemical sensors based on PIL-Fe3O4-modified glassy carbon electrode were fabricated, and each of these nanocomposites was examined for the ability to determine amlodipine besylate (AMD). The electrochemical study of the modified electrodes, as well as its efficiency for the electro-oxidation of AMD, was described in 0.1 M phosphate-buffered solution (pH 7.0) using voltammetric methods. The results exhibit a linear dynamic range from 1 to 500 nM and a detection limit of 0.36 nM. Finally, the modified electrode was used for the determination of AMD in pharmaceutical and biological samples.

  17. Modeling of Ionic Conductivity Enhancement of LiClO4-PVA-C System by TiO2 Addition Using Complex Numerical Model of PDE

    NASA Astrophysics Data System (ADS)

    Shokrollahi, Mahvash; Semnani, Dariush; Morshed, Mohammad; Rezaei, Behzad; Mirsoofian, Mehdi

    2013-12-01

    PVA-TiO2 nanocomposite polymer electrolytes (PEs) were produced with different amounts of TiO2 (0, 5, 10, 15, and 20 wt.%) using the electrospinning process. Morphological studies of PVA-TiO2 nanofibers were accomplished with SEM. PVA-TiO2 membranes exhibited a high porosity of 79-91%. The impedance results showed that incorporation of TiO2 into the nanofiber membrane improved its ionic conductivity from 0.7 × 10-5 to 2.5 × 10-5 S/cm at room temperature. Nanofiber PEs showed very good reversibility and electrochemical stability up to 4.7 V. Diffusion coefficient of Li ion into PVA-TiO2 nanocomposite PEs was estimated by using a complex numerical model of partial differential equation for evaluation of ion transmission. Diffusion coefficient of PVA-TiO2 PEs containing different amounts of TiO2 (0, 5, 10, 15, and 20 wt.%) increased with increasing the nanoparticles content.

  18. Microemulsions with surfactant TX100, cyclohexane, and an ionic liquid investigated by conductance, DLS, FTIR measurements, and study of solvent and rotational relaxation within this microemulsion.

    PubMed

    Pramanik, Rajib; Sarkar, Souravi; Ghatak, Chiranjib; Rao, Vishal Govind; Setua, Palash; Sarkar, Nilmoni

    2010-06-10

    Room-temperature ionic liquids (RTILs), N,N,N-trimethyl-N-propyl ammonium bis(trifluoromethanesulfonyl) imide ([N(3111)][Tf(2)N]), were substituted for polar water and formed nonaqueous microemulsions with cyclohexane by the aid of nonionic surfactant TX-100. The phase behavior of the ternary system was investigated, and microregions of [N(3111)][Tf(2)N]-in-cyclohexane (IL/O), bicontinuous, and cyclohexane-in-[N(3111)][Tf(2)N] (O/IL) were identified by traditional electrical conductivity measurements. Dynamic light scattering (DLS) revealed the formation of the IL microemulsions. The FTIR study of O-H stretching band of TX100 also supports this finding. The dynamics of solvent and rotational relaxation have been investigated in [N(3111)][Tf(2)N]/TX100/cyclohexane microemulsions using steady-state and time-resolved fluorescence spectroscopy as a tool and coumarin 480 (C-480) as a fluorescence probe. The size of the microemulsions increases with gradual addition of [N(3111)][Tf(2)N], which revealed from DLS measurement. This leads to the faster collective motions of cation and anions of [N(3111)][Tf(2)N], which contributes to faster solvent relaxation in microemulsions.

  19. From channel-forming ionic liquid crystals exhibiting humidity-induced phase transitions to nanostructured ion-conducting polymer membranes (adv. Mater. 26/2013).

    PubMed

    Zhang, Heng; Li, Lei; Möller, Martin; Zhu, Xiaomin; Rueda, Jaime J Hernandez; Rosenthal, Martin; Ivanov, Dimitri A

    2013-07-12

    A novel wedge-shaped amphiphilic molecule bearing a sulfonate group at the tip displays humidity-induced phase transitions from a hexagonal columnar structure to a bicontinuous cubic phase. The mesophases can be frozen by photopolymerization of acrylic end-groups resulting in free-standing membranes with different topology of ionic nanochannels. The obtained membranes with a well-ordered ionic channel structure hold promise for applications in separation and catalysis.

  20. 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.

  1. Poly(ethylene oxide)-co-poly(propylene oxide)-based gel electrolyte with high ionic conductivity and mechanical integrity for lithium-ion batteries.

    PubMed

    Wang, Shih-Hong; Hou, Sheng-Shu; Kuo, Ping-Lin; Teng, Hsisheng

    2013-09-11

    Using gel polymer electrolytes (GPEs) for lithium-ion batteries usually encounters the drawback of poor mechanical integrity of the GPEs. This study demonstrates the outstanding performance of a GPE consisting of a commercial membrane (Celgard) incorporated with a poly(ethylene oxide)-co-poly(propylene oxide) copolymer (P(EO-co-PO)) swelled by a liquid electrolyte (LE) of 1 M LiPF6 in carbonate solvents. The proposed GPE stably holds LE with an amount that is three times that of the Celgard-P(EO-co-PO) composite. This GPE has a higher ionic conductivity (2.8×10(-3) and 5.1×10(-4) S cm(-1) at 30 and -20 °C, respectively) and a wider electrochemical voltage range (5.1 V) than the LE-swelled Celgard because of the strong ion-solvation power of P(EO-co-PO). The active ion-solvation role of P(EO-co-PO) also suppresses the formation of the solid-electrolyte interphase layer. When assembling the GPE in a Li/LiFePO4 battery, the P(EO-co-PO) network hinders anionic transport, producing a high Li+ transference number of 0.5 and decreased the polarization overpotential. The Li/GPE/LiFePO4 battery delivers a discharge capacity of 156-135 mAh g(-1) between 0.1 and 1 C-rates, which is approximately 5% higher than that of the Li/LE/LiFePO4 battery. The IR drop of the Li/GPE/LiFePO4 battery was 44% smaller than that of the Li/LE/LiFePO4. The Li/GPE/LiFePO4 battery is more stable, with only a 1.2% capacity decay for 150 galvanostatic charge-discharge cycles. The advantages of the proposed GPE are its high stability, conductivity, Li+ transference number, and mechanical integrity, which allow for the assembly of GPE-based batteries readily scalable to industrial levels.

  2. Structure electronic and ionic conductivity study versus Ca content in Ca{sub 10-x}Sr{sub x}(PO{sub 4}){sub 6}F{sub 2} apatites

    SciTech Connect

    Sghir, B.; Hlil, E.K.; Laghzizil, A.; Boujrhal, F.Z.; Cherkaoui El Moursli, R.; Fruchart, D.

    2009-07-01

    Substitution effect on the crystallographic structure in Ca{sub 10-x}Sr{sub x}(PO{sub 4}){sub 6}F{sub 2} solid solution are studied by X-ray diffraction patterns and Rietveld refinements. Full potential electronic structure calculations based on LCAO (linear combination atomic orbital) are also performed using the obtained crystallographic parameters. DOS modification and the charge transfer are estimated versus the calcium content. According to the complex impedance method, ionic conductivity changes are explained.

  3. Strain tuning and strong enhancement of ionic conductivity in SrZrO3-RE2O3 (RE = Sm, Eu, Gd, Dy, and Er) nanocomposite films

    SciTech Connect

    Lee, Shinbuhm; Zhang, Wenrui; Khatkhatay, Fauzia; Jia, Quanxi; Wang, Haiyan; MacManus-Driscoll, Judith L.

    2015-06-05

    Fast ion transport channels at interfaces in thin films have attracted great attention due to a range of potential applications for energy materials and devices, for, solid oxide fuel cells, sensors, and memories. Here, it is shown that in vertical nanocomposite heteroepitaxial films of SrZrO3–RE2O3 (RE = Sm, Eu, Gd, Dy, and Er) the ionic conductivity of the composite can be tuned and strongly enhanced using embedded, stiff, and vertical nanopillars of RE2O3. With increasing lattice constant of RE2O3 from Er2O3 to Sm2O3, it is found that the tensile strain in the SrZrO3 increases proportionately, and the ionic conductivity of the composite increases accordingly, by an order of magnitude. Lastly, the results here conclusively show, for the first time, that strain in films can be effectively used to tune the ionic conductivity of the materials.

  4. Ionic Blocks

    ERIC Educational Resources Information Center

    Sevcik, Richard S.; Gamble, Rex; Martinez, Elizabet; Schultz, Linda D.; Alexander, Susan V.

    2008-01-01

    "Ionic Blocks" is a teaching tool designed to help middle school students visualize the concepts of ions, ionic compounds, and stoichiometry. It can also assist high school students in reviewing their subject mastery. Three dimensional blocks are used to represent cations and anions, with color indicating charge (positive or negative) and size…

  5. Crystal structure and ionic conductivity of Mg-doped apatite-type lanthanum silicates La10Si6-xMgxO27-x (x = 0-0.4)

    NASA Astrophysics Data System (ADS)

    Yin, Guang-Chao; Yin, Hong; Zhong, Lin-Hong; Sun, Mei-Ling; Zhang, Jun-Kai; Xie, Xiao-Jun; Cong, Ri-Dong; Wang, Xin; Gao, Wei; Cui, Qi-Liang

    2014-04-01

    Lanthanum silicates La10Si6-xMgxO27-x (x = 0-0.4) were prepared by solid state synthesis to investigate the effect of Mg doping on crystal structure and ionic conductivity. Rietveld analysis of the powder XRD patterns reveals that Mg substitution on Si site results in significant enlargement of channel triangles, favoring oxide-ion conduction. Furthermore, an increase of Mg concentration significantly influences the linear density of interstitial oxygen, which plays an important role in ionic conductivity. The Arrhenius plots of La10Si6-xMgxO27-x (x = 0-0.4) suggest that Mg-doped samples present higher conductivity and lower activation energy than non-doped La10Si6O27, and La10Si5.8Mg0.2O26.8 exhibits the highest conductivity with a value of 3.0×10-2 S ·cm-1 at 700 °C. Such conductive behavior agrees well with the refined results. The corresponding mechanism has been discussed in this paper.

  6. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    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.

  7. 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.

  8. IONIC CONDUCTION IN SUBSTITUTED SCHEELITE-TYPE OXIDE La2/3-xLi3xWO4

    NASA Astrophysics Data System (ADS)

    Esaka, Takao; Moto-Ike, Koichi

    In order to obtain high ionic conductors, a new solid solution of La2/3-xLi3xWO4 with a scheelite-type structure was synthesized and the lithium ionic conduction were confirmed by electrochemical measurements and neutron radiography(NR). For pure La2/3WO4, the conductivity was about 10-5 S cm-1 at 900°C. Enhanced conductivities are observed in the substituted samples. According to the oxygen gas concentration cell measurements and the electrolysis, it was found that the main charge carriers are not electrons but ions for the substituted samples. From the NR images of electrolyzed La0.56Li0.30WO4 samples, furthermore, it could be obviously seen the lithium movement in the sample. From the profile of lithium, the lithium ion transport number of the oxide was known to be 0.67 at 900°C, which would mean partly oxide ion contribution to the total electrical conduction.

  9. Crystal structure and ionic conductivity of ruthenium diphosphate ARu{sub 2}(P{sub 2}O{sub 7}){sub 2}, A=Li, Na, and Ag, with a tunnel structure

    SciTech Connect

    Fukuoka, Hiroshi; Matsunaga, Hideyuki; Yamanaka, Shoji

    2003-05-26

    Crystal structure and ionic conductivity of ruthenium diphosphates, ARu{sub 2}(P{sub 2}O{sub 7}){sub 2} A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P-1 with a=4.759(2) A, b=6.843(2) A, c=8.063(1) A, {alpha}=90.44(2) deg., {beta}=92.80(2) deg., {gamma}=104.88(2) deg., V=253.4(1) A{sup 3}. The host structure of it was composed of RuO{sub 6} and P{sub 2}O{sub 7} groups and formed tunnels running along the a-axis, in which Ag{sup +} ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0x10{sup -4} and 3.5x10{sup -5} S cm{sup -1} at 150 deg. C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru{sup 4+} ions.

  10. Forming solid electrolyte interphase in situ in an ionic conducting Li1.5Al0.5Ge1.5(PO4)3-polypropylene (PP) based separator for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Jiao-Yang, Wu; Shi-Gang, Ling; Qi, Yang; Hong, Li; Xiao-Xiong, Xu; Li-Quan, Chen

    2016-07-01

    A new concept of forming solid electrolyte interphases (SEI) in situ in an ionic conducting Li1.5Al0.5Ge1.5(PO4)3-polypropylene (LAGP-PP) based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS). The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries. Project supported by the Beijing Science and Technology Project, China (Grant No. Z13111000340000), the National Basic Research Program of China (Grant No. 2012CB932900), and the National Natural Science Foundation of China (Grant Nos. 51325206 and 51421002).

  11. Enhanced ionic conductivity with Li7O2Br3 phase in Li3OBr anti-perovskite solid electrolyte

    SciTech Connect

    Zhu, Jinlong; Li, Shuai; Zhang, Yi; Howard, John W.; Lu, Xujie; Li, Yutao; Wang, Yonggang; Kumar, Ravhi S.; Wang, Liping; Zhao, Yusheng

    2016-09-07

    Cubic anti-perovskites with general formula Li3OX (X = Cl, Br, I) were recently reported as superionic conductors with the potential for use as solid electrolytes in all-solid-state lithium ion batteries. These electrolytes are nonflammable, low-cost, and suitable for thermoplastic processing. However, the primary obstacle of its practical implementation is the relatively low ionic conductivity at room temperature. In this work, we synthesized a composite material consisting of two anti-perovskite phases, namely, cubic Li3OBr and layered Li7O2Br3, by solid state reaction routes. The results indicate that with the phase fraction of Li7O2Br3 increasing to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li3OBr. Formation energy calculations revealed the meta-stable nature of Li7O2Br3, which supports the great difficulty in producing phase-pure Li7O2Br3 at ambient pressure. Here, methods of obtaining phase-pure Li7O2Br3 will continue to be explored, including both high pressure and metathesis techniques.

  12. Nd2±xZr2∓xO7±x/2 (-0.2≤x≤0.4) complex oxides: Effect of anion disorder on ionic conductivity

    NASA Astrophysics Data System (ADS)

    Anithakumari, P.; Grover, V.; Tyagi, A. K.

    2016-05-01

    In the present work, a series of Nd2±xZr2∓xO7±x/2 (-0.2≤x≤0.4) was prepared by self assisted gel-combution method followed by high temperature sintering at 1673 K. Thorough structural characterizations were done by X-ray diffraction and Raman spectroscopic techniques. The nominal compositions Nd1.6Zr2.4O7.2 and Nd1.8Zr2.2O7.1 were found to possess single-phasic pyrochlore structure whereas Nd2.0Zr2.0O7 and Nd2.2Zr1.8O6.9 consisted of a pyrochlore phase and a small amount of hexagonal Nd2O3 as an impurity phase. Electrical behavior of the samples was examined by AC impedance analysis. Even though the activation energies of all the samples are not very different, a high pre-exponential factor for the Nd1.6Zr2.4O7.2 composition resulted in high ionic conductivity (3.37 × 10-3 Scm-1 at 773 K). This high ionic conductivity value makes it a superior candidate as an electrolyte material for SOFC applications.

  13. Fabrication of highly conductive and transparent thin films from single-walled carbon nanotubes using a new non-ionic surfactant via spin coating.

    PubMed

    Jo, Jea Woong; Jung, Jae Woong; Lee, Jea Uk; Jo, Won Ho

    2010-09-28

    Oligothiophene-terminated poly(ethylene glycol) was synthesized and used as a non-ionic and amphiphilic surfactant for fabricating high-quality single-walled carbon nanotube (SWCNT) films by a simple spin coating method. The absence of charge repulsion between SWCNT/surfactant complexes successfully leads to formation of a dense network of SWCNTs on the substrate through a single deposition of spin coating. When the SWCNT film was treated with nitric acid and thionyl chloride after washed with dichloromethane and water, a high-performance SWCNT film with the sheet resistance of 59 ohm/sq and the transparency of 71% at 550 nm was successfully obtained. Since the SWCNT film exhibits a high value of σ(dc)/σ(ac) (∼17) and excellent dimensional stability after releasing from the substrate, the film can be used as a transparent electrode in flexible optoelectronic devices.

  14. 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

  15. Ionic Channels in Thunderclouds

    NASA Astrophysics Data System (ADS)

    Losseva, T. V.; Fomenko, A. S.; Nemtchinov, I. V.

    2007-12-01

    We proceed to study the formation and propagation of ionic channels in thunderclouds in the framework of the model of the corona discharge wave propagation (Fomenko A.S., Losseva T.V., Nemtchinov I.V. The corona discharge waves in thunderclouds and formation of ionic channels // 2004 Fall Meeting. EOS Trans. AGU. 2004. V. 85. ¹ 47. Suppl. Abstract AE23A-0835.). In this model we proposed a hypothesis that the structure of a thundercloud becomes nonuniform due to corona discharge on the drops and ice particles and formation of ionic channels with higher conductivity than the surrounding air. When the onset strength of corona discharge becomes smaller than the electric field strength the corona discharge increases concentrations of ions in a small part of the cloud (a hot spot). An additional charge at opposite ends of the hot spot forms due to polarization process. The increased electric field initiates corona discharge in other parts of the cloud on ice particles and water drops with smaller sizes. The corona discharge front moves as a wave with the velocity of the order of ion drift and formes a highly conductive channel. We model this non-stationary problem with Poisson equation which is solved simultaneously with a simplified set of kinetic equations for ions, small charged particles and electrons (at high electric fields), including ionization due to electronic impact, attachment and formation of positive ions. By applying 3D numerical simulations we obtain the parameters of formed ionic channels with respect to onset electric fields both from large particles (in hot spot) and from small particles (surrounding hot spot), microscopic currents from particles with different sizes and the external electric field in the cloud. The interaction of ionic channels is also investigated. This work was supported by Russian Foundation of Basic Research (Project No 07-05-00998-à).

  16. Ionic electroactive hybrid transducers

    NASA Astrophysics Data System (ADS)

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

    2005-05-01

    Ionic electroactive actuators have received considerable attention in the past ten years. Ionic electroactive polymers, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typical types of ionic electroactive polymer transducers include ionic polymers, conducting polymers, and carbon nanotubes. Preliminary research combining multiple types of materials proved to enhance certain transduction properties such as speed of response, maximum strain, or quasi-static actuation. Recently it was demonstrated that ionomer-ionic liquid transducers can operate in air for long periods of time (>250,000 cycles) and showed potential to reduce or eliminate the back-relaxation issue associated with ionomeric polymers. In addition, ionic liquids have higher electrical stability window than those operated with water as the solvent thereby increasing the maximum strain that the actuator can produce. In this work, a new technique developed for plating metal particulates on the surface of ionomeric materials is applied to the development of hybrid transducers that incorporate carbon nanotubes and conducting polymers as electrode materials. The new plating technique, named the direct assembly process, consists of mixing a conducting powder with an ionomer solution. This technique has demonstrated improved response time and strain output as compared to previous methods. Furthermore, the direct assembly process is less costly to implement than traditional impregnation-reduction methods due to less dependence on reducing agents, it requires less time, and is easier to implement than other processes. Electrodes applied using this new technique of mixing RuO2 (surface area 45~65m2/g) particles and Nafion dispersion provided 5x the displacement and 10x the force compared to a transducer made with conventional methods. Furthermore, the study illustrated that the response speed of the transducer is optimized

  17. Defect structure and ionic conductivity of Ca{sub 1-x}Sc{sub x}F{sub 2+x} (0.02 {<=} x {<=} 0.15) single crystals

    SciTech Connect

    Sulyanova, E. A. Molchanov, V. N.; Sorokin, N. I.; Karimov, D. N.; Sulyanov, S. N.; Sobolev, B. P.

    2009-07-15

    Single crystals of the Ca{sub 1-x}Sc{sub x}F{sub 2+x}(x = 0.106, 0.132, 0.156) solid solutions (CaF{sub 2} structure type, space group Fm3-barm) are investigated using X-ray diffraction. It is revealed that the crystals under investigation contain vacancies in the 8c positions and interstitial fluorine ions in the 48i positions. The coordination number of Sc{sup 3+} ions in the structure of the Ca{sub 1-x}Sc{sub x}F{sub 2+x} solid solutions is equal to eight. The specific features of the concentration dependences of the ionic conductivity and the activation energy of ion transfer for the Ca{sub 1-x}Sc{sub x}F{sub 2+x}(0.02 {<=} x {<=} 0.15) solid solutions are explained in the framework of the percolation model of conducting 'defect regions.' The percolation threshold equal to 3-5 mol % ScF{sub 3} corresponds to the model of [Ca{sub 14-n}Sc{sub n}F{sub 68}] octacubic clusters containing fluorine ions in the 48i positions. The ionic conductivity of the Ca{sub 1-x}Sc{sub x}F{sub 2+x} solid solutions is analyzed in comparison with the change in this characteristic for the series of Ca{sub 0.8}R{sub 0.2}F{sub 2.2} crystals with rare-earth elements.

  18. Augmentation of hemagglutination by low ionic conditions.

    PubMed

    Rosenfield, R E; Shaikh, S H; Innella, F; Kaczera, Z; Kochwa, S

    1979-01-01

    Short incubation at 37 C, 80 per cent reduction in ionic concentration and removal of liquid phases after each reaction step, provided the basis for the construction of four new serologic tests for alloantibodies to human erythrocytes. In the first, the incubation fluid was replaced with protamine sulfate to aggregate intensely the evaluated red blood cells. After dispersal by phosphate buffer, residual antibody mediated agglutination could be discerned. As a second method, this low ionic polycation (LIP) test was followed by a normal ionic IgG antiglobulin test (LIP-AGT). A third method employed low ionic washing of erythrocytes and low ionic antiglobulin serum (LIAGT). Finally, a modified LIP test was conducted entirely under low ionic conditions and followed by a low ionic antiglobulin test (modified LIP-AGT). LIP, LIP-AGT and LIAGT were successfully employed for all routine blood bank serology tests. Their sensitivity and impact on blood bank performance are described.

  19. Electrochemical immunosensor for ultrasensitive detection of microcystin-LR based on graphene-gold nanocomposite/functional conducting polymer/gold nanoparticle/ionic liquid composite film with electrodeposition.

    PubMed

    Ruiyi, Li; Qianfang, Xia; Zaijun, Li; Xiulan, Sun; Junkang, Liu

    2013-06-15

    The study developed an electrochemical immunosensor for ultrasensitive detection of microcystin-LR in water. Graphene oxide and chloroauric acid were alternately electrodeposited on the surface of glassy carbon electrode for 20 cycles to fabricate graphene-gold nanocomposite. The composite was characterized and its apparent heterogeneous electron transfer rate constant (37.28±0.16 cm s (-1)) was estimated by Laviron's model. To immobilize microcystin-LR antibody and improve the electrical conductivity, 2,5-di-(2-thienyl)-1-pyrrole-1-(p-benzoic acid) and chloroauric acid were electrodeposited on the modified electrode in sequence. The ionic liquid was then dropped on the electrode surface and finally microcystin-LR antibody was covalently connected to the conducting polymer film. Experiment showed the electrochemical technique offers control over reaction parameters and excellent repeatability. The graphene-gold nanocomposite and gold nanoparticles enhance electron transfer of Fe(CN)6(3-/4-) to the electrode. The ionic liquid, 1-isobutyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide, improves stability of the antibody. The sensor displays good repeatability (RSD=1.2%), sensitive electrochemical response to microcystin-LR in the range of 1.0×10(-16)-8.0×10(-15)M and detection limit of 3.7×10(-17)M (S/N=3). The peak current change of the sensor after and before incubation with 2.0×10(-15)M of microcystin-LR can retain 95% over a 20-weeks storage period. Proposed method presents remarkable improvement of sensitivity, repeatability and stability when compared to present microcystin-LR sensors. It has been successfully applied to the microcystin-LR determination in water samples with a spiked recovery in the range of 96.3-105.8%.

  20. Liquid-like ionic conduction in solid lithium and sodium monocarba-closo-decaborates near or at room temperature

    SciTech Connect

    Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; Stavila, Vitalie; Zhou, Wei; Talin, Albert Alec; Soloninin, Alexei V.; Skoryunov, Roman V.; Babanova, Olga A.; Skripov, Alexander V.; Unemoto, Atsushi; Orimo, Shin -Ichi; Udovic, Terrence J.

    2016-02-05

    Both LiCB9H10 and NaCB9H10 exhibit liquid-like cationic conductivities (≥0.03 S cm–1) in their disordered hexagonal phases near or at room temperature. Furthermore, these unprecedented conductivities and favorable stabilities enabled by the large pseudoaromatic polyhedral anions render these materials in their pristine or further modified forms as promising solid electrolytes in next-generation, power devices.

  1. Individual and community responses in stream mesocosms with different ionic compositions of conductivity and compared to a field-based benchmark

    EPA Science Inventory

    Several anthropogenic activities cause excess total dissolved solids (TDS) content and its correlate, specific conductivity, in surface waters due to increases in the major geochemical ions (e.g., Na, Ca, Cl, SO4). However, the relative concentrations of major ions varies with t...

  2. Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La1.85Ca0.15(Cu1-xNix)O4-δ (δ = 0.0905)

    NASA Astrophysics Data System (ADS)

    Midouni, Adnene; Houchati, Mohamed Ikbal; Othman, Walid Belhaj; Chniba-Boudjada, Nassira; Ceretti, Monica; Paulus, Werner; Jaouadi, Mouna; Hamzaoui, Ahmed Hichem

    2016-08-01

    The results of the synthesis and characterization of the optimally doped La1.85Ca0.15(Cu1-xNix)O4-δ solid solution with x = 0, 0.1, 0.2 and 0.3 are reported. The versatility of these La1.85Ca0.15(Cu1-xNix)O4-δ materials is explained on the basis of structural features and the ability to accommodate oxygen nonstoichiometry. According to powder X-ray and neutron diffraction data, La1.85Ca0.15(Cu1-xNix)O4-δ adopts the tetragonal structure with oxygen vacancies occurring preferentially at the Oap sites within the {(La/Ca)O} layers of the perovskite blocks and the oxygen deviation from stoichiometry δ was found to be δ=0.0905(6). The bulk conductivity indicated an Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at T=270 °C. An increase of the conductivity was detected when Ni was introduced. With nickel ratio variation, a strong correlation was observed between the Cu(Ni)-Oap apical bond length variation and the conductivity variation through controlling the O2- ion migration.

  3. Structural and ionic conductivity studies of electrospun polymer blend P(VdF-co-HFP)/PMMA electrolyte membrane for lithium battery application

    SciTech Connect

    Padmaraj, O.; Satyanarayana, N.; Venkateswarlu, M.

    2015-06-24

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

  4. Effect of Complexation of NaCl Salt with Polymer Blend (PEO/PVP) Electrolytes on Ionic Conductivity and Optical Energy Band Gaps

    NASA Astrophysics Data System (ADS)

    Kumar, K. Kiran; Pavani, Y.; Ravi, M.; Bhavani, S.; Sharma, A. K.; Rao, V. V. R. Narasimha

    2011-10-01

    Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and poly vinyl pyrrolidone (PVP) complexed with NaCl salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and UV-vis spectroscopy. Frequency and temperature dependence of electrical conductivity of the films was studied with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. UV-vis absorption spectra in wavelength region 200-800 nm, were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase of Na+ ion concentration. This suggests that NaCl, as dopant, is a good choice to improve the electrical and optical properties of PEO/PVP polymer blend electrolytes.

  5. Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li2Sr2Al(PO4)3

    NASA Astrophysics Data System (ADS)

    Kim, Sung-Chul; Kwak, Hyun-Jung; Yoo, Chung-Yul; Yun, Hoseop; Kim, Seung-Joo

    2016-11-01

    A new layered metal phosphate, Li2Sr2Al(PO4)3, was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li2Sr2Al(PO4)3 crystallizes to the P21/n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO4)2] layers alternating regularly with [LiSrPO4] layers. In the [LiSrAl(PO4)2] sublattice, the AlO6 octahedra and PO4 tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO4)2]3- framework that can be regarded as a "distorted-glaserite" structure. The [LiSrPO4] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO4 and PO4 tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li+ ion conduction. The impedance measurement indicated that Li2Sr2Al(PO4)3 had a moderate ion conductivity (σ≈1.30×10-4 S cm-1 at 667 K), with an activation energy Ea≈1.02 eV.

  6. 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.

  7. Nanostructured crystals of fluorite phases Sr1- x R x F2 + x and their ordering: 11. Influence of structural cluster ordering on fluorine ionic conductivity of the Sr1- x Lu x F2 + x Phase

    NASA Astrophysics Data System (ADS)

    Sorokin, N. I.; Sobolev, B. P.

    2015-11-01

    Ionic conductivity σ of the ordered phase (binary compound) Sr4Lu3F17 (sp. gr. Roverline 3 , Z = 6) with a fluorite-derivative structure obtained from a melt has been studied for the first time by impedance spectroscopy. The octahedral-cubic clusters {Sr8[Lu6F37]F32} formed in the structure of the disordered (fluorite) phase Sr1- x Lu x F2 + x (sp. gr. Fmoverline 3 m, Z = 4) become structural blocks with long-range order in the Sr4Lu3F17 compound. The effect of the clusters on the conductivity of nonstoichiometric phases Sr1- x Lu x F2 + x (2-25 mol % LuF3) and Sr4Lu3F17 (42.86 mol % LuF3) has been studied for the first time. Cluster ordering in Sr4Lu3F17 is accompanied by a decrease in the conductivity (σ = 6.3 × 10-7 S/cm at 673 K and Δ H σ = 1.12 eV) by a factor of 25 with respect to a disordered Sr0.75Lu0.25F2.75 crystal (experiment) and by a factor of 125 with respect to the saturated fluorite phase Sr0.63Lu0.37F2.37 (extrapolation). The unit-cell volume changes per F- ion during ordering are small and should not significantly affect the fluorine ion conductivity.

  8. Correlation between micro-structural properties and ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 ceramics

    NASA Astrophysics Data System (ADS)

    Mariappan, Chinnasamy R.; Yada, Chihiro; Rosciano, Fabio; Roling, Bernhard

    2011-08-01

    We report on the structure and lithium ion transport properties of Li1.5Al0.5Ge1.5(PO4)3 (LAGP). This material is commercially available and is prepared as amorphous powders via a flame spray technique called Flash Creation Method (FCM). We crystallize and sinter the amorphous powders at different temperatures in order to alter grain size and grain boundary properties. The structure is then characterized by means of powder X-ray diffraction, atomic force microscopy, scanning electron microscopy and transmission electron microscopy with energy dispersive X-ray spectroscopy. AC impedance spectroscopy is used to study lithium ion transport. A maximum total conductivity of 2 × 10-4 S cm-1 at room temperature is found for a sample sintered at 750 °C for 2 h. In order to distinguish between grain and grain boundary contributions to the impedance spectra, equivalent circuit fits are carried out. The results are analysed in the framework of the classical brick layer model and of a finite-element approach taking into account non-ideal grain contacts. Our experimental results for the grain and grain boundary resistances are in good agreement with the predications of the finite-element approach.

  9. Ionic Liquids Database- (ILThermo)

    National Institute of Standards and Technology Data Gateway

    SRD 147 Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

  10. Ionic conductivity in LaCo{sub 1{minus}x}Mg{sub x}O{sub 3{minus}{delta}}: A potential cathode material for solid oxide fuel cells

    SciTech Connect

    Yu, A.; Haile, S.M.

    1995-12-31

    A serious concern with present designs of solid oxide fuel cells is the requirement that triple-point junctions exist, sites at which the cathode, electrolyte and oxidizing gas are in simultaneous contact. Only at these junctions can the cathode catalyze the reduction of oxygen into O{sup {minus}2} ions and initiate their subsequent transport through the electrolyte. Enhanced ionic conductivity in the cathode material may increase the surface area over which reduction can take place and relax the triple-point constraint. To this end, the authors have examined the electrical and structural properties of LaCo{sub 1{minus}x}Mg{sub x}O{sub 3{minus}{delta}} materials under various atmospheres. Oxygen ion transport in this and related ABO{sub 3} perovskites takes place via oxygen vacancy migration. They have opted to investigate the effect of Mg doping on the transition metal site in an effort to maintain a significant oxygen vacancy concentration in oxidizing atmospheres (as would be encountered during fuel cell operation) and to isolate the effects of A- and B-site doping.

  11. Capillary electrophoresis with contactless conductivity detection for the quantification of fluoride in lithium ion battery electrolytes and in ionic liquids-A comparison to the results gained with a fluoride ion-selective electrode.

    PubMed

    Pyschik, Marcelina; Klein-Hitpaß, Marcel; Girod, Sabrina; Winter, Martin; Nowak, Sascha

    2017-02-01

    In this study, an optimized method using capillary electrophoresis (CE) with a direct contactless conductivity detector (C(4) D) for a new application field is presented for the quantification of fluoride in common used lithium ion battery (LIB) electrolyte using LiPF6 in organic carbonate solvents and in ionic liquids (ILs) after contacted to Li metal. The method development for finding the right buffer and the suitable CE conditions for the quantification of fluoride was investigated. The results of the concentration of fluoride in different LIB electrolyte samples were compared to the results from the ion-selective electrode (ISE). The relative standard deviations (RSDs) and recovery rates for fluoride were obtained with a very high accuracy in both methods. The results of the fluoride concentration in the LIB electrolytes were in very good agreement for both methods. In addition, the limit of detection (LOD) and limit of quantification (LOQ) values were determined for the CE method. The CE method has been applied also for the quantification of fluoride in ILs. In the fresh IL sample, the concentration of fluoride was under the LOD. Another sample of the IL mixed with Li metal has been investigated as well. It was possible to quantify the fluoride concentration in this sample.

  12. Trivalent Cation Substitution Effect into Layered Double Hydroxides Co 2Fe y Al 1- y(OH) 6Cl· nH 2O: Study of the Local Order . Ionic Conductivity and Magnetic Properties

    NASA Astrophysics Data System (ADS)

    Intissar, Mourad; Segni, Rachid; Payen, Christophe; Besse, Jean-Pierre; Leroux, Fabrice

    2002-09-01

    A series of layered double hydroxide materials of composition Co 2Fe yAl 1- y(OH) 6Cl· nH 2O (0≤ y≤1) was prepared via chimie douce. The crystalline parameter related to the cation to cation distance obeys the expected variation, showing that the substitution is effective over the entire range. Local order around Co and Fe cations is studied by X-ray absorption spectroscopy. Moduli of the Fourier transform at the Fe K-edge are superimposable, in agreement with an ordered model, although present in small domains since no superlattice is depicted. The ionic resistivity of the samples is highly dependent on the water molecule content. The conductivity is found to be thermally assisted, and the variation of the slope in the Arrhenius diagram is explained by a Vogel-Tamman-Fulcher-type behavior. Magnetic susceptibility measurements support the proposed cation composition and indicate the onset of local magnetic order at low temperature (below 10 K). The inter-sheet distance influences the magnetic response at low temperature, showing the presence of weak interactions between lamellae.

  13. Structure and ionic conductivity of NaLnTiO{sub 4}: Comparison with those of Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = La, Nd, Sm, and Gd)

    SciTech Connect

    Byeon, Song-Ho; Park, Kileung; Itoh, Mitsuru

    1996-02-01

    The crystal structures of NaLnTiO{sub 4} (Ln = La, Nd, Sm, and Gd) were determined by Rietveld refinements on their powder X-ray diffraction patterns. They had K{sub 2}NiF{sub 4}-type related superstructure (space group P4/nmm (D{sub 4h}{sup 7})) in which NaO and LnO double layers are 1:1 ordered perpendicular to the c axis. Although the c parameter decreases form Ln-La to Nd, Sm, and Gd, the Na-O distance along the c axis was not proportional to the variation of the unit cell parameter. A strong corrugation parameter was observed, which would be induced by the poor charge compensation between NaO and LnO layers. Due to such a corrugation, the a parameter did not show decreasing tendency despite the fact that the constituting lanthanide ion becomes smaller. Ionic conductivity of NaLnTiO{sub 4} lower than that of Na{sub 2}Ln{sub 2}Ti{sub 3}O{sub 10} (Ln = La, Nd, Sm, and Gd) also resulted from the corrugation of LnO layer with coordination number 9 accompanied by contraction of the NaO layer.

  14. Nonaqueous Electrolyte Systems Ionic Transport in Nonaqueous Media.

    DTIC Science & Technology

    ALUMINATES, *IONIC CURRENT), (*ELECTROLYTES, ALUMINA), (*SULFITES, ELECTROLYTES), SODIUM COMPOUNDS, ELECTRICAL CONDUCTIVITY, TRANSPORT PROPERTIES, SOLUTIONS(MIXTURES), PERCHLORATES, FLUOBORATES , LITHIUM COMPOUNDS, VISCOSITY

  15. Synthesis of Ionic Conducting Interpenetrating Polymer Networks.

    DTIC Science & Technology

    1986-08-14

    Provo, Utah 84602 1 Departuent of Chemistry University of North Carolins I:-. 1. A. Marcus Chapel Rill, North Carolina 275141 r’yarcuent of Chemistry...Road 20 Kelly Court (vland, Ohio 44135 1Menlo Park, CA 94025-1418 Dv. D. 8ru.&.r rT:C Incorvoraced Dr. 1. P. Sch=idt ’.5 Capel S:reet. 1e;ecrtment of

  16. Ionic Conductivity in Lithium Hexaoxometallate Solid Solutions.

    DTIC Science & Technology

    1983-07-26

    Bi2O3 and ZrO 2. Mixtures of appropriate composition were throughly mixed using agate mortar in a He dry box. For example, Li7Tal-xNbxO6 and Li7Tal...xBixO6 were prepared from Li20, Ta205 and Nb2O5 , and Li20, Ta205 and Bi2O3 , respectively, according to the following equation 7Li2O + (l-x)Ta2O5

  17. Ionic molal conductivities, activity coefficients, and dissociation constants of HAsO42− and H2AsO4− from 5 to 90°C and ionic strengths from 0.001 up to 3 mol kg−1 and applications in natural systems

    USGS Publications Warehouse

    Zhu, Xiangyu; Nordstrom, D. Kirk; McCleskey, R. Blaine; Wang, Rucheng

    2016-01-01

    Arsenic is known to be one of the most toxic inorganic elements, causing worldwide environmental contamination. However, many fundamental properties related to aqueous arsenic species are not well known which will inhibit our ability to understand the geochemical behavior of arsenic (e.g. speciation, transport, and solubility). Here, the electrical conductivity of Na2HAsO4 solutions has been measured over the concentration range of 0.001–1 mol kg−1 and the temperature range of 5–90°C. Ionic strength and temperature-dependent equations were derived for the molal conductivity of HAsO42−and H2AsO4− aqueous ions. Combined with speciation calculations and the approach used by McCleskey et al. (2012b), these equations can be used to calculate the electrical conductivities of arsenic-rich waters having a large range of effective ionic strengths (0.001–3 mol kg−1) and temperatures (5–90°C). Individual ion activity coefficients for HAsO42− and H2AsO4− in the form of the Hückel equation were also derived using the mean salt method and the mean activity coefficients of K2HAsO4 (0.001–1 mol kg−1) and KH2AsO4 (0.001–1.3 mol kg−1). A check on these activity coefficients was made by calculating mean activity coefficients for Na2HAsO4 and NaH2AsO4 solutions and comparing them to measured values. At the same time Na-arsenate complexes were evaluated. The NaH2AsO40 ion pair is negligible in NaH2AsO4 solutions up to 1.3 mol kg−1. The NaHAsO4− ion pair is important in NaHAsO4 solutions >0.1 mol kg−1 and the formation constant of 100.69 was confirmed. The enthalpy, entropy, free energy and heat capacity for the second and third arsenic acid dissociation reactions were calculated from pH measurements. These properties have been incorporated into a widely used geochemical calculation code WATEQ4F and applied to natural arsenic waters. For arsenic spiked water samples from Yellowstone National Park, the mean difference between the

  18. Lithium-Air and ionic Liquids

    SciTech Connect

    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 the typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.

  19. Rietveld refinement and ionic conductivity of Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}

    SciTech Connect

    Tmar Trabelsi, I.; Madani, A.; Mercier, A.M.; Toumi, M.

    2013-01-15

    The structure of Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}, isostructural with Fluoroapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed that the formula of this compound is [Ca{sub 4}]{sup 4f}[Ca{sub 4.4}Bi{sub 1.6}]{sup 6h}(PO{sub 4}){sub 6}[O{sub 1.8}]{sup 2a}, space group P63/m (a=9.468 (3) A, c=6.957 (3) A). A total substitution of Bi{sup 3+} ions in the (6h) sites was related particularly to the high polarizability of the Bi{sup 3+} ion compared to Ca{sup 2+}. The observed frequencies in the Raman and infrared spectra were explained and discussed on the basis of unit-cell group analyses and in comparison with Fluoroapatite and other oxyapatites. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at {sigma}{sub 700 Degree-Sign C} =5.03 Multiplication-Sign 10{sup -7} S cm{sup -1} and E{sub a}=0.50 eV. - Graphical abstract: The final Rietveld refinement plot of the Ca{sub 8.4}Bi{sub 1.6} (PO{sub 4}){sub 6}O{sub 1.8}. Highlights: Black-Right-Pointing-Pointer The Rietveld refinement revealed that the formula of this compound is Ca{sub 8.4}Bi{sub 1.6}(PO{sub 4}){sub 6}O{sub 1.8}. Black-Right-Pointing-Pointer Vibrational spectroscopy supports the high symmetry P63/m space group for this apatite. Black-Right-Pointing-Pointer This apatite contained channels where oxygen ions were located in 2a sites. Black-Right-Pointing-Pointer The possibility of anionic conduction along these channels was considered.

  20. 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

    SciTech Connect

    Boughzala, Khaled; Debbichi, Mourad; Njema, Hela; Bouzouita, Khaled

    2016-07-15

    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 cell for Sr{sub 4}La{sub 6}Fap. Display Omitted.

  1. 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.

  2. Ionic conductors for solid oxide fuel cells

    SciTech Connect

    Krumpelt, M.; Bloom, I.D.; Pullockaran, J.D.; Myles, K.M.

    1991-12-31

    An electrolyte that operates at temperatures ranging from 600{degree}C to 800{degree}C is discussed. 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.

  3. 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.

  4. Ionic Liquids for Advanced Materials

    DTIC Science & Technology

    2008-12-01

    developed characterization set-ups for the electromechanical responses of conductive network/ ionomer composite (CNIC). The overall research goal... glass transition temperature (Tg) with an increase in dielectric constant and ion content. ILs uniquely combine high dielectric constant, low...from 230-440%. Dissociation of ionic aggregates was observed at 85-88 °C in DMA experiments, and the glass transition temperatures increased with

  5. 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.

  6. Modern ab initio valence bond theory calculations reveal charge shift bonding in protic ionic liquids.

    PubMed

    Patil, Amol Baliram; Bhanage, Bhalchandra Mahadeo

    2016-06-21

    The nature of bonding interactions between the cation and the anion of an ionic liquid is at the heart of understanding ionic liquid properties. A particularly interesting case is a special class of ionic liquids known as protic ionic liquids. The extent of proton transfer in protic ionic liquids has been observed to vary according to the interacting species. Back proton transfer renders protic ionic liquids volatile and to be considered as inferior ionic liquids. We try to address this issue by employing modern ab initio valence bond theory calculations. The results indicate that the bonding in the cation and the anion of a prototypical ionic liquid, ethylammonium nitrate, is fundamentally different. It is neither characteristic of covalent/polar covalent bonding nor ionic bonding but rather charge shift bonding as a resonance hybrid of two competing ionic molecular electronic structure configurations. An investigation of other analogous protic ionic liquids reveals that this charge shift bonding seems to be a typical characteristic of protic ionic liquids while the ionic solid analogue compound ammonium nitrate has less charge shift bonding character as compared to protic ionic liquids. Further the extent of charge shift bonding character has been found to be congruent with the trends in many physicochemical properties such as melting point, conductivity, viscosity, and ionicity of the studied ionic liquids indicating that percentage charge shift character may serve as a key descriptor for large scale computational screening of ionic liquids with desired properties.

  7. Radicals in ionic liquids.

    PubMed

    Strehmel, Veronika

    2012-05-14

    Stable radicals and recombination of photogenerated lophyl radicals are investigated in ionic liquids. The 2,2,6,6-tetramethylpiperidine-1-yloxyl derivatives contain various substituents at the 4-position to the nitroxyl group, including hydrogen-bond-forming or ionic substituents that undergo additional interactions with the individual ions of the ionic liquids. Some of these spin probes contain similar ions to ionic liquids to avoid counter-ion exchange with the ionic liquid. Depending on the ionic liquid anion, the Stokes-Einstein theory or the Spernol-Gierer-Wirtz theory can be applied to describe the temperature dependence of the average rotational correlation time of the spin probe in the ionic liquids. Furthermore, the spin probes give information about the micropolarity of the ionic liquids. In this context the substituent at the 4-position to the nitroxyl group plays a significant role. Covalent bonding of a spin probe to the imidazolium ion results in bulky spin probes that are strongly immobilized in the ionic liquid. Furthermore, lophyl radical recombination in the dark, which is chosen to understand the dynamics of bimolecular reactions in ionic liquids, shows a slow process at longer timescale and a rise time at a shorter timescale. Although various reactions may contribute to the slower process during lophyl radical recombination, it follows a second-order kinetics that does not clearly show solvent viscosity dependence. However, the rise time, which may be attributed to radical pair formation, increases with increasing solvent viscosity.

  8. Ionic liquids for rechargeable lithium batteries

    SciTech Connect

    Salminen, Justin; Papaiconomou, Nicolas; Kerr, John; Prausnitz,John; Newman, John

    2005-09-29

    We have investigated possible anticipated advantages of ionic-liquid electrolytes for use in lithium-ion batteries. Thermal stabilities and phase behavior were studied by thermal gravimetric analysis and differential scanning calorimetry. The ionic liquids studied include various imidazoliumTFSI systems, pyrrolidiniumTFSI, BMIMPF{sub 6}, BMIMBF{sub 4}, and BMIMTf. Thermal stabilities were measured for neat ionic liquids and for BMIMBF{sub 4}-LiBF{sub 4}, BMIMTf-LiTf, BMIMTFSI-LiTFSI mixtures. Conductivities have been measured for various ionic-liquid lithium-salt systems. We show the development of interfacial impedance in a Li|BMIMBF{sub 4} + LiBF{sub 4}|Li cell and we report results from cycling experiments for a Li|BMIMBF{sub 4} + 1 mol/kg LIBF{sub 4}|C cell. The interfacial resistance increases with time and the ionic liquid reacts with the lithium electrode. As expected, imidazolium-based ionic liquids react with lithium electrodes. We seek new ionic liquids that have better chemical stabilities.

  9. Ionic conductivity of Bi{sub 2}Ni{sub x}V{sub 1−x}O{sub 5.5−3x/2} (0.1 ≤ x ≤ 0.2) oxides prepared by a low temperature sol-gel route

    SciTech Connect

    Rusli, Rolan; Patah, Aep Prijamboedi, Bambang Ismunandar; Abrahams, Isaac

    2014-03-24

    Solid oxides fuel cells (SOFCs) is one technology that could contribute toward future sustainable energy. One of the most important components of an SOFC is the electrolyte, which must have high ionic conductivity. Cation substitution of vanadium in Bi{sub 4}V{sub 2}O{sub 11} yields a family of fast oxide ion conducting solids known collectively as the BIMEVOXes (bismuth metal vanadium oxide), which have the potential to be applied as electrolytes in SOFCs. The purpose of this work is to study the effect of Ni concentration, when used as a dopant, on the ionic conductivity of Bi{sub 2}Ni{sub x}V{sub 1−x}O{sub 5.5−3x/2} (BINIVOX) oxides (0.1 ≤ x ≤ 0.2) when prepared by a sol gel method. The gels were calcined at 600 °C for 24 h to produce pure BINIVOX. These oxides were found to exhibit the γ-phase structure with tetragonal symmetry in space group I4/mmm. Ionic conductivity of BINIVOX at 300 °C were 6.9 × 10{sup −3} S cm{sup −1}, 1.2 × 10{sup −3} S cm{sup −1}, and 8.2 × 10{sup −4} S cm{sup −1}, for x = 0.1; 0.15; and 0.2; respectively; and at 600 °C were 1.1 × 10{sup −1} S cm{sup −1}, 5.3 × 10{sup −2} S cm{sup −1}, and 2.8 ×10{sup −2} S cm{sup −1}, for x = 0.1; 0.15; and 0.2; respectively.

  10. Modeling of ionic liquids

    NASA Astrophysics Data System (ADS)

    Tatlipinar, Hasan

    2017-02-01

    Ionic liquids are very important entry to industry and technology. Because of their unique properties they may classified as a new class of materials. IL usually classified as a high temperature ionic liquids (HTIL) and room temperature ionic liquids (RTIL). HTIL are molten salts. There are many research studies on molten salts such as recycling, new energy sources, rare elements mining. RTIL recently become very important in daily life industry because of their "green chemistry" properties. As a simple view ionic liquids consist of one positively charged and one negatively charged components. Because of their Coulombic or dispersive interactions the local structure of ionic liquids emerges. In this presentation the local structural properties of the HTIL are discussed via correlation functions and integral equation theories. RTIL are much more difficult to do modeling, but still general consideration for the modeling of the HTIL is valid also for the RTIL.

  11. Plasticizer Influence on Ionic Morphology and Transport in PEO Ionomers

    NASA Astrophysics Data System (ADS)

    O'Reilly, Michael; Masser, Hanqing; King, Daniel; Painter, Paul; Colby, Ralph; Runt, James; Winey, Karen

    2013-03-01

    Sulfonated poly(ethylene oxide) ionomers have been blended with a miscible, oligomeric poly(ethylene glycol) in order to study the effect of plasticizers on ionomer performance. Plasticizers can increase ionic conductivity in ionomers by depressing the glass transition temperature and dissolving ionic aggregates. In this study, the relative volume fractions of ionic aggregates in various blend compositions is investigated by curve fitting the X-ray scattering aggregate peak. Two fitting parameters are utilized to quantify aggregate composition, peak area and peak position. Fitting results conclude that plasticizer content dilutes and dissolves ionic aggregates, providing higher conducting ion density than comparable neat ionomers. Dielectric relaxation spectroscopy data confirms that ionic conductivity improves with plasticizer content. Similar curve fitting methods were executed for FT-IR signals, and quantification of aggregate structure is compared with X-ray scattering.

  12. Aqueous Solutions of Ionic Liquids: Microscopic Assembly.

    PubMed

    Vicent-Luna, Jose Manuel; Dubbeldam, David; Gómez-Álvarez, Paula; Calero, Sofia

    2016-02-03

    Aqueous solutions of ionic liquids are of special interest, due to the distinctive properties of ionic liquids, in particular, their amphiphilic character. A better understanding of the structure-property relationships of such systems is hence desirable. One of the crucial molecular-level interactions that influences the macroscopic behavior is hydrogen bonding. In this work, we conduct molecular dynamics simulations to investigate the effects of ionic liquids on the hydrogen-bond network of water in dilute aqueous solutions of ionic liquids with various combinations of cations and anions. Calculations are performed for imidazolium-based cations with alkyl chains of different lengths and for a variety of anions, namely, [Br](-), [NO3](-), [SCN](-) [BF4](-), [PF6](-), and [Tf2N](-). The structure of water and the water-ionic liquid interactions involved in the formation of a heterogeneous network are analyzed by using radial distribution functions and hydrogen-bond statistics. To this end, we employ the geometric criterion of the hydrogen-bond definition and it is shown that the structure of water is sensitive to the amount of ionic liquid and to the anion type. In particular, [SCN](-) and [Tf2N](-) were found to be the most hydrophilic and hydrophobic anions, respectively. Conversely, the cation chain length did not influence the results.

  13. Supramolecular gelators based on benzenetricarboxamides for ionic liquids.

    PubMed

    Ishioka, Yumi; Minakuchi, Nami; Mizuhata, Minoru; Maruyama, Tatsuo

    2014-02-21

    Supramolecular gelators comprising 1,3,5-benzenetricarboxylic acids and amino acid methyl esters (glycine, L-alanine, L-valine, L-leucine, L-methionine, and L-phenylalanine) for ionic liquids were developed. Ten types of ionic liquids were gelated using the above-mentioned gelators at relatively low concentrations. Field emission-scanning electron microscopy and confocal laser scanning microscopy analyses revealed that these gelators self-assembled into an entangled fibrous structure in ionic liquids, leading to the gelation of the ionic liquids. Comparison studies, involving compounds analogous to the gelators, and Fourier transform infrared spectroscopy measurements suggested that hydrogen bonding played a key role in the self-assembly of the gelator molecules. The ionogels displayed reversible thermal transition characteristics and viscoelastic properties typical of a gel. The gelation of the ionic liquids studied under a wide range of gelator concentrations did not affect the intrinsic conductivity of the ionic liquids.

  14. Ionic liquids in tribology.

    PubMed

    Minami, Ichiro

    2009-06-24

    Current research on room-temperature ionic liquids as lubricants is described. Ionic liquids possess excellent properties such as non-volatility, non-flammability, and thermo-oxidative stability. The potential use of ionic liquids as lubricants was first proposed in 2001 and approximately 70 articles pertaining to fundamental research on ionic liquids have been published through May 2009. A large majority of the cations examined in this area are derived from 1,3-dialkylimidazolium, with a higher alkyl group on the imidazolium cation being beneficial for good lubrication, while it reduces the thermo-oxidative stability. Hydrophobic anions provide both good lubricity and significant thermo-oxidative stability. The anions decompose through a tribochemical reaction to generate metal fluoride on the rubbed surface. Additive technology to improve lubricity is also explained. An introduction to tribology as an interdisciplinary field of lubrication is also provided.

  15. Applications of ionic liquids.

    PubMed

    Patel, Divia Dinesh; Lee, Jong-Min

    2012-06-01

    Ionic liquids have recently gained popularity in the scientific community owing to their special properties and characteristics. One of the reasons why ionic liquids have been termed "green solvents" is due to their negligible vapour pressure. Their use in electrochemical, biological and metal extraction applications is discussed. Wide research has been carried out for their use in batteries, solar panels, fuel cells, drug deliveries and biomass pretreatments. This work aims to consolidate the various findings from previous works in these areas.

  16. Deposition of a thin film of TiOx from a titanium metal target as novel blocking layers at conducting glass/TiO2 interfaces in ionic liquid mesoscopic TiO2 dye-sensitized solar cells.

    PubMed

    Xia, Jiangbin; Masaki, Naruhiko; Jiang, Kejian; Yanagida, Shozo

    2006-12-21

    In dye-sensitized TiO2 solar cells, charge recombination processes at interfaces between fluorine-doped tin oxide (FTO), TiO2, dye, and electrolyte play an important role in limiting the photon-to-electron conversion efficiency. From this point of view, a high work function material such as titanium deposited by sputtering on FTO has been investigated as an effective blocking layer for preventing electron leakage from FTO without influencing electron injection. X-ray photoelectron spectroscopy analysis indicates that different species of Ti (Ti4+, Ti3+, Ti2+, and a small amount of Ti0) exist on FTO. Electrochemical and photoelectrochemical measurements reveal that thin films of titanium species, expressed as TiOx, work as a compact blocking layer between FTO and TiO2 nanocrystaline film, improving Voc and the fill factor, finally giving a better conversion efficiency for dye-sensitized TiO2 solar cells with ionic liquid electrolytes.

  17. Different roles of ionic liquids in lithium batteries

    NASA Astrophysics Data System (ADS)

    Eftekhari, Ali; Liu, Yang; Chen, Pu

    2016-12-01

    Ionic liquids are often named solvents of the future because of flexibility in design. This statement has given credence that ionic liquids should simply replace the problematic electrolytes of lithium batteries. As a result, the promising potentials of ionic liquids in electrochemical systems are somehow obscured by inappropriate expectations. We summarize recent advancements in this field, especially, ionic liquids as standalone electrolytes, additives, plasticizers in gel polymer electrolytes, and binders; and attempt to shed light on the future pathway of this area of research. Ionic liquids are not dilute media to serve as pure solvents in electrochemical systems where mobility of ions is the priority; instead, they can contribute to the ionic conductivity of various components in a battery system. Owing to the enormous possibilities of ionic liquids, it is not merely a matter of choice. Ionic liquids can be used to design novel types of electrolytes for a new generation of lithium batteries. A promising possibility, which is still at a very early stage, is supercooled ionic liquid crystals for fast ion diffusion through the guided channels of a liquid-like medium. This, of course, will be a breakthrough in the realm of electrochemistry, far beyond lithium battery field, when materialized.

  18. Chromosome observation by scanning electron microscopy using ionic liquid.

    PubMed

    Dwiranti, Astari; Lin, Linyen; Mochizuki, Eiko; Kuwabata, Susumu; Takaoka, Akio; Uchiyama, Susumu; Fukui, Kiichi

    2012-08-01

    Electron microscopy has been used to visualize chromosome since it has high resolution and magnification. However, biological samples need to be dehydrated and coated with metal or carbon before observation. Ionic liquid is a class of ionic solvent that possesses advantageous properties of current interest in a variety of interdisciplinary areas of science. By using ionic liquid, biological samples need not be dehydrated or metal-coated, because ionic liquid behaves as the electronically conducting material for electron microscopy. The authors have investigated chromosome using ionic liquid in conjunction with electron microscopy and evaluated the factors that affect chromosome visualization. Experimental conditions used in the previous studies were further optimized. As a result, prewarmed, well-mixed, and low concentration (0.5∼1.0%) ionic liquid provides well-contrasted images, especially when the more hydrophilic and the higher purity ionic liquid is used. Image contrast and resolution are enhanced by the combination of ionic liquid and platinum blue staining, the use of an indium tin oxide membrane, osmium tetroxide-coated coverslip, or aluminum foil as substrate, and the adjustment of electron acceleration voltage. The authors conclude that the ionic-liquid method is useful for the visualization of chromosome by scanning electron microscopy without dehydration or metal coating.

  19. Enhanced electrical transport in ionic liquid dispersed TMAI-PEO solid polymer electrolyte

    SciTech Connect

    Gupta, Neha; Rathore, Munesh Dalvi, Anshuman; Kumar, Anil

    2014-04-24

    A polymer composite is prepared by dispersing ionic liquid [Bmim][BF{sub 4}] in Polyethylene oxide-tetra methyl ammonium iodide composite and subsequent microwave treatment. X-ray diffraction patterns confirm the composite nature. To explore possibility of proton conductivity in these films, electrical transport is studied by impedance spectroscopy and DC polarization. It is revealed that addition of ionic liquid in host TMAI-PEO solid polymer electrolyte enhances the conductivity by ∼ 2 orders of magnitude. Polarization measurements suggest that composites are essentially ion conducting in nature. The maximum ionic conductivity is found to be ∼2 × 10{sup −5} for 10 wt % ionic liquid.

  20. Are Ionic Liquids Chemically Stable?

    PubMed

    Wang, Binshen; Qin, Li; Mu, Tiancheng; Xue, Zhimin; Gao, Guohua

    2017-02-27

    Ionic liquids have attracted a great deal of interest in recent years, illustrated by their applications in a variety of areas involved with chemistry, physics, biology, and engineering. Usually, the stabilities of ionic liquids are highlighted as one of their outstanding advantages. However, are ionic liquids really stable in all cases? This review covers the chemical stabilities of ionic liquids. It focuses on the reactivity of the most popular imidazolium ionic liquids at structural positions, including C2 position, N1 and N3 positions, and C4 and C5 positions, and decomposition on the imidazolium ring. Additionally, we discuss decomposition of quaternary ammonium and phosphonium ionic liquids and hydrolysis and nucleophilic reactions of anions of ionic liquids. The review aims to arouse caution on potential decomposition of ionic liquids and provides a guide for better utilization of ionic liquids.

  1. Electroosmotic flow hysteresis for dissimilar ionic solutions

    PubMed Central

    Lim, An Eng; Lam, Yee Cheong

    2015-01-01

    Electroosmotic flow (EOF) with two or more fluids is commonly encountered in various microfluidics applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during the displacement flow of solutions with dissimilar ionic species. In this investigation, electroosmotic displacement flow involving dissimilar ionic solutions was studied experimentally through a current monitoring method and numerically through finite element simulations. The flow hysteresis can be characterized by the turning and displacement times; turning time refers to the abrupt gradient change of current-time curve while displacement time is the time for one solution to completely displace the other solution. Both experimental and simulation results illustrate that the turning and displacement times for a particular solution pair can be directional-dependent, indicating that the flow conditions in the microchannel are not the same in the two different flow directions. The mechanics of EOF hysteresis was elucidated through the theoretical model which includes the ionic mobility of each species, a major governing parameter. Two distinct mechanics have been identified as the causes for the EOF hysteresis involving dissimilar ionic solutions: the widening/sharpening effect of interfacial region between the two solutions and the difference in ion concentration distributions (and thus average zeta potentials) in different flow directions. The outcome of this investigation contributes to the fundamental understanding of flow behavior in microfluidic systems involving solution pair with dissimilar ionic species. PMID:25945139

  2. Ionic liquids as active pharmaceutical ingredients.

    PubMed

    Ferraz, Ricardo; Branco, Luís C; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Zeljko

    2011-06-06

    Ionic liquids (ILs) are ionic compounds that possess a melting temperature below 100 °C. Their physical and chemical properties are attractive for various applications. Several organic materials that are now classified as ionic liquids were described as far back as the mid-19th century. The search for new and different ILs has led to the progressive development and application of three generations of ILs: 1) The focus of the first generation was mainly on their unique intrinsic physical and chemical properties, such as density, viscosity, conductivity, solubility, and high thermal and chemical stability. 2) The second generation of ILs offered the potential to tune some of these physical and chemical properties, allowing the formation of "task-specific ionic liquids" which can have application as lubricants, energetic materials (in the case of selective separation and extraction processes), and as more environmentally friendly (greener) reaction solvents, among others. 3) The third and most recent generation of ILs involve active pharmaceutical ingredients (API), which are being used to produce ILs with biological activity. Herein we summarize recent developments in the area of third-generation ionic liquids that are being used as APIs, with a particular focus on efforts to overcome current hurdles encountered by APIs. We also offer some innovative solutions in new medical treatment and delivery options.

  3. Composite mixed oxide ionic and electronic conductors for hydrogen separation

    DOEpatents

    Gopalan, Srikanth; Pal, Uday B.; Karthikeyan, Annamalai; Hengdong, Cui

    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.

  4. Electromechanical performance and membrane stability of novel ionic polymer transducers constructed in the presence of ionic liquids

    NASA Astrophysics Data System (ADS)

    Duncan, Andrew J.; Leo, Donald J.; Long, Timothy E.; Akle, Barbar J.; Park, Jong K.; Moore, Robert B.

    2009-03-01

    Ionic polymer transducers (IPT) are a class of devices that leverage electroactive polymers (EAP), specifically electrolyte-swollen ionomeric membranes, to perform energy conversions. Energy transformation from input to output is referred to as transduction and occurs between the electrical and mechanical domains. The present study expands on IPT investigations with a novel series of sulfonated polysulfones (sBPS), with specific interest in the effect of polymer topology on actuator performance. A hydrophilic ionic liquid was combined with a series of sBPS through a casting method to create hydrated membranes that contained target uptakes (f) of the diluent. The ionic liquid's hydrophilic, yet organic nature raised the issue of its degree of compatibility and miscibility with the microphase separated domains of the host ionomeric membrane. Initial studies of the ionomer - ionic liquid morphology were performed with synchrotron small angle X-ray scattering (SAXS). The effective plasticization of the membranes was identified with dynamic mechanical analysis (DMA) in terms of varied storage modulus and thermal transitions with ionic liquid uptake. Electrical impedance spectroscopy (EIS) was employed to quantify the changes in ionic conductivity for each sBPS ionomer across a range of uptake. Combined results from these techniques implied that the presence of large amounts of ionic liquid swelled the hydrophilic domains of the ionomer and greatly increased the ionic conductivity. Decreases in storage modulus and the glass transition temperature were proportional to one another but of a lesser magnitude than changes in conductivity. The present range of ionic liquid uptake for sBPS was sufficient to identify the critical uptake (fc) for three of the four ionomers in the series. Future work to construct IPTs with these components will use the critical uptake as a minimum allowable content of ionic liquid to optimize the balance of electrical and mechanical properties for

  5. Stretchable, transparent, ionic conductors.

    PubMed

    Keplinger, Christoph; Sun, Jeong-Yun; Foo, Choon Chiang; Rothemund, Philipp; Whitesides, George M; Suo, Zhigang

    2013-08-30

    Existing stretchable, transparent conductors are mostly electronic conductors. They limit the performance of interconnects, sensors, and actuators as components of stretchable electronics and soft machines. We describe a class of devices enabled by ionic conductors that are highly stretchable, fully transparent to light of all colors, and capable of operation at frequencies beyond 10 kilohertz and voltages above 10 kilovolts. We demonstrate a transparent actuator that can generate large strains and a transparent loudspeaker that produces sound over the entire audible range. The electromechanical transduction is achieved without electrochemical reaction. The ionic conductors have higher resistivity than many electronic conductors; however, when large stretchability and high transmittance are required, the ionic conductors have lower sheet resistance than all existing electronic conductors.

  6. Ionic model for highly compressed solid hydrogen

    NASA Astrophysics Data System (ADS)

    Yakub, E. S.

    2013-05-01

    We propose a simple ionic model for high-pressure conducting phase IV of solid hydrogen observed recently at room temperature. It is based on an assumption of dissociative ionization of hydrogen molecules 3H2=2H2(+)+2H(-) induced by high compression. The proposed model predicts the first order transition of molecular hydrogen solid into partly ionic conducting phase at megabar pressures and describes the temperature dependence of resistivity at room temperature. Its predictions are consistent with high temperature shock-compression experiments which exhibit conductivity of multiply shocked hydrogen. The location of phase transition line, the volume change, and the ionization degree in solid phase IV are estimated.

  7. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

    NASA Astrophysics Data System (ADS)

    Fadeeva, Tatiana A.; Husson, Pascale; DeVine, Jessalyn A.; Costa Gomes, Margarida F.; Greenbaum, Steven G.; Castner, Edward W.

    2015-08-01

    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 analyze 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.

  8. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

  9. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids.

    PubMed

    Fadeeva, Tatiana A; Husson, Pascale; DeVine, Jessalyn A; Costa Gomes, Margarida F; Greenbaum, Steven G; Castner, Edward W

    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 analyze 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.

  10. Interactions between water and 1-butyl-1-methylpyrrolidinium ionic liquids

    SciTech Connect

    Fadeeva, Tatiana A.; DeVine, Jessalyn A.; Castner, Edward W.; Husson, Pascale; Costa Gomes, Margarida F.; Greenbaum, Steven G.

    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 analyze 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.

  11. Polymerizable ionic liquid crystals.

    PubMed

    Jazkewitsch, Olga; Ritter, Helmut

    2009-09-17

    Polymerizable vinylimidazolium ionic liquids (ILs) that contain mesogenic coumarin and biphenyl units, respectively, have been synthesized. The N-alkylation of N-vinylimidazole with bromoalkylated mesogenic units 7-(6-bromohexyloxy)coumarin (1) and 4,4'-bis(6-bromohexyloxy)biphenyl (2) was then carried out. The thermal behavior of the obtained ILs 3 and 4 was investigated by differential scanning calorimetry and polarizing optical microscopy. These measurements showed that the attached mesogenic units induce the self-assembly of ILs and, therefore, the occurrence of liquid crystalline phases. Subsequently, the ionic liquid crystals (ILCs) 3 and 4 were polymerized by a free-radical mechanism.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    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 changes in dynamics are not mirrored in the ionicity of these ILs, which decreases nearly linearly with aliphatic volume fraction. Our results demonstrate that nanophase segregation in neat ILs strongly reduces ionic conductivity primarily due to an aggregation-induced suppression of dynamics.

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

    SciTech Connect

    Griffin, Philip J.; Wang, Yangyang; Holt, Adam P.; Sokolov, Alexei P.; Oak Ridge National Lab. , Oak Ridge, TN . Chemical Sciences Division

    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 changes 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.

  14. 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

  15. Ionic liquids in chemical engineering.

    PubMed

    Werner, Sebastian; Haumann, Marco; Wasserscheid, Peter

    2010-01-01

    The development of engineering applications with ionic liquids stretches back to the mid-1990s when the first examples of continuous catalytic processes using ionic liquids and the first studies of ionic liquid-based extractions were published. Ever since, the use of ionic liquids has seen tremendous progress in many fields of chemistry and engineering, and the first commercial applications have been reported. The main driver for ionic liquid engineering applications is to make practical use of their unique property profiles, which are the result of a complex interplay of coulombic, hydrogen bonding and van der Waals interactions. Remarkably, many ionic liquid properties can be tuned in a wide range by structural modifications at their cation and anion. This review highlights specific examples of ionic liquid applications in catalysis and in separation technologies. Additionally, the application of ionic liquids as working fluids in process machines is introduced.

  16. Ionic liquid tunes microemulsion curvature.

    PubMed

    Liu, Liping; Bauduin, Pierre; Zemb, Thomas; Eastoe, Julian; Hao, Jingcheng

    2009-02-17

    Middle-phase microemulsions formed from cationic dioctadecyldimethylammonium chloride (DODMAC), anionic sodium dodecylsulfate (SDS), n-butanol, and n-heptane were studied. An ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), was employed as the electrolyte in the aqueous media instead of inorganic salts usually used in microemulsion formulation. Studies have been carried out as a function of the concentrations of [bmim][BF4], n-butanol, total surfactant (cDODMAC+SDS), and temperature on the phase behavior and the ultralow interfacial tensions in which the anionic component is present in excess in the catanionic film. Ultralow interfacial tension measurements confirmed the formation of middle-phase microemulsions and the necessary conditions for stabilizing middle-phase microemulsions. Electrical conductivity, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) experiments were also performed, indicating that the typical heptane domain size has an average radius of 360 A and the ionic liquid induces softening of the charged catanionic film. Most interestingly, the IL concentration (cIL) is shown to act as an effective interfacial curvature-control parameter, representing a new approach to tuning the formulation of microemulsions and emulsions. The results expand the potential uses of ILs but also point to the design of new ILs that may achieve superefficient control over interfacial and self-assembly systems.

  17. Fun with Ionic Compounds

    ERIC Educational Resources Information Center

    Logerwell, Mollianne G.; Sterling, Donna R.

    2007-01-01

    Ionic bonding is a fundamental topic in high school chemistry, yet it continues to be a concept that students struggle to understand. Even if they understand atomic structure and ion formation, it can be difficult for students to visualize how ions fit together to form compounds. This article describes several engaging activities that help…

  18. 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

  19. Improvement of SOFC electrodes using mixed ionic-electronic conductors

    SciTech Connect

    Matsuzaki, Y.; Hishinuma, M.

    1996-12-31

    Since the electrode reaction of SOFC is limited to the proximity of a triple phase boundary (TPB), the local current density at the electrode and electrolyte interface is larger than mean current density, which causes large ohmic and electrode polarization. This paper describes an application of mixed ionic-electronic conductors to reduce such polarization by means of (1) enhancing ionic conductivity of the electrolyte surface layer by coating a high ionic conductors, and (2) reducing the local current density by increasing the electrochemically active sites.

  20. Ionic liquid based multifunctional double network gel

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Higashihara, Tomoya; Arafune, Hiroyuki; Kamijo, Toshio; Morinaga, Takashi; Sato, Takaya; Furukawa, Hidemitsu

    2015-04-01

    Gels are a promising class of soft and wet materials with diverse application in tissue engineering and bio-medical purpose. In order to accelerate the development of gels, it is required to synthesize multi-functional gels of high mechanical strength, ultra low surface friction and suitable elastic modulus with a variety of methods and new materials. Among many types of gel ionic gel made from ionic liquids (ILs) could be used for diverse applications in electrochemical devices and in the field of tribology. IL, a promising materials for lubrication, is a salt with a melting point lower than 100 °C. As a lubricant, ILs are characterized by an extremely low vapor pressure, high thermal stability and high ion conductivity. In this work a novel approach of making double network DN ionic gel using IL has been made utilizing photo polymerization process. A hydrophobic monomer Methyl methacrylate (MMA) has been used as a first network and a hydrophobic IL monomer, N,N-diethyl-N-(2-mthacryloylethyl)-N-methylammonium bistrifluoromethylsulfonyl)imide (DEMM-TFSI) has been used as a second network using photo initiator benzophenon and crosslinker triethylene glycol dimethacrylate (TEGDMA). The resulting DN ionic gel shows transparency, flexibility, high thermal stability, good mechanical toughness and low friction coefficient value which can be a potential candidate as a gel slider in different mechanical devices and can open a new area in the field of gel tribology.

  1. Extraction of proteins with ionic liquid aqueous two-phase system based on guanidine ionic liquid.

    PubMed

    Zeng, Qun; Wang, Yuzhi; Li, Na; Huang, Xiu; Ding, Xueqin; Lin, Xiao; Huang, Songyun; Liu, Xiaojie

    2013-11-15

    Eight kinds of green ionic liquids were synthesized, and an ionic liquid aqueous two-phase system (ILATPS) based on 1,1,3,3-tetramethylguandine acrylate (TMGA) guanidine ionic liquid was first time studied for the extraction of proteins. Single factor experiments proved that the extraction efficiency of bovine serum albumin (BSA) was influenced by the mass of IL, K2HPO4 and BSA, also related to the separation time and temperature. The optimum conditions were determined through orthogonal experiment by the five factors described above. The results showed that under the optimum conditions, the extraction efficiency could reach up to 99.6243%. The relative standard deviations (RSD) of extraction efficiencies in precision experiment, repeatability experiment and stability experiment were 0.8156% (n=5), 1.6173% (n=5) and 1.6292% (n=5), respectively. UV-vis and FT-IR spectra confirmed that there were no chemical interactions between BSA and ionic liquid in the extraction process, and the conformation of the protein was not changed after extraction. The conductivity, DLS and TEM were combined to investigate the microstructure of the top phase and the possible mechanism for the extraction. The results showed that hydrophobic interaction, hydrogen bonding interaction and the salt out effect played important roles in the transferring process, and the aggregation and embrace phenomenon was the main driving force for the separation. All these results proved that guanidine ionic liquid-based ATPSs have the potential to offer new possibility in the extraction of proteins.

  2. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

    PubMed

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-04-08

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

  3. Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

    PubMed Central

    Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

    2016-01-01

    Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

  4. Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes

    SciTech Connect

    Wang, Yangyang; Fan, Fei; Agapov, Alexander L; Saito, Tomonori; Yang, Jun; Yu, Xiang; Hong, Kunlun; Mays, Jimmy; Sokolov, Alexei P

    2014-01-01

    Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with superionic conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes.

  5. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

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

    DOE PAGES

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

    2015-01-01

    A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl3 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.

  7. Polymer--Ionic liquid Electrolytes for Electrochemical Capacitors

    NASA Astrophysics Data System (ADS)

    Ketabi, Sanaz

    Polymer electrolyte, comprised of ionic conductors, polymer matrix, and additives, is one of the key components that control the performance of solid flexible electrochemical capacitors (ECs). Ionic liquids (ILs) are highly promising ionic conductors for next generation polymer electrolytes due to their excellent electrochemical and thermal stability. Fluorinated ILs are the most commonly applied in polymer-IL electrolytes. Although possessing high conductivity, these ILs have low environmental favorability. The aim of this work was to develop environmentally benign polymer-ILs for both electrochemical double layer capacitors (EDLCs) and pseudocapacitors, and to provide insights into the influence of constituent materials on the ion conduction mechanism and the structural stability of the polymer-IL electrolytes. Solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and 1-ethyl-3-methylimidazolium hydrogen sulfate (EMIHSO4) were investigated for ECs. The material system was optimized to achieve the two criteria for high performance polymer-ILs: high ionic conductivity and highly amorphous structure. Thermal and structural analyses revealed that EMIHSO4 acted as an ionic conductor and a plasticizer that substantially decreased the crystallinity of PEO. Two types of inorganic nanofillers were incorporated into these polymer electrolytes. The effects of SiO2 and TiO2 nanofillers on ionic conductivity, crystallinity, and dielectric properties of PEO-EMIHSO 4 were studied over a temperature range from -10 °C and 80 °C. Using an electrochemical capacitor model, impedance (complex capacitance) and dielectric analyses were performed to understand the ionic conduction process with and without fillers in both semi crystalline and amorphous states of the polymer electrolytes. Despite their different nanostructures, both SiO2 and TiO2 promoted an amorphous structure in PEO-EMIHSO 4 and increased the ionic conductivity 2-fold. While in the amorphous state, the

  8. Vibrational Spectroscopy of Ionic Liquids.

    PubMed

    Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

    2017-01-04

    Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990's. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.

  9. VOC and HAP recovery using ionic liquids

    SciTech Connect

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy

  10. Study on analysis of ionic wind for heat transfer enhancement .

    NASA Astrophysics Data System (ADS)

    Ko, Han Seo; Shin, Dong Ho

    2016-11-01

    Local heat transfer technology was investigated using ionic wind generation in this study. Characteristics of ionic wind using wire and plate electrodes were studied by experimental and numerical methods. A particle image velocitimetry (PIV) test was conducted for a study of a boundary layer controlled by the ionic wind on the heated surface in the wind tunnel. It was found that the coulombic force consistently acted on the surface to reduce the effect of the viscous boundary layer. The boundary layer was formed on the heated surface and controlled by the ionic wind regardless of the Reynolds number of the bulk flow. The heat transfer coefficient increased and decreased, 11% and 19% in average on the heated surface by the ionic wind, for the condition of lower (100 200) and higher (2500 3500) Reynolds numbers of the bulk flow, respectively. It was concluded that the ionic wind can be used for enhancing the convection heat transfer rate or insulating the local surface according to its operating condition. The results of the local heat transfer controlled by the ionic wind were applied for the heat exchanger and the performance was confirmed by the experimental and numerical methods.

  11. A single crystal X-ray and powder neutron diffraction study on NASICON-type Li1+xAlxTi2-x(PO4)3 (0 ≤ x ≤ 0.5) crystals: Implications on ionic conductivity

    NASA Astrophysics Data System (ADS)

    Redhammer, G. J.; Rettenwander, D.; Pristat, S.; Dashjav, E.; Kumar, C. M. N.; Topa, D.; Tietz, F.

    2016-10-01

    Single crystals of NASICON-type material Li1+xTi2-xAlx(PO4)3 (LATP) with 0 ≤ x ≤ 0.5 were successfully grown using long-term sintering techniques. Sample material was studied by chemical analysis, single crystal X-ray and neutron diffraction. The Ti4+ replacement scales very well with the Al3+ and Li+ incorporation. The additional Li+ thereby enters the M3 cavity of the NASICON framework at x, y, z ∼ (0.07, 0.34, 0.09) and is regarded to be responsible for the enhanced Li+ conduction of LATP as compared to Al-free LTP. Variations in structural parameters, associated with the Ti4+ substitution with Al3+ + Li+ will be discussed in detail in this paper.

  12. Graphene-ionic liquid composites

    DOEpatents

    Aksay, Ilhan A.; Korkut, Sibel; Pope, Michael; Punckt, Christian

    2016-11-01

    Method of making a graphene-ionic liquid composite. The composite can be used to make elec-trodes for energy storage devices, such as batteries and supercapacitors. Dis-closed and claimed herein is method of making a graphene-ionic liquid com-posite, comprising combining a graphene source with at least one ionic liquid and heating the combination at a temperature of at least about 130 .degree. C.

  13. Design of Energetic Ionic Liquids

    DTIC Science & Technology

    2009-05-12

    effectiveness of the FMO method in both providing accurate results and reducing computational requirements, timings were performed for the ionic liquid ...Technical Paper 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Design of Energetic Ionic Liquids 5b. GRANT NUMBER 5c...Design of Energetic Ionic Liquids challenge project is to address several key technical issues and challenges associated with the characterization

  14. The natriuretic peptides BNP and CNP increase heart rate and electrical conduction by stimulating ionic currents in the sinoatrial node and atrial myocardium following activation of guanylyl cyclase-linked natriuretic peptide receptors.

    PubMed

    Springer, Jeremy; Azer, John; Hua, Rui; Robbins, Courtney; Adamczyk, Andrew; McBoyle, Sarah; Bissell, Mary Beth; Rose, Robert A

    2012-05-01

    Natriuretic peptides (NPs) are best known for their ability to regulate blood vessel tone and kidney function whereas their electrophysiological effects on the heart are less clear. Here, we measured the effects of BNP and CNP on sinoatrial node (SAN) and atrial electrophysiology in isolated hearts as well as isolated SAN and right atrial myocytes from mice. BNP and CNP dose-dependently increased heart rate and conduction through the heart as indicated by reductions in R-R interval, P wave duration and P-R interval on ECGs. In conjunction with these ECG changes BNP and CNP (100 nM) increased spontaneous action potential frequency in isolated SAN myocytes by increasing L-type Ca(2+) current (I(Ca,L)) and the hyperpolarization-activated current (I(f)). BNP had no effect on right atrial myocyte APs in basal conditions; however, in the presence of isoproterenol (10nM), BNP increased atrial AP duration and I(Ca,L). Quantitative gene expression and immunocytochemistry data show that all three NP receptors (NPR-A, NPR-B and NPR-C) are expressed in the SAN and atrium. The effects of BNP and CNP on SAN and right atrial myocytes were maintained in mutant mice lacking functional NPR-C receptors and blocked by the NPR-A antagonist A71915 indicating that BNP and CNP function through their guanylyl cyclase-linked receptors. Our data also show that the effects of BNP and CNP are completely absent in the presence of the phosphodiesterase 3 inhibitor milrinone. Based on these data we conclude that NPs can increase heart rate and electrical conduction by activating the guanylyl cyclase-linked NPR-A and NPR-B receptors and inhibiting PDE3 activity.

  15. 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.

  16. Facilitated Ion Transport in Smectic Ordered Ionic Liquid Crystals

    SciTech Connect

    Lee, Jin Hong; Han, Kee Sung; Lee, Je Seung; Lee, Albert S.; Park, Seo Kyung; Hong, Sung Yun; Lee, Jong-Chan; Mueller, Karl T.; Hong, Soon Man; Koo, Chong Min

    2016-09-08

    We investigated a novel ionic mixture of an imidazolium-based room temperature IL containing ethylene oxide functionalized phosphite anion and a lithium salt that self-assembles into a smectic-ordered IL crystal. The two key features in this work are the unique origin of the smectic order of the ionic mixtures and the facilitated ion transport behavior in the smectic ordered IL crystal. In fact, the IL crystals are self-assembled through Coulombic interactions between ion species, not through the hydrophilic-phobic interactions between charged ion heads and hydrophobic long alkyl pendants or the steric interaction between mesogenic moieties. Furthermore, the smectic order in the IL crystal ionogel facilitates exceptional and remarkable ionic transport. Large ionic conductivity, viscoelastic robustness, and additional electrochemical stability of the IL crystal ionogels provide promising opportunities for future electrochemical applications.

  17. 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

  18. Ionic properties of liquid crystals dispersed with carbon nanotubes and montmorillonite nanoplatelets

    NASA Astrophysics Data System (ADS)

    Liu, Hsuan-Hung; Lee, Wei

    2010-10-01

    The ionic properties of liquid crystals doped with one-dimensional carbon nanotubes, two-dimensional montmorillonite, and a mixture of both are investigated. The results indicate that the relaxation times of electrode polarization and ionic conductivity are time-dependent after the cell fabrication regardless of doping. While all of the dopants are effective in capturing impurity ions, the cells containing the hybrid dopant exhibit the feeblest ionic effect at room temperature.

  19. Nontoxic Ionic Liquid Fuels for Exploration Applications

    NASA Technical Reports Server (NTRS)

    Coil, Millicent

    2015-01-01

    The toxicity of propellants used in conventional propulsion systems increases not only safety risks to personnel but also costs, due to special handling required during the entire lifetime of the propellants. Orbital Technologies Corporation (ORBITEC) has developed and tested novel nontoxic ionic liquid fuels for propulsion applications. In Phase I of the project, the company demonstrated the feasibility of several ionic liquid formulations that equaled the performance of conventional rocket propellant monomethylhydrazine (MMH) and also provided low volatility and low toxicity. In Phase II, ORBITEC refined the formulations, conducted material property tests, and investigated combustion behavior in droplet and microreactor experiments. The company also explored the effect of injector design on performance and demonstrated the fuels in a small-scale thruster. The ultimate goal is to replace propellants such as MMH with fuels that are simultaneously high-performance and nontoxic. The fuels will have uses in NASA's propulsion applications and also in a range of military and commercial functions.

  20. Magnetic microemulsions based on magnetic ionic liquids.

    PubMed

    Klee, Andreas; Prevost, Sylvain; Kunz, Werner; Schweins, Ralf; Kiefer, Klaus; Gradzielski, Michael

    2012-11-28

    Microemulsions with magnetic properties were formed by employing a magnetic room temperature ionic liquid (MRTIL) as polar phase, cyclohexane as oil, and an appropriate mixture of ionic surfactant and decanol as a cosurfactant. By means of small-angle neutron scattering (SANS) and electric conductivity the microemulsion structure could be confirmed, where the classical structural sequence of oil-continuous-bicontinuous-polar phase continuous is observed with increasing ratio [polar phase]/[oil]. Accordingly a maximum of the structural size is observed at about equal volumes of oil and MRTIL contained. Therefore this system is structurally the same as normal microemulsions but with the magnetic properties added to it by the incorporation into the systems formulation.

  1. Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

    SciTech Connect

    Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

    2015-12-08

    An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

  2. Nanostructured crystals of fluorite phases Sr{sub 1-x}R{sub x}F{sub 2+x} (R are rare earth elements) and their ordering: 5. A study of the ionic conductivity of as-grown Sr{sub 1-x}R{sub x}F{sub 2+x} crystals

    SciTech Connect

    Sorokin, N. I. Karimov, D. N.; Sulyanova, E. A.; Zhmurova, Z. I.; Sobolev, B. P.

    2010-07-15

    The ionic conductivity {sigma} of Sr{sub 1-x}R{sub x}F{sub 2+x} crystals (R = Y, La-Lu) has been measured in the temperature range of 324-933 K. The isomorphic introduction of R{sup 3+} ions into SrF{sub 2} is accompanied by an increase in conductivity up to four orders of magnitude, which makes these crystals superionic conductors. It is shown that the conduction mechanism in Sr{sub 1-x}R{sub x}F{sub 2+x} crystals changes when passing from R = La-Nd to R = Sm-Lu. A change in the type of cluster of structural defects between Nd and Sm is suggested. The concentration dependences of {sigma} and the activation energy of charge-carrier migration (E{sub a}) for Sr{sub 1-x}R{sub x}F{sub 2+x} are nonlinear. For crystals with R = La or Nd, these dependences are interpreted within the percolation model of 'defect regions,' the minimum size of which is estimated to be {approx}700 A{sup 3}. It is shown that the electrical properties of the crystals can be controlled by varying the RF{sub 3} type and concentration. The Sr{sub 1-x}R{sub x}F{sub 2+x} crystals (R = La-Nd, 0.3 {<=} x {<=} 0.5), for which {sigma} = (2-3) x 10{sup -2} S/cm at 673 K and E{sub a} = 0.6-0.7 eV, have the best electrolytic characteristics.

  3. Pyrrolidinium ionic liquid crystals.

    PubMed

    Goossens, Karel; Lava, Kathleen; Nockemann, Peter; Van Hecke, Kristof; Van Meervelt, Luc; Driesen, Kris; Görller-Walrand, Christiane; Binnemans, Koen; Cardinaels, Thomas

    2009-01-01

    N-alkyl-N-methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2- thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group C(n)H(2n+1) was varied from eight to twenty carbon atoms (n = 8, 10-20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X-ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self-assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium-containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium-containing compound shows intense red photoluminescence with high colour purity.

  4. Proton Conductivity Studies on Biopolymer Electrolytes

    SciTech Connect

    Harun, N. I.; Sabri, N. S.; Rosli, N. H. A.; Taib, M. F. M.; Saaid, S. I. Y.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.

    2010-07-07

    Proton conducting solid biopolymer electrolyte membranes consisting of methyl cellulose (MC) and different wt.% of ammonium nitrate (NH{sub 4}NO{sub 3}) were prepared by solution cast technique. Impedance spectroscopy was carried out to study electrical characteristics of bulk materials. The ionic conductivity of the prepared samples was calculated using the bulk resistance (R{sub b}) obtained from impedance spectroscopy plot. The highest ionic conductivity obtained was 1.17x10{sup -4} Scm{sup -1} for the sample with composition ratio of MC(50): NH{sub 4}NO{sub 3}(50). To enhance the ionic conductivity, propylene carbonate (PC) and ethylene carbonate (EC) plasticizers were introduced. It was found that the ionic conductivity of polymer electrolyte membranes increased with the increase in plasticizers concentration. The ionic conductivities of solid polymer electrolytes based on MC-NH{sub 4}NO{sub 3}-PC was enhanced up to 4.91x10{sup -3} Scm{sup -1} while for the MC-NH{sub 4}NO{sub 3}-EC system, the highest conductivity was 1.74x10{sup -2} Scm{sup -1}. The addition of more plasticizer however decreases in mechanical stability of the membranes.

  5. Microregion detection of ionic liquid microemulsions.

    PubMed

    Gao, Yanan; Wang, Suqing; Zheng, Liqiang; Han, Shuaibing; Zhang, Xuan; Lu, Deming; Yu, Li; Ji, Yongqiang; Zhang, Gaoyong

    2006-09-15

    Nonaqueous ionic liquid (IL) microemulsion consisting of IL, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)), surfactant TX-100, and toluene was prepared and the phase behavior of the ternary system was investigated. Electrical conductivity measurement was used for investigating the microregions of the nonaqueous IL microemulsions. On the basis of the percolation theory, the bmimBF(4)-in-toluene (IL/O), bicontinuous, and toluene-in-bmimBF(4) (O/IL) microregions of the microemulsions were successfully identified using insulative toluene as the titration phase. However, this method was invalid when conductive bmimBF(4) acted as the titration phase. The microregions obtained by conductivity measurements were further proved by electrochemical cyclic voltammetry experiments. The results indicated that the conductivity method was feasible for identifying microstructures of the nonaqueous IL microemulsions.

  6. A Bioinspired Multifunctional Heterogeneous Membrane with Ultrahigh Ionic Rectification and Highly Efficient Selective Ionic Gating.

    PubMed

    Zhang, Zhen; Kong, Xiang-Yu; Xiao, Kai; Xie, Ganhua; Liu, Qian; Tian, Ye; Zhang, Huacheng; Ma, Jie; Wen, Liping; Jiang, Lei

    2016-01-06

    A bioinspired multifunctional heterogeneous membrane composed of a block copolymer (PS-b-P4VP) membrane and a porous anodic alumina membrane is fabricated. The ionic rectification is so strong that the maximum ratio is ≈489, and the chemical actuation of the anion or cation gate from the "OFF" to the "ON" state promotes a 98.5% increase in the channel conductance.

  7. Atomistic Simulations of Ternary Polymer Electrolytes Containing Ionic Liquids: Ion Transport and Viscoelastic Behavior

    NASA Astrophysics Data System (ADS)

    Mogurampelly, Santosh; Ganesan, Venkat

    Influence of the BMIMPF6 ionic liquid on ion transport and viscoelastic properties of ternary polymer electrolytes containing polyethylene oxide solvated with LiPF6 salt and the underlying mechanisms are investigated. By employing atomistic molecular dynamics and trajectory extended kinetic Monte Carlo simulation techniques, we observe enhanced ionic mobilities and conductivities of the PEOLiPF6-BMIMPF ternary electrolytes upon the addition ionic liquid into the PEOLiPF6 binary electrolyte. The dispersion of the BMIMPF6 ionic liquid into the PEOLiPF6 electrolyte is found to (a) promote dissociation of existing LiPF6 ion-pairs and (b) slightly accelerate the polymer segmental dynamics. Together, these effects are observed to collectively give rise to an increase in ionic mobilities and conductivities of the ternary polymer electrolyte. On the other hand, Rouse analysis reveals that the storage and loss modulus of the ternary polymer electrolytes are coupled to their ion conducting properties.

  8. 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…

  9. Ionic liquids as heat transfer fluids: comparison with known systems, possible applications, advantages and disadvantages

    NASA Astrophysics Data System (ADS)

    Chernikova, E. A.; Glukhov, L. M.; Krasovskiy, V. G.; Kustov, L. M.; Vorobyeva, M. G.; Koroteev, A. A.

    2015-08-01

    The practical aspects and prospects of application of ionic liquids as heat transfer fluids are discussed. The physicochemical properties of ionic liquids (heat capacity, thermal conductivity, thermal and radiation stability, viscosity, density, saturated vapour pressure and corrosion activity) are compared with the properties of some commercial heat transfer fluids. The issues of toxicity of ionic liquids are considered. Much attention is paid to known organosilicon heat transfer fluids, which are considered to have much in common with ionic liquids in the set of properties and are used in the review as reference materials. The bibliography includes 132 references.

  10. CADDIS Volume 2. Sources, Stressors and Responses: Ionic Strength

    EPA Pesticide Factsheets

    Introduction to the ionic strength module, when to list ionic strength as a candidate cause, ways to measure ionic strength, simple and detailed conceptual diagrams for ionic strength, ionic strength module references and literature reviews.

  11. Ionic liquids as surfactants

    NASA Astrophysics Data System (ADS)

    Smirnova, N. A.; Safonova, E. A.

    2010-10-01

    Problems of self-assembling in systems containing ionic liquids (ILs) are discussed. Main attention is paid to micellization in aqueous solutions of dialkylimidazolium ILs and their mixtures with classical surfactants. Literature data are reviewed, the results obtained by the authors and co-workers are presented. Thermodynamic aspects of the studies and problems of molecular-thermodynamic modeling receive special emphasis. It is shown that the aggregation behavior of dialkylimidazolium ILs is close to that of alkyltrimethylammonium salts (cationic surfactants) though ILs have a higher ability to self-organize, especially as it concerns long-range ordering. Some aspects of ILs applications are outlined where their common features with classical surfactants and definite specificity are of value.

  12. Ionic Switch Induced by a Rectangular-Hexagonal Phase Transition in Benzenammonium Columnar Liquid Crystals.

    PubMed

    Soberats, Bartolome; Yoshio, Masafumi; Ichikawa, Takahiro; Zeng, Xiangbing; Ohno, Hiroyuki; Ungar, Goran; Kato, Takashi

    2015-10-21

    We demonstrate switching of ionic conductivities in wedge-shaped liquid-crystalline (LC) ammonium salts. A thermoreversible phase transition between the rectangular columnar (Colr) and hexagonal columnar (Colh) phases is used for the switch. The ionic conductivities in the Colh phase are about four orders of magnitude higher than those in the Colr phase. The switching behavior of conductivity can be ascribed to the structural change of assembled ionic channels. X-ray experiments reveal a highly ordered packing of the ions in the Colr phase, which prevents the ion transport.

  13. Electronic and Ionic Transport in Processable Conducting Polymers

    DTIC Science & Technology

    1991-04-12

    Reynolds, J. R. "Charge and Ion Transport in Poly(pyrrole copper phthalocyanine - sulfonate ) During Redox Switching," J. Electroanal. Chem., submitted...the following polymers: (1) copolymers of heterocyclic rings such as pyrrole or furan with disubstituted ( methyl or methoxy groups ) benzene; (2...SUBJECT TERMS (Continue on reverse if necessary and identify by block number) FIEL GRUP I SUB- GROUP IPoly[1,4-bis(2-furanyl)-2,5-disubstituted-p

  14. Electronic and Ionic Transport in Processable Conducting Polymers

    DTIC Science & Technology

    1991-10-21

    including Cl-, NO3-, dodecyl sulfate, copper phthalocyanine tetrasulfonate and poly(styrene sulfonate ). Studies on the Pt/polypyrrole nanocomposites...SUBJECT TERMS (Continue on reverse if necessary and identify by block number) =FIELD GROUP SUB- GROUP EPR spec tros copy, electrochemistry, polaron...2-thienylphenylenes) substituted with alkoxy groups . The longer side chains stabilize the polaronic form of the polymers. In aqueous perchiorate and

  15. Predicting Carbonate Species Ionic Conductivity in Alkaline Anion Exchange Membranes

    DTIC Science & Technology

    2012-06-01

    anion exchange membranes. Andrew M. Kiss, Timothy D . Myles, Kyle N. Grew, Aldo A. Peracchio, George J. Nelson, and Wilson K. S. Chiu University of...Alkaline Anion Exchange Membranes Andrew M. Kiss1, Timothy D . Myles1, Kyle N. Grew2, Aldo A. Peracchio1, George J. Nelson1, and Wilson K. S. Chiu1* 1...Vol. 301, 93-106, 2007. 16. Satterfleld,M.B., Benziger,J.B., J. Phys. Chem. B, Vol. 112,12, 3693 -3704, 2008. 17. Motupally,S., Becker,A.J

  16. Hydrogen bonding in ionic liquids.

    PubMed

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-07

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  17. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

    2005-11-01

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

  18. An imidazolium based ionic liquid electrolyte for lithium batteries

    NASA Astrophysics Data System (ADS)

    Kim, Jae-Kwang; Matic, Aleksandar; Ahn, Jou-Hyeon; Jacobsson, Per

    An electrolyte for lithium batteries based on the ionic liquid 3-methy-1-propylimidazolium bis(trifluoromethysulfony)imide (PMIMTFSI) complexed with lithium bis(trifluoromethysulfony)imide (LiTFSI) at a molar ratio of 1:1 has been investigated. The electrolyte shows a high ionic conductivity (∼1.2 × 10 -3 S cm -1) at room temperature. Over the whole investigated temperature range the ionic conductivity is more than one order of magnitude higher than for an analogue electrolyte based on N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide (Py 14TFSI) complexed with LiTFSI and used here as a benchmark. Raman results indicate furthermore that the degree of lithium coordinated TFSI is slightly lower in the electrolyte based on PMIMTFSI and thus that the Li + charge carriers should be higher than in electrolytes based on Py 14TFSI. An ionic liquid gel electrolyte membrane was obtained by soaking a fibrous fully interconnected membrane, made of electrospun P(VdF-HFP), in the electrolyte. The gel electrolyte was cycled in Li/ionic liquid polymer electrolyte/Li cells over 15 days and in Li/LiFePO 4 cells demonstrating good interfacial stability and highly stable discharge capacities with a retention of >96% after 50 cycles (∼146 mAh g -1).

  19. Chiral discrimination by ionic liquids: impact of ionic solutes.

    PubMed

    Brown, Christopher J; Hopkins, Todd A

    2015-04-01

    Chiral ionic liquids hold promise in many asymmetric applications. This study explores the impact of ionic solutes on the chiral discrimination of five amino acid methyl ester-based ionic liquids, including L- and D-alanine methyl ester, L-proline methyl ester, L-leucine methyl ester, and L-valine methyl ester cations combined with bis(trifluoromethanesulfonimide) anion. Circularly polarized luminescence spectroscopy was used to study the chiral discrimination by measuring the racemization equilibrium of a dissymmetric europium complex, Eu(dpa)3(3-) (where dpa = 2,6-pyridinedicarboxylate). The chiral discrimination measured was dependent on the concentration of Eu(dpa)3(3-) and this concentration-dependence was different in each of the ionic liquids. Ionic liquids with L-leucine methyl ester and L-valine methyl ester even switched enantiomeric preference based on the solute concentration. Changing the cation of the Eu(dpa)3(3-) salt from tetrabutylammonium to tetramethylammonium ion also affected the chiral discrimination demonstrated by the ionic liquids.

  20. 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.

  1. 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,...

  2. 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.

  3. Ionic Liquid Crystals: Versatile Materials.

    PubMed

    Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

    2016-04-27

    This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

  4. Ionic thermoelectric gating organic transistors

    PubMed Central

    Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

    2017-01-01

    Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (∼100 μV K−1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (∼10,000 μV K−1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins. PMID:28139738

  5. Ionic thermoelectric gating organic transistors

    NASA Astrophysics Data System (ADS)

    Zhao, Dan; Fabiano, Simone; Berggren, Magnus; Crispin, Xavier

    2017-01-01

    Temperature is one of the most important environmental stimuli to record and amplify. While traditional thermoelectric materials are attractive for temperature/heat flow sensing applications, their sensitivity is limited by their low Seebeck coefficient (~100 μV K-1). Here we take advantage of the large ionic thermoelectric Seebeck coefficient found in polymer electrolytes (~10,000 μV K-1) to introduce the concept of ionic thermoelectric gating a low-voltage organic transistor. The temperature sensing amplification of such ionic thermoelectric-gated devices is thousands of times superior to that of a single thermoelectric leg in traditional thermopiles. This suggests that ionic thermoelectric sensors offer a way to go beyond the limitations of traditional thermopiles and pyroelectric detectors. These findings pave the way for new infrared-gated electronic circuits with potential applications in photonics, thermography and electronic-skins.

  6. Modeling electrokinetics in ionic liquids.

    PubMed

    Wang, Chao; Bao, Jie; Pan, Wenxiao; Sun, Xin

    2017-03-17

    Using direct numerical simulations, we provide a thorough study regarding the electrokinetics of ionic liquids. In particular, modified Poisson-Nernst-Planck (MPNP) equations are solved to capture the crowding and overscreening effects characteristic of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the MPNP equations are coupled with Navier-Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel charged surfaces, charging dynamics in a nanopore, capacitance of electric double-layer capacitors, electro-osmotic flow in a nanochannel, electroconvective instability on a plane ion-selective surface, and electroconvective flow on a curved ion-selective surface. We also discuss how crowding and overscreening and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems. This article is protected by copyright. All rights reserved.

  7. Novel approaches to ionic chromatography

    SciTech Connect

    Dasgupta, P.K.

    1990-11-01

    Research during this reporting period, continued on ionic chromatography. Major progress has been made towards on-line on-demand generation of ultrapure chemicals by electrochemical means. The concentration of the generated material is governed electrochemically.

  8. Biopolymer Processing Using Ionic Liquids

    DTIC Science & Technology

    2014-08-07

    AFRL-OSR-VA-TR-2014-0181 (YIP-11) BIOPOLYMER PROCESSING USING IONIC LIQUIDS William Reichert UNIVERSITY OF SOUTH ALABAMA 08/07/2014 Final Report...3. DATES COVERED (From - To) May 2011-May 2014 4. TITLE AND SUBTITLE iopolymer Processing using Ionic Liquids for Feedstock Chemicals 5a...reaction and degradation products of the conversion of chitin and chitosan, and 3) investigate the effects of various reaction conditions, such as

  9. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

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

  10. Sonofragmentation of Ionic Crystals.

    PubMed

    Kim, Hyo Na; Suslick, Kenneth S

    2017-02-24

    Mechanochemistry deals with the interface between the chemical and the mechanical worlds and explores the physical and chemical changes in materials caused by an input of mechanical energy. As such, the chemical and physical effects of ultrasound, i.e., sonochemistry, are forms of mechanochemistry. In this paper, the fragmentation of ionic crystals during ultrasonic irradiation of slurries has been quantitatively investigated: the rate of fragmentation depends strongly on the strength of the materials (as measured by Vickers hardness or by Young's modulus). This is a mechanochemical extension of the Bell-Evans-Polanyi Principle or Hammond's Postulate: activation energies for solid fracture correlate with binding energies of solids. Sonofragmentation is unaffected by slurry loading or liquid vapor pressure, but is suppressed by increasing liquid viscosity. The mechanism of the particle breakage is consistent with a direct interaction between the shockwaves created by the ultrasound (through acoustic cavitation) and the solid particles in the slurry. Fragmentation is proposed to occur from defects in the solids induced by compression-expansion, bending, or torsional distortions of the crystals.

  11. Hydrophobic ionic liquids

    SciTech Connect

    Koch, V.R.; Nanjundiah, C.; Carlin, R.T.

    1998-10-27

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas shown in a diagram wherein R{sub 1}, R{sub 2}, R{sub 3}, R{sub 4}, R{sub 5}, and R{sub 6} are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F-, Cl-, CF{sub 3}-, SF{sub 5}-, CF{sub 3}S-, (CF{sub 3}){sub 2}CHS- or (CF{sub 3}){sub 3}CS-; and X{sup {minus}} is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 {angstrom}{sup 3}. 4 figs.

  12. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R.; Nanjundiah, Chenniah; Carlin, Richard T.

    1998-01-01

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F--, Cl--, CF.sub.3 --, SF.sub.5 --, CF.sub.3 S--, (CF.sub.3).sub.2 CHS-- or (CF.sub.3).sub.3 CS--; and X.sup.- is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 .ANG..sup.3.

  13. 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.

  14. Mesoscopic fast ion conduction in nanometre-scale planar heterostructures

    NASA Astrophysics Data System (ADS)

    Sata, N.; Eberman, K.; Eberl, K.; Maier, J.

    2000-12-01

    Ion conduction is of prime importance for solid-state reactions in ionic systems, and for devices such as high-temperature batteries and fuel cells, chemical filters and sensors. Ionic conductivity in solid electrolytes can be improved by dissolving appropriate impurities into the structure or by introducing interfaces that cause the redistribution of ions in the space-charge regions. Heterojunctions in two-phase systems should be particularly efficient at improving ionic conduction, and a qualitatively different conductivity behaviour is expected when interface spacing is comparable to or smaller than the width of the space-charge regions in comparatively large crystals. Here we report the preparation, by molecular-beam epitaxy, of defined heterolayered films composed of CaF2 and BaF2 that exhibit ionic conductivity (parallel to the interfaces) increasing proportionally with interface density-for interfacial spacing greater than 50 nanometres. The results are in excellent agreement with semi-infinite space-charge calculations, assuming a redistribution of fluoride ions at the interfaces. If the spacing is reduced further, the boundary zones overlap and the predicted mesoscopic size effect is observed. At this point, the single layers lose their individuality and an artificial ionically conducting material with anomalous transport properties is generated. Our results should lead to fundamental insight into ionic contact processes and to tailored ionic conductors of potential relevance for medium-temperature applications.

  15. Development of Practical Supported Ionic Liquid Membranes: A Systematic Approach

    SciTech Connect

    Luebke, D.R.; Ilconich, J.B.; Myers, C.R.; Pennline, H.W.

    2007-11-01

    Supported liquid membranes (SLMs) are a class of materials that allow the researcher to utilize the wealth of knowledge available on liquid properties to optimize membrane performance. These membranes also have the advantage of liquid phase diffusivities, which are higher than those observed in polymers and grant proportionally greater permeabilities. The primary shortcoming of the supported liquid membranes demonstrated in past research has been the lack of stability caused by volatilization of the transport liquid. Ionic liquids, which may possess high CO2 solubility relative to light gases such as H2, are excellent candidates for this type of membrane since they are stable at elevated temperatures and have negligible vapor pressure. A study has been conducted evaluating the use of a variety of ionic liquids in supported ionic liquid membranes for the capture of CO2 from streams containing H2. In a joint project, researchers at the University of Notre Dame synthesized and characterized ionic liquids, and researchers at the National Energy Technology Laboratory incorporated candidate ionic liquids into supports and evaluated membrane performance for the resulting materials. Several steps have been taken in the development of practical supported ionic liquid membranes. Proof-of-concept was established by showing that ionic liquids could be used as the transport media in SLMs. Results showed that ionic liquids are suitable media for gas transport, but the preferred polymeric supports were not stable at temperatures above 135oC. The use of cross-linked nylon66 supports was found to produce membranes mechanically stable at temperatures exceeding 300oC but CO2/H2 selectivity was poor. An ionic liquid whose selectivity does not decrease with increasing temperature was needed, and a functionalized ionic liquid that complexes with CO2 was used. An increase in CO2/H2 selectivity with increasing temperature over the range of 37 to 85oC was observed and the dominance of a

  16. Synthesis, characterization and applications of ionic supramolecular assemblies

    NASA Astrophysics Data System (ADS)

    Lin, Xinrong

    thermal stability, high lithium salt solubility, and good conductivity in a lithium metal battery. The prototype battery performed safely at 100 degree celsius for more than 30 days. Thermally stable Li metal batteries are of interest in the oil industry for downhole applications. These studies were extended to an ionic polymer that exhibits a lamellar structure as a new polymer electrolyte.

  17. Indicators: Conductivity

    EPA Pesticide Factsheets

    Conductivity is a measure of the ability of water to pass an electrical current. Because dissolved salts and other inorganic chemicals conduct electrical current, conductivity increases as salinity increases.

  18. Accelerated materials design of fast oxygen ionic conductors based on first principles calculations

    NASA Astrophysics Data System (ADS)

    He, Xingfeng; Mo, Yifei

    Over the past decades, significant research efforts have been dedicated to seeking fast oxygen ion conductor materials, which have important technological applications in electrochemical devices such as solid oxide fuel cells, oxygen separation membranes, and sensors. Recently, Na0.5Bi0.5TiO3 (NBT) was reported as a new family of fast oxygen ionic conductor. We will present our first principles computation study aims to understand the O diffusion mechanisms in the NBT material and to design this material with enhanced oxygen ionic conductivity. Using the NBT materials as an example, we demonstrate the computation capability to evaluate the phase stability, chemical stability, and ionic diffusion of the ionic conductor materials. We reveal the effects of local atomistic configurations and dopants on oxygen diffusion and identify the intrinsic limiting factors in increasing the ionic conductivity of the NBT materials. Novel doping strategies were predicted and demonstrated by the first principles calculations. In particular, the K doped NBT compound achieved good phase stability and an order of magnitude increase in oxygen ionic conductivity of up to 0.1 S cm-1 at 900 K compared to the experimental Mg doped compositions. Our results provide new avenues for the future design of the NBT materials and demonstrate the accelerated design of new ionic conductor materials based on first principles techniques. This computation methodology and workflow can be applied to the materials design of any (e.g. Li +, Na +) fast ion-conducting materials.

  19. Pressure dependence of electrical conductivity in forsterite

    NASA Astrophysics Data System (ADS)

    Yoshino, Takashi; Zhang, Baohua; Rhymer, Brandon; Zhao, Chengcheng; Fei, Hongzhan

    2017-01-01

    Electrical conductivity of dry forsterite has been measured in muli-anvil apparatus to investigate the pressure dependence of ionic conduction in forsterite. The starting materials for the conductivity experiments were a synthetic forsterite single crystal and a sintered forsterite aggregate synthesized from oxide mixture. Electrical conductivities were measured at 3.5, 6.7, 9.6, 12.1, and 14.9 GPa between 1300 and 2100 K. In the measured temperature range, the conductivity of single crystal forsterite decreases in the order of [001], [010], and [100]. In all cases, the conductivity decreases with increasing pressure and then becomes nearly constant for [100] and [001] and slightly increases above 7 GPa for [010] orientations and a polycrystalline forsterite sample. Pressure dependence of forsterite conductivity was considered as a change of the dominant conduction mechanism composed of migration of both magnesium and oxygen vacancies in forsterite. The activation energy (ΔE) and activation volume (ΔV) for ionic conduction due to migration of Mg vacancy were 1.8-2.7 eV and 5-19 cm3/mol, respectively, and for that due to O vacancy were 2.2-3.1 eV and -1.1 to 0.3 cm3/mol, respectively. The olivine conductivity model combined with small polaron conduction suggests that the most part of the upper mantle is controlled by ionic conduction rather than small polaron conduction. The previously observed negative pressure dependence of the conductivity of olivine with low iron content (Fo90) can be explained by ionic conduction due to migration of Mg vacancies, which has a large positive activation volume.

  20. 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

  1. Ion-polyether coordination complexes: crystalline ionic conductors for clean energy storage.

    PubMed

    Bruce, Peter G

    2006-03-21

    Ion-polyether complexes are the solid state analogues of crown ether and cryptand complexes. They represent a fascinating class of coordination compounds in their own right, with the ability to support ionic conductivity and the potential to be used as electrolytes in all-solid-state rechargeable lithium batteries. Here the recent discovery of ionic conductivity in crystalline ion-polyether complexes, when for 30 years such materials were considered to be insulators, is described, along with their closely related structural chemistry.

  2. Multilayer ionic polymer transducer

    NASA Astrophysics Data System (ADS)

    Akle, Barbar J.; Leo, Donald J.

    2003-07-01

    A transducer consisting of multiple layers of ionic polymer material is developed for applications in sensing, actuation, and control. The transducer consists of two to four individual layers each approximately 200 microns thick. The transducers are connected in parallel to minimize the electric field requirements for actuation. The tradeoff in deflection and force can be controlled by controlling the mechanical constraint at the interface. Packaging the transducer in an outer coating produces a hard constraint between layers and reduces the deflection with a force that increases linearly with the number of layers. This configuration also increases the bandwidth of the transducer. Removing the outer packaging produces an actuator that maintains the deflection of a single layer but has an increased force output. This is obtained by allowing the layers to slide relative to one another during bending. Experiments on transducers with one to three layers are performed and the results are compared to Newbury"s equivalent circuit model, which was modified to accommodate the multilayer polymers. The modification was performed on four different boundary conditions, two electrical the series and the parallel connection, and two mechanical the zero interfacial friction and the zero slip on the interface. Results demonstrate that the largest obstacle to obtaining good performance is water transport between the individual layers. Water crossover produces a near short circuit electrical condition and produces feedthrough between actuation layers and sensing layers. Electrical feedthrough due to water crossover eliminates the ability to produce a transducer that has combined sensing and actuation properties. Eliminating water crossover through good insulation enables the development of a small (5 mm x 30 mm) transducer that has sensing and actuation bandwidth on the order of 100 Hz.

  3. Physicochemical properties and toxicities of hydrophobicpiperidinium and pyrrolidinium ionic liquids

    SciTech Connect

    Salminen, Justin; Papaiconomou, Nicolas; Kumar, R. Anand; Lee,Jong-Min; Kerr, John; Newman, John; Prausnitz, John M.

    2007-06-25

    Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro]{sup +}, 1-methyl-1-butyl pyrrolidinium [MBPyrro]{sup +}, 1-methyl-1-propyl piperidinium [MPPip]{sup +}, 1-methyl-1-butyl piperidinium [MBPip]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPyrro]{sup +} and 1-methyl-1-octylpiperidinium [MOPip]{sup +} cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and other electrochemical devices. Thermal properties, ionic conductivities, viscosities, and mutual solubilities with water are reported. In addition, toxicities of selected ionic liquids have been measured using a human cancer cell-line. The ILs studied here are sparingly soluble in water but hygroscopic. We show some structure-property relationships that may help to design green solvents for specific applications. While ionic liquids are claimed to be environmentally-benign solvents, as yet few data have been published to support these claims.

  4. Structural studies of ionic liquid-modified microemulsions.

    PubMed

    Rojas, Oscar; Koetz, Joachim; Kosmella, Sabine; Tiersch, Brigitte; Wacker, Philipp; Kramer, Markus

    2009-05-15

    This work is focused on the influence of an ionic liquid (IL), i.e. ethyl-methylimidazolium hexylsulfate, on the spontaneous formation of microemulsions with ionic surfactants. The influence of the ionic liquid on structure formation in the optically clear phase region in water/toluene/pentanol mixtures in presence of the cationic surfactant CTAB was studied in more detail. The results show a significant increase of the transparent phase region by adding the ionic liquid. Conductometric investigations demonstrate that adding the ionic liquid can drastically reduce the droplet-droplet interactions in the L(2) phase. (1)H nuclear magnetic resonance ((1)H NMR) diffusion coefficient measurements in combination with dynamic light scattering measurements clearly show that inverse microemulsion droplets still exist, but the droplet size is decreased to 2 nm. A more detailed characterisation of the isotropic phase channel by means of conductivity measurements, dynamic light scattering (DLS), (1)H NMR and cryo-scanning electron microscopy (SEM), allows the identification of a bicontinuous sponge phase between the L(1) and L(2) phase. When the poly(ethyleneimine) is added, the isotropic phase range is reduced drastically, but the inverse microemulsion range still exists.

  5. Charge Transport and Glassy Dynamics in Ionic Liquids

    SciTech Connect

    Sangoro, Joshua R; Kremer, Friedrich

    2012-01-01

    Ionic liquids (ILs) exhibit unique features such as low melting points, low vapor pressures, wide liquidus temperature ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. As a result, they show promise for use in variety of applications: as reaction media, in batteries and supercapacitors, in solar and fuel cells, for electrochemical deposition of metals and semiconductors, for protein extraction and crystallization, and many others. Because of the ease with which they can be supercooled, ionic liquids offer new opportunities to investigate long-standing questions regarding the nature of the dynamic glass transition and its possible link to charge transport. Despite the significant steps achieved from experimental and theoretical studies, no generally accepted quantitative theory of dynamic glass transition to date has been capable of reproducing all the experimentally observed features. In this Account, we discuss recent studies of the interplay between charge transport and glassy dynamics in ionic liquids as investigated by a combination of several experimental techniques including broadband dielectric spectroscopy, pulsed field gradient nuclear magnetic resonance, dynamic mechanical spectroscopy, and differential scanning calorimetry. Based on EinsteinSmoluchowski relations, we use dielectric spectra of ionic liquids to determine diffusion coefficients in quantitative agreement with independent pulsed field gradient nuclear magnetic resonance measurements, but spanning a broader range of more than 10 orders of magnitude. This approach provides a novel opportunity to determine the electrical mobility and effective number density of charge carriers as well as their types of thermal activation from the measured dc conductivity separately. We also unravel the origin of the remarkable universality of charge transport in different classes of glass-forming ionic liquids.

  6. Dual Ionic and Organic Nature of Ionic Liquids

    PubMed Central

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  7. Recrystallized quinolinium ionic liquids for electrochemical analysis

    NASA Astrophysics Data System (ADS)

    Selvaraj, Gowri; Wilfred, Cecilia Devi; Eang, Neo Kian

    2016-11-01

    Ionic liquids have received a lot of attention due to their unique properties. In this work the prospect of quinolinium based ionic liquids as electrolyte for dye sensitised solar cell were tested using cyclic voltammetry. The results have shown electron transfer in the ionic liquid without undergoing any permanent chemical changes. Prior to testing, the ionic liquids were purified through recrystallization as electrochemical properties of ionic liquids are highly dependent on the purity of the ionic liquids. This results have shone new light for this work.

  8. Design and Evaluation of Ionic Liquids as Novel CO2 Absorbents

    SciTech Connect

    Edward Maginn

    2007-07-15

    This is the final report for project DE-FG26-04NT42122 'Design and Evaluation of Ionic Liquids as Novel CO{sub 2} Absorbents'. The objective of this 'breakthrough concepts' project was to investigate the feasibility of using ionic liquids for post-combustion CO{sub 2} capture and obtain a fundamental understanding of the solubility of CO{sub 2} and other components present in flue gas in ionic liquids. Our plan was to obtain information on how composition and structure of ionic liquid molecules affected solubility and other important physical properties via two major efforts: synthesis and experimental measurements and molecular simulation. We also planned to perform preliminary systems modeling study to assess the economic viability of a process based on ionic liquids. We accomplished all the milestones and tasks specified in the original proposal. Specifically, we carried out extensive quantum and classical atomistic-level simulations of a range of ionic liquids. These calculations provided detailed information on how the chemical composition of ionic liquids affects physical properties. We also learned important factors that govern CO{sub 2} solubility. Using this information, we synthesized or acquired 33 new ionic liquids. Many of these had never been made before. We carried out preliminary tests on all of these compounds, and more extensive tests on those that looked most promising for CO{sub 2} capture. We measured CO{sub 2} solubility in ten of these ionic liquids. Through our efforts, we developed an ionic liquid that has a CO{sub 2} solubility 2.6 times greater than the 'best' ionic liquid available to us at the start of the project. Moreover, we demonstrated that SO{sub 2} is also extremely soluble in ionic liquids, opening up the possibility of using ionic liquids to remove both SO{sub 2} and CO{sub 2} from flue gas. In collaboration with Trimeric Inc., a preliminary systems analysis was conducted and the results used to help identify physical

  9. 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

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

    SciTech Connect

    Gainaru, Catalin P.; Technische Univ. Dortmund, Dortmund ; Stacy, Eric W.; Bocharova, Vera; Gobet, Mallory; Holt, Adam P.; Saito, Tomonori; Greenbaum, Steve; Sokolov, Alexei P.; Oak Ridge National Lab. , Oak Ridge, TN

    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 is 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.

  11. Influence of ionic association, transport properties, and solvation on the catalytic hydrogenation of 1,3-cyclohexadiene in ionic liquids.

    PubMed

    Podgoršek, Ajda; Salas, Gorka; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Fenet, Bernard; Chauvin, Yves

    2011-10-27

    The influence of the nature of two different ionic liquids, namely 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(1)C(4)Im][NTf(2)], on the catalytic hydrogenation of 1,3-cyclohexadiene with [Rh(COD)(PPh(3))(2)][NTf(2)] (COD = 1,5-cyclooctadiene) was studied. Initially, the effect of different concentrations of 1,3-cyclohexadiene on the molecular interactions and on the structure in two ionic liquids was investigated by NMR and by molecular dynamic simulations. It was found that in both ionic liquids 1,3-cyclohexadiene is solvated preferentially in the lipophilic regions. Furthermore, the higher solubility of 1,3-cyclohexadiene in [C(1)C(4)Im][NTf(2)] and the smaller positive values of the excess molar enthalpy of mixing for the 1,3-cyclohexadiene + [C(1)C(4)Im][NTf(2)] system in comparison with 1,3-cyclohexadiene + [C(1)C(1)C(4)Im][NTf(2)] indicate more favorable interactions between 1,3-cyclohexadiene and the C(1)C(4)Im(+) cation than with the C(1)C(1)C(4)Im(+) cation. Subsequently, diffusivity and conductivity measurements of the 1,3-cyclohexadiene + ionic liquid mixtures at different compositions allowed a characterization of mass and charge transport in the media and access to the ionicity of ionic liquids in the mixture. From the dependence of the ratio between molar conductivity and the conductivity inferred from NMR diffusion measurements, Λ(imp)/Λ(NMR), on concentration of 1,3-cyclohexadiene in the ionic liquid mixture, it was found that increasing the amount of 1,3-cyclohexadiene leads to a decrease in the ionicity of the medium. Finally, the reactivity of the catalytic hydrogenation of 1,3-cyclohexadiene using [Rh(COD)(PPh(3))(2)][NTf(2)] performed in [C(1)C(4)Im][NTf(2)] at different compositions of 1,3-cyclohexadiene and in [C(1)C(1)C(4)Im][NTf(2)] at one composition was related linearly to the viscosity, hence the reaction rate is

  12. Lorentz effect imaging of ionic currents in solution

    NASA Astrophysics Data System (ADS)

    Truong, Trong-Kha; Avram, Alexandru; Song, Allen W.

    2008-03-01

    Current functional MRI techniques relying on hemodynamic modulations are inherently limited in their ability to accurately localize neural activity in space and time. To address these limitations, we previously proposed a novel technique based on the Lorentz effect and demonstrated its ability to directly image minute electrical activity with a millisecond temporal resolution in gel phantoms containing conductive wires as well as in the human median nerve in vivo. To better characterize its contrast mechanism and ultimately further improve its sensitivity for in vivo applications, we now apply this technique to image ionic currents in solution, which serve as a better model for neural conduction in biological systems than the electronic currents in conductive wires used in previous phantom studies. Our results demonstrate that ionic currents with durations and current densities on the same order of magnitude as those induced by neuroelectric activity in nerve fibers and in the brain can be detected.

  13. Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids

    PubMed Central

    Reis, P. M.; Carvalho, P. J.; Lopes-da-Silva, J. A.; Esperança, J. M. S. S.; Araújo, J. M. M.; Rebelo, L. P. N.; Freire, M. G.; Pereiro, A. B.

    2016-01-01

    This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids. PMID:27642190

  14. Electrical Conductivity.

    ERIC Educational Resources Information Center

    Allen, Philip B.

    1979-01-01

    Examines Drude's classical (1900) theory of electrical conduction, details the objections to and successes of the 1900 theory, and investigates the Quantum (1928) theory of conduction, reviewing its successes and limitations. (BT)

  15. Polymerizable ionic liquid with state of the art transport properties.

    PubMed

    Jeremias, Sebastian; Kunze, Miriam; Passerini, Stefano; Schönhoff, Monika

    2013-09-12

    The physicochemical properties of diallyldimethylammonium-bis(trifluoromethanesulfonyl)imide (DADMATFSI) and its binary mixture with LiTFSI are presented herein, also showing this novel compound as a polymerizable room temperature ionic liquid with excellent transport properties for Li(+) ions. In particular, results of pulsed field gradient (PFG)-NMR diffusion experiments and impedance measurements show that DADMATFSI exhibits state of the art properties of ionic liquids. Similar ionic diffusion coefficients and a similarly high conductivity as seen in the benchmark compound N-butyl-N-methylpyrrolidinium-bis(trifluoromethanesulfonyl)imide (PYR14TFSI) are observed. In accordance, the Li transference number in the binary mixture matches the trend seen for PYR14TFSI-LiTFSI mixtures. In addition to these impressive properties as ionic liquid, DADMATFSI was polymerized by UV treatment. The polymerization is demonstrated and the ion conducting properties of the resulting gel polymer electrolyte are investigated, showing that DADMATFSI can be transformed into an ionogel and may have applications where polymerization is desirable.

  16. Surface tension of ionic liquids and ionic liquid solutions.

    PubMed

    Tariq, Mohammad; Freire, Mara G; Saramago, Benilde; Coutinho, João A P; Lopes, José N Canongia; Rebelo, Luís Paulo N

    2012-01-21

    Some of the most active scientific research fronts of the past decade are centered on ionic liquids. These fluids present characteristic surface behavior and distinctive trends of their surface tension versus temperature. One way to explore and understand their unique nature is to study their surface properties. This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references).

  17. Lithium ion conducting electrolytes

    DOEpatents

    Angell, C.A.; Liu, C.

    1996-04-09

    A liquid, predominantly lithium-conducting, ionic electrolyte is described having exceptionally high conductivity at temperatures of 100 C or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH{sub 3}CN), succinnonitrile (CH{sub 2}CN){sub 2}, and tetraglyme (CH{sub 3}--O--CH{sub 2}--CH{sub 2}--O--){sub 2} (or like solvents) solvated to a Mg{sup +2} cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100 C conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone. 2 figs.

  18. Lithium ion conducting electrolytes

    DOEpatents

    Angell, C. Austen; Liu, Changle

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte having exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature, and comprising the lithium salts selected from the group consisting of the thiocyanate, iodide, bromide, chloride, perchlorate, acetate, tetrafluoroborate, perfluoromethane sulfonate, perfluoromethane sulfonamide, tetrahaloaluminate, and heptahaloaluminate salts of lithium, with or without a magnesium-salt selected from the group consisting of the perchlorate and acetate salts of magnesium. Certain of the latter embodiments may also contain molecular additives from the group of acetonitrile (CH.sub.3 CN) succinnonitrile (CH.sub.2 CN).sub.2, and tetraglyme (CH.sub.3 --O--CH.sub.2 --CH.sub.2 --O--).sub.2 (or like solvents) solvated to a Mg.sup.+2 cation to lower the freezing point of the electrolyte below room temperature. Other particularly useful embodiments contain up to about 40, but preferably not more than about 25, mol percent of a long chain polyether polymer dissolved in the lithium salts to provide an elastic or rubbery solid electrolyte of high ambient temperature conductivity and exceptional 100.degree. C. conductivity. Another embodiment contains up to about but not more than 10 mol percent of a molecular solvent such as acetone.

  19. Ionic diffusion in single crystals of vermiculite

    SciTech Connect

    Maraqah, H.R.

    1993-01-01

    Novel guest-host compounds, based on single crystal vermiculite, were synthesized by diffusive techniques through a new hydrogen vermiculite. Single crystals were chosen because of the ease of characterization. An investigation of the ion transport properties of these single crystals was done to determine the mechanism of conductivity including the predominant charge carrier. Measurements of the ionic conductivity using impedance spectroscopy and X-ray lattice parameters of the ion-exchanged samples strongly suggest that the native cations and not protons are the major current carriers. Single crystals of hydrogen vermiculite were synthesized at room temperature by ion exchange from sodium-vermiculite using 1 molar acetic acid for a one week. Subsequent ion exchange with other cations was found to be much enhanced. Thus transition metals were exchanged in about a week in contrast to the need of several months using previous methods. The ionic conductivity of hydrogen vermiculite was measured and shown to be much lower than that of many other monovalent cations in the same host lattice. Its enthalpy of motion is also much lower. These marked differences suggest that protonic species do not play a significant role in charge transport in these layered materials. These materials were characterized by x-ray powder diffraction, thermogravimetric analysis and acid-base titration. Hydrogen-vermiculite was found to react with organic bases, like methylamine, ethylamine, n-butylamine, n-hexylamine, n-octylamine, n-decylamine, aniline, acrylamide, methacrylaminde, urea, 1,10phenanthroline, and 1,1phenanthroline ferrous sulfate complex, to undergo ion exchange with metal cations like sodium, zinc, copper(II) ions and polymerization reactions could be performed in the galleries of the structure like pyrrole and aniline. Its behavior was compared with that of powdered montmorillonite.

  20. Ionic Covalent Organic Frameworks with Spiroborate Linkage.

    PubMed

    Du, Ya; Yang, Haishen; Whiteley, Justin Michael; Wan, Shun; Jin, Yinghua; Lee, Se-Hee; Zhang, Wei

    2016-01-26

    A novel type of ionic covalent organic framework (ICOF), which contains sp(3)  hybridized boron anionic centers and tunable countercations, was constructed by formation of spiroborate linkages. These ICOFs exhibit high BET surface areas up to 1259 m(2)  g(-1) and adsorb a significant amount of H2 (up to 3.11 wt %, 77 K, 1 bar) and CH4 (up to 4.62 wt %, 273 K, 1 bar). Importantly, the materials show good thermal stabilities and excellent resistance to hydrolysis, remaining nearly intact when immersed in water or basic solution for two days. The presence of permanently immobilized ion centers in ICOFs enables the transportation of lithium ions with room-temperature lithium-ion conductivity of 3.05×10(-5)  S cm(-1) and an average Li(+) transference number value of 0.80±0.02. Our approach thus provides a convenient route to highly stable COFs with ionic linkages, which can potentially serve as absorbents for alternative energy sources such as H2, CH4, and also as solid lithium electrolytes/separators for the next-generation lithium batteries.