Science.gov

Sample records for solid electrolyte interphase

  1. A Review of Solid Electrolyte Interphases on Lithium Metal Anode

    PubMed Central

    Cheng, Xin‐Bing; Zhang, Rui; Zhao, Chen‐Zi; Wei, Fei; Zhang, Ji‐Guang

    2015-01-01

    Lithium metal batteries (LMBs) are among the most promising candidates of high‐energy‐density devices for advanced energy storage. However, the growth of dendrites greatly hinders the practical applications of LMBs in portable electronics and electric vehicles. Constructing stable and efficient solid electrolyte interphase (SEI) is among the most effective strategies to inhibit the dendrite growth and thus to achieve a superior cycling performance. In this review, the mechanisms of SEI formation and models of SEI structure are briefly summarized. The analysis methods to probe the surface chemistry, surface morphology, electrochemical property, dynamic characteristics of SEI layer are emphasized. The critical factors affecting the SEI formation, such as electrolyte component, temperature, current density, are comprehensively debated. The efficient methods to modify SEI layer with the introduction of new electrolyte system and additives, ex‐situ‐formed protective layer, as well as electrode design, are summarized. Although these works afford new insights into SEI research, robust and precise routes for SEI modification with well‐designed structure, as well as understanding of the connection between structure and electrochemical performance, is still inadequate. A multidisciplinary approach is highly required to enable the formation of robust SEI for highly efficient energy storage systems. PMID:27774393

  2. Highly Quantitative Electrochemical Characterization of Non-Aqueous Electrolytes & Solid Electrolyte Interphases

    SciTech Connect

    Sergiy V. Sazhin; Kevin L. Gering; Mason K. Harrup; Harry W. Rollins

    2012-10-01

    The methods to measure solid electrolyte interphase (SEI) electrochemical properties and SEI formation capability of non-aqueous electrolyte solutions are not adequately addressed in the literature. And yet, there is a strong demand in new electrolyte generations that promote stabilized SEIs and have an influence to resolve safety, calendar life and other limitations of Li-ion batteries. To fill this gap, in situ electrochemical approach with new descriptive criteria for highly quantitative characterization of SEI and electrolytes is proposed. These criteria are: SEI formation capacity, SEI corrosion rate, SEI maintenance rate, and SEI kinetic stability. These criteria are associated with battery parameters like irreversible capacity, self-discharge, shelf-life, power, etc. Therefore, they are especially useful for electrolyte development and standard fast screening, allowing a skillful approach to narrow down the search for the best electrolyte. The characterization protocol also allows retrieving information on interfacial resistance for SEI layers and the electrochemical window of electrolytes, the other important metrics of characterization. The method validation was done on electrolyte blends containing phosphazenes, developed at Idaho National Laboratory, as 1.2M LiPF6 [80 % EC-MEC (2:8) (v/v) + 20% Phosphazene variety] (v/v), which were targeted for safer electrolyte variations.

  3. Modeling mechanical degradation in lithium ion batteries during cycling: Solid electrolyte interphase fracture

    NASA Astrophysics Data System (ADS)

    Laresgoiti, Izaro; Käbitz, Stefan; Ecker, Madeleine; Sauer, Dirk Uwe

    2015-12-01

    During cycling, mechanical stresses can occur in the composite electrode, inside the active material, but also in the solid electrolyte interphase layer. A mechanical model is proposed based on a system made of a spherical graphite particle surrounded by the solid electrolyte interphase layer. During lithium intercalation or de-intercalation, stresses in the graphite are produced, governed by the diffusion induced stress phenomena and in the solid electrolyte interphase, driven by the graphite expansion. The stresses in both materials were simulated and a sensitivity analysis was performed to clarify the influence of principal parameters on both processes. Finally, assuming that the solid electrolyte interphase is the weakest material and therefore more prone to fracture than graphite, the experimental capacity fade during cycling was modeled based on its break and repair effect rather than on the fracture of the active material. The mechanical model of the solid electrolyte interphase was implemented in a single particle lithium ion battery model in order to reproduce capacity fade during battery lifetime. The model results were compared against cycle life aging experimental data, reproducing accurately the influence of the depth of discharge as well as the average state of charge on the capacity fade.

  4. Confined Solid Electrolyte Interphase Growth Space with Solid Polymer Electrolyte in Hollow Structured Silicon Anode for Li-Ion Batteries.

    PubMed

    Ma, Tianyi; Yu, Xiangnan; Cheng, Xiaolu; Li, Huiyu; Zhu, Wentao; Qiu, Xinping

    2017-04-07

    Silicon anodes for lithium-ion batteries are of much interest owing to their extremely high specific capacity but still face some challenges, especially the tremendous volume change which occurs in cycling and further leads to the disintegration of electrode structure and excessive growth of solid electrolyte interphase (SEI). Here, we designed a novel approach to confine the inward growth of SEI by filling solid polymer electrolyte (SPE) into pores of hollow silicon spheres. The as-prepared composite delivers a high specific capacity of more than 2100 mAh g(-1) and a long-term cycle stability with a reversible capacity of 1350 mAh g(-1) over 500 cycles. The growing behavior of SEI was investigated by electrochemical impedance spectroscopy and differential scanning calorimetry, and the results revealed that SPE occupies the major space of SEI growth and thus confines its excessive growth, which significantly improves cycle performance and Coulombic efficiency of cells embracing hollow silicon spheres.

  5. Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

    PubMed

    Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

    2014-07-09

    Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

  6. Artificial Solid Electrolyte Interphase to Address the Electrochemical Degradation of Silicon Electrodes

    SciTech Connect

    Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu; Li, Juchuan

    2014-01-01

    Electrochemical degradation on Si anodes prevents them from being successfully used in lithium-ion full cells. Unlike the case of graphite anodes, natural solid electrolyte interphase (SEI) films generated from carbonate electrolyte do not self-passivate on Si and causes continuous electrolyte decomposition. In this work we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphor oxynitride (Lipon), that conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, significant effect is observed in suppressing the electrolyte decomposition, while Lipon of thinner than 40 nm has little effect. Ionic and electronic conductivity measurement reveals that the artificial SEI is effective when it is a pure ionic conductor, and the electrolyte decomposition is not suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40~50 nm. This work provides guidance for designing artificial SEI for high capacity lithium-ion battery electrodes using solid electrolyte materials.

  7. Artificial solid electrolyte interphase with in-situ formed porosity for enhancing lithiation of silicon wafer

    NASA Astrophysics Data System (ADS)

    Lin, Jie; Guo, Jianlai; Liu, Chang; Guo, Hang

    2016-12-01

    In order to utilize silicon wafer as electrode and substrate for integrated lithium-ion batteries, a composite film with in-situ formed porosity (lithium phosphorous oxynitride/tin oxide, LiPON/SnO2) is fabricated and directly exploited as the artificial solid electrolyte interphase film. Without the compromise of Coulombic efficiency, the capacity and cycle performance of silicon wafer are both developed, resulting from the reduced resistance and the dynamically stable coating. This work provides guidance to enhance the lithiation of bulk silicon, and the strategy of surface modification can be applied to other advanced materials or fields.

  8. Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts

    NASA Astrophysics Data System (ADS)

    Busche, Martin R.; Drossel, Thomas; Leichtweiss, Thomas; Weber, Dominik A.; Falk, Mareike; Schneider, Meike; Reich, Maria-Louisa; Sommer, Heino; Adelhelm, Philipp; Janek, Jürgen

    2016-05-01

    The discharging and charging of batteries require ion transfer across phase boundaries. In conventional lithium-ion batteries, Li+ ions have to cross the liquid electrolyte and only need to pass the electrode interfaces. Future high-energy batteries may need to work as hybrids, and so serially combine a liquid electrolyte and a solid electrolyte to suppress unwanted redox shuttles. This adds new interfaces that might significantly decrease the cycling-rate capability. Here we show that the interface between a typical fast-ion-conducting solid electrolyte and a conventional liquid electrolyte is chemically unstable and forms a resistive solid-liquid electrolyte interphase (SLEI). Insights into the kinetics of this new type of interphase are obtained by impedance studies of a two-chamber cell. The chemistry of the SLEI, its growth with time and the influence of water impurities are examined by state-of-the-art surface analysis and depth profiling.

  9. Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts.

    PubMed

    Busche, Martin R; Drossel, Thomas; Leichtweiss, Thomas; Weber, Dominik A; Falk, Mareike; Schneider, Meike; Reich, Maria-Louisa; Sommer, Heino; Adelhelm, Philipp; Janek, Jürgen

    2016-05-01

    The discharging and charging of batteries require ion transfer across phase boundaries. In conventional lithium-ion batteries, Li(+) ions have to cross the liquid electrolyte and only need to pass the electrode interfaces. Future high-energy batteries may need to work as hybrids, and so serially combine a liquid electrolyte and a solid electrolyte to suppress unwanted redox shuttles. This adds new interfaces that might significantly decrease the cycling-rate capability. Here we show that the interface between a typical fast-ion-conducting solid electrolyte and a conventional liquid electrolyte is chemically unstable and forms a resistive solid-liquid electrolyte interphase (SLEI). Insights into the kinetics of this new type of interphase are obtained by impedance studies of a two-chamber cell. The chemistry of the SLEI, its growth with time and the influence of water impurities are examined by state-of-the-art surface analysis and depth profiling.

  10. Examining the solid electrolyte interphase on binder-free graphite electrodes.

    SciTech Connect

    Xiao, A.; Yang, L.; Lucht, B. L.; Kang, S.-H.; Abraham, D. P.

    2009-01-01

    The solid electrode interphase (SEI) on graphite electrodes is important to the performance, calendar life, and safety characteristics of lithium-ion cells. This article examines the SEI formed on binder-free graphite electrodes prepared by electrophoretic deposition. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis data were obtained on electrodes cycled in cells containing four electrolytes comprising ethylene carbonate: ethylmethyl carbonate (3:7 by weight) solvent and 1.2 M LiPF{sub 6}, 1 M LiF{sub 2}BC{sub 2}O{sub 4}, 1 M LiBF{sub 4}, or 0.7 M LiB(C{sub 2}O{sub 4}){sub 2} salt. Our observations suggest that, in addition to solvent reduction, the reduction of electrolyte salts plays an important role in SEI formation. Mechanisms to account for the formation of these SEI constituents are included in the article.

  11. Analysis of the solid electrolyte interphase formed with an ionic liquid electrolyte for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Xiong, Shizhao; Xie, Kai; Blomberg, Erik; Jacobsson, Per; Matic, Aleksandar

    2014-04-01

    We have investigated the formation of the solid electrolyte interphase (SEI) on lithium electrodes in the presence of an ionic liquid electrolyte with a particular focus on the influence of polysulfides present in the electrolyte on the SEI. The electrochemical performance of symmetric cells with lithium electrodes and electrolytes composed of N-Methyl-(n-butyl)pyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14-TFSI) and LiTFSI, with and without the addition of polysulfides, were analyzed as well as the chemical composition of the SEI, before and after cycling. The cycling behavior of the symmetrical cells shows that the SEI films are relatively stable in the ionic liquid electrolyte, also in the presence of polysulfides. However, the presence of polysulfides results in a higher SEI layer resistance (RSEI) and a higher activation energy. From X-ray photoelectron spectroscopy spectra (XPS), with argon-ion sputtering for depth profiling, we find that the SEI is formed by decomposition products from both cations and anions of the electrolyte. The XPS spectra show that the presence of polysulfides alters the decomposition process of the electrolyte, resulting in a SEI film with different chemical composition and structure, in line with the results from the electrochemical performance.

  12. Tuning the Solid Electrolyte Interphase for Selective Li- and Na-Ion Storage in Hard Carbon.

    PubMed

    Soto, Fernando A; Yan, Pengfei; Engelhard, Mark H; Marzouk, Asma; Wang, Chongmin; Xu, Guiliang; Chen, Zonghai; Amine, Khalil; Liu, Jun; Sprenkle, Vincent L; El-Mellouhi, Fedwa; Balbuena, Perla B; Li, Xiaolin

    2017-03-07

    Solid-electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li- and Na-ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li- or Na-based electrolyte, and that ionic transport can be kinetically controlled. Selective Li- and Na-based SEI membranes are produced using Li- or Na-based electrolytes, respectively. The Na-based SEI allows easy transport of Li ions, while the Li-based SEI shuts off Na-ion transport. Na-ion storage can be manipulated by tuning the SEI layer with film-forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g(-1) ; ≈ 1/10 of the normal capacity (250 mAh g(-1) ). Unusual selective/preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion-selective conductors using electrochemical approaches.

  13. Surface-Sensitive NMR Detection of the Solid Electrolyte Interphase Layer on Reduced Graphene Oxide.

    PubMed

    Leskes, Michal; Kim, Gunwoo; Liu, Tao; Michan, Alison L; Aussenac, Fabien; Dorffer, Patrick; Paul, Subhradip; Grey, Clare P

    2017-03-02

    Forming a stable solid electrolyte interphase (SEI) is critical for rechargeable batteries' performance and lifetime. Understanding its formation requires analytical techniques that provide molecular-level insight. Here, dynamic nuclear polarization (DNP) is utilized for the first time to enhance the sensitivity of solid-state NMR (ssNMR) spectroscopy to the SEI. The approach is demonstrated on reduced graphene oxide (rGO) cycled in Li-ion cells in natural abundance and (13)C-enriched electrolyte solvents. Our results indicate that DNP enhances the signal of outer SEI layers, enabling detection of natural abundance (13)C spectra from this component of the SEI on reasonable time frames. Furthermore, (13)C-enriched electrolyte measurements at 100 K provide ample sensitivity without DNP due to the vast amount of SEI filling the rGO pores, thereby allowing differentiation of the inner and outer SEI layer composition. Developing this approach further will benefit the study of many electrode materials, equipping ssNMR with the necessary sensitivity to probe the SEI efficiently.

  14. Degradation of the solid electrolyte interphase induced by the deposition of manganese ions

    NASA Astrophysics Data System (ADS)

    Shin, Hosop; Park, Jonghyun; Sastry, Ann Marie; Lu, Wei

    2015-06-01

    The deposition of manganese ions dissolved from the cathode onto the interface between the solid electrolyte interphase (SEI) and graphite causes severe capacity fading in manganese oxide-based cells. The evolution of the SEI layer containing these Mn compounds and the corresponding instability of the layer are thoroughly investigated by artificially introducing soluble Mn ions into a 1 mol L-1 LiPF6 electrolyte solution. Deposition of dissolved Mn ions induces an oxygen-rich SEI layer that results from increased electrolyte decomposition, accelerating SEI growth. The spatial distribution of Mn shows that dissolved Mn ions diffuse through the porous layer and are deposited mostly at the inorganic layer/graphite interface. The Mn compound deposited on the anode, identified as MnF2, originates from a metathesis reaction between LiF and dissolved Mn ion. It is confirmed that ion-exchange reaction occurs in the inorganic layer, converting SEI species to Mn compounds. Some of the Mn is observed inside the graphite; this may cause surface structural disordering in the graphite, limiting lithium-ion intercalation. The continuous reaction that occurs at the inorganic layer/graphite interfacial regions and the modification of the original SEI layer in the presence of Mn ions are critically related to capacity fade and impedance rise currently plaguing Li-ion cells.

  15. In Situ Measurement of Solid Electrolyte Interphase Evolution on Silicon Anodes Using Atomic Force Microscopy

    SciTech Connect

    Yoon, Insun; Abraham, Daniel P.; Lucht, Brett L.; Bower, Allan F.; Guduru, Pradeep R.

    2016-04-18

    In situ measurements of the growth of solid electrolyte interphase (SEI) layer on silicon and the lithiation-induced volume changes in silicon in lithium ion half-cells are reported. Thin film amorphous silicon electrodes are fabricated in a configuration that allows unambiguous separation of the total thickness change into contribution from SEI thickness and silicon volume change. Electrodes are assembled into a custom-designed electrochemical cell, which is integrated with an atomic force microscope. The electrodes are subjected to constant potential lithiation/delithiation at a sequence of potential values and the thickness measurements are made at each potential after equilibrium is reached. Experiments are carried out with two electrolytes—1.2 m lithium hexafluoro-phosphate (LiPF6) in ethylene carbonate (EC) and 1.2 m LiPF6 in propylene carbonate (PC)—to investigate the influence of electrolyte composition on SEI evolution. It is observed that SEI formation occurs predominantly during the first lithiation and the maximum SEI thickness is ≈17 and 10 nm respectively for EC and PC electrolytes. This study also presents the measured Si expansion ratio versus equilibrium potential and charge capacity versus equilibrium potential; both relationships display hysteresis, which is explained in terms of the stress–potential coupling in silicon.

  16. 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.

  17. Lithium dendrite and solid electrolyte interphase investigation using OsO4

    NASA Astrophysics Data System (ADS)

    Zier, Martin; Scheiba, Frieder; Oswald, Steffen; Thomas, Jürgen; Goers, Dietrich; Scherer, Torsten; Klose, Markus; Ehrenberg, Helmut; Eckert, Jürgen

    2014-11-01

    Osmium tetroxide (OsO4) staining, commonly used to enhance scattering contrast in electron microscopy of biologic tissue and polymer blends, has been adopted for studies of graphite anodes in lithium-ion batteries. OsO4 shows a coordinated reaction with components of the solid electrolyte interphase (SEI) and lithium dendrites, thereby increasing material contrast for scanning electron microscopy investigations. Utilizing the high affinity of lithium metal to react with osmium tetroxide it was possible to localize even small lithium deposits on graphite electrodes. In spite of their reaction with the OsO4 fume, the lithium dendrite morphology remains almost untouched by the staining procedure, offering information on the dendrite growth process. Correlating the quantity of osmium detected with the amount of residual ("dead") lithium of a discharged electrode, it was possible to obtain a practical measure for lithium plating and stripping efficiencies. EDX mappings allowed for a localization of electrochemically stripped lithium dendrites by their residual stained SEI shells. Cross sections, prepared by focused ion beam (FIB) of cycled graphite electrodes treated with OsO4, revealed important information about deposition and distribution of metallic lithium and the electrolyte reduction layer across the electrode.

  18. In situ observation of electrolyte-concentration-dependent solid electrolyte interphase on graphite in dimethyl sulfoxide.

    PubMed

    Liu, Xing-Rui; Wang, Lin; Wan, Li-Jun; Wang, Dong

    2015-05-13

    High lithium salt concentration strategy has been recently reported to be an effective method to enable various organic solvents as electrolyte of Li-ion batteries. Here, we utilize in situ atomic force microscopy (AFM) to investigate the interfacial morphology on the graphite electrode in dimethyl sulfoxide (DMSO)-based electrolyte of various concentrations. The significant differences in interfacial features of the graphite in electrolytes of different concentrations are revealed. In the concentrated electrolyte, stable films form primarily at the step edges and defects on the graphite surface after initial electrochemical cycling. On the other hand, in the dilute electrolyte, DMSO-solvated lithium ions constantly intercalate into graphite layers, and serious decomposition of solvent accompanied by structural deterioration of the graphite surface is observed. The in situ AFM results provide direct evidence for the concentration-dependent interface reactions between graphite electrode and DMSO-based electrolyte.

  19. An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes.

    PubMed

    Liu, Yayuan; Lin, Dingchang; Yuen, Pak Yan; Liu, Kai; Xie, Jin; Dauskardt, Reinhold H; Cui, Yi

    2017-03-01

    An artificial solid electrolyte interphase (SEI) is demonstrated for the efficient and safe operation of a lithium metal anode. Composed of lithium-ion-conducting inorganic nanoparticles within a flexible polymer binder matrix, the rationally designed artificial SEI not only mechanically suppresses lithium dendrite formation but also promotes homogeneous lithium-ion flux, significantly enhancing the efficiency and cycle life of the lithium metal anode.

  20. Direct visualization of solid electrolyte interphase formation in lithium-ion batteries with in situ electrochemical transmission electron microscopy.

    PubMed

    Unocic, Raymond R; Sun, Xiao-Guang; Sacci, Robert L; Adamczyk, Leslie A; Alsem, Daan Hein; Dai, Sheng; Dudney, Nancy J; More, Karren L

    2014-08-01

    Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

  1. Direct Visualization of Solid Electrolyte Interphase Formation in Lithium-Ion Batteries with In Situ Electrochemical Transmission Electron Microscopy

    SciTech Connect

    Unocic, Raymond R.; Sun, Xiao-Guang; Sacci, Robert L.; Adamczyk, Leslie A.; Alsem, Daan Hein; Dai, Sheng; Dudney, Nancy J.; More, Karren Leslie

    2014-08-01

    Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

  2. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    SciTech Connect

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; Dudney, Nancy J.; More, Karren Leslie; Unocic, Raymond R.

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquid cell.

  3. Multiphysics modeling of lithium ion battery capacity fading process with solid-electrolyte interphase growth by elementary reaction kinetics

    NASA Astrophysics Data System (ADS)

    Xie, Yuanyuan; Li, Jianyang; Yuan, Chris

    2014-02-01

    A pseudo two-dimensional mathematical model is developed for a lithium ion battery, integrating the elementary reaction based solid-electrolyte interphase (SEI) growth model with multiple transport processes. The model is validated using the experimental data. Simulation results indicate that the operating temperature has great effect on the SEI layer generation and growth. Under different charging-discharging rates, it is found that high charging-discharging rate can intensify the battery capacity fading process. Different cooling conditions are then applied and show that enhanced surface convective cooling condition can effectively slow down the battery capacity fading. After that, the effect of electrolyte salt concentration and exchange current density are studied. It is found that raising the electrolyte salt concentration can improve the diffusion property of lithium ions, and stabilize the battery performance under lithium ion consumption induced resistance rising. It also suggests that improving exchange current density could greatly decrease the lithium ion battery capacity fading.

  4. Role of the solid electrolyte interphase on a Li metal anode in a dimethylsulfoxide-based electrolyte for a lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

    2015-10-01

    The effect of the solid electrolyte interphase (SEI) on a Li anode on the charge-discharge cycling performance in 1 M LiTFSI/dimethylsulfoxide electrolyte solution is examined by using charge-discharge cycling. The chemical structure of the surface and interior of the SEI strongly affects the cycling performance of the anode. The observed coulombic efficiency is low (<45%) when organic compounds such as lithium alkyl carbonates and polycarbonate form predominantly on the surface and interior. However, when inorganic compounds such as Li2CO3, Li2O, and LiF form instead, the coulombic efficiency increases to >85%. This enhanced efficiency remains constant regardless of the O2 content and despite <1000 ppm concentration of the contaminant H2O in the electrolyte. Thus, the lithium surface should be protected by inorganic compounds prior to cycling to prevent it from undergoing side reactions with the electrolyte during cycling in the electrolyte.

  5. In Situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries.

    PubMed

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Rama Sesha; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R; Wang, Chong-Min

    2015-09-09

    Dynamic structural and chemical evolution at solid-liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe a solid-liquid interface under reaction conditions. We describe the creation and usage of in situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid-liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to be depleted of the salt anions and with reduced concentration of Li(+) ions, essentially leading to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributing to the overpotential of the cell. This observation provides unprecedented molecular level dynamic information on the initial formation of the solid electrolyte interphase (SEI) layer. The present work also ultimately opens new avenues for implanting the in situ liquid SIMS concept to probe the chemical reaction process that intimately involves solid-liquid interface, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization.

  6. Structure of spontaneously formed solid-electrolyte interphase on lithiated graphite determined using small-angle neutron scattering

    DOE PAGES

    Sacci, Robert L.; Banuelos, Jose Leobardo; Veith, Gabriel M.; ...

    2015-03-25

    We report the first small-angle neutron scattering of a chemically formed solid-electrolyte interphase from LixC6 reacting with ethylene carbonate/dimethyl carbon solvent. This provides a different and perhaps simpler view of SEI formation than the usual electrochemically-driven reaction. We show that an organic layer coats the graphite particles filling in micro-pores and is polymeric in nature being 1-3 nm thick. We used inelastic neutron scattering to probe the chemistry, and we found that the SEI showed similar inelastic scattering to polyethylene oxide.

  7. Nanoscale imaging of fundamental Li battery chemistry: solid-electrolyte interphase formation and preferential growth of lithium metal nanoclusters

    DOE PAGES

    Sacci, Robert L; Black, Jennifer M.; Wisinger, Nina; ...

    2015-02-23

    The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase formation and Li electrodeposition from a standard battery electrolyte, we use in situ electrochemical scanning transmission electron microscopy for controlled potential sweep-hold electrochemical measurements with simultaneous BF and ADF STEM image acquisition. Through a combined quantitative electrochemical measurement and quantitative STEM imaging approach, based upon electron scattering theory, we show that chemically sensitive ADF STEM imaging can be used to estimate the density of evolving SEI constituents and distinguish contrast mechanisms of Li-bearing components in the liquidmore » cell.« less

  8. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    DOE PAGES

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; ...

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition bymore » X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.« less

  9. The Effect of Fluoroethylene Carbonate as an Additive on the Solid Electrolyte Interphase on Silicon Lithium-Ion Electrodes

    SciTech Connect

    Schroder, Kjell; Li, Juchuan; Dudney, Nancy J.; Meng, Ying Shirley; Stevenson, Keith J.; Alvarado, Judith

    2015-08-03

    Fluoroethylene carbonate (FEC) has become a standard electrolyte additive for use with silicon negative electrodes, but how FEC affects solid electrolyte interphase (SEI) formation on the silicon anode’s surface is still not well understood. Herein, SEI formed from LiPF6-based carbonate electrolytes, with and without FEC, were investigated on 50 nm thick amorphous silicon thin film electrodes to understand the role of FEC on silicon electrode surface reactions. In contrast to previous work, anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films. This allowed for accurate characterization of the SEI structure and composition by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry depth profiling. These results show that FEC reduction leads to fluoride ion and LiF formation, consistent with previous computational and experimental results. Surprisingly, we also find that these species decrease lithium-ion solubility and increase the reactivity of the silicon surface. We conclude that the effectiveness of FEC at improving the Coulombic efficiency and capacity retention is due to fluoride ion formation from reduction of the electrolyte, which leads to the chemical attack of any silicon-oxide surface passivation layers and the formation of a kinetically stable SEI comprising predominately lithium fluoride and lithium oxide.

  10. Operando Measurement of Solid Electrolyte Interphase Formation at Working Electrode of Li-Ion Battery by Time-Slicing Neutron Reflectometry.

    PubMed

    Kawaura, Hiroyuki; Harada, Masashi; Kondo, Yasuhito; Kondo, Hiroki; Suganuma, Yoshitake; Takahashi, Naoko; Sugiyama, Jun; Seno, Yoshiki; Yamada, Norifumi L

    2016-04-20

    We report the first operando measurement of solid electrolyte interphase (SEI) formation at an electrode using in situ neutron reflectometry. The results revealed the growth of the SEI and intercalation of ions during the charge reaction. Furthermore, we propose a way of evaluating the charge used for the SEI formation.

  11. Synergetic Effects of Inorganic Components in Solid Electrolyte Interphase on High Cycle Efficiency of Lithium Ion Batteries.

    PubMed

    Zhang, Qinglin; Pan, Jie; Lu, Peng; Liu, Zhongyi; Verbrugge, Mark W; Sheldon, Brian W; Cheng, Yang-Tse; Qi, Yue; Xiao, Xingcheng

    2016-03-09

    The solid electrolyte interphase (SEI), a passivation layer formed on electrodes, is critical to battery performance and durability. The inorganic components in SEI, including lithium carbonate (Li2CO3) and lithium fluoride (LiF), provide both mechanical and chemical protection, meanwhile control lithium ion transport. Although both Li2CO3 and LiF have relatively low ionic conductivity, we found, surprisingly, that the contact between Li2CO3 and LiF can promote space charge accumulation along their interfaces, which generates a higher ionic carrier concentration and significantly improves lithium ion transport and reduces electron leakage. The synergetic effect of the two inorganic components leads to high current efficiency and long cycle stability.

  12. Single nanowire electrode electrochemistry of silicon anode by in situ atomic force microscopy: solid electrolyte interphase growth and mechanical properties.

    PubMed

    Liu, Xing-Rui; Deng, Xin; Liu, Ran-Ran; Yan, Hui-Juan; Guo, Yu-Guo; Wang, Dong; Wan, Li-Jun

    2014-11-26

    Silicon nanowires (SiNWs) have attracted great attention as promising anode materials for lithium ion batteries (LIBs) on account of their high capacity and improved cyclability compared with bulk silicon. The interface behavior, especially the solid electrolyte interphase (SEI), plays a significant role in the performance and stability of the electrodes. We report herein an in situ single nanowire atomic force microscopy (AFM) method to investigate the interface electrochemistry of silicon nanowire (SiNW) electrode. The morphology and Young's modulus of the individual SiNW anode surface during the SEI growth were quantitatively tracked. Three distinct stages of the SEI formation on the SiNW anode were observed. On the basis of the potential-dependent morphology and Young's modulus evolution of SEI, a mixture-packing structural model was proposed for the SEI film on SiNW anode.

  13. Interface stability of a TiO₂/3-methoxypropionitrile-based electrolyte: first evidence for solid electrolyte interphase formation and implications.

    PubMed

    Flasque, Miguel; Van Nhien, Albert Nguyen; Swiatowska, Jolanta; Seyeux, Antoine; Davoisne, Carine; Sauvage, Frédéric

    2014-04-14

    We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2.

  14. Multiprobe Study of the Solid Electrolyte Interphase on Silicon-Based Electrodes in Full-Cell Configuration

    PubMed Central

    Moreau, P.; De Vito, E.; Quazuguel, L.; Boniface, M.; Bordes, A.; Rudisch, C.; Bayle-Guillemaud, P.; Guyomard, D.

    2016-01-01

    The failure mechanism of silicon-based electrodes has been studied only in a half-cell configuration so far. Here, a combination of 7Li, 19F MAS NMR, XPS, TOF-SIMS, and STEM-EELS, provides an in-depth characterization of the solid electrolyte interphase (SEI) formation on the surface of silicon and its evolution upon aging and cycling with LiNi1/3Mn1/3Co1/3O2 as the positive electrode in a full Li-ion cell configuration. This multiprobe approach indicates that the electrolyte degradation process observed in the case of full Li-ion cells exhibits many similarities to what has been observed in the case of half-cells in previous works, in particular during the early stages of the cycling. Like in the case of Si/Li half-cells, the development of the inorganic part of the SEI mostly occurs during the early stage of cycling while an incessant degradation of the organic solvents of the electrolyte occurs upon cycling. However, for extended cycling, all the lithium available for cycling is consumed because of parasitic reactions and is either trapped in an intermediate part of the SEI or in the electrolyte. This nevertheless does not prevent the further degradation of the organic electrolyte solvents, leading to the formation of lithium-free organic degradation products at the extreme surface of the SEI. At this point, without any available lithium left, the cell cannot function properly anymore. Cycled positive and negative electrodes do not show any sign of particles disconnection or clogging of their porosity by electrolyte degradation products and can still function in half-cell configuration. The failure mechanism for full Li-ion cells appears then very different from that known for half-cells and is clearly due to a lack of cyclable lithium because of parasitic reactions occurring before the accumulation of electrolyte degradation products clogs the porosity of the composite electrode or disconnects the active material particles. PMID:27212791

  15. Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?

    PubMed

    Rezvani, S Javad; Gunnella, Roberto; Witkowska, Agnieszka; Mueller, Franziska; Pasqualini, Marta; Nobili, Francesco; Passerini, Stefano; Cicco, Andrea Di

    2017-02-08

    Advanced metal oxide electrodes in Li-ion batteries usually show reversible capacities exceeding the theoretically expected ones. Despite many studies and tentative interpretations, the origin of this extra-capacity is not assessed yet. Lithium storage can be increased through different chemical processes developing in the electrodes during charging cycles. The solid electrolyte interface (SEI), formed already during the first lithium uptake, is usually considered to be a passivation layer preventing the oxidation of the electrodes while not participating in the lithium storage process. In this work, we combine high resolution soft X-ray absorption spectroscopy with tunable probing depth and photoemission spectroscopy to obtain profiles of the surface evolution of a well-known prototype conversion-alloying type mixed metal oxide (carbon coated ZnFe2O4) electrode. We show that a partially reversible layer of alkyl lithium carbonates is formed (∼5-7 nm) at the SEI surface when reaching higher Li storage levels. This layer acts as a Li reservoir and seems to give a significant contribution to the extra-capacity of the electrodes. This result further extends the role of the SEI layer in the functionality of Li-ion batteries.

  16. Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer.

    PubMed

    Li, Yunsong; Leung, Kevin; Qi, Yue

    2016-10-18

    A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have "selective" transport properties: blocking electrons from attacking the electrolytes, while allowing Li(+) ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li(+) + e → Li(0), occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. This passivation layer is called "solid electrolyte interphase (SEI)" and is considered as "the most important but the least understood in rechargeable Li-ion batteries," partly due to the lack of understanding of its structure-property relationship. Predictive modeling, starting from the ab initio level, becomes an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li(+) ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li(+) and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li(+) transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure-property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li2CO3, LiF, Li2O, and their mixtures. After sorting out the Li(+) ion diffusion carriers and their diffusion

  17. The Importance of Solid Electrolyte Interphase Formation for Long Cycle Stability Full-Cell Na-Ion Batteries

    SciTech Connect

    Li, Xiaolin; Yan, Pengfei; Engelhard, Mark H.; Crawford, Aladsair J.; Viswanathan, Vilayanur V.; Wang, Chong M.; Liu, Jun; Sprenkle, Vincent L.

    2016-07-30

    Na-ion battery, as an alternative high-efficiency and low-cost energy storage device to Li-ion battery, has attracted wide interest for electrical grid and vehicle applications. However, demonstration of a full-cell battery with high energy and long cycle life remains a significant challenge. Here, we investigated the role of solid electrolyte interphase (SEI) formation on both cathodes and anodes and revealed a potential way to achieve long-term stability for Na-ion battery full-cells. Pre-cycling of cathodes and anodes leads to preformation of SEI, and hence mitigates the consumption of Na ions in full-cells. The example full-cell of Na0.44MnO2-hard carbon with pre-cycled and capacity-matched electrodes can deliver a specific capacity of ~116 mAh/g based on Na0.44MnO2 at 1C rate (1C = 120 mA/g). The corresponding specific energy is ~313 Wh/kg. Excellent cycling stability with ~77% capacity retention over 2000 cycles was demonstrated at 2C rate. Our work represents a leap forward in Na-ion battery development.

  18. Direct determination of solid-electrolyte interphase thickness and composition as a function of state of charge on a silicon anode

    DOE PAGES

    Veith, Gabriel M.; Doucet, Mathieu; Baldwin, J. K.; ...

    2015-08-17

    Using neutron reflectometry we have determined the thickness and chemistry of the solid-electrolyte interphase (SEI) layer grown on a silicon anode as a function of state of charge and during cycling. We show the chemistry of this SEI layer becomes more LiF like with increasing lithiation and more Li-C-O-F like with delithiation. More importantly the SEI layer thickness appears to increase (about 250 ) as the electrode becomes less lithiated and thins to 180 with increasing Li content (Li3.7Si). We attribute this breathing to the continual consumption of electrolyte with cycling.

  19. Direct determination of solid-electrolyte interphase thickness and composition as a function of state of charge on a silicon anode

    SciTech Connect

    Veith, Gabriel M.; Doucet, Mathieu; Baldwin, J. K.; Sacci, Robert L.; Fears, Tyler M.; Wang, Yongqiang; Browning, Jim

    2015-08-17

    Using neutron reflectometry we have determined the thickness and chemistry of the solid-electrolyte interphase (SEI) layer grown on a silicon anode as a function of state of charge and during cycling. We show the chemistry of this SEI layer becomes more LiF like with increasing lithiation and more Li-C-O-F like with delithiation. More importantly the SEI layer thickness appears to increase (about 250 ) as the electrode becomes less lithiated and thins to 180 with increasing Li content (Li3.7Si). We attribute this breathing to the continual consumption of electrolyte with cycling.

  20. Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer [Computational exploration of the Li-electrode|electrolyte interface complicated by a nanometer thin solid-electrolyte interphase (SEI) layer

    SciTech Connect

    Li, Yunsong; Leung, Kevin; Qi, Yue

    2016-09-30

    A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li+ ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li+ + e → Li0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphase (SEI)”, as “the most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li+ ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li+ and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li+ transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li2CO3, LiF, Li

  1. Computational Exploration of the Li-Electrode|Electrolyte Interface in the Presence of a Nanometer Thick Solid-Electrolyte Interphase Layer [Computational exploration of the Li-electrode|electrolyte interface complicated by a nanometer thin solid-electrolyte interphase (SEI) layer

    DOE PAGES

    Li, Yunsong; Leung, Kevin; Qi, Yue

    2016-09-30

    A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li+ ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li+ + e → Li0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphase (SEI)”, as “themore » most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li+ ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li+ and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li+ transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li2CO3, LiF, Li2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and

  2. New insights into the electroreduction of ethylene sulfite as an electrolyte additive for facilitating solid electrolyte interphase formation in lithium ion batteries.

    PubMed

    Sun, Youmin; Wang, Yixuan

    2017-03-01

    To help understand the solid electrolyte interphase (SEI) formation facilitated by electrolyte additives of lithium-ion batteries (LIBs) the supermolecular clusters [(ES)Li(+)(PC)m](PC)n (m = 1-2; n = 0, 6 and 9) were used to investigate the electroreductive decompositions of the electrolyte additive ethylene sulfite (ES) as well as the solvent propylene carbonate (PC) with density functional theory. The results show that ES can be reduced prior to PC, resulting in a reduction precursor that will then undergo a ring opening decomposition to yield a radical anion. A new concerted pathway (path B) was located for the ring opening of the reduced ES, which has a much lower energy barrier than the previously reported stepwise pathway (path A). The transition state for the ring opening of PC induced by the reduced ES (path C, indirect path) is closer to that of path A than path B in energy. The direct ring opening of the reduced PC (path D) has a lower energy barrier than paths A, B and C, yet it is less favorable than the latter paths in terms of thermodynamics (vertical electron affinity or reduction potential and dissociation energy). The overall rate constant including the initial reduction and the subsequent ring opening for path B is the largest among the four paths, followed by paths A > C > D, which further signifies the importance of the concerted new path in facilitating the SEI formation. The hybrid models, the supermolecular clusters augmented by a polarized continuum model, PCM-[(ES)Li(+)(PC)2](PC)n (n = 0, 6 and 9), were used to further estimate the reduction potential by taking into account both explicit and implicit solvent effects. The second solvation shell of Li(+) in [(ES)Li(+)(PC)2](PC)n (n = 6 and 9) partially compensates the overestimation of solvent effects arising from the PCM for the naked (ES)Li(+)(PC)2, and the theoretical reduction potential of PCM-[(ES)Li(+)(PC)2](PC)6 (1.90-1.93 V) agrees very well with the experimental one (1.8-2.0 V).

  3. In-situ Mass Spectrometric Determination of Molecular Structural Evolution at the Solid Electrolyte Interphase in Lithium-Ion Batteries

    SciTech Connect

    Zhu, Zihua; Zhou, Yufan; Yan, Pengfei; Vemuri, Venkata Rama Ses; Xu, Wu; Zhao, Rui; Wang, Xuelin; Thevuthasan, Suntharampillai; Baer, Donald R.; Wang, Chong M.

    2015-08-19

    Dynamic molecular evolution at solid/liquid electrolyte interface is always a mystery for a rechargeable battery due to the challenge to directly probe/observe the solid/liquid interface under reaction conditions, which in essence appears to be similarly true for all the fields involving solid/liquid phases, such as electrocatalysis, electrodeposition, biofuel conversion, biofilm, and biomineralization, We use in-situ liquid secondary ion mass spectroscopy (SIMS) for the first time to directly observe the molecular structural evolution at the solid electrode/liquid electrolyte interface for a lithium (Li)-ion battery under dynamic operating conditions. We have discovered that the deposition of Li metal on copper electrode leads to the condensation of solvent molecules around the electrode. Chemically, this layer of solvent condensate tends to deplete the salt anion and with low concentration of Li+ ions, which essentially leads to the formation of a lean electrolyte layer adjacent to the electrode and therefore contributes to the overpotential of the cell. This unprecedented molecular level dynamic observation at the solid electrode/liquid electrolyte interface provides vital chemical information that is needed for designing of better battery chemistry for enhanced performance, and ultimately opens new avenues for using liquid SIMS to probe molecular evolution at solid/liquid interface in general.

  4. Lithium metal protection through in-situ formed solid electrolyte interphase in lithium-sulfur batteries: The role of polysulfides on lithium anode

    NASA Astrophysics Data System (ADS)

    Yan, Chong; Cheng, Xin-Bing; Zhao, Chen-Zi; Huang, Jia-Qi; Yang, Shu-Ting; Zhang, Qiang

    2016-09-01

    The dissolution and diffusion of Li polysulfide (LiPS) intermediates are regarded as one of the most serious problems for capacity decay and cell failure of lithium-sulfur (Li-S) batteries. Herein we proposed a failure mechanism of Li metal anode in Li-S cells based on the mechanistic investigation into the complex interactions between LiPSs and Li metal. The LiPSs participate the formation of inorganic layers in the solid electrolyte interphase (SEI) in a LiPS-LiNO3 containing ether-based electrolyte. Li metal anode is well protected by the stable inorganic layer in-situ formed in an electrolyte containing 0.020 M Li2S5 (0.10 M sulfur) and 5.0 wt % LiNO3. The metal anode with LiF-Li2Sx riched SEI rendered a stable Coulombic efficiency of 95% after 233 cycles for Li-Cu half cells. A dendrite-free morphology of Li metal anode is observed under the harsh condition. When the LiPS is with a very high concentration of higher than 0.50 M sulfur in the organic electrolyte, the in-situ formed SEI cannot well maintain and the Li metal is gradually etched. Therefore, the polysulfide dissolution and diffusion should be delicately regulated to render a practical Li-S cell when the areal sulfur loading is high.

  5. Composition and evolution of the solid-electrolyte interphase in Na2Ti3O7 electrodes for Na-ion batteries: XPS and Auger parameter analysis.

    PubMed

    Muñoz-Márquez, Miguel A; Zarrabeitia, Maider; Castillo-Martínez, Elizabeth; Eguía-Barrio, Aitor; Rojo, Teófilo; Casas-Cabanas, Montse

    2015-04-15

    Na2Ti3O7 is considered a promising negative electrode for Na-ion batteries; however, poor capacity retention has been reported and the stability of the solid-electrolyte interphase (SEI) could be one of the main actors of this underperformance. The composition and evolution of the SEI in Na2Ti3O7 electrodes is hereby studied by means of X-ray photoelectron spectroscopy (XPS). To overcome typical XPS limitations in the photoelectron energy assignments, the analysis of the Auger parameter is here proposed for the first time in battery materials characterization. We have found that the electrode/electrolyte interface formed upon discharge, mostly composed by carbonates and semicarbonates (Na2CO3, NaCO3R), fluorides (NaF), chlorides (NaCl) and poly(ethylene oxide)s, is unstable upon electrochemical cycling. Additionally, solid state nuclear magnetic resonance (NMR) studies prove the reaction of the polyvinylidene difluoride (PVdF) binder with sodium. The powerful approach used in this work, namely Auger parameter study, enables us to correctly determine the composition of the electrode surface layer without any interference from surface charging or absolute binding energy calibration effects. As a result, the suitability for Na-ion batteries of binders and electrolytes widely used for Li-ion batteries is questioned here.

  6. Direct observation of electronic conductivity transitions and solid electrolyte interphase stability of Na2Ti3O7 electrodes for Na-ion batteries

    NASA Astrophysics Data System (ADS)

    Zarrabeitia, Maider; Nobili, Francesco; Muñoz-Márquez, Miguel Ángel; Rojo, Teófilo; Casas-Cabanas, Montse

    2016-10-01

    This communication reports the first experimental evidence of an interesting change of transport properties, and particularly of electron conductivity, during the Na+ insertion/extraction process in Na2Ti3O7 negative electrodes. Probed by electrochemical impedance spectroscopy, for 0.0 ≤ x < 1.4 in Na2+xTi3O7 the material exhibits insulator behaviour, the bulk electronic conductivity being the limiting factor in the insertion process. After further Na+ insertion, the material becomes electronic conductor and at around 0.13 V vs. Na+/Na the rate of interfacial charge-transfer becomes the limiting factor. The observed conductivity transition is reversible upon cycling. Additionally, this impedance study sheds new light on the solid electrolyte interphase layer performance which is found to be unstable upon electrochemical cycling and negatively contributes on the capacity fading observed for this electrode material.

  7. Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

    SciTech Connect

    Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan; Li, Qiuyan; Lv, Dongping; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

    2015-11-10

    Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupled with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.

  8. Evaluating the solid electrolyte interphase formed on silicon electrodes: A comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry

    SciTech Connect

    Doucet, Mathieu; Browning, Jim; Baldwin, J. K.; Winiarz, Jeffrey; Kaiser, Helmut; Taub, H.; Veith, Gabriel M.

    2016-04-15

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 x 10-2 mS/cm-1). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling was observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggests the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, required to remove electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterizations in situ.

  9. Evaluating the solid electrolyte interphase formed on silicon electrodes: A comparison of ex situ X-ray photoelectron spectroscopy and in situ neutron reflectometry

    DOE PAGES

    Doucet, Mathieu; Browning, Jim; Baldwin, J. K.; ...

    2016-04-15

    This work details the in situ characterization of the interface between a silicon electrode and an electrolyte using a linear fluorinated solvent molecule, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in deuterated dimethyl perfluoroglutarate (d6-PF5M2) (1.87 x 10-2 mS/cm-1). The solid electrolyte interphase (SEI) composition and thickness determined via in situ neutron reflectometry (NR) and ex situ X-ray photoelectron spectroscopy (XPS) were compared. The data show that SEI expansion and contraction (breathing) during electrochemical cycling was observed via both techniques; however, ex situ XPS suggests that the SEI thickness increases during Si lithiation and decreases during delithiation, while in situ NR suggestsmore » the opposite. The most likely cause of this discrepancy is the selective removal of SEI components (top 20 nm of the SEI) during the electrode rinse process, required to remove electrolyte residue prior to ex situ analysis, demonstrating the necessity of performing SEI characterizations in situ.« less

  10. Decomposition of the fluoroethylene carbonate additive and the glue effect of lithium fluoride products for the solid electrolyte interphase: an ab initio study.

    PubMed

    Okuno, Yukihiro; Ushirogata, Keisuke; Sodeyama, Keitaro; Tateyama, Yoshitaka

    2016-03-28

    Additives in the electrolyte solution of lithium-ion batteries (LIBs) have a large impact on the performance of the solid electrolyte interphase (SEI) that forms on the anode and is a key to the stability and durability of LIBs. We theoretically investigated effects of fluoroethylene carbonate (FEC), a representative additive, that has recently attracted considerable attention for the enhancement of cycling stability of silicon electrodes and the improvement of reversibility of sodium-ion batteries. First, we intensively examined the reductive decompositions by ring-opening, hydrogen fluoride (HF) elimination to form a vinylene carbonate (VC) additive and intermolecular chemical reactions of FEC in the ethylene carbonate (EC) electrolyte, by using density functional theory (DFT) based molecular dynamics and the blue-moon ensemble technique for the free energy profile. The results show that the most plausible product of the FEC reductive decomposition is lithium fluoride (LiF), and that the reactivity of FEC to anion radicals is found to be inert compared to the VC additive. We also investigated the effects of the generated LiF on the SEI by using two model systems; (1) LiF molecules distributed in a model aggregate of organic SEI film components (SFCs) and (2) a LiF aggregate interfaced with the SFC aggregate. DFT calculations of the former system show that F atoms form strong bindings with the Li atoms of multiple organic SFC molecules and play as a joint connecting them. In the latter interface system, the LiF aggregate adsorbs the organic SFCs through the F-Li bindings. These results suggest that LiF moieties play the role of glue in the organic SFC within the SEI film. We also examined the interface structure between a LiF aggregate and a lithiated silicon anode, and found that they are strongly bound. This strong binding is likely to be related to the effectiveness of the FEC additive in the electrolyte for the silicon anode.

  11. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    DOE PAGES

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; ...

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression.more » A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.« less

  12. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Xiao; Liu, Zhe; Leung, Kevin; Chen, Long-Qing; Lu, Peng; Qi, Yue

    2016-03-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. The agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.

  13. Connecting the irreversible capacity loss in Li-ion batteries with the electronic insulating properties of solid electrolyte interphase (SEI) components.

    SciTech Connect

    Leung, Kevin; Lin, Yu -Xiao; Liu, Zhe; Chen, Long -Qing; Lu, Peng; Qi, Yue

    2016-01-01

    The formation and continuous growth of a solid electrolyte interphase (SEI) layer are responsible for the irreversible capacity loss of batteries in the initial and subsequent cycles, respectively. In this article, the electron tunneling barriers from Li metal through three insulating SEI components, namely Li2CO3, LiF and Li3PO4, are computed by density function theory (DFT) approaches. Based on electron tunneling theory, it is estimated that sufficient to block electron tunneling. It is also found that the band gap decreases under tension while the work function remains the same, and thus the tunneling barrier decreases under tension and increases under compression. A new parameter, η, characterizing the average distances between anions, is proposed to unify the variation of band gap with strain under different loading conditions into a single linear function of η. An analytical model based on the tunneling results is developed to connect the irreversible capacity loss, due to the Li ions consumed in forming these SEI component layers on the surface of negative electrodes. As a result, the agreement between the model predictions and experimental results suggests that only the initial irreversible capacity loss is due to the self-limiting electron tunneling property of the SEI.

  14. Layer Number Dependence of Li(+) Intercalation on Few-Layer Graphene and Electrochemical Imaging of Its Solid-Electrolyte Interphase Evolution.

    PubMed

    Hui, Jingshu; Burgess, Mark; Zhang, Jiarui; Rodríguez-López, Joaquín

    2016-04-26

    A fundamental question facing electrodes made out of few layers of graphene (FLG) is if they display chemical properties that are different to their bulk graphite counterpart. Here, we show evidence that suggests that lithium ion intercalation on FLG, as measured via stationary voltammetry, shows a strong dependence on the number of layers of graphene that compose the electrode. Despite its extreme thinness and turbostratic structure, Li ion intercalation into FLG still proceeds through a staging process, albeit with different signatures than bulk graphite or multilayer graphene. Single-layer graphene does not show any evidence of ion intercalation, while FLG with four graphene layers displays limited staging peaks, which broaden and increase in number as the layer number increases to six. Despite these mechanistic differences on ion intercalation, the formation of a solid-electrolyte interphase (SEI) was observed on all electrodes. Scanning electrochemical microscopy (SECM) in the feedback mode was used to demonstrate changes in the surface conductivity of FLG during SEI evolution. Observation of ion intercalation on large area FLG was conditioned to the fabrication of "ionic channels" on the electrode. SECM measurements using a recently developed Li-ion sensitive imaging technique evidenced the role of these channels in enabling Li-ion intercalation through localized flux measurements. This work highlights the impact of nanostructure and microstructure on macroscopic electrochemical behavior and provides guidance to the mechanistic control of ion intercalation using graphene, an atomically thin interface where surface and bulk reactivity converge.

  15. Dual-Phase Lithium Metal Anode Containing a Polysulfide-Induced Solid Electrolyte Interphase and Nanostructured Graphene Framework for Lithium-Sulfur Batteries.

    PubMed

    Cheng, Xin-Bing; Peng, Hong-Jie; Huang, Jia-Qi; Zhang, Rui; Zhao, Chen-Zi; Zhang, Qiang

    2015-06-23

    Lithium-sulfur (Li-S) batteries, with a theoretical energy density of 2600 Wh kg(-1), are a promising platform for high-energy and cost-effective electrochemical energy storage. However, great challenges such as fast capacity degradation and safety concerns prevent it from widespread application. With the adoption of Li metal as the anode, dendritic and mossy metal depositing on the negative electrode during repeated cycles leads to serious safety concerns and low Coulombic efficiency. Herein, we report a distinctive graphene framework structure coated by an in situ formed solid electrolyte interphase (SEI) with Li depositing in the pores as the anode of Li-S batteries. The graphene-based metal anode demonstated a superior dendrite-inhibition behavior in 70 h of lithiation, while the cell with a Cu foil based metal anode was short-circuited after only 4 h of lithiation at 0.5 mA cm(-2). The graphene-modified Li anode with SEI induced by the polysulfide-containing electrolyte improved the Coulombic efficiency to ∼97% for more than 100 cycles, while the control sample with Cu foil as the current collector exhibited huge fluctuations in Coulombic efficiency. The unblocked ion pathways and high electron conductivities of frameworks in the modified metal anode led to the rapid transfer of Li ions through the SEI and endowed the anode framework with an ion conductivity of 7.81 × 10(-2) mS cm(-1), nearly quintuple that of the Cu foil based Li metal anode. Besides, the polarization in the charge-discharge process was halved to 30 mV. The stable and efficient Li deposition was maintained after 2000 cycles. Our results indicated that nanoscale interfacial electrode engineering could be a promising strategy to tackle the intrinsic problems of lithium metal anodes, thus improving the safety of Li-S cells.

  16. Solid electrolytes

    DOEpatents

    Abraham, Kuzhikalail M.; Alamgir, Mohamed

    1993-06-15

    This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

  17. Effect of LiNO3 additive and pyrrolidinium ionic liquid on the solid electrolyte interphase in the lithium-sulfur battery

    NASA Astrophysics Data System (ADS)

    Barghamadi, Marzieh; Best, Adam S.; Bhatt, Anand I.; Hollenkamp, Anthony F.; Mahon, Peter J.; Musameh, Mustafa; Rüther, Thomas

    2015-11-01

    The lithium-sulfur (Li-S) battery in which the ionic liquid (IL) C4mpyr-TFSI is a major component of the electrolyte has attracted much attention by researchers due to the ability of the IL to suppress the polysulfide shuttle effect, combined with advantageous properties of thermal, chemical and electrochemical stability. In a largely parallel stream of research, LiNO3 has come to be known as an additive for improving Li-S battery performance through its influence on protecting the lithium anode and beneficial interaction with the polysulfide shuttle. In this work a deeper understanding is sought of the combined effects of LiNO3 and C4mpyr-TFSI on the factors that impact Li-S cell performance. Specifically, we investigate the formation of the protective surface film on lithium anode and results are compared with those for a typical organic electrolyte for the Li-S battery, DOL:DME. Electrochemical impedance spectroscopy (EIS) confirms that the LiNO3 additive is vital to achieving acceptable levels of performance with the organic electrolyte. Although LiNO3 improves the performance of a battery assembled with IL containing electrolyte, it shows a higher impact in the organic electrolyte based battery. Furthermore X-ray photoelectron spectroscopy (XPS) spectra confirm the participation of C4mpyr-TFSI on the formation of the interphase layer on the anode.

  18. Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Nordh, Tim; Younesi, Reza; Brandell, Daniel; Edström, Kristina

    2015-10-01

    The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase. Li||LTO cells with electrolytes consisting of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate:diethyl carbonate (LiPF6 in EC:DEC) were cycled in two different voltage windows of 1.0-2.0 V and 1.4-2.0 V. LTO electrodes were characterized after 5 and 100 cycles. Also the pristine electrode as such, and an electrode soaked in the electrolyte were analyzed by varying the photon energies enabling depth profiling of the outermost surface layer. The main components of the surface layer were found to be ethers, P-O containing compounds, and lithium fluoride.

  19. 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).

  20. Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

    PubMed

    Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

    2016-12-14

    Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py1,4]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

  1. Solid polymer electrolyte compositions

    DOEpatents

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

    2001-01-01

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

  2. Graphite electrode thermal behavior and solid electrolyte interphase investigations: Role of state-of-the-art binders, carbonate additives and lithium bis(fluorosulfonyl)imide salt

    NASA Astrophysics Data System (ADS)

    Forestier, Coralie; Grugeon, Sylvie; Davoisne, Carine; Lecocq, Amandine; Marlair, Guy; Armand, Michel; Sannier, Lucas; Laruelle, Stephane

    2016-10-01

    The risk of thermal runaway is, for Li-ion batteries, a critical issue for large-scale applications. This results in manufacturers and researchers placing great emphasis on minimizing the heat generation and thereby mitigating safety-related risks through the search for suitable materials or additives. To this end, an in-depth stepwise investigation has been undertaken to provide a better understanding of the exothermic processes that take place at the negative electrode/electrolyte interface as well as an increased visibility of the role of the state-of-the-art electrode binders, additives and lithium salt by means of the classical DSC technique. A reliable experimental set up helped quantify the beneficial or harmful contribution of binder polymers to the exothermic behavior of the CMC/SBR containing graphite electrode film in contact with 1 M LiPF6 in EC:DMC:EMC (1:1:1 v/v/v) electrolyte. Further, the role of the VC, FEC and VEC electrolyte additives (2 wt%) in reinforcing the protective SEI layer towards thermally induced electrolyte reduction is discussed in the light of infrared spectroscopy and transmission electron microscopy analyzes results. Moreover, after a preliminary corrosion study of LiPF6/LiFSI mixtures, we showed that the 0.66/0.33 M composition can be used in commercial NMC-based LiBs with a positive effect on the thermal runaway.

  3. Solid electrolyte cell

    NASA Technical Reports Server (NTRS)

    Richter, R. (Inventor)

    1982-01-01

    A solid electrolyte cell including a body of solid ionized gas-conductive electrolyte having mutually spaced surfaces and on which is deposited a multiplicity of mutually spaced electrodes is described. Strips and of bare substances are interposed between electrodes, so that currents of ionic gas may be established between the electrodes via the bare strips, whereby electrical resistance for the cells is lowered and the gas conductivity is enhanced.

  4. Solid Electrolyte Interphase (SEI) at TiO2 Electrodes in Li-Ion Batteries: Defining Apparent and Effective SEI Based on Evidence from X-ray Photoemission Spectroscopy and Scanning Electrochemical Microscopy.

    PubMed

    Ventosa, Edgar; Madej, Edyta; Zampardi, Giorgia; Mei, Bastian; Weide, Philipp; Antoni, Hendrik; La Mantia, Fabio; Muhler, Martin; Schuhmann, Wolfgang

    2017-01-25

    The high (de)lithiation potential of TiO2 (ca. 1.7 V vs Li/Li(+) in 1 M Li(+)) decreases the voltage and, thus, the energy density of a corresponding Li-ion battery. On the other hand, it offers several advantages such as the (de)lithiation potential far from lithium deposition or absence of a solid electrolyte interphase (SEI). The latter is currently under controversial debate as several studies reported the presence of a SEI when operating TiO2 electrodes at potentials above 1.0 V vs Li/Li(+). We investigate the formation of a SEI at anatase TiO2 electrodes by means of X-ray photoemission spectroscopy (XPS) and scanning electrochemical microscopy (SECM). The investigations were performed in different potential ranges, namely, during storage (without external polarization), between 3.0-2.0 V and 3.0-1.0 V vs Li/Li(+), respectively. No SEI is formed when a completely dried and residues-free TiO2 electrode is cycled between 3.0 and 2.0 V vs Li/Li(+). A SEI is detected by XPS in the case of samples stored for 6 weeks or cycled between 3.0 and 1.0 V vs Li/Li(+). With use of SECM, it is verified that this SEI does not possess the electrically insulating character as expected for a "classic" SEI. Therefore, we propose the term apparent SEI for TiO2 electrodes to differentiate it from the protecting and effective SEI formed at graphite electrodes.

  5. A thermal-electrochemical model that gives spatial-dependent growth of solid electrolyte interphase in a Li-ion battery

    NASA Astrophysics Data System (ADS)

    Liu, Lin; Park, Jonghyun; Lin, Xianke; Sastry, Ann Marie; Lu, Wei

    2014-12-01

    The formation of a SEI layer and its growth cause internal resistance increase and capacity loss, leading to performance degradation of lithium-ion batteries. In order to comprehensively investigate the effects of SEI growth on battery performance, a one-dimensional thermal-electrochemical model was developed. This model is equipped with a growth mechanism of the SEI layer coupled with thermal evolution, based on the diffusional process of the solvent through the SEI layer and the kinetic process at the interface between the solid and liquid phases. The model is able to reveal the effects of diffusivity, reaction kinetics and temperature on SEI layer growth and cell capacity fade. We show that depending on the SEI thickness, the growth can be kinetics-limited or diffusion-limited. With the layer becoming thicker, its growth rate slows down gradually due to increased diffusion resistance. The SEI layer grows faster during charge than discharge due to the difference in the electron flux through the SEI layer and the temperature change during cycling. Temperature rise due to reaction and joule heating accelerates the SEI layer growth, leading to more capacity loss. Our model can provide insights on position-dependent SEI growth rate and be used to guide the strategic monitoring location.

  6. Solid polymer electrolytes

    DOEpatents

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

    1995-01-01

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

  7. Solid polymer electrolytes

    DOEpatents

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

    1995-12-12

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

  8. Solid electrolyte structure

    DOEpatents

    Fraioli, Anthony V.

    1984-01-01

    A solid electrolyte structure for fuel cells and other electrochemical devices providing oxygen ion transfer by a multiplicity of exposed internal surfaces made of a composition containing an oxide of a multivalent transition metal and forming small pore-like passages sized to permit oxygen ion transfer while limiting the transfer of oxygen gas.

  9. Mapping the anode surface-electrolyte interphase: investigating a life limiting process of lithium primary batteries.

    PubMed

    Bock, David C; Tappero, Ryan V; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

    2015-03-11

    Cathode solubility in batteries can lead to decreased and unpredictable long-term battery behavior due to transition metal deposition on the negative electrode such that it no longer supports high current. Analysis of negative electrodes from cells containing vanadium oxide or phosphorus oxide based cathode systems retrieved after long-term testing was conducted. This report demonstrates the use of synchrotron based X-ray microfluorescence (XRμF) to map negative battery electrodes in conjunction with microbeam X-ray absorption spectroscopy (μXAS) to determine the oxidation states of the metal centers resident in the solid electrolyte interphase (SEI) and at the electrode surface. Based on the empirical findings, a conceptual model for the location of metal ions in the SEI and their role in impacting lithium ion mobility at the electrode surfaces is proposed.

  10. Solid state electrolyte systems

    SciTech Connect

    Pederson, L.R.; Armstrong, B.L.; Armstrong, T.R.

    1997-12-01

    Lanthanum gallates are a new family of solid electrolytes that exhibit high ionic conductivity and are stable to high temperatures. Compositions have been developed that are as much as a factor of two more conductive than yttria-stabilized zirconia at a given temperature, through partial replacement of lanthanum by calcium, strontium, and/or barium and through partial replacement of gallium by magnesium. Oxide powders were prepared using combustion synthesis techniques developed in this laboratory; these were sintered to >95% of theoretical density and consisted of a single crystalline phase. Electrical conductivities, electron and ion transference numbers, thermal expansion, and phase behavior were evaluated as a function of temperature and oxygen partial pressure. A key advantage of the use of lanthanum gallate electrolytes in solid oxide fuel cells is that the temperature of operation may be lowered to perhaps 800 C, yet provide approximately the same power density as zirconia-based cells operating at 1000 C. Ceramic electrolytes that conduct both oxygen ions and electrons are potentially useful to passively separate pure oxygen from an air source at low cost. In such materials, an oxygen ion flux in one direction is charge-compensated by an opposing electron flux. The authors have examined a wide range of mixed ion and electron conducting perovskite ceramics in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, where M = Sr, Ca, and Ba, and N = Pr, Mn, Ni, Cu, Ti, and Al, as well as mixed conducting brownmillerite ceramics, and have characterized oxygen permeation behavior, defect chemistry, structural and phase stability, and performance as cathodes.

  11. Application of Organic Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    Sekido, S.

    1982-01-01

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

  12. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, Mohamed; Abraham, Kuzhikalail M.

    1993-01-01

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

  13. Solid polymer electrolyte lithium batteries

    DOEpatents

    Alamgir, M.; Abraham, K.M.

    1993-10-12

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

  14. Composite solid polymer electrolyte membranes

    DOEpatents

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

    2001-06-19

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

  15. Composite solid polymer electrolyte membranes

    DOEpatents

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

    2006-05-30

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

  16. Solid lithium-ion electrolyte

    DOEpatents

    Zhang, J.G.; Benson, D.K.; Tracy, C.E.

    1998-02-10

    The present invention relates to the composition of a solid lithium-ion electrolyte based on the Li{sub 2}O--CeO{sub 2}--SiO{sub 2} system having good transparent characteristics and high ion conductivity suitable for uses in lithium batteries, electrochromic devices and other electrochemical applications. 12 figs.

  17. Solid lithium-ion electrolyte

    DOEpatents

    Zhang, Ji-Guang; Benson, David K.; Tracy, C. Edwin

    1998-01-01

    The present invention relates to the composition of a solid lithium-ion electrolyte based on the Li.sub.2 O--CeO.sub.2 --SiO.sub.2 system having good transparent characteristics and high ion conductivity suitable for uses in lithium batteries, electrochromic devices and other electrochemical applications.

  18. Rechargeable solid polymer electrolyte battery cell

    DOEpatents

    Skotheim, Terji

    1985-01-01

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

  19. Solid electrolyte oxygen regeneration system

    NASA Technical Reports Server (NTRS)

    Shumar, J. W.; See, G. G.; Schubert, F. H.; Powell, J. D.

    1976-01-01

    A program to design, develop, fabricate and assemble a one-man, self-contained, solid electrolyte oxygen regeneration system (SX-1) incorporating solid electrolyte electrolyzer drums was completed. The SX-1 is a preprototype engineering model designed to produce 0.952 kg (2.1 lb)/day of breathable oxygen (O2) from the electrolysis of metabolic carbon dioxide (CO2) and water vapor. The CO2 supply rate was established based on the metabolic CO2 generation rate for one man of 0.998 kg (2.2 lb)/day. The water supply rate (0.254 kg (0.56 lb)/day) was designed to be sufficient to make up the difference between the 0.952 kg (2.1 lb)/day O2 generation specification and the O2 available through CO2 electrolysis, 0.726 kg (1.6 lb)/day. The SX-1 was successfully designed, fabricated and assembled. Design verification tests (DVT) or the CO Disproportionators, H2 separators, control instrumentation, monitor instrumentation, water feed mechanism were successfully completed. The erratic occurrence of electrolyzer drum leakage prevented the completion of the CO2 electrolyzer module and water electrolyzer module DVT's and also prevented the performance of SX-1 integrated testing. Further development work is required to improve the solid electrolyte cell high temperature seals.

  20. Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

    NASA Technical Reports Server (NTRS)

    DeSilva, J .H. S. R.; Udinwe, V.; Sideris, P. J.; Smart, M. C.; Krause, F. C.; Hwang, C.; Smith, K. A.; Greenbaum, S. G.

    2012-01-01

    Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

  1. Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes.

    PubMed

    Lu, Dongping; Tao, Jinhui; Yan, Pengfei; Henderson, Wesley A; Li, Qiuyan; Shao, Yuyan; Helm, Monte L; Borodin, Oleg; Graff, Gordon L; Polzin, Bryant; Wang, Chong-Min; Engelhard, Mark; Zhang, Ji-Guang; De Yoreo, James J; Liu, Jun; Xiao, Jie

    2017-03-08

    Li-ion batteries (LIB) have been successfully commercialized after the identification of ethylene-carbonate (EC)-containing electrolyte that can form a stable solid electrolyte interphase (SEI) on carbon anode surface to passivate further side reactions but still enable the transportation of the Li(+) cation. These electrolytes are still utilized, with only minor changes, after three decades. However, the long-term cycling of LIB leads to continuous consumption of electrolyte and growth of SEI layer on the electrode surface, which limits the battery's life and performance. Herein, a new anode protection mechanism is reported in which, upon changing of the cell potential, the electrolyte components at the electrode-electrolyte interface reorganize reversibly to form a transient protective surface layers on the anode. This layer will disappear after the applied potential is removed so that no permanent SEI layer is required to protect the carbon anode. This phenomenon minimizes the need for a permanent SEI layer and prevents its continuous growth and therefore may lead to largely improved performance for LIBs.

  2. Solid-oxide fuel cell electrolyte

    DOEpatents

    Bloom, Ira D.; Hash, Mark C.; Krumpelt, Michael

    1993-01-01

    A solid-oxide electrolyte operable at between 600.degree. C. and 800.degree. C. and a method of producing the solid-oxide electrolyte are provided. The solid-oxide electrolyte comprises a combination of a compound having weak metal-oxygen interactions with a compound having stronger metal-oxygen interactions whereby the resulting combination has both strong and weak metal-oxygen interaction properties.

  3. Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode

    NASA Astrophysics Data System (ADS)

    Qian, Yunxian; Niehoff, Philip; Börner, Markus; Grützke, Martin; Mönnighoff, Xaver; Behrends, Pascal; Nowak, Sascha; Winter, Martin; Schappacher, Falko M.

    2016-10-01

    Traditional solid electrolyte interphase (SEI) forming additives of vinylene carbonate (VC), fluoroethylene carbonate (FEC) and ethylene sulfite (ES) are studied with respect to their impact on the formation and growth of the cathode electrolyte interphase (CEI) layer. T-half cells are assembled and undergo three different electrochemical investigation plans: after formation (0.1C, 5 cycles) and long term cycling (0.1C, 5 constant current cycles + 1C, 100/150 constant current/voltage cycles), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS) are combined to investigate morphology, CEI composition, CEI thickness and aging products for cells with different electrolyte systems. The obtained results reveal a significant influence of these additives on the CEI composition and CEI growth. With the help of SEM, it is found that large areas of electrolyte decomposition products are formed at the aged electrode surfaces (=after cycling), with the exception when 2 vol% of FEC is added into the reference electrolyte. From XPS measurements, CEI thicknesses are calculated. The reference electrolyte with 2 vol% of FEC shows the thinnest layer after long time aging (0.8 ± 0.2 nm). For the addition of 2 vol% of VC, an incremental growth of the CEI thickness occurs from the 100th to 150th cycle (from 1.0 ± 0.1 nm to 2.9 ± 0.4 nm). By correlating the CEI thickness values with the electrochemical performance, it can be observed that for lithium metal based half cells, the existence of a thinner CEI layer corresponds to a better cycling behavior, with 2 vol% of FEC showing the highest discharge capacity of 114.4 ± 0.2 mAh/g after 150 cycles at 1C. GC-MS shows that both VC and FEC help to prevent fast electrolyte aging.

  4. Solid composite electrolytes for lithium batteries

    DOEpatents

    Kumar, Binod; Scanlon, Jr., Lawrence G.

    2000-01-01

    Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a ceramic-ceramic composite electrolyte is provided containing lithium nitride and lithium phosphate. The ceramic-ceramic composite is also preferably annealed and exhibits an activation energy of about 0.1 eV.

  5. Secondary calcium solid electrolyte high temperature battery

    NASA Astrophysics Data System (ADS)

    Sammells, A. F.; Schumacher, B.

    1986-01-01

    The application of polycrystalline Ca(2+) conducting beta-double prime alumina solid electrolytes to a new type of high temperature battery is investigated, experimentally. The negative electrode in the battery consisted of a calcium-silicon alloy whose redox electrochemistry was mediated by the solid electrolyte via molten salt eutectic CaCl2 (51.4 m/o), and CaI2 (mp 550 C). The molten salt and the calcium alloy material were separated from the positive active material via the Ca2 Ca(2+) conducting polycrystalline electrolyte. The positive electrode consisted of a solid-state matrix having related crystallographic structure. The electrochemical reversibility of the cells was measured at 580 C. The charge-discharge characteristics of the cells are plotted vs. time in a graph.

  6. Monolithic solid electrolyte oxygen pump

    DOEpatents

    Fee, Darrell C.; Poeppel, Roger B.; Easler, Timothy E.; Dees, Dennis W.

    1989-01-01

    A multi-layer oxygen pump having a one-piece, monolithic ceramic structure affords high oxygen production per unit weight and volume and is thus particularly adapted for use as a portable oxygen supply. The oxygen pump is comprised of a large number of small cells on the order of 1-2 millimeters in diameter which form the walls of the pump and which are comprised of thin, i.e., 25-50 micrometers, ceramic layers of cell components. The cell components include an air electrode, an oxygen electrode, an electrolyte and interconnection materials. The cell walls form the passages for input air and for exhausting the oxygen which is transferred from a relatively dilute gaseous mixture to a higher concentration by applying a DC voltage across the electrodes so as to ionize the oxygen at the air electrode, whereupon the ionized oxygen travels through the electrolyte and is converted to oxygen gas at the oxygen electrode.

  7. Solid polymer electrolyte from phosphorylated chitosan

    SciTech Connect

    Fauzi, Iqbal Arcana, I Made

    2014-03-24

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

  8. Composite Solid Electrolyte Containing Li+- Conducting Fibers

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  9. Performance comparison: Aluminum electrolytic and solid tantalum capacitor

    NASA Technical Reports Server (NTRS)

    Hawthornthwaite, B. G.; Piper, J.; Holland, H. W.

    1981-01-01

    Several key electrical and environmental parameters of latest technology aluminum electrolytic and solid tantalum capacitors were evaluated in terms of price fluctuations of tantalum metal. Performance differences between solid tantalums and aluminum electrolytics are examined.

  10. Lithium-ion batteries having conformal solid electrolyte layers

    DOEpatents

    Kim, Gi-Heon; Jung, Yoon Seok

    2014-05-27

    Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

  11. Non-aqueous electrolytes for electrochemical cells

    DOEpatents

    Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

    2016-06-14

    An electrolyte electrochemical device includes an anodic material and an electrolyte, the electrolyte including an organosilicon solvent, a salt, and a hybrid additiving having a first and a second compound, the hybrid additive configured to form a solid electrolyte interphase film on the anodic material upon application of a potential to the electrochemical device.

  12. Electrolytic hydrogen fuel production with solid polymer electrolyte technology.

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Fickett, A. P.

    1973-01-01

    A water electrolysis technology based on a solid polymer electrolyte (SPE) concept is presented for applicability to large-scale hydrogen production in a future energy system. High cell current density operation is selected for the application, and supporting cell test performance data are presented. Demonstrated cell life data are included to support the adaptability of the SPE system to large-size hydrogen generation utility plants as needed for bulk energy storage or transmission. The inherent system advantages of the acid SPE electrolysis technology are explained. System performance predictions are made through the year 2000, along with plant capital and operating cost projections.

  13. Miniaturized Amperometric Solid Electrolyte Carbon Dioxide Sensors

    NASA Technical Reports Server (NTRS)

    Hunter, G. W.; Xu, J. C.; Liu, C. C.; Hammond, J. W.; Ward, B.; Lukco, D.; Lampard, P.; Artale, M.; Androjna, D.

    2006-01-01

    A miniaturized electrochemical carbon dioxide (CO2) sensor using Na3Z r2Si2PO12 (NASICON) as a solid electrolyte has been fabricated and de monstrated. Microfabrication techniques were used for sensor fabricat ion to yield a sensing area around 1.0 mm x 1.1 mm. The NASICON solid electrolyte and the Na2CO3/BaCO3 (1:1.7 molar ratio) auxiliary elect rolyte were deposited by sputtering in between and on top of the inte rdigitated finger-shaped platinum electrodes. This structure maximize s the length of the three-phase boundary (electrode, solid electrolyt e, and auxiliary electrolyte), which is critical for gas sensing. The robust CO2 sensor operated up to 600 C in an amperometric mode and a ttempts were made to optimize sensor operating parameters. Concentrat ions of CO2 between 0.02% and 4% were detected and the overall sensor performance was evaluated. Linear response of sensor current output to ln[CO2 concentration] ranging from 0.02% to 1% was achieved.

  14. Solid electrolytes strengthened by metal dispersions

    DOEpatents

    Lauf, Robert J.; Morgan, Chester S.

    1983-01-01

    An improvement in solid electrolytes of advanced secondary batteries of the sodium-sulfur, sodium-halogen, and like combinations is achieved by providing said battery with a cermet electrolyte containing a metal dispersion ranging from 0.1 to 10.0 vol. % of a substantially nonreactive metal selected from the group consisting essentially of Pt, Cr, Fe, Co, Ni, Nb, their alloys, and their physical mixtures in the elemental or uncombined state, the remainder of said cermet being an ion-conductive ceramic material.

  15. Solid composite electrolytes for lithium batteries

    DOEpatents

    Kumar, Binod; Scanlon, Jr., Lawrence G.

    2001-01-01

    Solid composite electrolytes are provided for use in lithium batteries which exhibit moderate to high ionic conductivity at ambient temperatures and low activation energies. In one embodiment, a polymer-ceramic composite electrolyte containing poly(ethylene oxide), lithium tetrafluoroborate and titanium dioxide is provided in the form of an annealed film having a room temperature conductivity of from 10.sup.-5 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1 and an activation energy of about 0.5 eV.

  16. Inorganic-organic composite solid polymer electrolytes

    SciTech Connect

    Abraham, K.M.; Koch, V.R.; Blakley, T.J.

    2000-04-01

    Inorganic-organic composite solid polymer electrolytes (CSPEs) have been prepared from the poly(ethylene oxide) (PEO)-like electrolytes of the general formula polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-PEO{sub n}-LiX and Li{sup +}-conducting ceramic powders. In the PEO-like electrolytes, PVdF-HFP is the copolymer of PVdF and HFP, PEO{sub n} is a nonvolatile oligomeric polyethylene oxide of {approximately}400 g/mol molecular weight, and LiX is lithium bis(trifluoroethylsulfonyl)imide. Two types of inorganic oxide ceramic powders were used: a highly Li{sup +}-conducting material of the composition 14 mol % Li{sub 2}O-9Al{sub 2}O{sub 3}-38TiO{sub 2}-39P{sub 2}O{sub 5}, and the poorly Li{sup +}-conducting Li-silicates Li{sub 4{minus}x}M{sub x}SiO{sub 4} where M is Ca or Mg and x is 0 or 0.05. The composite electrolytes can be prepared as thin membranes in which the Li{sup +} conductivity and good mechanical strength of the Li{sup +}-conducting inorganic ceramics are complemented by the structural flexibility and high conductivity of organic polymer electrolytes. Excellent electrochemical and thermal stabilities have been demonstrated for the electrolyte films. Li//composite electrolyte//LiCoO{sub 2} rechargeable cells have been fabricated and cycled at room temperature and 50 C.

  17. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.

    1986-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  18. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.; Zymboly, Gregory E.

    1985-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  19. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Isenberg, Arnold O.; Ruka, Roswell J.

    1987-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

  20. Multinuclear NMR Study of the Solid Electrolyte Interface Formed in Lithium Metal Batteries.

    PubMed

    Wan, Chuan; Xu, Suochang; Hu, Mary Y; Cao, Ruiguo; Qian, Jiangfeng; Qin, Zhaohai; Liu, Jun; Mueller, Karl T; Zhang, Ji-Guang; Hu, Jian Zhi

    2017-04-04

    The composition of the solid electrolyte interphase (SEI) layers formed in Cu|Li cells using lithium bis(fluorosulfonyi)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-dimethoxyethane (DME) electrolytes is determined by a multinuclear solid-state MAS NMR study at high magnetic field. It is found that the "dead" metallic Li is largely reduced in the SEI layers formed in a 4 M LiFSI-DME electrolyte system compared with those formed in a 1 M LiFSI-DME electrolyte system. This finding relates directly to the safety of Li metal batteries, as one of the main safety concerns for these batteries is associated with the "dead" metallic Li formed after long term cycling. It is also found that a large amount of LiF, which exhibits superior mechanical strength and good Li(+) ionic conductivity, is observed in the SEI layer formed in the concentrated 4 M LiFSI-DME and 3 M LiTFSI-DME systems, but not in the diluted 1 M LiFSI-DME system. Quantitative (6)Li MAS NMR results indicate that the SEI associated with the 4 M LiFSI-DME electrolyte is denser than those formed in the 1 M LiFSI-DME and 3 M LiTFSI-DME systems. These studies reveal the fundamental mechanisms behind the excellent electrochemical performance associated with higher concentration LiFSI-DME electrolyte systems.

  1. Anti-perovskite solid electrolyte compositions

    DOEpatents

    Zhao, Yusheng; Daemen, Luc Louis

    2015-12-26

    Solid electrolyte antiperovskite compositions for batteries, capacitors, and other electrochemical devices have chemical formula Li.sub.3OA, Li.sub.(3-x)M.sub.x/2OA, Li.sub.(3-x)N.sub.x/3OA, or LiCOX.sub.zY.sub.(1-z), wherein M and N are divalent and trivalent metals respectively and wherein A is a halide or mixture of halides, and X and Y are halides.

  2. Improved Liquid-Electrode/Solid-Electrolyte Cell

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; Distefano, Salvador; Williams, Roger M.; Bankston, Clyde P.

    1990-01-01

    Organic liquid in cathode extends working life. Rechargeable solid-electrolyte electrochemical cell includes novel mixture of organic and inorganic materials in liquid cathode. Operates at temperature about 120 to 170 degrees C lower than sodium/sulfur cells. Offers energy density comparable to that of sodium/sulfur cells - about 10 Wh/kg - and suited to such applications as military systems and electric vehicles.

  3. Solid electrolyte-electrode system for an electrochemical cell

    DOEpatents

    Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.

    1995-01-01

    An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided.

  4. Solid electrolyte-electrode system for an electrochemical cell

    DOEpatents

    Tuller, H.L.; Kramer, S.A.; Spears, M.A.

    1995-04-04

    An electrochemical device including a solid electrolyte and solid electrode composed of materials having different chemical compositions and characterized by different electrical properties but having the same crystalline phase is provided. A method for fabricating an electrochemical device having a solid electrode and solid electrolyte characterized by the same crystalline phase is also provided. 17 figures.

  5. Composite Solid Electrolyte for Li Battery Applications

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, G.; Attia, A. I.; Halpert, G.; Peled, E.

    1993-01-01

    The electrochemical, bulk and interfacial properties of the polyethylene oxide (PEO) based composite solid electrolyte (CSE) comprising LiI, PEO, and Al2O3 have been evaluated for Li battery applications. The bulk interfacial and transport properties of the CSEs seem to strongly depend on the alumina particle size. For the CSE films with 0.05 micron alumina while the bulk conductivity is around 10(exp -4) (mho/cm) at 103 C, the Li ion transport number seems to be close to unity at the same temperature. Compared to the PEO electrolyte this polymer composite electrolyte seems to exhibit robust mechanical and interfacial properties. We have studied three different films with three different alumina sizes in the range 0.01-0.3 micron. Effects of Al2O3 particle size on the electrochemical performance of polymer composite electrolyte is discussed. With TiS2 as cathode a 10 mAh small capacity cell was charged and discharged at C/40 and C/20 rates respectively.

  6. Interfacial Stability of Li Metal-Solid Electrolyte Elucidated via in Situ Electron Microscopy.

    PubMed

    Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo; Luo, Jian; Sharafi, Asma; Sakamoto, Jeff; Li, Juchuan; More, Karren L; Dudney, Nancy J; Chi, Miaofang

    2016-11-09

    Despite their different chemistries, novel energy-storage systems, e.g., Li-air, Li-S, all-solid-state Li batteries, etc., face one critical challenge of forming a conductive and stable interface between Li metal and a solid electrolyte. An accurate understanding of the formation mechanism and the exact structure and chemistry of the rarely existing benign interfaces, such as the Li-cubic-Li7-3xAlxLa3Zr2O12 (c-LLZO) interface, is crucial for enabling the use of Li metal anodes. Due to spatial confinement and structural and chemical complications, current investigations are largely limited to theoretical calculations. Here, through an in situ formation of Li-c-LLZO interfaces inside an aberration-corrected scanning transmission electron microscope, we successfully reveal the interfacial chemical and structural progression. Upon contact with Li metal, the LLZO surface is reduced, which is accompanied by the simultaneous implantation of Li(+), resulting in a tetragonal-like LLZO interphase that stabilizes at an extremely small thickness of around five unit cells. This interphase effectively prevented further interfacial reactions without compromising the ionic conductivity. Although the cubic-to-tetragonal transition is typically undesired during LLZO synthesis, the similar structural change was found to be the likely key to the observed benign interface. These insights provide a new perspective for designing Li-solid electrolyte interfaces that can enable the use of Li metal anodes in next-generation batteries.

  7. Ceramic and polymeric solid electrolytes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Fergus, Jeffrey W.

    Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

  8. Relaxation of interphase stresses on the later stages of the heterogeneous decomposition of solid solutions. I. Functional of the energy

    NASA Astrophysics Data System (ADS)

    Ustyugov, Yu. M.; Kondrat'ev, V. V.

    2008-05-01

    For describing the isomorphic heterogeneous decomposition of binary supersaturated solid solutions at the stage of coalescence under conditions of dislocation-matrix diffusion with a relaxation of stresses caused by phase separation, we consider a system representing a precipitation-phase particle in a surrounding matrix + dislocations intersecting the interphase surface and supplying an alloying component to it. In the approximations based on the continuity of the distribution of misfit dislocations on the interphase surface and of the average concentration field, we obtained an expression for the total energy of the system in the form of a functional which depends on the fraction of the relaxed regions of the interphase surface, the number of supplying (feeding) dislocations, and their mutual arrangement. The need for the use of a model functional appears within the framework of the variational problem for determining the equilibrium parameters of the system.

  9. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, Terje A.

    1985-01-01

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte wherein an assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  10. Method of synthesizing polymers from a solid electrolyte

    DOEpatents

    Skotheim, T.A.

    1984-10-19

    A method of synthesizing electrically conductive polymers from a solvent-free solid polymer electrolyte is disclosed. An assembly of a substrate having an electrode thereon, a thin coating of solid electrolyte including a solution of PEO complexed with an alkali salt, and a thin transparent noble metal electrode are disposed in an evacuated chamber into which a selected monomer vapor is introduced while an electric potential is applied across the solid electrolyte to hold the thin transparent electrode at a positive potential relative to the electrode on the substrate, whereby a highly conductive polymer film is grown on the transparent electrode between it and the solid electrolyte.

  11. Annealing Would Improve beta" - Alumina Solid Electrolyte

    NASA Technical Reports Server (NTRS)

    Williams, Roger; Homer, Margie; Ryan, Margaret; Cortez, Roger; Shields, Virgil; Kisor, Adam

    2003-01-01

    A pre-operational annealing process is under investigation as a potential means of preventing a sudden reduction of ionic conductivity in a Beta"-alumina solid electrolyte (BASE) during use. On the basis of tests, the sudden reduction of ionic conductivity, followed by a slow recovery, has been found to occur during testing of the solid electrolyte and electrode components of an alkali metal thermal-to-electric converter (AMTEC) cell. At this time, high-temperature tests of limited duration have indicated the superiority of the treated BASE, but reproducible tests over thousands of hours are necessary to confirm that microcracking has been eliminated. The ionic conductivity of the treated BASE is also measured to be higher than untreated BASE at 1,073 K in low-pressure sodium vapor. Microcracking resulting in loss of conductivity was not observed with treated BASE in one high-temperature experiment, but this result must be duplicated over very long testing times to be sure of the effect. Shorter annealing times (10 to 20 hours) were found to result in significantly less loss of mass; it may be necessary for the packed powder mixture to evolve some Na2O before the Na2O can leave the ceramic.

  12. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  13. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    SciTech Connect

    Sharp, D.J.; Armstrong, P.S.; Paintz, J.K.G.

    1998-04-01

    This report discusses the design of a solid electrolytic capacitor having a solid electrolyte comprised of manganese dioxide dispersed in an aromatic polyamide capable of to forming polyimide linkages. This solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

  14. Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

    DOEpatents

    Sharp, Donald J.; Armstrong, Pamela S.; Panitz, Janda Kirk G.

    1998-01-01

    A solid electrolytic capacitor having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects.

  15. Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    West, William; Whitacre, Jay; Lim, James

    2008-01-01

    Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

  16. Ion Engine With Solid-Electrolyte Ion Generator

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1984-01-01

    Working fluid utilized efficiently. Working fluid positive ions conducted through solid electrolyte to outside, then accelerated in external electric field. While in solid-electrolyte material, ions do not recombine with electrons: transported to surface with high ionization efficiency. Provides new way to generate beam of ions for implantation in semiconductors or other applications.

  17. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  18. Solid-polymer-electrolyte fuel cells

    NASA Astrophysics Data System (ADS)

    Fuller, T. F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25 C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich's solution and analysis.

  19. Solid polymeric electrolytes for lithium batteries

    DOEpatents

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

    2006-03-14

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

  20. Solid polymer electrolyte composite membrane comprising laser micromachined porous support

    DOEpatents

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

    2011-01-11

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

  1. MultiLayer solid electrolyte for lithium thin film batteries

    DOEpatents

    Lee, Se -Hee; Tracy, C. Edwin; Pitts, John Roland; Liu, Ping

    2015-07-28

    A lithium metal thin-film battery composite structure is provided that includes a combination of a thin, stable, solid electrolyte layer [18] such as Lipon, designed in use to be in contact with a lithium metal anode layer; and a rapid-deposit solid electrolyte layer [16] such as LiAlF.sub.4 in contact with the thin, stable, solid electrolyte layer [18]. Batteries made up of or containing these structures are more efficient to produce than other lithium metal batteries that use only a single solid electrolyte. They are also more resistant to stress and strain than batteries made using layers of only the stable, solid electrolyte materials. Furthermore, lithium anode batteries as disclosed herein are useful as rechargeable batteries.

  2. Solid biopolymer electrolytes came from renewable biopolymer

    NASA Astrophysics Data System (ADS)

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

    2009-07-01

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

  3. New Solid Polymer Electrolytes for Improved Lithium Batteries

    NASA Technical Reports Server (NTRS)

    Hehemann, David G.

    2002-01-01

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

  4. Solid-polymer-electrolyte fuel cells

    SciTech Connect

    Fuller, T.F.

    1992-07-01

    A transport model for polymer electrolytes is presented, based on concentrated solution theory and irreversible thermodynamics. Thermodynamic driving forces are developed, transport properties are identified and experiments devised. Transport number of water in Nafion 117 membrane is determined using a concentration cell. It is 1.4 for a membrane equilibrated with saturated water vapor at 25{degrees}C, decreases slowly as the membrane is dehydrated, and falls sharply toward zero as the water content approaches zero. The relation between transference number, transport number, and electroosmotic drag coefficient is presented, and their relevance to water-management is discussed. A mathematical model of transport in a solid-polymer-electrolyte fuel cell is presented. A two-dimensional membrane-electrode assembly is considered. Water management, thermal management, and utilization of fuel are examined in detail. The membrane separators of these fuel cells require sorbed water to maintain conductivity; therefore it is necessary to manage the water content in membranes to ensure efficient operation. Water and thermal management are interrelated. Rate of heat removal is shown to be a critical parameter in the operation of these fuel cells. Current-voltage curves are presented for operation on air and reformed methanol. Equations for convective diffusion to a rotating disk are solved numerically for a consolute point between the bulk concentration and the surface. A singular-perturbation expansion is presented for the condition where the bulk concentration is nearly equal to the consolute-point composition. Results are compared to Levich`s solution and analysis.

  5. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes

    SciTech Connect

    Tenhaeff, Wyatt E; Yu, Xiang; Hong, Kunlun; Perry, Kelly A; Dudney, Nancy J

    2011-01-01

    A study of lithium cation transport across solid-solid electrolyte interfaces to identify critical resistances in nanostructured solid electrolytes is reported. Bilayers of glass and polymer thin film electrolytes were fabricated and characterized for this study. The glass electrolyte was lithium phosphorous oxynitride (Lipon), and two polymer electrolytes were studied: poly(methyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) and poly(styrene-co-poly(ethylene glycol) methyl ether methacrylate). Both copolymers contained LiClO{sub 4} salt. In bilayers where polymer electrolyte layers are fabricated on top of Lipon, the interfacial resistance dominates transport. At 25 C, the interfacial resistance is at least three times greater than the sum of the Lipon and polymer electrolyte resistances. By reversing the structure and fabricating Lipon on top of the polymer electrolytes, the interfacial resistance is eliminated. Experiments to elucidate the origin of the interfacial resistance in the polymer-on-Lipon bilayers reveal that the solvent mixtures used to fabricate the polymer layers do not degrade the Lipon layer. The importance of the polymer electrolytes' mechanical properties is also discussed.

  6. Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

    2006-01-01

    Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals

  7. Basic investigation into the electrical performance of solid electrolyte membranes

    NASA Technical Reports Server (NTRS)

    Richter, R.

    1982-01-01

    The electrical performance of solid electrolyte membranes was investigated analytically and the results were compared with experimental data. It is concluded that in devices that are used for pumping oxygen the major power losses have to be attributed to the thin film electrodes. Relations were developed by which the effectiveness of tubular solid electrolyte membranes can be determined and the optimum length evaluated. The observed failure of solid electrolyte tube membranes in very localized areas is explained by the highly non-uniform current distribution in the membranes. The analysis points to a possible contact resistance between the electrodes and the solid electrolyte material. This possible contact resistance remains to be investigated experimentally. It is concluded that film electrodes are not appropriate for devices which operate with current flow, i.e., pumps though they can be employed without reservation in devices that measure oxygen pressures if a limited increase in the response time can be tolerated.

  8. High temperature solid electrolyte fuel cell configurations and interconnections

    DOEpatents

    Isenberg, Arnold O.

    1984-01-01

    High temperature fuel cell configurations and interconnections are made including annular cells having a solid electrolyte sandwiched between thin film electrodes. The cells are electrically interconnected along an elongated axial outer surface.

  9. Detailed electrical measurements on sago starch biopolymer solid electrolyte

    NASA Astrophysics Data System (ADS)

    Singh, Rahul; Baghel, Jaya; Shukla, S.; Bhattacharya, B.; Rhee, Hee-Woo; Singh, Pramod K.

    2014-12-01

    The biopolymer solid electrolyte has been synthesized and characterized. Potassium iodide (KI) has been added in polymer matrix to develop solid polymer electrolyte. Relationships between electrical, ionic transport parameter and mechanism have been studied in detail. Impedance spectroscopy reveals the detailed electrical studies and ion transport mechanism. The ion dissociation factor is compared with a measured dielectric constant at a fixed frequency. The dielectric data are calculated which support the ionic conductivity data.

  10. Relaxation of interphase stresses on the later stages of the heterogeneous decomposition of solid solutions. II. Variational problem

    NASA Astrophysics Data System (ADS)

    Ustyugov, Yu. M.; Kondrat'ev, V. V.

    2008-06-01

    The study of relaxation processes upon the decomposition of solid solutions at the stage of coalescence in the regime of dislocation-matrix diffusion is performed using a “precipitated-phase-particle-feeding-dislocations” system as an example. Within the framework of the variational approach, the cases of the independent and interdependent variation of the fraction of the relaxed regions of the interphase surface and of the number of edge dislocations which supply the alloying component to the precipitated phase have been investigated. Under the assumption that implies the linearity of the possible connection between these parameters, the model approximation of the continuous nucleation of epitaxial defects, and the absence of free matrix dislocations near the particle in the initial state, it is shown that the decrease in the number of edge feeding dislocations in the process of relaxation of interphase stresses can occur only by means of “leakage” of dislocation segments localized in the precipitate outside the limits of the precipitate with the formation of structural dislocation loops on the interphase surface.

  11. Modeling for CVD of Solid Oxide Electrolyte

    SciTech Connect

    Starr, T.L.

    2002-09-18

    Because of its low thermal conductivity, high thermal expansion and high oxygen ion conductivity yttria-stabilized zirconia (YSZ) is the material of choice for high temperature electrolyte applications. Current coating fabrication methods have their drawbacks, however. Air plasma spray (APS) is a relatively low-cost process and is suitable for large and relatively complex shapes. it is difficult to produce uniform, relatively thin coatings with this process, however, and the coatings do not exhibit the columnar microstructure that is needed for reliable, long-term performance. The electron-beam physical vapor deposition (EB-PVD) process does produce the desirable microstructure, however, the capital cost of these systems is very high and the line-of-sight nature of the process limits coating uniformity and the ability to coat large and complex shapes. The chemical vapor deposition (CVD) process also produces the desirable columnar microstructure and--under proper conditions--can produce uniform coatings over complex shapes. CVD has been used for many materials but is relatively undeveloped for oxides, in general, and for zirconia, in particular. The overall goal of this project--a joint effort of the University of Louisville and Oak Ridge National Laboratory (ORNL)--is to develop the YSZ CVD process for high temperature electrolyte applications. This report describes the modeling effort at the University of Louisville, which supports the experimental work at ORNL. Early work on CVD of zirconia and yttria used metal chlorides, which react with water vapor to form solid oxide. Because of this rapid gas-phase reaction the water generally is formed in-situ using the reverse water-gas-shift reaction or a microwave plasma. Even with these arrangements gas-phase nucleation and powder formation are problems when using these precursors. Recent efforts on CVD of zirconia and YSZ have focused on use of metal-organic precursors (MOCVD). These are more stable in the gas

  12. Polyethylene glycol as a solid polymer electrolyte

    SciTech Connect

    Cha, D.K.; Park, S.M.

    1997-12-01

    Polymer electrolytes were prepared from polyethylene glycol (PEG)-lithium perchlorate complexes and characterized at a stainless steel electrode using a variety of electrochemical techniques. The charge transfer process was affected by the oxide film on the stainless steel electrode surface in the early stages of redox processes. The polymer electrolytes showed a transference number of 0.2 for Li{sup +}. The conductivity of the PEG-10000 electrolyte has been determined to be 4.7 {times} 10{sup {minus}5} S/cm. This rather high value is attributed to the anionic end groups increasing the polarity of the matrix.

  13. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    NASA Astrophysics Data System (ADS)

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-05-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm-3 at 0.8 A cm-3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm-3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors.

  14. A zwitterionic gel electrolyte for efficient solid-state supercapacitors

    PubMed Central

    Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

    2016-01-01

    Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

  15. Nanoscale mechanics of ductile interphases in solid solution directionally solidified eutectic composites

    NASA Astrophysics Data System (ADS)

    Alem, Nasim

    Ceramic matrix composites are known for their low density, high strength and high stiffness, but lower fracture toughness compared to metal matrix composites. The addition of a reinforcing agent within the matrix can increase the toughness of the composite via many strain energy absorption mechanisms such as plastic deformation. This dissertation attempts to shed light on the competing deformation and fracture mechanisms in ductile/brittle nanoscale lamellar systems where the conventional deformation mechanisms may not apply. NixCo1-xO/ZrO2 Directionally Solidified Eutectic (DSE) composite series has been chosen as a model system for this study. In the first part of this dissertation, it is demonstrated that formation of a novel metal-ceramic multi-layered structure is feasible via reduction of NixCo1-xO/ZrO2 composite as a result of the interfaces forming an electrochemical cell in a reducing atmosphere at high temperatures. The second part of the thesis is dedicated in understanding the correlative deformation and fracture mechanisms in the reduced NixCo1-x O/ZrO2 model system with a nanoscale Ni(Co) confined interphase. These investigations were inspired by a novel observation that there is striking dissimilarity in the interfacial fracture behavior of the reduced Ni xCo1-xO/ZrO2 composite compared to that of the fully oxidized NixCo1-xO/ZrO2 system. A multitude of conventional and analytical electron microscopy techniques are utilized to investigate the role of the size scale, chemistry of this model system on the strain energy absorption upon deformation. FIB TEM lift-off technique is further employed to investigate the crack tip interactions with the nanoscale confined interphases in this model system. To study the role of size scale, the nanoscale deformation mechanism within the metallic interphase is investigated across 50-300 nm thickness range for the confined Ni(Co) interphase. The role of chemistry on the small scale deformation mechanisms in this

  16. Solid lithium ion conducting electrolytes and methods of preparation

    DOEpatents

    Narula, Chaitanya K.; Daniel, Claus

    2015-11-19

    A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

  17. Solid lithium ion conducting electrolytes and methods of preparation

    DOEpatents

    Narula, Chaitanya K; Daniel, Claus

    2013-05-28

    A composition comprised of nanoparticles of lithium ion conducting solid oxide material, wherein the solid oxide material is comprised of lithium ions, and at least one type of metal ion selected from pentavalent metal ions and trivalent lanthanide metal ions. Solution methods useful for synthesizing these solid oxide materials, as well as precursor solutions and components thereof, are also described. The solid oxide materials are incorporated as electrolytes into lithium ion batteries.

  18. Solid electrolyte: The key for high-voltage lithium batteries

    DOE PAGES

    Li, Juchuan; Ma, Cheng; Chi, Miaofang; ...

    2014-10-14

    A solid-state high-voltage (5 V) lithium battery is demonstrated to deliver a cycle life of 10 000 with 90% capacity retention. Furthermore, the solid electrolyte enables the use of high-voltage cathodes and Li anodes with minimum side reactions, leading to a high Coulombic efficiency of 99.98+%.

  19. Lithium Bis(fluorosulfonyl)imide/Poly(ethylene oxide) Polymer Electrolyte for All Solid-State Li-S Cell.

    PubMed

    Judez, Xabier; Zhang, Heng; Li, Chunmei; González-Marcos, José Antonio; Zhou, Zhi-Bin; Armand, Michel; Rodriguez-Martinez, Lide Mercedes

    2017-04-13

    Solid polymer electrolytes (SPEs) comprising lithium bis(fluorosulfonyl)imide (Li[N(SO2F)2], LiFSI) and poly(ethylene oxide) (PEO) have been studied as electrolyte material and binder for the Li-S polymer cell. The LiFSI-based Li-S all solid polymer cell can deliver high specific discharge capacity of 800 mAh gsulfur-1 (i.e., 320 mAh gcathode-1), high areal capacity of 0.5 mAh cm-2 and relatively good rate capability. The cycling performances of Li-S polymer cell with LiFSI are significantly improved compared to with those with conventional LiTFSI (Li[N(SO2CF3)2]) salt in the polymer membrane, due to the improved stability of the Li anode/electrolyte interphases formed in the LiFSI-based SPEs. These results suggest that the LiFSI-based SPEs are attractive electrolyte materials for solid-state Li-S batteries.

  20. Solid electrolyte material manufacturable by polymer processing methods

    DOEpatents

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

    2012-09-18

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

  1. Solid polymer electrolyte composite membrane comprising plasma etched porous support

    DOEpatents

    Liu, Han; LaConti, Anthony B.

    2010-10-05

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

  2. Making Three-Layer Solid Electrolyte/Electrode Sandwiches

    NASA Technical Reports Server (NTRS)

    Schroeder, James E.

    1991-01-01

    Tape-casting-and-sintering process joins two ceramic materials having widely different sintering temperatures into integral sandwich structure. Layers retain their identities, without migration of constituents. Used to make three-layer structure composed of outer porous layers of strontium-doped lanthanum manganite and inner dense layer of yttria-stabilized zirconia. Structures used to make electrolytic and fuels cells with solid electrolytes for use at high temperatures. Other potential applications include oxygen pumps and oxygen sensors.

  3. High temperature solid electrolyte fuel cell with ceramic electrodes

    DOEpatents

    Bates, J.L.; Marchant, D.D.

    A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO/sub 2/ or ZrO/sub 2/ ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In/sub 2/O/sub 3/. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.

  4. High temperature solid electrolyte fuel cell with ceramic electrodes

    DOEpatents

    Marchant, David D.; Bates, J. Lambert

    1984-01-01

    A solid oxide electrolyte fuel cell is described having a central electrolyte comprised of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized and rendered ionically conductive by the addition of Ca, Mg, Y, La, Nd, Sm, Gd, Dy Er, or Yb. The electrolyte is sandwiched between porous electrodes of a HfO.sub.2 or ZrO.sub.2 ceramic stabilized by the addition of a rare earth and rendered electronically conductive by the addition of In.sub.2 O.sub.3. Alternatively, the anode electrode may be made of a metal such as Co, Ni, Ir Pt, or Pd.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  6. Development of high performance proton-conducting solid electrolytes

    SciTech Connect

    Linkous, C.A.; Kopitzke, R.W.

    1998-08-01

    This work seeks to improve the efficiency of fuel cell and electrolyzer operation by developing solid electrolytes that will function at higher temperatures. Two objectives were pursued: (1) determine the mechanism of hydrolytic decomposition of aromatic sulfonic acid ionomers, with the intent of identifying structural weaknesses that can be avoided in future materials; and (2) identify new directions in solid electrolyte development. After evaluating a number of aromatic sulfonates, it became apparent that no common mechanism was going to be found; instead, each polymer had its own sequence of degradation steps, involving some combination of desulfonation and/or chain scission. For electrochemical cell operation at temperatures > 200 C, it will be necessary to develop solid electrolytes that do not require sulfonic acids and do not require water to maintain its conductivity mechanism.

  7. Fuel cells with solid polymer electrolyte and their application on vehicles

    SciTech Connect

    Fateev, V.

    1996-04-01

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

  8. Quasi Solid Polymer Electrolytes for Dye Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Dissanayake, M. A. K. Lakshman

    2013-07-01

    Dye-sensitized solar cell (DSSC) has been considered as an alternative to the conventional silicon solar cell because of low cost, easy fabrication and relatively high conversion efficiency. A DSSC consists of a dye-sensitized nanoparticulated TiO2 electrode, an electrolyte containing redox couple and a Pt coated counter electrode. Such solar cells based on an I-/I3- redox couple in an organic solvent usually have conversion efficiencies reaching around 11%. However, a major drawback of these solution based solar cells, originally developed by Gratzel and coworkers is the lack of long-term stability due to liquid leakage, usage of volatile liquids such as acetonitrile, electrode corrosion, and photodecomposition of the dye in the solvent medium. Therefore considerable research efforts have been made in recent years to replace the liquid electrolytes with solid polymer or quasi-solid polymer (gel) electrolytes. Among these approaches, the use of gel polymer electrolytes appears to give rise to successful results in terms of conversion efficiency. Conventional poly (ethylene oxide)(PEO)-based solid polymer electrolytes exhibit poor ionic conductivities at room temperature, which is not sufficient for practical applications. Therefore, most of the recent studies have been directed to the preparation and characterization of gel polymer electrolytes which exhibit higher ionic conductivity at ambient temperature while maintain quai-solid structure. These gel polymer electrolytes prepared by incorporating a liquid electrolyte into a matrix polymer such as polyacrylonitrile(PAN), poly(vinylidene fluoride)(PVdF), poly (methyl methacrylate) (PMMA) and PEO have been employed in quasi-solid-state DSSCs to achieve power conversion efficiencies of more than 5%. Significant improvements have been achieved in recent years by modifications of the electrolytes by optimizing the ionic salt, introducing additives such as inorganic nanofillers, organic molecules and ionic liquids in

  9. Solid Polymer Electrolyte (SPE) fuel cell technology program

    NASA Technical Reports Server (NTRS)

    1979-01-01

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

  10. Solid polymer electrolytes for rechargeable batteries. Final report

    SciTech Connect

    Narang, S.C.; Ventura, S.C.

    1992-02-01

    SRI International has synthesized and tested new, dimensionally stable polymer electrolytes for high energy density rechargeable lithium batteries. We have prepared semi-interpenetrating networks of sulfur-substituted polyethyleneoxide with tetmethylorthosilicate (TEOS). The in situ hydrolysis of TEOS produces a mechanically stable three-dimensional network that entangles the polymer electrolytes and makes the film dimensionally flexible and stable. With this approach, the best dimensionally stable polymer electrolyte of this type produced so far, has a room temperature lithium ion conductivity of 7.5 {times} 10{sup {minus}4} S cm{sup {minus}1}. Another type of solid polymer electrolytes, polydiacetylene-based single-ion conductors with high room temperature proton conductivity were also developed. The best conductivity of these polymers is two orders of magnitude higher than that of Nafion under comparable experimental conditions. With further appropriate chemical modification, the new polymers could be used in fuel cells.

  11. Passivation of Lithium Metal Anode via Hybrid Ionic Liquid Electrolyte toward Stable Li Plating/Stripping.

    PubMed

    Li, Nian-Wu; Yin, Ya-Xia; Li, Jin-Yi; Zhang, Chang-Huan; Guo, Yu-Guo

    2017-02-01

    Hybrid electrolyte of ionic liquid and ethers is used to passivate the surface of Li metal surface via modification of the as-formed solid electrolyte interphase with N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (Py13TFSI), thereby reducing the side reactions between the Li metal and electrolyte, leading to remarkably suppressed Li dendrite growth and mitigating Li metal corrosion.

  12. Oxygen separation from air using zirconia solid electrolyte membranes

    NASA Technical Reports Server (NTRS)

    Suitor, J. W.; Marner, W. J.; Schroeder, J. E.; Losey, R. W.; Ferrall, J. F.

    1988-01-01

    Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

  13. Quasi-Solid Electrolytes for High Temperature Lithium Ion Batteries.

    PubMed

    Kalaga, Kaushik; Rodrigues, Marco-Tulio F; Gullapalli, Hemtej; Babu, Ganguli; Arava, Leela Mohana Reddy; Ajayan, Pulickel M

    2015-11-25

    Rechargeable batteries capable of operating at high temperatures have significant use in various targeted applications. Expanding the thermal stability of current lithium ion batteries requires replacing the electrolyte and separators with stable alternatives. Since solid-state electrolytes do not have a good electrode interface, we report here the development of a new class of quasi-solid-state electrolytes, which have the structural stability of a solid and the wettability of a liquid. Microflakes of clay particles drenched in a solution of lithiated room temperature ionic liquid forming a quasi-solid system has been demonstrated to have structural stability until 355 °C. With an ionic conductivity of ∼3.35 mS cm(-1), the composite electrolyte has been shown to deliver stable electrochemical performance at 120 °C, and a rechargeable lithium battery with Li4Ti5O12 electrode has been tested to deliver reliable capacity for over several cycles of charge-discharge.

  14. Design of Hybrid Solid Polymer Electrolytes: Structure and Properties

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  15. Electrode-Electrolyte Interfaces in Solid Polymer Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Hu, Qichao

    This thesis studies the performance of solid polymer lithium batteries from room temperature to elevated temperatures using mainly electrochemical techniques, with emphasis on the bulk properties of the polymer electrolyte and the electrode-electrolyte interfaces. Its contributions include: 1) Demonstrated the relationship between polymer segmental motion and ionic conductivity indeed has a Vogel-Tammann-Fulcher (VTF) dependence, and improved the conductivity of the graft copolymer electrolyte (GCE) by almost an order of magnitude by changing the ion-conducting block from poly(oxyethylene) methacrylate (POEM) to a block with a lower glass transition temperature (Tg) poly(oxyethylene) acrylate (POEA). 2) Identified the rate-limiting step in the battery occurs at the cathode-electrolyte interface using both full cell and symmetric cell electrochemical impedance spectroscopy (EIS), improved the battery rate capability by using the GCE as both the electrolyte and the cathode binder to reduce the resistance at the cathode-electrolyte interface, and used TEM and SEM to visualize the polymer-particle interface (full cells with LiFePO4 as the cathode active material and lithium metal as the anode were assembled and tested). 3) Applied the solid polymer battery to oil and gas drilling application, performed high temperature (up to 210 °C) cycling (both isothermal and thermal cycling), and demonstrated for the first time, current exchange between a solid polymer electrolyte and a liquid lithium metal. Both the cell open-circuit-voltage (OCV) and the overall GCE mass remained stable up to 200 °C, suggesting that the GCE is electrochemically and gravimetrically stable at high temperatures. Used full cell EIS to study the behavior of the various battery parameters as a function of cycling and temperature. 4) Identified the thermal instability of the cell was due to the reactivity of lithium metal and its passivation film at high temperatures, and used Li/GCE/Li symmetric cell

  16. Solid-state graft copolymer electrolytes for lithium battery applications.

    PubMed

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

    2013-08-12

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

  17. Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

    PubMed Central

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

    2013-01-01

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

  18. Recent advances in solid polymer electrolyte fuel cell technology

    SciTech Connect

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

    1988-01-01

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

  19. Elongated solid electrolyte cell configurations and flexible connections therefor

    DOEpatents

    Reichner, P.

    1989-10-17

    A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations, each cell combination containing an interior electrode having a top surface and a plurality of interior gas feed conduits, through its axial length, electrolyte contacting the interior electrode and exterior electrode contacting electrolyte, where a major portion of the air electrode top surface is covered by interconnection material, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material in electronic connection with the air electrode through contact with a major portion of the interconnection material, the metal fiber felt being effective as a shock absorbent body between the cells. 4 figs.

  20. Elongated solid electrolyte cell configurations and flexible connections therefor

    DOEpatents

    Reichner, Philip

    1989-01-01

    A flexible, high temperature, solid oxide electrolyte electrochemical cell stack configuration is made, comprising a plurality of flattened, elongated, connected cell combinations 1, each cell combination containing an interior electrode 2 having a top surface and a plurality of interior gas feed conduits 3, through its axial length, electrolyte 5 contacting the interior electrode and exterior electrode 8 contacting electrolyte, where a major portion of the air electrode top surface 7 is covered by interconnection material 6, and where each cell has at least one axially elongated, electronically conductive, flexible, porous, metal fiber felt material 9 in electronic connection with the air electrode 2 through contact with a major portion of the interconnection material 6, the metal fiber felt being effective as a shock absorbent body between the cells.

  1. Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions

    PubMed Central

    Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.

    2016-01-01

    Ion transport–driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. We find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator. PMID:27453943

  2. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

    NASA Astrophysics Data System (ADS)

    Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.

    2014-10-01

    Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.

  3. TOPICAL REVIEW: Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview

    NASA Astrophysics Data System (ADS)

    Agrawal, R. C.; Pandey, G. P.

    2008-11-01

    Polymer electrolytes are promising materials for electrochemical device applications, namely, high energy density rechargeable batteries, fuel cells, supercapacitors, electrochromic displays, etc. The area of polymer electrolytes has gone through various developmental stages, i.e. from dry solid polymer electrolyte (SPE) systems to plasticized, gels, rubbery to micro/nano-composite polymer electrolytes. The polymer gel electrolytes, incorporating organic solvents, exhibit room temperature conductivity as high as ~10-3 S cm-1, while dry SPEs still suffer from poor ionic conductivity lower than 10-5 S cm-1. Several approaches have been adopted to enhance the room temperature conductivity in the vicinity of 10-4 S cm-1 as well as to improve the mechanical stability and interfacial activity of SPEs. In this review, the criteria of an ideal polymer electrolyte for electrochemical device applications have been discussed in brief along with presenting an overall glimpse of the progress made in polymer electrolyte materials designing, their broad classification and the recent advancements made in this branch of materials science. The characteristic advantages of employing polymer electrolyte membranes in all-solid-state battery applications have also been discussed.

  4. Solid polymer battery electrolyte and reactive metal-water battery

    DOEpatents

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

    2000-01-01

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

  5. Solid Electrolytes: Alkali-Ion Transport in Skeleton Structures

    DTIC Science & Technology

    1976-06-30

    side if necessary and identify by block number) solid electrolytes alkali -ion transport sodium -sulfur batteries fast -ion transport O ABSTRACT...molten Na 2 S4 for 10 days at 400’C indicated chemical stability, similar testing i-1 molten sodium was initiated, and it has been established that...tests under dynamic conditions are necessary before long-term stability of tile material can be established. Tests for stability in molten sodium have

  6. Oxygen production using solid-state zirconia electrolyte technology

    NASA Technical Reports Server (NTRS)

    Suitor, Jerry W.; Clark, Douglas J.

    1991-01-01

    High purity oxygen is required for a number of scientific, medical, and industrial applications. Traditionally, these needs have been met by cryogenic distillation or pressure swing adsorption systems designed to separate oxygen from air. Oxygen separation from air via solid-state zirconia electrolyte technology offers an alternative to these methods. The technology has several advantages over the traditional methods, including reliability, compactness, quiet operation, high purity output, and low power consumption.

  7. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

    1996-01-01

    The invention comprises of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb.sub.x Ta.sub.y Ce.sub.1-x-y O.sub.2 where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy.

  8. Protective interlayer for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Singh, P.; Vasilow, T.R.; Richards, V.L.

    1996-05-14

    The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

  9. Superior ion-conducting hybrid solid electrolyte for all-solid-state batteries.

    PubMed

    Kim, Jae-Kwang; Scheers, Johan; Park, Tae Joo; Kim, Youngsik

    2015-02-01

    Herein, we developed a high-performance lithium ion conducting hybrid solid electrolyte, consisted of LiTFSI salt, Py14 TFSI ionic liquid, and TiO2 nanoparticles. The hybrid solid electrolyte prepared by a facile method had high room temperature ionic conductivity, excellent thermal stability and low interface resistance with good contact. In addition, the lithium transference number was highly increased by the scavenger effect of TiO2 nanoparticles. With the hybrid solid electrolyte, the pouch-type solid-state battery exhibited high initial discharge capacity of 150 mA h g(-1) at room temperature, and even at 1 C, the reversible capacity was as high as 106 mA h g(-1) .

  10. Comparative investigation of solid electrolyte interphases created by the electrolyte additives vinyl ethylene carbonate and dicyano ketene vinyl ethylene acetal

    NASA Astrophysics Data System (ADS)

    Forestier, Coralie; Jankowski, Piotr; Wizner, Agnieszka; Davoisne, Carine; Gachot, Grégory; Sannier, Lucas; Grugeon, Sylvie; Johansson, Patrik; Armand, Michel; Laruelle, Stephane

    2017-03-01

    The effect of the replacement of the carbonyl oxygen in VEC additive by dbnd C(CN)2 in the analogous dicyano ketene vinyl ethylene acetal (DCKVEA) on the electrochemical reduction profile is significant. Yet, the additives were proven, through IR spectroscopy supported by DFT computations, by applying EELS techniques and performing synthesis of a reduction product, to reduce in a similar way. Interestingly, the reduction-induced capacities were found to be quite different and can be explained either by the different properties of the SEI, from lithium carbonate and its malononitrile homologue, or by the different abilities of the two additives to solvate Li+.

  11. Ozone electrosynthesis in an electrolyzer with solid polymer electrolyte

    SciTech Connect

    Babak, A.A.; Fateev, V.N.; Amadelli, R.; Potapova, G.F.

    1994-06-01

    Environmental problems have provided a focus of growing attention within the past few years. Of particular interest are preparation techniques for ozone, which is known to be an environmentally clean oxidant applicable to conditioning of potable water, sewage treatment, and disinfection of various domestic media. It also can be employed in chemical synthesis and a number of other applications. An electrolyzer with PbO{sub 2}-covered anode pressed against a membrane of a solid polymer electrolyte of sulfocationite type is shown to exhibit high operational qualities in electrochemical production of ozone.

  12. Electrolytic Enrichment of Tritium with Solid Polymer Electrolyte for Application to Environmental Measurements

    SciTech Connect

    Momoshima, Noriyuki; Nagao, Yusaku; Toyoshima, Takahiro

    2005-07-15

    We evaluated electrolytic separation factors of hydrogen isotopes by SPE (Solid Polymer Electrolyte) for application to environmental tritium analysis. The apparent separation factors {alpha}{sub a} for deuterium and {beta}{sub a} for tritium were determined as 3.5 {+-} 0.1 and 6.2 {+-} 0.5, respectively. The tritium enrichment of 8.4 times was achieved, when a 1000 ml of sample water was electrolyzed to about 60 ml. The chemical composition changes before and after the electrolysis were examined, showing an increase in H{sup +} and Na{sup +} concentrations and a decrease in Mg{sup 2+} and Ca{sup 2+}concentrations. F{sup -}, which was not contained in the sample water, was detected after electrolysis accompanying with a reduction of SO{sub 4}{sup 2-}, Cl{sup -} and NO{sub 3}{sup -}. The memory of tritium and ions in the electrolysis cell after electrolysis was possible to be eliminated by washings with de-ionized water. Tritium concentrations of rain at Kumamoto, Japan were determined with a combination of the present electrolytic enrichment system and liquid scintillation counting.

  13. Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium Powder Anode for Lithium Metal Batteries.

    PubMed

    Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

    2017-04-03

    Lithium metal anode has fundamental problems concerning formation and growth of lithium dendrites which prevents practical applications of next generation of high-capacity lithium metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode materials. The effect of physical state of electrolyte (solid/liquid) and morphology of lithium metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium powder anode suggests effective solution to suppress the dendrite growth due to formation of stable solid electrolyte interphase (SEI) layer and delocalized current density.

  14. Strength of an electrolyte supported solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Fleischhauer, Felix; Bermejo, Raul; Danzer, Robert; Mai, Andreas; Graule, Thomas; Kuebler, Jakob

    2015-11-01

    For the proper function of solid oxide fuel cells (SOFC) their structural integrity must be maintained during their whole lifetime. Any cell fracture would cause leakage and partial oxidization of the anode, leading to a reduced performance, if not catastrophic failure of the whole stack. In this study, the mechanical strength of a state of the art SOFC, developed and produced by Hexis AG/Switzerland, was investigated with respect to the influence of temperature and ageing, whilst for the anode side of the cell the strength was measured under reducing and oxidizing atmospheres. Ball-on-3-Ball bending strength tests and fractography conducted on anode and cathode half-cells revealed the underlying mechanisms, which lead to cell fracture. They were found to be different for the cathode and the anode side and that they change with temperature and ageing. Both anode and cathode sides exhibit the lowest strength at T = 850 °C, which is greatly reduced to the initial strength of the bare electrolyte. This reduction is the consequence of the formation of cracks in the electrode layer which either directly penetrate into the electrolyte (anode side) or locally increase the stress intensity level of pre-existing flaws of the electrolytes at the interface (cathode side).

  15. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    SciTech Connect

    Kartini, Evvy; Manawan, Maykel

    2016-02-08

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  16. Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

    NASA Astrophysics Data System (ADS)

    Kartini, Evvy; Manawan, Maykel

    2016-02-01

    With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say "the most important emerging energy technology" is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner's cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes

  17. Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Goldsby, John C.; Choi, Sung R.

    2004-01-01

    Tests have shown that modification of chemical compositions can increase the strengths and fracture toughnesses of solid oxide fuel-cell (SOFC) electrolytes. Heretofore, these solid electrolytes have been made of yttria-stabilized zirconia, which is highly conductive for oxygen ions at high temperatures, as needed for operation of fuel cells. Unfortunately yttria-stabilized zirconia has a high coefficient of thermal expansion, low resistance to thermal shock, low fracture toughness, and low mechanical strength. The lack of strength and toughness are especially problematic for fabrication of thin SOFC electrolyte membranes needed for contemplated aeronautical, automotive, and stationary power-generation applications. The modifications of chemical composition that lead to increased strength and fracture toughness consist in addition of alumina to the basic yttria-stabilized zirconia formulations. Techniques for processing of yttria-stabilized zirconia/alumina composites containing as much as 30 mole percent of alumina have been developed. The composite panels fabricated by these techniques have been found to be dense and free of cracks. The only material phases detected in these composites has been cubic zirconia and a alumina: this finding signifies that no undesired chemical reactions between the constituents occurred during processing at elevated temperatures. The flexural strengths and fracture toughnesses of the various zirconia-alumina composites were measured in air at room temperature as well as at a temperature of 1,000 C (a typical SOFC operating temperature). The measurements showed that both flexural strength and fracture toughness increased with increasing alumina content at both temperatures. In addition, the modulus of elasticity and the thermal conductivity were found to increase and the density to decrease with increasing alumina content. The oxygen-ion conductivity at 1,000 C was found to be unchanged by the addition of alumina.

  18. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    DOE PAGES

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

    2015-06-23

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

  19. Tetraarylborate polymer networks as single-ion conducting solid electrolytes

    SciTech Connect

    Van Humbeck, Jeffrey F.; Aubrey, Michael L.; Alsbaiee, Alaaeddin; Ameloot, Rob; Coates, Geoffrey W.; Dichtel, William R.; Long, Jeffrey R.

    2015-06-23

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

  20. Solid polymeric electrolytes obtained from modified natural polymers

    NASA Astrophysics Data System (ADS)

    Pawlicka, Agnieszka; Machado, G. O.; Guimaraes, K. V.; Dragunski, Douglas C.

    2003-10-01

    Polysaccharides like starch and cellulose derivatives, hydroxyethylcellulose (HEC) or hydroxypropylcellulose (HPC) were modified to obtain solid polymeric electrolytes. The chemical modifications were performed by the grafting of polymers with poly(ethylene oxide) mono and diisocyanates or JEFFAMINE (Shiff base). The physical modifications were made by the plasticization process of starch and cellulose derivatives with glycerol and ethylene glycol. All the samples obtained from polysaccharides were characterized by X-ray, thermal analysis (DSC) and impedance spectroscopy. The plasticized samples showed low glass transition temperatures (Tg); for HEC the value was about -60°C and for starch it was about -30°C. Tg values for grafted samples were of about -58°C for starch and -7°C for HPC. The low Tg values obtained are important to ensure good ionic conductivity that reached the values of about 10-5 Scm-1 for plasticized samples and 10-6 Scm-1 for grafted ones at room temperature. The good film forming and ionic conductivity properties of the samples of HEC, HPC and starch are very interesting candidates to be used as solid polymer electrolytes.

  1. Stability of the Solid Electrolyte Interface on the Li Electrode in Li–S Batteries

    SciTech Connect

    Zheng, Dong; Yang, Xiao-Qing; Qu, Deyang

    2016-04-05

    In this study, by means of high performance liquid chromatography–mass spectroscopy, the concentration of sulfur and polysulfides was determined in nonaqueous electrolytes. The stability of sulfur and Li in eight electrolytes was studied quantitatively. It was found that sulfur reacted with Li in most of the commonly used electrolytes for lithium–sulfur batteries. The reaction products between sulfur and Li were qualitatively identified. In some cases, the solid electrolyte interface on the Li can successfully prevent the interaction between S and Li; however, it was found that the solid electrolyte interface was damaged by polysulfide ions.

  2. PREPARATION AND CHARACTERIZATION OF SOLID ELECTROLYTES: FUEL CELL APPLICATIONS

    SciTech Connect

    Rambabu Bobba; Josef Hormes; T. Wang; Jaymes A. Baker; Donald G. Prier; Tommy Rockwood; Dinesha Hawkins; Saleem Hasan; V. Rayanki

    1997-12-31

    The intent of this project with Federal Energy Technology Center (FETC)/Morgantown Energy Technology Center (METC) is to develop research infrastructure conductive to Fuel Cell research at Southern University and A and M College, Baton Route. A state of the art research laboratory (James Hall No.123 and No.114) for energy conversion and storage devices was developed during this project duration. The Solid State Ionics laboratory is now fully equipped with materials research instruments: Arbin Battery Cycling and testing (8 channel) unit, Electrochemical Analyzer (EG and G PAR Model 273 and Solartron AC impedance analyzer), Fuel Cell test station (Globe Tech), Differential Scanning Calorimeter (DSC-10), Thermogravimetric Analyzer (TGA), Scanning Tunneling Microscope (STM), UV-VIS-NIR Absorption Spectrometer, Fluorescence Spectrometer, FT-IR Spectrometer, Extended X-ray Absorption Fine Structure (EXAFS) measurement capability at Center for Advanced Microstructure and Devices (CAMD- a multimillion dollar DOE facility), Glove Box, gas hood chamber, high temperature furnaces, hydraulic press and several high performance computers. IN particular, a high temperature furnace (Thermodyne 6000 furnace) and a high temperature oven were acquired through this project funds. The PI Dr. R Bobba has acquired additional funds from federal agencies include NSF-Academic Research Infrastructure program and other DOE sites. They have extensively used the multimillion dollar DOE facility ''Center'' for Advanced Microstructures and Devices (CAMD) for electrochemical research. The students were heavily involved in the experimental EXAFS measurements and made use of their DCM beamline for EXAFS research. The primary objective was to provide hands on experience to the selected African American undergraduate and graduate students in experimental energy research.The goal was to develop research skills and involve them in the Preparation and Characterization of Solid Electrolytes. Ionically

  3. Relaxation of interphase stresses on the later stages of the heterogeneous decomposition of solid solutions: III. Conditions for the infiltration of feeding dislocations

    NASA Astrophysics Data System (ADS)

    Ustyugov, Yu. M.; Kondrat'ev, V. V.

    2008-07-01

    In this paper, we have studied the relaxation processes that occur upon the decomposition of solid solutions at the stage of coalescence in the regime of dislocation-matrix diffusion using the precipitated-phase-particle-feeding-dislocations system as an example. The cases of linear and nonlinear interrelations between the controlling parameters of the system (the fraction of the relaxed regions of the interphase surface and the number of edge dislocations that supply the alloying component to the precipitated phase) have been analyzed. It has been established that in real cases it is advantageous for the system to reduce its total energy via the “infiltration” of feeding dislocations, i.e., the escape of segments of edge feeding dislocations localized in the precipitate outside the limits of the precipitate with the formation of structural dislocation loops at the interphase surface by the reaction of the following type: 1 feeding dislocation = 1 structural loop + 1 matrix dislocation. In the presence of an enhanced density of feeding dislocations, this reaction is blocked, and the relaxation of interphase stresses is accomplished as a result of sequential acts of the loss of coherence, which are accompanied by a partial “escape” of edge feeding dislocations. For the edge dislocations that remain unescaped, there is formulated a condition for the subsequent “leakage” of their segments localized in the precipitate outside the limits of the precipitate according to the following reaction: 2 feeding dislocations = 1 structural loop + 2 matrix dislocations.

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

    DOEpatents

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

    2015-02-24

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

  5. High strength porous support tubes for high temperature solid electrolyte electrochemical cells

    DOEpatents

    Rossing, Barry R.; Zymboly, Gregory E.

    1986-01-01

    A high temperature, solid electrolyte electrochemical cell is made, having an electrode and a solid electrolyte disposed on a porous, sintered support material containing thermally stabilized zirconia powder particles and from about 3 wt. % to about 45 wt. % of thermally stable oxide fibers.

  6. High discharge capacity solid composite polymer electrolyte lithium battery

    NASA Astrophysics Data System (ADS)

    Chen, Y. T.; Chuang, Y. C.; Su, J. H.; Yu, H. C.; Chen-Yang, Y. W.

    2011-03-01

    In this study, a series of nanocomposite polymer electrolytes (CPEs), PAN/LiClO4/SAP, with high conductivity are prepared based on polyacrylonitrile (PAN), LiClO4 and low content of the silica aerogel powder (SAP) prepared by the sol-gel method with ionic liquid (IL) as the template. The effect of addition of SAP on the properties of the CPEs is investigated by FTIR, AC impedance, linear sweep voltagrams and cyclic voltammetry measurements as well as the charge-discharge performance. It is found that the ionic conductivity of the CPE is significantly improved by addition of SAP. The maximum ambient ionic conductivity of CPEs is about 12.5 times higher than that without addition of SAP. The results of the voltammetry measurements of CPE-3, which contained 3 wt% of SAP, show that the anodic and cathodic peaks are well maintained after 100 cycles, showing excellent electrochemical stability and cyclability over the potential range between 0 V and 4 V vs. Li/Li+. Besides, the room temperature discharge capacity measured at 0.5C for the coin cell based on CPE-3 is 120 mAh g-1 and the capacity is retained after 20 cycles discharge, indicating the potential for practical use. This is perhaps the first report of the room temperature charge-discharge performance on the solid composite polymer electrolyte to the best of our knowledge.

  7. Development of solid electrolytes for water electrolysis at higher temperature

    SciTech Connect

    Linkous, C.A.

    1996-10-01

    This report describes efforts in developing new solid polymer electrolytes that will enable operation of proton exchange membrane electrolyzers at higher temperatures than are currently possible. Several ionomers have been prepared from polyetheretherketone (PEEK), polyethersulfone (PES), and polyphenylquinoxaline (PPQ) by employing various sulfonation procedures. By controlling the extent of sulfonation, a range of proton conductivities could be achieved, whose upper limit actually exceeded that of commercially available perfluoralkyl sulfonates. Thermoconductimetric analysis of samples at various degrees of sulfonation showed an inverse relationship between conductivity and maximum operating temperature. This was attributed to the dual effect of adding sulfonate groups to the polymer: more acid groups produce more protons for increased conductivity, but they also increase water uptake, which mechanically weakens the membrane. This situation was exacerbated by the limited acidity of the aromatic sulfonic acids (pK{sub A} {approx} 2-3). The possibility of using partial fluorination to raise the acid dissociation constant is discussed.

  8. Electrical contact structures for solid oxide electrolyte fuel cell

    DOEpatents

    Isenberg, Arnold O.

    1984-01-01

    An improved electrical output connection means is provided for a high temperature solid oxide electrolyte type fuel cell generator. The electrical connection of the fuel cell electrodes to the electrical output bus, which is brought through the generator housing to be connected to an electrical load line maintains a highly uniform temperature distribution. The electrical connection means includes an electrode bus which is spaced parallel to the output bus with a plurality of symmetrically spaced transversely extending conductors extending between the electrode bus and the output bus, with thermal insulation means provided about the transverse conductors between the spaced apart buses. Single or plural stages of the insulated transversely extending conductors can be provided within the high temperatures regions of the fuel cell generator to provide highly homogeneous temperature distribution over the contacting surfaces.

  9. Nanoscale electrochemistry using dielectric thin films as solid electrolytes

    NASA Astrophysics Data System (ADS)

    Valov, Ilia; Lu, Wei D.

    2016-07-01

    It is now well known that at the nanoscale matters behave differently compared to bulk phases. Increased reactivity, deviations in structural, thermodynamic and kinetic properties make nanoscale materials and processes attractive for both fundamental research and applications. Here we show that nanometer thin films of materials with dielectric properties at the macroscopic level such as SiO2, Ta2O5 and HfO2 behave as solid electrolytes and exhibit evident ionic transport and electrochemical redox reactions. Experimental studies demonstrate that classical electrochemical potentiodynamic and steady state methods can be used to study the mass and charge transport at the nanoscale. We believe these reported properties of nanomatter open new opportunities for fundamental research and applications.

  10. Ferroelectric Dispersed Composite Solid Electrolyte for CO2 Gas Sensor

    NASA Astrophysics Data System (ADS)

    Singh, K.; Ambekar, P.; Bhoga, S. S.

    2002-12-01

    The Li2CO3:LiNbO3 composite system was investigated for the application in electrochemical gas sensor. The conductivity maximum is observed for 50Li2CO3+50LiNbO3. An enhancement in conductivity is understood to be due to the percolation threshold. The composite is also seen less sensitive to moisture. Potentiometric sensors are obtained using optimized composition. At the reference electrode, the activity of Li+ is fixed by using open reference electrode material. Good reversibility of cell emf was observed for PCO2 ranging from 200 ppm to 20% at 400°C. The cell response was Nernstian, following nearly two-electron reaction. The sensor showed negligible cross-sensitivity to moisture. Developed solid electrolyte not only exhibit shorter response time but also improves over all performance relative to the sensor based on pure carbonate.

  11. Solid State Electrolytes Prepared from PEO (360) Silanated Silica

    NASA Technical Reports Server (NTRS)

    Maitra, P.; Ding, J.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Chua, D.; Salomon, M.

    2002-01-01

    All solid state composite electrolytes were prepared using fumed silica (SiO2) silanated with an oligomeric polyethylene oxide (PEO) silane containing 6-9 ethylene oxide repeat units, a PEO matrix and LiClO4 (8/1 O/Li). The PEO-silane covalently attached to the silica was amorphous, with a T(sub g) that increased from -90 C to -53 C after attachment. The conductivity of films prepared using the PEO-silanated silica increased to approx. 6 x 10(exp -5) S/cm at RT compared with approx. 1 x 10(-5) S/cm for films prepared with unsilanated SiO2.

  12. Support tube for high temperature solid electrolyte electrochemical cell

    DOEpatents

    Ruka, Roswell J.; Rossing, Barry R.

    1986-01-01

    Disclosed is a compound having a fluorite-like structure comprising a solid solution having the general formula [(ZrO.sub.2).sub.1-x (MO.sub.s).sub.x ].sub.1-y [(La.sub.m A.sub.1-m).sub.2-z (Mn.sub.n B.sub.1-n).sub.z O.sub.r ].sub.y where MO.sub.5 is an oxide selected from the group consisting of calcia, yttria, rare earth oxides, and mixtures thereof, x is about 0.1 to 0.3, y is about 0.005 to about 0.06, z is about 0.1 to about 1.9, A is yttrium, rare earth element, alkaline earth element, or mixture thereof, B is iron, nickel, cobalt, or mixture thereof, m is 0.3 to 1, n is 0.5 to 1, and r is 2 to 4. A porous tube made from such a composition can be coated with an electrically conducting mixed oxide electrode such as lanthanum manganite, and can be used in making high temperature electrochemical cells such as solid electrolyte fuel cells.

  13. Composite Electrolyte for All-Solid-State Lithium Batteries: Low-Temperature Fabrication and Conductivity Enhancement.

    PubMed

    Lee, Sang-Don; Jung, Kyu-Nam; Kim, Hyeongil; Shin, Hyun-Seop; Song, Seung-Wan; Park, Min-Sik; Lee, Jong-Won

    2017-03-20

    All-solid-state lithium batteries offer notable advantages over conventional Li-ion batteries with liquid electrolytes in terms of energy density, stability, and safety. To realize this technology, it is critical to develop highly reliable solid-state inorganic electrolytes with high ionic conductivities and adequate processability. Li1+x Alx Ti2-x (PO4 )3 (LATP) with a NASICON (Na superionic conductor)-like structure is regarded as a potential solid electrolyte, owing to its high "bulk" conductivity (ca. 10(-3)  S cm(-1) ) and excellent stability against air and moisture. However, the solid LATP electrolyte still suffers from a low "total" conductivity, mainly owing to the blocking effect of grain boundaries to Li(+) conduction. In this study, an LATP-Bi2 O3 composite solid electrolyte shows very high total conductivity (9.4×10(-4)  S cm(-1) ) at room temperature. Bi2 O3 acts as a microstructural modifier to effectively reduce the fabrication temperature of the electrolyte and to enhance its ionic conductivity. Bi2 O3 promotes the densification of the LATP electrolyte, thereby improving its structural integrity, and at the same time, it facilitates Li(+) conduction, leading to reduced grain-boundary resistance. The feasibility of the LATP-Bi2 O3 composite electrolyte in all-solid-state Li batteries is also examined in this study.

  14. Lithium-ion-based solid electrolyte tuning of the carrier density in graphene

    PubMed Central

    Zhao, Jialin; Wang, Meng; Li, Hui; Zhang, Xuefu; You, Lixing; Qiao, Shan; Gao, Bo; Xie, Xiaoming; Jiang, Mianheng

    2016-01-01

    We have developed a technique to tune the carrier density in graphene using a lithium-ion-based solid electrolyte. We demonstrate that the solid electrolyte can be used as both a substrate to support graphene and a back gate. It can induce a change in the carrier density as large as 1 × 1014 cm−2, which is much larger than that induced with oxide-film dielectrics, and it is comparable with that induced by liquid electrolytes. Gate modulation of the carrier density is still visible at 150 K, which is lower than the glass transition temperature of most liquid gating electrolytes. PMID:27698413

  15. Lithium-ion-based solid electrolyte tuning of the carrier density in graphene

    NASA Astrophysics Data System (ADS)

    Zhao, Jialin; Wang, Meng; Li, Hui; Zhang, Xuefu; You, Lixing; Qiao, Shan; Gao, Bo; Xie, Xiaoming; Jiang, Mianheng

    2016-10-01

    We have developed a technique to tune the carrier density in graphene using a lithium-ion-based solid electrolyte. We demonstrate that the solid electrolyte can be used as both a substrate to support graphene and a back gate. It can induce a change in the carrier density as large as 1 × 1014 cm‑2, which is much larger than that induced with oxide-film dielectrics, and it is comparable with that induced by liquid electrolytes. Gate modulation of the carrier density is still visible at 150 K, which is lower than the glass transition temperature of most liquid gating electrolytes.

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

    NASA Astrophysics Data System (ADS)

    Sakamoto, Y.; Ishii, Y.; Kawasaki, S.

    2016-07-01

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

  17. Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery.

    PubMed

    Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li

    2016-01-01

    The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10(-3) S cm(-1) at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.

  18. Solidified inorganic-organic hybrid electrolyte for all solid state flexible lithium battery

    NASA Astrophysics Data System (ADS)

    Baek, Seung-Wook; Honma, Itaru; Kim, Jedeok; Rangappa, Dinesh

    2017-03-01

    Solidified lithium conducting hybrid electrolyte is designed and processed to realize the large scale and flexible solid state Li battery satisfying energy capability and safety issue. This paper presents a solidified inorganic-organic hybrid electrolyte to obtain commercially-acceptable ionic conductivity and a stable electrochemical window to prevent electrolyte decomposition in Li ion batteries. Li3PO4 coated with solidified [Li][EMI][TFSI] ionic liquid is developed as hybrid electrolyte material. The material has high electrochemical stability on a high-voltage cathode and metallic anode, and the solid electrolyte has high ionic conductivity. This Li3PO4-[Li][EMI][TFSI] hybrid electrolyte has the advantages of long-term operation, safety and flexibility, so it may be suitable for use in high-voltage cathodes and Li anode.

  19. Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery

    PubMed Central

    Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li

    2016-01-01

    The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385

  20. Yttria-stabilized zirconia solid oxide electrolyte fuel cells--- monolithic solid oxide fuel cells

    SciTech Connect

    Not Available

    1990-10-01

    The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H{sub 2} or simulated coal gas and air or oxygen. 68 figs., 29 tabs.

  1. Yttria-stabilized zirconia solid oxide electrolyte fuel cells: Monolithic solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    1990-10-01

    The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at: (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H2 or simulated coal gas and air or oxygen.

  2. Separation of gases with solid electrolyte ionic conductors

    SciTech Connect

    Balachandran, U.; Dusek, J.T.; Maiya, P.S.; Mieville, R.L.; Ma, B.; Kleefisch, M.S.; Udovich, C.A.

    1996-11-01

    The authors have developed a novel method of gas separation based on electrolyte ionic membrane technology. Separation of one gas from another occurs through an ion-conducting membrane by the passage of selected ions. Most systems studied have focused on oxygen ion conduction for the separation of oxygen from air, although protonic and halide-conducting solid materials also exist. As an example of this system, this paper concentrates on a study of a membrane reactor used in the production of syngas (CO + H{sub 2}) from methane. The membrane material is a modified perovskite-type oxide exhibiting mixed (electronic/ionic) conductivity. Mixed-conductivity oxides are promising materials for oxygen-permeating membranes that can operate without electrodes or external electrical circuitry. Extruded tubes of this material have been evaluated in a reactor operating at {approx} 850 C for partial oxidation of methane into syngas in the presence of a reforming catalyst. Separated oxygen on one side of the reactor wall was obtained from air on the other side. Methane conversion efficiencies of > 99% were observed, and some of the reactor tubes have been operated for > 1,000 h. Membrane tubes were fabricated from calcined powders by a plastic extrusion technique. Characterization of the mechanical, physical, and chemical properties of this material confirmed the stability exhibited in the reactor.

  3. Investigation of solid state electrolyte silver-zinc battery

    NASA Technical Reports Server (NTRS)

    1970-01-01

    Study of the solid electrolyte ZnCl2-2NH3 rechargeable silver zinc electrochemical cell by X-ray diffraction analysis of the reaction products led to the conclusion that some water is consumed when the cell is discharged. Replacement of ZnCl2-2NH3 by ZnCl2-4Zn(OH)2 gave cells with high internal resistance and limited capacity. The salt formed by exposing a fibrous membrane saturated with ZnCl2 solution to fumes from ammonium carbonate in a dry desiccator comprised ZnCl2-4Zn(OH)2, ZnCl2,3NH4Cl and a third unidentified component. The temperature coefficient of open circuit EMF was nearly zero over the range from -25 C to 50 C. The internal resistance and polarization increased substantially below -25 C. There is some indication that exposure to 50 C for 29 hours causes some deterioration.

  4. Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

    NASA Astrophysics Data System (ADS)

    Isenberg, Arnold O.

    1989-06-01

    The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

  5. Nonlinear ionic transport through microstructured solid electrolytes: homogenization estimates

    NASA Astrophysics Data System (ADS)

    Curto Sillamoni, Ignacio J.; Idiart, Martín I.

    2016-10-01

    We consider the transport of multiple ionic species by diffusion and migration through microstructured solid electrolytes in the presence of strong electric fields. The assumed constitutive relations for the constituent phases follow from convex energy and dissipation potentials which guarantee thermodynamic consistency. The effective response is heuristically deduced from a multi-scale convergence analysis of the relevant field equations. The resulting homogenized response involves an effective dissipation potential per species. Each potential is mathematically akin to that of a standard nonlinear heterogeneous conductor. A ‘linear-comparison’ homogenization technique is then used to generate estimates for these nonlinear potentials in terms of available estimates for corresponding linear conductors. By way of example, use is made of the Maxwell-Garnett and effective-medium linear approximations to generate estimates for two-phase systems with power-law dissipation. Explicit formulas are given for some limiting cases. In the case of threshold-type behavior, the estimates exhibit non-analytical dilute limits and seem to be consistent with fields localized in low energy paths.

  6. Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

    NASA Technical Reports Server (NTRS)

    Isenberg, Arnold O.

    1989-01-01

    The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

  7. PEALD YSZ-based bilayer electrolyte for thin film-solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Yu, Wonjong; Cho, Gu Young; Hong, Soonwook; Lee, Yeageun; Kim, Young Beom; An, Jihwan; Cha, Suk Won

    2016-10-01

    Yttria-stabilized zirconia (YSZ) thin film electrolyte deposited by plasma enhanced atomic layer deposition (PEALD) was investigated. PEALD YSZ-based bi-layered thin film electrolyte was employed for thin film solid oxide fuel cells on nanoporous anodic aluminum oxide substrates, whose electrochemical performance was compared to the cell with sputtered YSZ-based electrolyte. The cell with PEALD YSZ electrolyte showed higher open circuit voltage (OCV) of 1.0 V and peak power density of 182 mW cm-2 at 450 °C compared to the one with sputtered YSZ electrolyte(0.88 V(OCV), 70 mW cm-2(peak power density)). High OCV and high power density of the cell with PEALD YSZ-based electrolyte is due to the reduction in ohmic and activation losses as well as the gas and electrical current tightness.

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

    DOE PAGES

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

    2016-10-31

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

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

    SciTech Connect

    Zhang, Zhizhen; Yang, Xiao -Qing; Zhang, Qinghua; Shi, Jinan; Chu, Yong S.; Yu, Xiqian; Xu, Kaiqi; Ge, Mingyuan; Yan, Hanfei; Li, Wenjun; Gu, Lin; Hu, Yong -Sheng; Li, Hong; Chen, Liquan; Huang, Xuejie

    2016-10-31

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  11. Hybrid Lithium-Sulfur Batteries with a Solid Electrolyte Membrane and Lithium Polysulfide Catholyte.

    PubMed

    Yu, Xingwen; Bi, Zhonghe; Zhao, Feng; Manthiram, Arumugam

    2015-08-05

    Lithium-sulfur (Li-S) batteries are receiving great attention as the most promising next-generation power source with significantly high charge-storage capacity. However, the implementation of Li-S batteries is hampered by a critical challenge because of the soluble nature of the intermediate polysulfide species in the liquid electrolyte. The use of traditional porous separators unavoidably allows the migration of the dissolved polysulfide species from the cathode to the lithium-metal anode and results in continuous loss of capacity. In this study, a LiSICON (lithium super ionic conductor) solid membrane is used as a cation-selective electrolyte for lithium-polysulfide (Li-PS) batteries to suppress the polysulfide diffusion. Ionic conductivity issue at the lithium metal/solid electrolyte interface is successfully addressed by insertion of a "soft", liquid-electrolyte integrated polypropylene interlayer. The solid LiSICON lithium-ion conductor maintains stable ionic conductivity during the electrochemical cycling of the cells. The Li-PS battery system with a hybrid solid/liquid electrolyte exhibits significantly enhanced cyclability relative to the cells with the traditional liquid-electrolyte integrated porous separator.

  12. All-Solid-State Lithium-Ion Batteries with Grafted Ceramic Nanoparticles Dispersed in Solid Polymer Electrolytes.

    PubMed

    Lago, Nerea; Garcia-Calvo, Oihane; Lopez del Amo, Juan Miguel; Rojo, Teofilo; Armand, Michel

    2015-09-21

    Lithium-based rechargeable batteries offer superior specific energy and power, and have enabled exponential growth in industries focused on small electronic devices. However, further increases in energy density, for example for electric transportation, face the challenge of harnessing the lithium metal as negative electrode instead of limited-capacity graphite and its heavy copper current collector. All-solid-state batteries utilize solid polymer electrolytes (SPEs) to overcome the safety issues of liquid electrolytes. We demonstrate an all-solid-state lithium-ion battery by using plasticized poly(ethylene oxide)-based SPEs comprising anions grafted or co-grafted onto ceramic nanoparticles. This new approach using grafted ceramic nanoparticles enables the development of a new generation of nanohybrid polymer electrolytes with high ionic conductivity as well as high electrochemical and mechanical stability, enabling Li-ion batteries with long cycle life.

  13. An all-solid-state lithium-sulfur battery using two solid electrolytes having different functions

    NASA Astrophysics Data System (ADS)

    Nagata, Hiroshi; Chikusa, Yasuo

    2016-10-01

    All-solid-state lithium-sulfur batteries are expected to be valuable next generation batteries. To improve the performance of all-solid-state lithium-sulfur batteries, it is essential to raise both the reactivity of sulfur and the ionic conductivity of the positive composite electrode. For achieving this, we investigate a positive composite electrode prepared using P2S5 and a solid electrolyte with a high ionic conductivity. As a result, we have found that the lithium-sulfur cell exhibits a relatively low activation energy together with high ionic conductivity. The positive composite electrode exhibits an extremely high capacity of 1550 mA h g-1 (sulfur) at 1.3 mA cm-2 and 25 °C. Moreover, when using the positive electrode, the energy densities at the cell level (18650) are 540 W h kg-1 and 990 W h L-1, estimated from the equivalent structure of a current lithium-ion battery.

  14. High temperature lithium cells with solid polymer electrolytes

    DOEpatents

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

    2017-03-07

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

  15. All-solid-state proton battery using gel polymer electrolyte

    SciTech Connect

    Mishra, Kuldeep; Pundir, S. S.; Rai, D. K.

    2014-04-24

    A proton conducting gel polymer electrolyte system; PMMA+NH{sub 4}SCN+EC/PC, has been prepared. The highest ionic conductivity obtained from the system is 2.5 × 10−4 S cm{sup −1}. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO{sub 4}⋅7H{sub 2}O anode and MnO{sub 2} cathode. The open circuit voltage of the battery is 1.4 V and the highest energy density is 5.7 W h kg−1 for low current drain.

  16. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    SciTech Connect

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; Herbert, Erik G.; Dudney, Nancy J.; Wolfenstine, Jeff; Sakamoto, Jeff; Seigel, Donald

    2015-12-16

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. In the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.

  17. Elastic Properties of the Solid Electrolyte Li7La3Zr2O12 (LLZO)

    DOE PAGES

    Yu, Seungho; Schmidt, Robert D.; Garcia-mendez, Regina; ...

    2015-12-16

    The oxide known as LLZO, with nominal composition Li7La3Zr2O12, is a promising solid electrolyte for Li-based batteries due to its high Li-ion conductivity and chemical stability with respect to lithium. Solid electrolytes may also enable the use of metallic Li anodes by serving as a physical barrier that suppresses dendrite initiation and propagation during cycling. Prior linear elasticity models of the Li electrode/solid electrolyte interface suggest that the stability of this interface is highly dependent on the elastic properties of the solid separator. For example, dendritic suppression is predicted to be enhanced as the electrolyte s shear modulus increases. Inmore » the present study a combination of first-principles calculations, acoustic impulse excitation measurements, and nanoindentation experiments are used to determine the elastic constants and moduli for highconductivity LLZO compositions based on Al and Ta doping. The calculated and measured isotropic shear moduli are in good agreement and fall within the range of 56-61 GPa. These values are an order of magnitude larger than that for Li metal and far exceed the minimum value ( 8.5 GPa) believed to be necessary to suppress dendrite initiation. These data suggest that LLZO exhibits sufficient stiffness to warrant additional development as a solid electrolyte for Li batteries.« less

  18. Metallization pattern on solid electrolyte or porous support of sodium battery process

    DOEpatents

    Kim, Jin Yong; Li, Guosheng; Lu, Xiaochuan; Sprenkle, Vincent L.; Lemmon, John P.

    2016-05-31

    A new battery configuration and process are detailed. The battery cell includes a solid electrolyte configured with an engineered metallization layer that distributes sodium across the surface of the electrolyte extending the active area of the cathode in contact with the anode during operation. The metallization layer enhances performance, efficiency, and capacity of sodium batteries at intermediate temperatures at or below about 200.degree. C.

  19. Fabrication of Thin Electrolytes for Second-Generation Solid Oxide Fuel Cells

    DTIC Science & Technology

    1999-05-05

    methods for oxides, especially for stabilized zirconia and compares them with regard to SOFC applications. These methods will be classified into chemical...Keywords: SOFC ; Thin films; Zirconia; PVD; CVD; Liquid precursor methods 1. Introduction components [1-6]. One problem associated with lowering the...electrolyte material for Solid Oxide Fuel lowering the electrolyte resistance either by decreas- Cells ( SOFCs ) because of its unique combination of ing the

  20. Fluoride-based, low temperature solid electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Oh, Seajin; Otagawa, T.; Madou, M.

    Lanthanum fluoride electrolytes were tested to determine whether fluoride electrolytes can be used as fuel cell electrolytes at low temperatures. The planar-type fuel cell were operated in oxygen/hydrogen gases with nickel oxide/nickel as the anode and a perovskite structure oxide (La(0.6)Sr(0.4)CoO3) as the cathode. In order to reduce the fuel cell operating temperature while maintaining the highest possible current, various thin and thick film techniques were assessed. They include e-beam evaporation and dc plasma spray methods. Fuel cells incorporating plasma-sprayed LaF3 films yielded a short-circuit current density on the order of 0.4 mA/sq cm at 450 C, and the current density under an overpotential of 0.2V showed no sign of decay over 17 hours. In the co-ionic (fluoride and oxide ion) conduction mode, the lanthanum fluoride electrolyte based fuel cells could sustain current in oxygen/hydrogen gases.

  1. High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

    PubMed

    Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

    2013-06-21

    Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

  2. Electrolytes

    MedlinePlus

    ... part of blood that doesn't contain cells. Sodium, potassium, and chloride levels can also be measured as part of ... in urine. It test the levels of calcium, chloride, potassium, sodium, and other electrolytes. References Chernecky CC, Berger BJ. ...

  3. 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.

  4. Preparation of Li2S-P2S5 solid electrolyte from N-methylformamide solution and application for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Teragawa, Shingo; Aso, Keigo; Tadanaga, Kiyoharu; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2014-02-01

    Electrode-solid electrolyte composite materials for all-solid-state lithium batteries were prepared by coating of the Li2S-P2S5 solid electrolyte onto LiCoO2 particles using a N-methylformamide (NMF) solution of 80Li2S·20P2S5 (mol%) solid electrolyte. SEM and EDX analysis showed that the Li2S-P2S5 solid electrolyte was uniformly coated on LiCoO2 particles. The all-solid-state cell using the LiCoO2 particles coated with the solid electrolyte showed higher charge-discharge capacity than the cells using uncoated LiCoO2 particles.

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

    PubMed

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

    2014-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  7. Novel Solid Electrolytes for Li-Ion Batteries: A Perspective from Electron Microscopy Studies

    SciTech Connect

    Ma, Cheng; Chi, Miaofang

    2016-06-08

    Solid electrolytes can simultaneously overcome two of the most formidable challenges of Li-ion batteries: the severe safety issues and insufficient energy densities. However, before they can be implemented in actual batteries, the ionic conductivity needs to be improved and the interface with electrodes must be optimized. The prerequisite for addressing these issues is a thorough understanding of the material’s behavior at the microscopic and/or the atomic level. (Scanning) transmission electron microscopy is a powerful tool for this purpose, as it can reach an ultrahigh spatial resolution. Here, we review recent electron microscopy investigations on the ion transport behavior in solid electrolytes and their interfaces. Specifically, three aspects will be highlighted: the influence of grain interior atomic configuration on ionic conductivity, the contribution of grain boundaries, and the behavior of solid electrolyte/electrode interfaces. In conclusion, based on this, the perspectives for future research will be discussed.

  8. Isn't the space-charge potential in ceria-based solid electrolytes largely overestimated?

    PubMed

    Kim, Sangtae

    2016-07-20

    The effective ionic conductivity of polycrystalline solid electrolytes that conduct oxide ions or protons is known to be markedly below those of the corresponding single crystals due to substantial current obstruction across the grain boundary. Numerous studies have previously demonstrated that the ionic charge carriers deplete in the vicinity of the grain boundary to form a potential barrier at the grain boundary, which further impedes the current across the grain boundary. Hence an accurate estimation of the barrier height is essential to acquire a comprehensive and precise mechanistic picture of the ionic current in solid electrolytes. The values of the potential barrier height, i.e. equivalent to the equilibrium space-charge potential with the opposite sign, in prominent solid electrolytes such as ceria solid solutions are available in the literature and were determined exclusively from the ratio of the resistivity of the grain boundary to that of the crystal interior. Here I present the results clearly demonstrating that the resistivity ratio yields considerable overestimation of the barrier height even in relatively diluted solid solutions of ceria. These results imply that the space charge is unlikely the sole origin of the large current obstruction across the grain boundary in ceria-based solid electrolytes.

  9. Screening possible solid electrolytes by calculating the conduction pathways using Bond Valence method

    NASA Astrophysics Data System (ADS)

    Gao, Jian; Chu, Geng; He, Meng; Zhang, Shu; Xiao, RuiJuan; Li, Hong; Chen, LiQuan

    2014-08-01

    Inorganic solid electrolytes have distinguished advantages in terms of safety and stability, and are promising to substitute for conventional organic liquid electrolytes. However, low ionic conductivity of typical candidates is the key problem. As connective diffusion path is the prerequisite for high performance, we screen for possible solid electrolytes from the 2004 International Centre for Diffraction Data (ICDD) database by calculating conduction pathways using Bond Valence (BV) method. There are 109846 inorganic crystals in the 2004 ICDD database, and 5295 of them contain lithium. Except for those with toxic, radioactive, rare, or variable valence elements, 1380 materials are candidates for solid electrolytes. The rationality of the BV method is approved by comparing the existing solid electrolytes' conduction pathways we had calculated with those from experiments or first principle calculations. The implication for doping and substitution, two important ways to improve the conductivity, is also discussed. Among them Li2CO3 is selected for a detailed comparison, and the pathway is reproduced well with that based on the density functional studies. To reveal the correlation between connectivity of pathways and conductivity, α/ γ-LiAlO2 and Li2CO3 are investigated by the impedance spectrum as an example, and many experimental and theoretical studies are in process to indicate the relationship between property and structure. The BV method can calculate one material within a few minutes, providing an efficient way to lock onto targets from abundant data, and to investigate the structure-property relationship systematically.

  10. Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. In situ micro-FTIR study of the solid-solid interface between lithium electrode and polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Cheng, H.; Zhu, C. B.; Lu, M.; Yang, Y.

    In situ micro-FTIR spectroscopy was explored to characterize the solid-solid interface between lithium electrode and polymer electrolytes. The cyclic voltammetric (CV) results indicated that the reduction reactions of oxygen and water as well as the formation of underpotential deposition (UPD) Li occur in the Li/PEO 20-LiN(CF 3SO 2) 2 electrolyte interface in the different potential region. The infrared spectral changes observed during the CV process revealed that there is a direct correlation between the CV peaks and the magnitude of the infrared peaks. It is shown that the infrared reflectivity from the solid-solid interface is very sensitive to the formation of the passive layer on the lithium electrodes. The results obtained from optical micrographs also displayed directly the formation of the passive layer along with lithium deposition and dissolution process. It is correlated well with in situ FTIR and electrochemical experiments.

  12. 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.

  13. Thin Film Electrodes with an Integral Current Collection Grid for Use with Solid Electrolytes

    NASA Technical Reports Server (NTRS)

    Ryan, M. A.; Kisor, A.; Williams, R. M.; Jeffries-Nakamura, B.; O'Connor, D.

    1994-01-01

    Thin film, high performance electrodes which can operate in high temperature environments are necessary for many devices which use a solid electrolyte. Electrodes of rhodium-tungsten alloy have been deposited on solid electrolyte using photolytic chemical vapor deposition (PCVD). A technique for depositing electrodes and current collection grids simultaneously has been developed using the prenucleation characteristics of PCVD. This technique makes it possible to fabricate electrodes which allow vapor transport through the thin (<1 (micro)m) portions of the electrode while integral thick grid lines improve the electronic conductivity of the electrode, thus improving overall performance.

  14. Solvent activities of the fluorinated solid polymer electrolyte/water system in fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Tae Hwan; Bae, Young Chan

    We modified the lattice fluid equation-of-state by the introducing Debye-Hückel equation. A thermodynamic model taking into account the specific interaction and ionic strength between the polymer and the solvent is proposed. The proposed model successfully predicts the vapor/liquid equilibria (VLE) of solvents and the solid polymer electrolyte (SPE). A generalized lattice fluid model is modified to describe the change of water activity in solid polymer electrolyte (SPE)/water systems. The calculated activity curves using the proposed model agree remarkably well with the experimental data.

  15. Electromotive force measurements on cells involving beta-alumina solid electrolyte

    NASA Technical Reports Server (NTRS)

    Choudhury, N.

    1973-01-01

    Open circuit emf measurements have been made to demonstrate that a two-phase, polycrystalline mixture of beta- alumina and alpha-alumina could be used as a solid electrolyte in galvanic cells with reversible electrodes fixing oxygen or aluminum chemical potentials. These measurements indicate that such a two phase solid electrolyte can be used to monitor oxygen chemical potentials as low as that corresponding to Al, Al2O3 coexistence. The activity of Na2O in beta-alumina in coexistence with alpha-alumina was also determined by emf measurements.

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

    PubMed

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

    2012-04-07

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

  17. Rubbery solid electrolytes with dominant cationic transport and high ambient conductivity

    NASA Astrophysics Data System (ADS)

    Angell, C. A.; Liu, C.; Sanchez, E.

    1993-03-01

    EFFORTS to develop a high-voltage, lightweight rechargeable battery for electrically powered vehicles have focused on batteries based on solid electrolytes, which offer good mechanical strength, easy packaging and high energy densities. An important objective is to identify an electrolyte with the desired combination of mechanical properties, electrical conductivity and stability against powerfully oxidizing and reducing electrodes (lithium is preferred for the anode). Among the most promising materials are rubbery 'salt-in-polymer' electrolytes and highly conducting but brittle superionic glass electrolytes. In the latter category are salts with good lithium-ion conductivity, which are compatible with lithium-anode systems. Here we describe new ionic conductors - 'polymer-in-salt' materials - in which lithium salts are mixed with small quantities of the polymers polypropylene oxide and polyethylene oxide. These materials have glass transitions low enough to remain rubbery at room temperature while preserving good lithium-ion conductivities and high electrochemical stability.

  18. Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries.

    PubMed

    Ruzmetov, Dmitry; Oleshko, Vladimir P; Haney, Paul M; Lezec, Henri J; Karki, Khim; Baloch, Kamal H; Agrawal, Amit K; Davydov, Albert V; Krylyuk, Sergiy; Liu, Yang; Huang, Jiany; Tanase, Mihaela; Cumings, John; Talin, A Alec

    2012-01-11

    Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.

  19. [Some aspects of water electrolysis with the use of a solid polymer electrolyte].

    PubMed

    Zorina, N G

    2006-01-01

    Electrochemical process in cells with a solid polymer electrolyte is dependent on catalyst durability in harsh environments and catalyst sputtering technology to ensure efficient power consumption. Active polymer electrolytes will permit to reduce substantially non-productive layouts and design a cost-effective, compact and safe system generator of high-purity oxygen and hydrogen. The existing designs of combined oxide systems integrating rear-earth and earth metals with a structure of Ln3+x Me2+1-x CoO3 containing perofskites were shown to be active catalysts in cells with a solid polymer electrolyte, and the sputtering technology was proven to reduce non-productive layouts in 2 or 2.5 times.

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  1. Novel Solid Electrolytes for Li-Ion Batteries: A Perspective from Electron Microscopy Studies

    DOE PAGES

    Ma, Cheng; Chi, Miaofang

    2016-06-08

    Solid electrolytes can simultaneously overcome two of the most formidable challenges of Li-ion batteries: the severe safety issues and insufficient energy densities. However, before they can be implemented in actual batteries, the ionic conductivity needs to be improved and the interface with electrodes must be optimized. The prerequisite for addressing these issues is a thorough understanding of the material’s behavior at the microscopic and/or the atomic level. (Scanning) transmission electron microscopy is a powerful tool for this purpose, as it can reach an ultrahigh spatial resolution. Here, we review recent electron microscopy investigations on the ion transport behavior in solidmore » electrolytes and their interfaces. Specifically, three aspects will be highlighted: the influence of grain interior atomic configuration on ionic conductivity, the contribution of grain boundaries, and the behavior of solid electrolyte/electrode interfaces. In conclusion, based on this, the perspectives for future research will be discussed.« less

  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. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    SciTech Connect

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lu, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B.

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  4. Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Li, Yutao; Zhou, Weidong; Xin, Sen; Li, Shuai; Zhu, Jinlong; Lü, Xujie; Cui, Zhiming; Jia, Quanxi; Zhou, Jianshi; Zhao, Yusheng; Goodenough, John B

    2016-08-16

    A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles.

  5. Fluorine-doped antiperovskite electrolyte for all-solid-state Lithium-ion batteries

    DOE PAGES

    Li, Yutao; Zhou, Weidong; Xin, Sen; ...

    2016-06-30

    A fluorine-doped antiperovskite Li-ion conducto Li2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li+/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li2OHCl. As a result, an all-solid-state Li/LiFePO4 with F-dope Li2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

  6. Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

    NASA Astrophysics Data System (ADS)

    He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

    2014-03-01

    With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

  7. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    DOE PAGES

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; ...

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces canmore » be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.« less

  8. Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

    SciTech Connect

    Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; Eliseev, Eugene A.; Kalinin, Sergei V.

    2014-10-10

    Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces can be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.

  9. Nano-Sponge Ionic Liquid-Polymer Composite Electrolytes for Solid-State Lithium Power Sources

    DTIC Science & Technology

    2010-01-01

    images of these solid thin films indicate that these polymer gel electrolytes have the structure of nano-sponges, with a sub-micron pore size. For these... thin film batteries, 150 charge–discharge cycles are run for LixCoO2 where x is cycled between 0.95 down to 0.55. Minimal internal resistance effects...9702;C; exhibiting a significant advancement in the safety of lithium batteries. Atomic force microscopy images of these solid thin films indicate

  10. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  11. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  12. Extremely thin bilayer electrolyte for solid oxide fuel cells (SOFCs) fabricated by chemical solution deposition (CSD).

    PubMed

    Oh, Eun-Ok; Whang, Chin-Myung; Lee, Yu-Ri; Park, Sun-Young; Prasad, Dasari Hari; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Lee, Hae-Weon

    2012-07-03

    An extremely thin bilayer electrolyte consisting of yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is successfully fabricated on a sintered NiO-YSZ substrate. Major processing flaws are effectively eliminated by applying local constraints to YSZ nanoparticles, and excellent open circuit voltage and cell performance are demonstrated in a solid oxide fuel cell (SOFC) at intermediate operating temperatures.

  13. Air-Stable, High-Conduction Solid Electrolytes of Arsenic-Substituted Li4SnS4

    SciTech Connect

    Sahu, Gayatri; Lin, Zhan; Li, Juchuan; Liu, Zengcai; Dudney, Nancy J; Liang, Chengdu

    2014-01-01

    Lithium-ion-conducting solid electrolytes show promise for enabling high-energy secondary battery chemistries and solving safety issues associated with conventional lithium batteries. Achieving the combination of high ionic conductivity and outstanding chemical stability in solid electrolytes is a grand challenge for the synthesis of solid electrolytes. Herein we report the design of aliovalent substitution of Li4SnS4 to achieve high conduction and excellent air stability based on the hard and soft acids and bases theory. The composition of Li3.833Sn0.833As 0.166S4 has a high ionic conductivity of 1.39 mS/cm 1 at 25 C. Considering the high Li+ transference number, this phase conducts Li+ as well as carbonate-based liquid electrolytes. This research also addresses the compatibility of the sulfide-based solid electrolytes through chemical passivation.

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

    SciTech Connect

    Parthasarathy, Meera; Pillai, Vijayamohanan K. Mulla, Imtiaz S.; Shabab, Mohammed; Khan, M.I.

    2007-12-07

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

  15. Report Information for Project 2: Solid Organic Electrolytes

    DTIC Science & Technology

    2013-01-01

    C.M. Sulyma, C. Goia, D.Goia, D. Roy, “Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion...manganate spinel for rapid-charge cathodes of lithium ion batteries, J. Solid State Electrochem. 16 (2012) 2605- 2615. 8. J.P. Zheng, D.J. Crain and D. Roy

  16. Mesoscopic Framework Enables Facile Ionic Transport in Solid Electrolytes for Li Batteries

    SciTech Connect

    Ma, Cheng; Cheng, Yongqiang; Chen, Kai; Li, Juchuan; Sumpter, Bobby G.; Nan, Ce-Wen; More, Karren L.; Dudney, Nancy J.; Chi, Miaofang

    2016-03-29

    In Li-ion-conducting solid electrolytes can simultaneously overcome two grand challenges for Li-ion batteries: the severe safety concerns that limit the large-scale application and the poor electrolyte stability that forbids the use of high-voltage cathodes. Nevertheless, the ionic conductivity of solid electrolytes is typically low, compromising the battery performances. Precisely determining the ionic transport mechanism(s) is a prerequisite for the rational design of highly conductive solid electrolytes. For decades, the research on this subject has primarily focused on the atomic and microscopic scales, where the main features of interest are unit cells and microstructures, respectively. We show that the largely overlooked mesoscopic scale lying between these extremes could be the key to fast ionic conduction. In a prototype system, (Li0.33La0.56)TiO3, a mesoscopic framework is revealed for the first time by state-of-the-art scanning transmission electron microscopy. Corroborated by theoretical calculations and impedance measurements, it is demonstrated that such a unique configuration maximizes the number of percolation directions and thus most effectively improves the ionic conductivity. Finally, this discovery reconciles the long-standing structure–property inconsistency in (Li0.33La0.56)TiO3 and also identifies mesoscopic ordering as a promising general strategy for optimizing Li+ conduction.

  17. Mesoscopic Framework Enables Facile Ionic Transport in Solid Electrolytes for Li Batteries

    DOE PAGES

    Ma, Cheng; Cheng, Yongqiang; Chen, Kai; ...

    2016-03-29

    In Li-ion-conducting solid electrolytes can simultaneously overcome two grand challenges for Li-ion batteries: the severe safety concerns that limit the large-scale application and the poor electrolyte stability that forbids the use of high-voltage cathodes. Nevertheless, the ionic conductivity of solid electrolytes is typically low, compromising the battery performances. Precisely determining the ionic transport mechanism(s) is a prerequisite for the rational design of highly conductive solid electrolytes. For decades, the research on this subject has primarily focused on the atomic and microscopic scales, where the main features of interest are unit cells and microstructures, respectively. We show that the largely overlookedmore » mesoscopic scale lying between these extremes could be the key to fast ionic conduction. In a prototype system, (Li0.33La0.56)TiO3, a mesoscopic framework is revealed for the first time by state-of-the-art scanning transmission electron microscopy. Corroborated by theoretical calculations and impedance measurements, it is demonstrated that such a unique configuration maximizes the number of percolation directions and thus most effectively improves the ionic conductivity. Finally, this discovery reconciles the long-standing structure–property inconsistency in (Li0.33La0.56)TiO3 and also identifies mesoscopic ordering as a promising general strategy for optimizing Li+ conduction.« less

  18. Photocured PEO-based solid polymer electrolyte and its application to lithium-polymer batteries

    NASA Astrophysics Data System (ADS)

    Kang, Yongku; Kim, Hee Jung; Kim, Eunkyoung; Oh, Bookeun; Cho, Jae Hyun

    A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10 -4 S cm -1 at 30°C. These electrolytes display oxidation stability up to 4.5 V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn 2O 4 as well as C(Li)/SPE/LiCoO 2 cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium-polymer batteries.

  19. Current limit diagrams for dendrite formation in solid-state electrolytes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Raj, R.; Wolfenstine, J.

    2017-03-01

    We build upon the concept that nucleation of lithium dendrites at the lithium anode-solid state electrolyte interface is instigated by the higher resistance of grain boundaries that raises the local electro-chemical potential of lithium, near the lithium-electrode. This excess electro-chemo-mechanical potential, however, is reduced by the mechanical back stress generated when the dendrite is formed within the electrolyte. These parameters are coalesced into an analytical model that prescribes a specific criterion for dendrite formation. The results are presented in the form of current limit diagrams that show the "safe" and "fail" regimes for battery function. A higher conductivity of the electrolyte can reduce dendrite formation.

  20. Novel approaches for fabrication of thin film layers for solid oxide electrolyte fuel cells

    NASA Technical Reports Server (NTRS)

    Murugesamoorthi, K. A.; Srinivasan, S.; Cocke, D. L.; Appleby, A. J.

    1990-01-01

    The main objectives of the SOFC (solid oxide fuel cell) project are to (1) identify viable and cost-effective techniques to prepare cell components for stable MSOFCs (monolithic SOFCs); (2) fabricate half and single cells; and (3) evaluate their performances. The approach used to fabricate stable MSOFCs is as follows: (1) the electrolyte layer is prepared in the form of a honeycomb structure by alloy oxidation and other cell components are deposited on it; (2) the electrolyte and anode layers are deposited on the cathode layer, which has a porous, honeycomb structure; and (3) the electrolyte and cathode layers are deposited on the anode layer. The current status of the project is reported.

  1. Interface wave propagation and edge conversion at a low stiffness interphase layer between two solids: A numerical study.

    PubMed

    Cho, Hideo; Rokhlin, Stanislav I

    2015-09-01

    The Rayleigh-to-interface wave conversion and the propagation of the resulting symmetric and antisymmetric modes on a bonded interface between solids is analyzed by the two dimensional finite difference time domain method. The propagated patterns were visualized to improve understanding of the phenomena. It is found that the partition of the energy of the interface waves above and below the interface changes repeatedly with propagation distance due to interference between the two modes which have slightly different phase velocities. The destructive interference of those two modes results in dips in the amplitude spectrum of the interface waves, which shift in frequency with propagation distance. The Rayleigh wave received that is created by the interface wave at the exit corner of the joint also shows interference dips in its spectrum. Those dips depend on the interface properties and can potentially be used for interface characterization. Conversion factors related to the interface wave at the upward and downward corners are determined and discussed. As a result, the total transition factor through the upward and downward corners for the interface wave was estimated as 0.37 and would be sufficiently large to probe the interface by coupling from the Rayleigh to the interface wave.

  2. An all-solid-state lithium ion battery electrolyte membrane fabricated by hot-pressing method

    NASA Astrophysics Data System (ADS)

    Han, Pengfei; Zhu, Yuewu; Liu, Jin

    2015-06-01

    A cross-linked polymer electrolyte membrane (SPE) was fabricated by a solvent-free hot-pressing method for all-solid-state lithium ion battery. The ionic conductivity of the electrolyte is 1.34 × 10-3 S cm-1 and the decomposition potential is 4.87 V at the ethylene oxide (EO):LiN(SO2CF3)2 (LiTFSI) molar ratio of 20:1 and 120 °C. TG-DSC results show that the SPE is thermally stable up to 230 °C in argon atmosphere. The assembled LiFePO4/SPE/Li all-solid-state battery can stably work in the temperature range of 80-140 °C. At 120 °C, the initial discharge capacity of the battery is 156.7 mAh g-1 at 1C which is close to the theoretical capacity of the cathode material, showing that the solvent-free filming method is low-cost and environment-friendly for solid polymer electrolyte and all-solid-state lithium ion battery.

  3. Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction.

    PubMed

    Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis; Chang, Hao-Hsun; Pour, Nir; Lux, Simon F; Paschos, Odysseas; Maglia, Filippo; Lupart, Saskia; Lamp, Peter; Giordano, Livia; Shao-Horn, Yang

    2016-01-13

    This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochemical energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the conductivity through interfacial effects-specifically controlling grain boundaries and strain at the interfaces-is introduced. High-frequency dielectric constants and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Experimental studies and theoretical results are discussed in parallel to give a pathway for further improvement of solid-state electrolytes. Through this discussion, the present Review aims to provide insight into the physical parameters affecting the diffusion process, to allow for more efficient and target-oriented research on improving solid-state ion conductors.

  4. Solid Electrolyte/Electrode Interfaces: Atomistic Behavior Analyzed Via UHV-AFM, Surface Spectroscopies, and Computer Simulations Computational and Experimental Studies of the Cathode/Electrolyte Interface in Oxide Thin Film Batteries

    SciTech Connect

    Garofalini, Stephen H

    2012-03-21

    The goals of the research were to understand the structural, dynamic, and chemical properties of solid electrolyte surfaces and the cathode/electrolyte interface at an atomistic and nanometer level using both computational and experimental techniques.

  5. Hierarchically oriented macroporous anode-supported solid oxide fuel cell with thin ceria electrolyte film.

    PubMed

    Chen, Yu; Zhang, Yanxiang; Baker, Jeffrey; Majumdar, Prasun; Yang, Zhibin; Han, Minfang; Chen, Fanglin

    2014-04-09

    Application of anode-supported solid oxide fuel cell (SOFC) with ceria based electrolyte has often been limited by high cost of electrolyte film fabrication and high electrode polarization. In this study, dense Gd0.1Ce0.9O2 (GDC) thin film electrolytes have been fabricated on hierarchically oriented macroporous NiO-GDC anodes by a combination of freeze-drying tape-casting of the NiO-GDC anode, drop-coating GDC slurry on NiO-GDC anode, and co-firing the electrolyte/anode bilayers. Using 3D X-ray microscopy and subsequent analysis, it has been determined that the NiO-GDC anode substrates have a porosity of around 42% and channel size from around 10 μm at the electrolyte side to around 20 μm at the other side of the NiO-GDC (away from the electrolyte), indicating a hierarchically oriented macroporous NiO-GDC microstructure. Such NiO-GDC microstructure shows a tortuosity factor of ∼1.3 along the thickness direction, expecting to facilitate gas diffusion in the anode during fuel cell operation. SOFCs with such Ni-GDC anode, GDC film (30 μm) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3-GDC (LSCF-GDC) cathode show significantly enhanced cell power output of 1.021 W cm(-2) at 600 °C using H2 as fuel and ambient air as oxidant. Electrochemical Impedance Spectroscopy (EIS) analysis indicates a decrease in both activation and concentration polarizations. This study has demonstrated that freeze-drying tape-casting is a very promising approach to fabricate hierarchically oriented porous substrate for SOFC and other applications.

  6. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    PubMed Central

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

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic −EO− based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm−1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions. PMID:26791572

  7. Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells.

    PubMed

    Volkov, Sergey; Vonk, Vedran; Khorshidi, Navid; Franz, Dirk; Kubicek, Markus; Kilic, Volkan; Felici, Roberto; Huber, Tobias M; Navickas, Edvinas; Rupp, Ghislain M; Fleig, Jürgen; Stierle, Andreas

    2016-06-14

    We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % yttria-stabilized zirconia (YSZ) single crystal electrolyte below a La0.6Sr0.4CoO3-δ (LSC) electrode. We observe yttrium segregation toward the YSZ/LSC electrolyte/electrode interface under reducing conditions. Under oxidizing conditions, the interface becomes Y depleted. The yttrium segregation is corroborated by an enhanced outward relaxation of the YSZ interfacial metal ion layer. At the same time, an increase in point defect concentration in the electrolyte at the interface was observed, as evidenced by reduced YSZ crystallographic site occupancies for the cations as well as the oxygen ions. Such changes in composition are expected to strongly influence the oxygen ion transport through this interface which plays an important role for the performance of solid oxide fuel cells. The structure of the interface is compared to the bare YSZ(100) surface structure near the microelectrode under identical conditions and to the structure of the YSZ(100) surface prepared under ultrahigh vacuum conditions.

  8. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    Here we demonstrate that by regulating the mobility of classic ‑EO‑ based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm‑1 are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li+), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

  9. Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells

    PubMed Central

    2016-01-01

    We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % yttria-stabilized zirconia (YSZ) single crystal electrolyte below a La0.6Sr0.4CoO3−δ (LSC) electrode. We observe yttrium segregation toward the YSZ/LSC electrolyte/electrode interface under reducing conditions. Under oxidizing conditions, the interface becomes Y depleted. The yttrium segregation is corroborated by an enhanced outward relaxation of the YSZ interfacial metal ion layer. At the same time, an increase in point defect concentration in the electrolyte at the interface was observed, as evidenced by reduced YSZ crystallographic site occupancies for the cations as well as the oxygen ions. Such changes in composition are expected to strongly influence the oxygen ion transport through this interface which plays an important role for the performance of solid oxide fuel cells. The structure of the interface is compared to the bare YSZ(100) surface structure near the microelectrode under identical conditions and to the structure of the YSZ(100) surface prepared under ultrahigh vacuum conditions. PMID:27346923

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

    NASA Astrophysics Data System (ADS)

    Li, Qin; Ardebili, Haleh

    2016-01-01

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

  11. Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries.

    PubMed

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

    2016-01-21

    Here we demonstrate that by regulating the mobility of classic -EO- based backbones, an innovative polymer electrolyte system can be architectured. This polymer electrolyte allows the construction of all solid lithium-based polymer cells having outstanding cycling behaviour in terms of rate capability and stability over a wide range of operating temperatures. Polymer electrolytes are obtained by UV-induced (co)polymerization, which promotes an effective interlinking between the polyethylene oxide (PEO) chains plasticized by tetraglyme at various lithium salt concentrations. The polymer networks exhibit sterling mechanical robustness, high flexibility, homogeneous and highly amorphous characteristics. Ambient temperature ionic conductivity values exceeding 0.1 mS cm(-1) are obtained, along with a wide electrochemical stability window (>5 V vs. Li/Li(+)), excellent lithium ion transference number (>0.6) as well as interfacial stability. Moreover, the efficacious resistance to lithium dendrite nucleation and growth postulates the implementation of these polymer electrolytes in next generation of all-solid Li-metal batteries working at ambient conditions.

  12. Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

    SciTech Connect

    Raza, Rizwan; Ahmed, Akhlaq; Akram, Nadeem; Saleem, Muhammad; Niaz Akhtar, Majid; Ajmal Khan, M.; Abbas, Ghazanfar; Alvi, Farah; Yasir Rafique, M.; Sherazi, Tauqir A.; Shakir, Imran; Mohsin, Munazza; Javed, Muhammad Sufyan; Zhu, Bin E-mail: zhubin@hubu.edu.cn

    2015-11-02

    In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O{sup −2} (oxygen ions) and H{sup +} (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport number of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm{sup 2}, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.

  13. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2002-03-31

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible hydrocarbons, CO, or NO{sub x} and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at low to intermediate temperatures tremendous benefits may be accrued. At low temperatures, in particular, it becomes feasible to use ferritic steel for interconnects instead of expensive and brittle ceramic materials such as those based on LaCrO{sub 3}. In addition, sealing the fuel cell becomes easier and more reliable; rapid startup is facilitated; thermal stresses (e.g., those caused by thermal expansion mismatches) are reduced; radiative losses ({approx}T{sup 4}) become minimal; electrode sintering becomes negligible and (due to a smaller thermodynamic penalty) the SOFC operating cycle (heating from ambient) would be more efficient. Combined, all these improvements further result in reduced initial and operating costs. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research is to develop a stable high conductivity (> 0.05 S cm{sup -1} at {le} 550 C) electrolyte for lower

  14. A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries.

    PubMed

    Zhai, Haowei; Xu, Pengyu; Ning, Mingqiang; Cheng, Qian; Mandal, Jyotirmoy; Yang, Yuan

    2017-04-14

    Replacing flammable organic liquid electrolytes with solid Li-ion conductors is a promising approach to realize safe rechargeable batteries with high energy density. Composite solid electrolytes, which are comprised of a polymer matrix with ceramic Li-ion conductors dispersed inside, are attractive, since they combine the flexibility of polymer electrolytes and high ionic conductivities of ceramic electrolytes. However, the high conductivity of ceramic fillers is largely compromised by the low conductivity of the matrix, especially when nanoparticles (NPs) are used. Therefore, optimizations of the geometry of ceramic fillers are critical to further enhance the conductivity of composite electrolytes. Here we report the vertically aligned and connected Li1+xAlxTi2-x(PO4)3 (LATP) NPs in the polyethylene oxide (PEO) matrix to maximize the ionic conduction, while maintaining the flexibility of the composite. This vertically aligned structure can be fabricated by an ice-templating-based method, and its conductivity reaches 0.52 × 10^-4 S/cm, which is 3.6 times that of the composite electrolyte with randomly dispersed LATP NPs. The composite electrolyte also shows enhanced thermal and electrochemical stability compared to the pure PEO electrolyte. This method opens a new approach to optimize ion conduction in composite solid electrolytes for next-generation rechargeable batteries.

  15. A solid dielectric gated graphene nanosensor in electrolyte solutions.

    PubMed

    Zhu, Yibo; Wang, Cheng; Petrone, Nicholas; Yu, Jaeeun; Nuckolls, Colin; Hone, James; Lin, Qiao

    2015-03-23

    This letter presents a graphene field effect transistor (GFET) nanosensor that, with a solid gate provided by a high-κ dielectric, allows analyte detection in liquid media at low gate voltages. The gate is embedded within the sensor and thus is isolated from a sample solution, offering a high level of integration and miniaturization and eliminating errors caused by the liquid disturbance, desirable for both in vitro and in vivo applications. We demonstrate that the GFET nanosensor can be used to measure pH changes in a range of 5.3-9.3. Based on the experimental observations and quantitative analysis, the charging of an electrical double layer capacitor is found to be the major mechanism of pH sensing.

  16. Effective solid electrolyte based on benzothiazolium for dye-sensitized solar cells.

    PubMed

    Han, Lu; Wang, Ye Feng; Zeng, Jing Hui

    2014-12-24

    Thiaozole/benzothiaozole-based dicationic conductors were synthesized and applied as solid-state electrolyte in dye-sensitized solar cells (DSSCs). X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, steady-state voltammogram, photocurrent intensity-photovoltage test, and electrochemical impedance spectroscopy are used to characterize the materials and the mechanism of the cell performance. Compared to the traditional monocationic crystals, the dicationic crystals have a larger size and can provide more opportunities to fine-tune their physical/chemical properties. As a consequence, this solid-state electrolyte-based DSSC achieved photoelectric conversion efficiency of 7.90% under full air-mass (AM 1.5) sunlight (100 mW·cm(-2)).

  17. Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

  18. Solid electrolytes for use in lead-bismuth eutectic cooled nuclear reactors

    NASA Astrophysics Data System (ADS)

    Mariën, A.; Lim, J.; Rosseel, K.; Vandermeulen, W.; Van den Bosch, J.

    2012-08-01

    The operating temperature of electrochemical oxygen sensors can likely be lowered by reducing the solid electrolyte resistance. Most often, these sensors use yttria partially stabilized zirconia (e.g. (Y2O3)0.05(ZrO2)0.95, (5-YSZ)) as solid electrolyte. In this paper, we discuss the use of better conducting ceramics than yttria partially stabilized zirconia, as solid electrolytes for oxygen sensors that can be applied in lead-bismuth eutectic (LBE) cooled nuclear reactors. Two stabilized zirconia ceramics ((Y2O3)0.08(ZrO2)0.92, (8-YSZ); (Sc2O3)0.1(CeO2)0.01(ZrO2)0.89) are investigated as well as a hypostoichiometric perovskite-type La0.8Sr0.2Ga0.8Mg0.2O3-δ. The results of microstructural analyses, thermochemical stability tests in LBE (at 360 °C), as well as mechanical tests and four-probe d.c. conductivity measurements (at 300-800 °C) are discussed and compared with the results that were obtained for a commercially available 5-YSZ (Friatec AG, Germany). Of the three studied ceramics, 8-YSZ was identified as the most promising solid electrolyte to reduce the operating temperature of electrochemical oxygen sensors. http://www.friatec.de/content/friatec/en/Ceramics/FRIALIT-DEGUSSIT-Oxide-Ceramics/downloads/Materials.pdf (this URL was last accessed on February 7th, 2012).

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

    DOE PAGES

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

    2015-11-02

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

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

    SciTech Connect

    Zhang, Pengfei; Li, Mingtao; Jiang, Xueguang; Fang, Youxing; Veith, Gabriel M.; Sun, Xiao-Guang; Dai, Sheng

    2015-11-02

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

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

    NASA Technical Reports Server (NTRS)

    1975-01-01

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

  2. Superionic solid-state polymer electrolyte membrane for high temperature applications

    NASA Astrophysics Data System (ADS)

    Kyu, Thein; He, Ruixuan; Cao, Jinwei

    2015-03-01

    Completely amorphous, flexible, solid-state polymer electrolyte membranes (ss-PEM) consisted of polyethylene glycol diacrylate /succinonitrile plasticizer (SCN)/lithium trifluorosulfonyl imide were fabricated via UV polymerization. The room temperature ionic conductivity of our ss-PEM is extremely high (i.e., 10-3S/cm), which is already in the superionic conductor range of inorganic and/or liquid electrolyte counterparts. Of particular interest is that our ss-PEM is thermally stable up to 140°C, which is superior to the liquid electrolyte counterpart that degrades above 80°C. The ss-PEM exhibits cyclic stability in both LiFePO4/Li and Li4Ti5O12 /Li half-cells up to 50 cycles tested. The trend of conductivity enhancement with temperature is reproducible in the repeated cycles, showing melting transitions of the SCN plastic crystals. In the compositions close to the solid (SCN plastic crystal)-liquid coexistence line, polymerization-induced crystallization occurs during photo-curing. The effect of solid-liquid segregation on ionic conductivity behavior is discussed. Supported by NSF-DMR 1161070.

  3. Modifying zirconia solid electrolyte surface property to enhance oxide transport

    SciTech Connect

    Liaw, B.Y.; Song, S.Y.

    1996-12-31

    Bismuth-strontium-calcium-copper oxide (Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, BSCCO) is known for its high T{sub c} superconducting behavior and mixed conducting property. The applicability of similar high T{sub c} cuprates for intermediate-temperature solid oxide fuel cell (SOFC) application has been studied recently. We investigated the electrochemical behavior of several Ag{vert_bar}BSCCO{vert_bar}10 mol% yttria-stabilized zirconia (YSZ){vert_bar}Ag and Ag{vert_bar}YSZ{vert_bar}Ag cells using complex impedance spectroscopy. A highly uniform and porous microstructure was observed at the interface of the YSZ and BSCCO. The ionic conductivity determined from the Nyquest plots in the temperature range of 200-700{degrees}C agrees with the values reported in the literature. The specific resistance of the BSCCO{vert_bar}YSZ interface was also determined to be lower than those of the conventional manganite electrode, suggesting that BSCCO seems attractive for cathode applications in SOFC.

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

    SciTech Connect

    Bi, Sheng; Sun, Che-Nan; Zawodzinski, Thomas A.; Ren, Fei; Keum, Jong Kahk; Ahn, Suk-Kyun; Li, Dawen; Chen, Jihua

    2015-08-06

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

  5. 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.

  6. Strength and Fracture Toughness of Solid Oxide Fuel Cell Electrolyte Material Improved

    NASA Technical Reports Server (NTRS)

    Bansal, Narottam P.; Choi, Sung R.

    2002-01-01

    Solid oxide fuel cells (SOFC) are being developed for various applications in the automobile, power-generation, and aeronautics industries. Recently, the NASA Glenn Research Center has been exploring the possibility of using SOFC's for aeropropulsion under its Zero Carbon Dioxide Emission Technology (ZCET) Program. 10-mol% yttriastabilized zirconia (10YSZ) is a very good anionic conductor at high temperatures and is, therefore, used as an oxygen solid electrolyte in SOFC. However, it has a high thermal expansion coefficient, low thermal shock resistance, low fracture toughness, and poor mechanical strength. For aeronautic applications, the thin ceramic electrolyte membrane of the SOFC needs to be strong and tough. Therefore, we have been investigating the possibility of enhancing the strength and fracture toughness of the 10YSZ electrolyte without degrading its electrical conductivity to an appreciable extent. We recently demonstrated that the addition of alumina to zirconia electrolyte increases its strength as well as its fracture toughness. Zirconia-alumina composites containing 0 to 30 mol% of alumina were fabricated by hot pressing. The hot pressing procedure was developed and various hot pressing parameters were optimized, resulting in dense, crackfree panels of composite materials. Cubic zirconia and a-alumina were the only phases detected, indicating that there was no chemical reaction between the constituents during hot pressing at elevated temperatures. Flexure strength sf and fracture toughness K(sub IC) of the various zirconia-alumina composites were measured at room temperature as well as at 1000 C in air. Both properties showed systematic improvement with increased alumina addition at room temperature and at 1000 C. Use of these modified electrolytes with improved strength and fracture toughness should prolong the life and enhance the performance of SOFC in aeronautics and other applications.

  7. Nanocrystalline porous TiO2 electrode with ionic liquid impregnated solid polymer electrolyte for dye sensitized solar cells.

    PubMed

    Singh, Pramod K; Kim, Kang-Wook; Kim, Ki-Il; Park, Nam-Gyu; Rhee, Hee-Woo

    2008-10-01

    This communication reports the detailed fabrication of electrodes and solid polymer electrolyte with ionic liquid (IL) as an electrolyte for dye sensitized solar cell (DSSC). Thick porous TiO2 film has been obtained by spreading and sintering TiO2 colloidal paste using "doctor blade" and characterized by SEM, TEM and XRD. The polymer electrolyte was PEO:KI/I2 incorporated with 1-ethyl 3-methylimidazolium thiocyanate (EMImSCN) as IL. Dispersal of IL in the polymer electrolyte improved the ionic conductivity and cell efficiency.

  8. Germanium sulfide-based solid electrolytes for non-volatile memory

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Muralikrishnan

    Programmable Metallization Cell (PMC) technology involves the storage of data as reduced metal ions in a solid electrolyte. Earlier work on Selenide-based (Ag-Ge-Se) PMC devices requires relatively low back-end-of-line processing (BEOL) since the electrolyte may undergo undesirable changes at process temperatures in excess of 200°C. This dissertation is focused on Sulfide-based (Ag/Cu-Ge-S) solid electrolytes which have better temperature stability and the PMC technology based on these materials is compatible with most BEOL process in CMOS Integrated Circuits. The devices fabricated using Ag-Ge-S and Cu-Ge-S solid electrolytes were tested after annealing at 300°C and 430°C. Extensive material analysis was performed on both the systems in an effort to understand the behavior of the devices at elevated temperatures. Electrical characterization testing involved standard memory characterization techniques such as quasi-static measurements tests, retention tests, speed tests, elevated temperature operation tests and endurance tests. The Ag-Ge-S PMC devices were made with different compositions to find out the optimum composition which would ensure reliable operation even after the high temperature anneal. The Sulfide-based PMC devices were also tested for reconfigurable logic applications with special test structures that would demonstrate the low resistance connections that can be achieved by programming the PMC elements using higher currents. Optimum composition of the starting glass was found from the material and data analysis, to ensure reliable operation of the Sulfide-based PMC devices with no degradation in the electrical characteristics even after the typical BEOL anneal.

  9. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2001-09-30

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible hydrocarbons, CO, or NO{sub x} and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at low to intermediate1 temperatures tremendous benefits may be accrued. At low temperatures, in particular, it becomes feasible to use ferritic steel for interconnects instead of expensive and brittle ceramic materials such as those based on LaCrO{sub 3}. In addition, sealing the fuel cell becomes easier and more reliable; rapid start-up is facilitated; thermal stresses (e.g., those caused by thermal expansion mismatches) are reduced; radiative losses ({approx}T{sup 4}) become minimal; electrode sintering becomes negligible and (due to a smaller thermodynamic penalty) the SOFC operating cycle (heating from ambient) would be more efficient. Combined, all these improvements further result in reduced initial and operating costs. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research are to develop a stable high conductivity (> 0.05 S cm{sup -1} at {le} 550 C) electrolyte for lower

  10. Single- and double-ion type cross-linked polysiloxane solid electrolytes for lithium cells

    NASA Astrophysics Data System (ADS)

    Tsutsumi, Hiromori; Yamamoto, Masahiro; Morita, Masayuki; Matsuda, Yoshiharu; Nakamura, Takashi; Asai, Hiroyuki

    Polymeric solid electrolytes, that have poly(dimethylsiloxane) (PMS) backbone and cross-linked network, were applied to a rechargeable lithium battery system. Single- (PMS-Li) and double-ion type (PMS-LiClO 4) electrolytes were prepared from the same prepolymers. Lithium electrode in the both electrolytes showed reversible stripping and deposition of lithium. Intercalation and deintercalation processes of lithium ion between lithium-manganese composite oxide (Li xMnO 2) electrode and the electrolytes were also confirmed by cyclic voltammetry, however, peak current decreased with several cycles in both cases. The model cell, Li/PMS-Li/Li xMnO 2 cell had 1.4 mA h g -1 (per 1 g of active material, current density: 3.77 μA cm -2), and the Li/PMS-LiClO 4/Li xMnO 2 cell had 1.6 mA h g -1 (current density: 75.3 μA cm -2).

  11. Conductivity and electrical studies of plasticized carboxymethyl cellulose based proton conducting solid biopolymer electrolytes

    NASA Astrophysics Data System (ADS)

    Isa, M. I. N.; Noor, N. A. M.

    2015-12-01

    In this paper, a proton conducting solid biopolymer electrolytes (SBE) comprises of carboxymethyl cellulose (CMC) as polymer host, ammonium thiocyanate (NH4SCN) as doping salt and ethylene carbonate (EC) as plasticizer has been prepared via solution casting technique. Electrical Impedance Spectroscopy (EIS) was carried out to study the conductivity and electrical properties of plasticized CMC-NH4SCN SBE system over a wide range of frequency between 50 Hz and 1 MHz at temperature range of 303 to 353 K. Upon addition of plasticizer into CMC-NH4SCN SBE system, the conductivity increased from 10-5 to 10-2 Scm-1. The highest conductivity was obtained by the electrolyte containing 10 wt.% of EC. The conductivity of plasticized CMC-NH4SCN SBE system by various temperatures obeyed Arrhenius law where the ionic conductivity increased as the temperature increased. The activation energy, Ea was found to decrease with enhancement of EC concentration. Dielectric studies for the highest conductivity electrolyte obeyed non-Debye behavior. The conduction mechanism for the highest conductivity electrolyte was determined by employing Jonsher's universal power law and thus, can be represented by the quantum mechanical tunneling (QMT) model.

  12. State-of-the-art Thin Film Electrolytes For Solid Oxide Fuel Cells

    SciTech Connect

    Thevuthasan, Suntharampillai; Nandasiri, Manjula I.

    2015-02-19

    State-of-the-Art solid oxide fuel cells (SOFC) are amongst the main candidates for clean energy technology due to their high efficiency, fuel flexibility, low air pollution, and minimal greenhouse gas emission. However, high operational temperature of SOFC is a greater challenge in commercialization these devices for low cost and portable applications. High temperature operation of SOFC degrades its performance with aging, limits the selection of materials for fuel cell components, and increases the fabrication cost. Thus, there have been enormous efforts to improve the properties of existing materials and develop new materials for SOFC components in order to lower the operating temperature of SOFC. Recent advances in thin film technology have also been utilized to develop new materials with improved properties for SOFC. One of the key components in SOFC is the electrolyte and several research groups are working on developing new electrolyte materials. In this chapter, we will discuss the recent advances in thin film SOFC electrolytes. This extensive discussion includes the evolution of doped ceria, doped zirconia, and multilayer hetero-structured thin film electrolytes. The newly developed nanoscale thin films and multi-layer hetero-structures with improved oxygen ionic conductivity will have significant impact on SOFC devices.

  13. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    DOE PAGES

    Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achievemore » ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

  14. High-performance flexible all-solid-state microbatteries based on solid electrolyte of lithium boron oxynitride

    NASA Astrophysics Data System (ADS)

    Song, Seung-Wan; Lee, Ki-Chang; Park, Ho-Young

    2016-10-01

    Rapidly growing interest and demand for wearable electronics require the development of flexible and lightweight all-solid-state batteries as power sources that guarantee high performance and safety with the absence of the risk of fire or explosion that can occur with traditional liquid electrolyte systems. Herein, we successfully fabricate new flexible all-solid-state microbatteries integrating a solid electrolyte film of lithium boron oxynitride (LiBON) on a flexible substrate using sophisticated thin-film fabrication technology. The new microbattery of Li/LiBON/LiCoO2 exhibits excellent mechanical integrity even under severe bending and twisting test conditions, enabling the realization of flexible microbatteries. The microbatteries demonstrate superior electrochemical cycling stability relative to conventional batteries, delivering an outstanding capacity retention of 90% on the 1000th cycle. Furthermore, operation at various temperatures from -10 °C to +60 °C and fast charging within 3-6 min are achieved. With various types of flexible substrates, the microbatteries can provide diverse opportunities for flexible and wearable electronics.

  15. Enhancement of Li+ ion conductivity in solid polymer electrolytes using surface tailored porous silica nanofillers

    NASA Astrophysics Data System (ADS)

    Mohanta, Jagdeep; Singh, Udai P.; Panda, Subhendu K.; Si, Satyabrata

    2016-09-01

    The current study represents the design and synthesis of polyethylene oxide (PEO)-based solid polymer electrolytes by solvent casting approach using surface tailored porous silica as nanofillers. The surface tailoring of porous silica nanostructure is achieved through silanization chemistry using 3-glycidyloxypropyl trimethoxysilane in which silane part get anchored to the silica surface whereas epoxy group get stellated from the silica surface. Surface tailoring of silica with epoxy group increases the room temperature electrochemical performances of the resulting polymer electrolytes. Ammonical hydrolysis of organosilicate precursor is used for both silica preparation and their surface tailoring. The composite solid polymer electrolyte films are prepared by solution mixing of PEO with lithium salt in presence of silica nanofillers and cast into film by solvent drying, which are then characterized by impedance measurement for conductivity study and wide angle x-ray diffraction for change in polymer crystallinity. Room temperature impedance measurement reveals Li+ ion conductivity in the order of 10-4 S cm-1, which is correlated to the decrease in PEO crystallinity. The enhancement of conductivity is further observed to be dependent on the amount of silica as well as on their surface characteristics.

  16. Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane

    NASA Technical Reports Server (NTRS)

    Surampudi, Subbarao (Inventor); Narayanan, Sekharipuram R. (Inventor); Vamos, Eugene (Inventor); Frank, Harvey A. (Inventor); Halpert, Gerald (Inventor); Olah, George A. (Inventor); Prakash, G. K. Surya (Inventor)

    1997-01-01

    A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

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

    DOE PAGES

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

    2015-10-08

    Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na2B12H12, which contains large, icosahedral, divalent B12H122– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, andmore » truly stellar ionic conductivities (>0.1 S cm–1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.« less

  18. Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Abdullah, Omed Gh.; Aziz, Shujahadeen B.; Rasheed, Mariwan A.

    Solid polymer electrolyte films of polyvinyl alcohol (PVA) doped with a different weight percent of potassium permanganate (KMnO4) were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR) spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content.

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

    SciTech Connect

    Tang, Wan Si; Unemoto, Atsushi; Zhou, Wei; Stavila, Vitalie; Matsuo, Motoaki; Wu, Hui; Orimo, Shin-ichi; Udovic, Terrence J.

    2015-10-08

    Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na2B12H12, which contains large, icosahedral, divalent B12H122– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm–1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.

  20. In-situ, non-destructive acoustic characterization of solid state electrolyte cells

    NASA Astrophysics Data System (ADS)

    Schmidt, Robert D.; Sakamoto, Jeffrey

    2016-08-01

    Solid-state electrolytes such as cubic Li6.25Al0.25La3Zr2O12 (LLZO) can enable solid-state batteries, metallic lithium anodes and higher voltage cathodes. However, the stability of cubic LLZO is affected by current density. In beta alumina solid electrolyte, microstructural failure was caused by Na dendrite penetration, and was shown to be a function of the fracture toughness, KIC. The relationship between dendrite penetration and KIC indicates electronic failure is related to creation of microstructural damage, and the microstructural damage may be used as an indicator of imminent electronic failure. To monitor microstructural damage during cycling, we developed a non-invasive, in-situ cell monitoring apparatus to help to correlate mechanical stability with Li-ion current density in LLZO. A pulse-echo transducer was integrated into all solid-state Li-LLZO-Li cells. The capability enables the characterization of microscopic inhomogeneities through the careful measurement of changes to the elastic moduli. The elastic moduli and fracture toughness have been previously reported for dense (>99%) specimens, but monitoring of the relative change in moduli during cycling has not been explored. In this study, an acoustic monitoring method is presented to monitor LLZO specimens during cycling.

  1. A Unique Hybrid Quasi-Solid-State Electrolyte for Li-O2 Batteries with Improved Cycle Life and Safety.

    PubMed

    Yi, Jin; Zhou, Haoshen

    2016-09-08

    In the context of the development of electric vehicle to solve the contemporary energy and environmental issues, the possibility of pushing future application of Li-O2 batteries as a power source for electric vehicles is particularly attractive. However, safety concerns, mainly derived from the use of flammable organic liquid electrolytes, become a major bottleneck for the strategically crucial applications of Li-O2 batteries. To overcome this issue, rechargeable solid-state Li-O2 batteries with enhanced safety is regarded as an appealing candidate. In this study, a hybrid quasi-solid-state electrolyte combing a polymer electrolyte with a ceramic electrolyte is first designed and explored for Li-O2 batteries. The proposed rechargeable solid-state Li-O2 battery delivers improved cycle life (>100 cycles) and safety. The feasibility study demonstrates that the hybrid quasi-solid-state electrolytes could be employed as a promising alternative strategy for the development of rechargeable Li-O2 batteries, hence encouraging more efforts devoted to explore other hybrid solid-state electrolytes for Li-O2 batteries upon future application.

  2. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman

    2000-10-01

    Solid oxide fuel cells (SOFCs) are the future of energy production in America. They offer great promise as a clean and efficient process for directly converting chemical energy to electricity while providing significant environmental benefits (they produce negligible CO, HC, or NOx and, as a result of their high efficiency, produce about one-third less CO{sub 2} per kilowatt hour than internal combustion engines). Unfortunately, the current SOFC technology, based on a stabilized zirconia electrolyte, must operate in the region of 1000 C to avoid unacceptably high ohmic losses. These high temperatures demand (a) specialized (expensive) materials for the fuel cell interconnects and insulation, (b) time to heat up to the operating temperature and (c) energy input to arrive at the operating temperature. Therefore, if fuel cells could be designed to give a reasonable power output at lower temperatures tremendous benefits may be accrued, not the least of which is reduced cost. The problem is, at lower temperatures the conductivity of the conventional stabilized zirconia electrolyte decreases to the point where it cannot supply electrical current efficiently to an external load. The primary objectives of the proposed research is to develop a stable high conductivity (>0.05 S cm{sup -1} at 550 C) electrolyte for lower temperature SOFCs. This objective is specifically directed toward meeting the lowest (and most difficult) temperature criteria for the 21st Century Fuel Cell Program. Meeting this objective provides a potential for future transportation applications of SOFCs, where their ability to directly use hydrocarbon fuels could permit refueling within the existing transportation infrastructure. In order to meet this objective we are developing a functionally gradient bilayer electrolyte comprised of bismuth oxide on the air side and ceria on the fuel side. Bismuth oxide and doped ceria are among the highest ionic conducting electrolytes and in fact bismuth oxide based

  3. Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

    DOEpatents

    Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

    2016-03-29

    Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

  4. Electrode assembly for use in a solid polymer electrolyte fuel cell

    DOEpatents

    Raistrick, Ian D.

    1989-01-01

    A gas reaction fuel cell may be provided with a solid polymer electrolyte membrane. Porous gas diffusion electrodes are formed of carbon particles supporting a catalyst which is effective to enhance the gas reactions. The carbon particles define interstitial spaces exposing the catalyst on a large surface area of the carbon particles. A proton conducting material, such as a perfluorocarbon copolymer or ruthenium dioxide contacts the surface areas of the carbon particles adjacent the interstitial spaces. The proton conducting material enables protons produced by the gas reactions adjacent the supported catalyst to have a conductive path with the electrolyte membrane. The carbon particles provide a conductive path for electrons. A suitable electrode may be formed by dispersing a solution containing a proton conducting material over the surface of the electrode in a manner effective to coat carbon surfaces adjacent the interstitial spaces without impeding gas flow into the interstitial spaces.

  5. Jumping liquid metal droplet in electrolyte triggered by solid metal particles

    NASA Astrophysics Data System (ADS)

    Tang, Jianbo; Wang, Junjie; Liu, Jing; Zhou, Yuan

    2016-05-01

    We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electric breakdown of the electrolyte.

  6. Solid lithium electrolyte via addition of lithium salts to metal-organic frameworks

    SciTech Connect

    Wiers, Brian M.; Balsara, Nitash P.; Long, Jeffrey R.

    2016-12-20

    Various embodiments of the invention disclose that the uptake of LiO.sup.iPr in Mg.sub.2(dobdc) (dobdc.sup.4-=1,4-dioxido-2,5-benzenedicarboxylate) followed by soaking in a typical electrolyte solution leads to a new solid lithium electrolyte Mg.sub.2(dobdc).0.35LiO.sup.iPr.0.25LiBF.sub.4.EC.DEC. Two-point ac impedance data show a pressed pellet of this material to have a conductivity of 3.1.times.10.sup.-4 S/cm at 300 K. In addition, the results from variable-temperature measurements reveal an activation energy of approximately 0.15 eV, while single-particle data suggest that intraparticle transport dominates conduction.

  7. Influence of carbon nanotubes on the optical properties of plasticized solid polymer electrolytes

    NASA Astrophysics Data System (ADS)

    Ibrahim, Suriani; Yasin, Siti Mariah Mohd; Johan, Mohd Rafie

    2013-07-01

    Polyethylene oxide (PEO) based solid polymer electrolyte films complexed with lithium hexafluorophosphate (LiPF6), ethylene carbonate (EC) and carbon nanotubes (CNTs) are prepared by solution-casting technique. The complexation of doping materials with polymer is confirmed by X-ray diffraction and infrared studies. The incorporation of LiPF6, EC and CNTs into the host polymer shows a significant increase in conductivity of 10-10 and 10-3 S cm-1. The optical properties such as direct and indirect band gaps are investigated for pure and doped polymer films within a wavelength range of 200-400 nm. It is found that the energy gaps and band edge values shift towards lower energies upon doping. It is shown that LiPF6, EC and CNTs are responsible for the formation of defects in polymer electrolytes, which increases the degree of disorder in the films.

  8. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

    DOEpatents

    Zaromb, S.

    1994-06-21

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity [>=]10[sup [minus]4] (ohm-cm)[sup [minus]1], and preferably [>=]0.01 (ohm-cm)[sup [minus]1]. The conductivity may be due predominantly to Ag[sup +] ions, as in Ag[sub 2]WO[sub 4], or to F[sup [minus

  9. Temperature dependent dielectric properties and ion transportation in solid polymer electrolyte for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sengwa, R. J.; Dhatarwal, Priyanka; Choudhary, Shobhna

    2016-05-01

    Solid polymer electrolyte (SPE) film consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend matrix with lithium tetrafluroborate (LiBF4) as dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer has been prepared by solution casting method followed by melt pressing. Dielectric properties and ionic conductivity of the SPE film at different temperatures have been determined by dielectric relaxation spectroscopy. It has been observed that the dc ionic conductivity of the SPE film increases with increase of temperature and also the decrease of relaxation time. The temperature dependent relaxation time and ionic conductivity values of the electrolyte are governed by the Arrhenius relation. Correlation observed between dc conductivity and relaxation time confirms that ion transportation occurs with polymer chain segmental dynamics through hopping mechanism. The room temperature ionic conductivity is found to be 4 × 10-6 S cm-1 which suggests the suitability of the SPE film for rechargeable lithium batteries.

  10. Solid-state sodium batteries using polymer electrolytes and sodium intercalation electrode materials

    SciTech Connect

    Ma, Y. |

    1996-08-01

    Solid-state sodium cells using polymer electrolytes (polyethylene oxide mixed with sodium trifluoromethanesulfonate: PEO{sub n}NaCF{sub 3}SO{sub 3}) and sodium cobalt oxide positive electrodes are characterized in terms of discharge and charge characteristics, rate capability, cycle life, and energy and power densities. The P2 phase Na{sub x}CoO{sub 2} can reversibly intercalate sodium in the range of x = 0.3 to 0.9, giving a theoretical specific energy of 440 Wh/kg and energy density of 1,600 Wh/l. Over one hundred cycles to 60% depth of discharge have been obtained at 0.5 mA/cm{sup 2}. Experiments show that the electrolyte/Na interface is stable and is not the limiting factor to cell cycle life. Na{sub 0.7}CoO{sub 2} composite electrodes containing various amounts of carbon black additive are investigated. The transport properties of polymer electrolytes are the critical factors for performance. These properties (the ionic conductivity, salt diffusion coefficient, and ion transference number) are measured for the PEO{sub n}NaCF{sub 3}SO{sub 3} system over a wide range of concentrations at 85 C. All the three transport properties are very salt-concentration dependent. The ionic conductivity exhibits a maximum at about n = 20. The transference number, diffusion coefficient, and thermodynamic factor all vary with salt concentration in a similar fashion, decreasing as the concentration increases, except for a local maximum. These results verify that polymer electrolytes cannot be treated as ideal solutions. The measured transport-property values are used to analyze and optimize the electrolytes by computer simulation and also cell testing. Salt precipitation is believed to be the rate limiting process for cells using highly concentrated solutions, as a result of lower values of these properties, while salt depletion is the limiting factor when a dilute solution is used.

  11. Evaluation of lanthanum tungstates as electrolytes for proton conductors Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Zayas-Rey, M. J.; dos Santos-Gómez, L.; Porras-Vázquez, J. M.; Losilla, E. R.; Marrero-López, D.

    2015-10-01

    La27W4NbO55-δ (LWNO) has been tested as electrolyte for proton conductor Solid Oxide Fuel Cells (PC-SOFCs). For this purpose, different electrodes and composite electrodes are considered, including: La0.8Sr0.2MnO3-δ, La0.6Sr0.4Co1-xFexO3-δ, La0.75Sr0.25Cr0.5Mn0.5O3-δ, SrFe0.75Nb0.25O3-δ and NiO. Chemical compatibility between the cell components is investigated by X-ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS). Furthermore, area specific resistance (ASR) for the different electrodes is determined in symmetrical cells by impedance spectroscopy. XRPD and EDS analysis does not reveal significant bulk reactivity between most of these electrodes and LWNO electrolyte in the typical operating temperature range of an SOFC (600-900 °C). However, minor interdiffusion of elements at the electrolyte/electrode interface has negative effects on both the ohmic losses and electrode polarization of the cells. ASR values are significantly improved by using a porous buffer layer of Ce0.8Gd0.2O1.9 (CGO), deposited between the electrolyte and electrode materials, to prevent reactivity. A single cell with a 350 μm-thick electrolyte, NiO-CGO and La0.6Sr0.4Co0.8Fe0.2O3-δ-CGO composite as anode and cathode, respectively, generates maximum power densities of 140 and 18 mWcm-2 at 900 and 650 °C, respectively.

  12. Use of nafion as a solid polymer electrolyte for the electroreduction of tungsten (VI) fluoride

    SciTech Connect

    Bettelheim, A.; Raven, A.; Polak, M.; Ozer, D. )

    1992-01-01

    In this paper a new method is described in which WF{sub 6} is electroreduced in a solid-state cell configuration with a Nafion membrane serving as a solid polymer electrolyte. Cyclic voltammetry indicates a behavior similar to that of metallic tungsten for coatings obtained at dry conditions and similar to that of tungsten oxide species when water vapor is not totally expelled. Surface analysis using Auger electroscope and x-ray photoelectron spectroscopy shows that solid-state electro-reduction of WF{sub 6} in dry conditions yields coatings free of fluorine, which contain much less oxygen than electrodeposits obtained from aqueous solutions. However, due to possible oxidation and reduction reactions occurring before and during the surface-analysis process, it is not possible at this state to determine the exact content of metallic and oxide species in the deposits obtained by the present method.

  13. Direct Electrolytic Reduction of Solid Ta2O5 to Ta with SOM Process

    NASA Astrophysics Data System (ADS)

    Chen, Chaoyi; Yang, Xiaqiong; Li, Junqi; Lu, Xionggang; Yang, Shufeng

    2016-06-01

    A process that uses the solid-oxide-oxygen-ion conducting membrane has been investigated to produce tantalum directly from solid Ta2O5 in molten CaCl2 or a molten mixture of 55.5MgF2-44.5CaF2 (in wt pct). The sintered porous Ta2O5 pellet was employed as the cathode, while the liquid copper alloy, saturated with graphite powder and encased in a one-end-closed yttria-stabilized-zirconia (YSZ) tube, acted as the anode. The electrolysis potential in this method is higher than that of the Fray-Farthing-Chen Cambridge process because the YSZ membrane tube blocks the melts to electrolyze, and only Ta2O5 is will be electrolyzed. The microstructures of reduced pellets and a cyclic voltammogram of solid Ta2O5 in molten CaCl2 were analyzed. In addition, the influence of particle size and porosity of the cathode pellets on metal-oxide-electrolyte, three-phase interlines was also discussed. The results demonstrate that the sintering temperature of cathode pellets and electrolytic temperature play important roles in the electrochemical process. Furthermore, this process can be used to produce Ta metal efficiently without the expensive cost of pre-electrolysis and generation of harmful by-products.

  14. All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

    PubMed

    Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

    2014-11-26

    The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

  15. Si micropyramid patterned anodes that can suppress fracture and solid electrolyte interface formation during electrochemical cycling

    NASA Astrophysics Data System (ADS)

    Deng, Haokun; Chu, Geng; Luo, Fei; Li, Hong; Chen, Liquan; Aifantis, Katerina E.

    2016-10-01

    Two new types of Si patterned surfaces are presented that have either a solid micropyramid structure or a double microstructure in which nanopores are induced on the pyramid surface. The pyramid diameter ranges between 1 and 6 μm, while the pores are 50-100 nm in diameter and ∼100-400 nm deep. It is illustrated that when they are employed as anodes, in Li-ion batteries, these patterned anodes, at high current densities of 1C, can (i) retain their initial morphology intact, despite the ∼400% expansion that Si experiences upon lithiation, and (ii) minimize the formation of the solid electrolyte interface (SEI) that forms upon decomposition of the electrolyte. Furthermore, for the nanoporous-micropyramids, scanning electron microscopy after twenty-five electrochemical cycles reveals that no fracture occurs in either high (1 C) or low (0.1 C) current densities. This is a unique and significant observation as similar experiments, at 0.1 C, on the solid micropyramid surfaces indicate severe fracture from the first Li-insertion. It is therefore concluded that introducing a nanostructure on micropyramids significantly enhances their structural stability. This suggests that microscale Si with induced nanopores is an alternative anode candidate to nanoscale Si.

  16. 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.

  17. Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

    NASA Technical Reports Server (NTRS)

    Savinell, R. F.; Fritts, S. D.

    1988-01-01

    A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

  18. Modeling of liquid electrolyte films on non-uniformly charged solid substrates

    NASA Astrophysics Data System (ADS)

    Jutley, Mahnprit; Ajaev, Vladimir

    2015-11-01

    We consider a thin electrolyte film on a solid substrate characterized by a space-dependent electrical charge density. Using the Debye-Hückel equation to model the electrostatic potential and the Navier-Stokes equations for fluid flow, we consider both steady-state interface shapes and their stability resulting from small perturbations of arbitrary wavelength. Calculations are carried out by two different approaches: Fourier expansion of all terms is used and the corresponding coefficients of the first order correction to the interface shape are found, and, secondly, an evolution equation is obtained within the framework of a lubrication-type model. Stability analysis of the linearized problem is conducted.

  19. Method for forming thin composite solid electrolyte film for lithium batteries

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  20. Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

    NASA Astrophysics Data System (ADS)

    Cheng, Hua; Scott, Keith

    The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

  1. In situ transmission electron microscopy analysis of conductive filament during solid electrolyte resistance switching

    SciTech Connect

    Fujii, Takashi; Arita, Masashi; Takahashi, Yasuo; Fujiwara, Ichiro

    2011-05-23

    An in situ transmission electron microscopy (TEM) analysis of a solid electrolyte, Cu-GeS, during resistance switching is reported. Real-time observations of the filament formation and disappearance process were performed in the TEM instrument and the conductive-filament-formation model was confirmed experimentally. Narrow conductive filaments were formed corresponding to resistance switching from high- to low-resistance states. When the resistance changed to high-resistance state, the filament disappeared. It was also confirmed by use of selected area diffractometry and energy-dispersive x-ray spectroscopy that the conductive filament was made of nanocrystals composed mainly of Cu.

  2. Surface engineering of nanoporous substrate for solid oxide fuel cells with atomic layer-deposited electrolyte

    PubMed Central

    Ji, Sanghoon; Tanveer, Waqas Hassan; Yu, Wonjong; Kang, Sungmin; Cho, Gu Young; Kim, Sung Han

    2015-01-01

    Summary Solid oxide fuel cells with atomic layer-deposited thin film electrolytes supported on anodic aluminum oxide (AAO) are electrochemically characterized with varying thickness of bottom electrode catalyst (BEC); BECs which are 0.5 and 4 times thicker than the size of AAO pores are tested. The thicker BEC ensures far more active mass transport on the BEC side and resultantly the thicker BEC cell generates ≈11 times higher peak power density than the thinner BEC cell at 500 °C. PMID:26425432

  3. Method for forming thin composite solid electrolyte film for lithium batteries

    NASA Technical Reports Server (NTRS)

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

    1997-01-01

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

  4. Properties of solid polymer electrolyte fluorocarbon film. [used in hydrogen/oxygen fuel cells

    NASA Technical Reports Server (NTRS)

    Alston, W. B.

    1973-01-01

    The ionic fluorocarbon film used as the solid polymer electrolyte in hydrogen/oxygen fuel cells was found to exhibit delamination failures. Polarized light microscopy of as-received film showed a lined region at the center of the film thickness. It is shown that these lines were not caused by incomplete saponification but probably resulted from the film extrusion process. The film lines could be removed by an annealing process. Chemical, physical, and tensile tests showed that annealing improved or sustained the water contents, spectral properties, thermo-oxidative stability, and tensile properties of the film. The resistivity of the film was significantly decreased by the annealing process.

  5. Oxygen substitution effects in Li10GeP2S12 solid electrolyte

    NASA Astrophysics Data System (ADS)

    Sun, Yulong; Suzuki, Kota; Hara, Kosuke; Hori, Satoshi; Yano, Taka-aki; Hara, Masahiko; Hirayama, Masaaki; Kanno, Ryoji

    2016-08-01

    For the lithium super-ionic conductor Li10GeP2S12, the partial substitution of sulfur by oxygen is achieved via a solid-state reaction. The solid-solution range of oxygen is found to be 0 ≤ x < 0.9 in Li10GeP2S12-xOx. Structure refinements using synchrotron X-ray diffraction data confirm the preference for oxygen substitution in the PS4 tetrahedra. The local structural change in the P(S/O)4 tetrahedra upon substitution is also indicated by Raman spectroscopy. Ionic conduction properties are maintained even after the oxygen substitution in Li10GeP2S12; the ionic conductivity of Li10GeP2S12-xOx (0.3 ≤ x ≤ 0.6) ranges from 1.03 × 10-2 to 8.43 × 10-3 S cm-1 at 298 K. No redox current is observed by cyclic voltammetry from nearly 0 to 10 V versus Li/Li+ except for that due to the lithium deposition/dissolution reactions. All-solid-state batteries using Li10GeP2S12-xOx (x = 0.3 and 0.6) as solid electrolytes with Li metal anodes show discharge capacities exceeding 100 mAh g-1 and better cycling performance compared to batteries using the original Li10GeP2S12. The partial substitution of oxygen for sulfur in Li10GeP2S12 affords a novel solid electrolyte, Li10GeP2S12-xOx, with high conductive properties and electrochemical stability.

  6. High performance zirconia-bismuth oxide nanocomposite electrolytes for lower temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Joh, Dong Woo; Park, Jeong Hwa; Kim, Do Yeub; Yun, Byung-Hyun; Lee, Kang Taek

    2016-07-01

    We develop a novel nanocomposite electrolyte, consisting of yttria-stabilized zirconia (YSZ) and erbia-stabilized bismuth oxide (ESB). The 20 mol% ESB-incorporated YSZ composite (20ESB-YSZ) achieves the high density (>97%) at the low sintering temperature of 800 °C. The microstructural analysis of 20ESB-YSZ reveals the characteristic nanocomposite structure of the highly percolated ESB phase at the YSZ grain boundaries (a few ∼ nm thick). The ionic conductivity of 20ESB-YSZ is increased by 5 times compared to that of the conventional YSZ due to the fast oxygen ion transport along the ESB phase. Moreover, this high conductivity is maintained up to 580 h, indicating high stability of the ESB-YSZ nanocomposite. In addition, the oxygen reduction reaction at the composite electrolyte/cathode interface is effectively enhanced (∼70%) at the temperature below 650 °C, mainly due to the fast dissociative oxygen adsorption on the ESB surface as well as the rapid oxygen ion incorporation into the ESB lattice. Thus, we believe this ESB-YSZ nanocomposite is a promising electrolyte for high performance solid oxide fuel cells at reduced temperatures.

  7. Structural and transport properties of PVC blend PEG doped with Mg(ClO4)2 solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Ramesh, C. H.; Reddy, M. Jaipal; Kumar, J. Siva; Reddy, K. Narasimha

    2014-04-01

    An attempt was made to investigate the effect of Mg(ClO4)2 concentration in PVC-PEG blend polymer electrolyte system. Solid polymer electrolyte films of PVC-PEG-Mg(ClO4)2 have been prepared by using solution - casting process. Structural and transport properties have been studied by employing experimental tools like XRD, FT-IR and DC electrical conductivity. The XRD, FTIR studies were confirmed the formation of a polymer-salt complex. The conductivity results indicated that the incorporation of Mg(ClO4)2 salt into PVC-PEG polymer; at low concentrations the increase in the conductivity is large, but at higher concentrations the increase in conductivity is modest. Using this electrolyte, an electrochemical cells have been fabricated with the configuration Mg/ (PVC-PEG-Mg(ClO4)2) electrolyte / (I2 + C + electrolyte) and its discharge characteristics were determined.

  8. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    NASA Astrophysics Data System (ADS)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

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

    PubMed

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

    2017-02-06

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2014-09-03

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

  12. Rechargeable solid-state battery using a proton-conducting composite as electrolyte

    NASA Astrophysics Data System (ADS)

    Lakshmi, N.; Chandra, S.

    Proton-conducting composites of heteropolyacid hydrates (phospbotungstic acid, PTA and phosphomolybdic acid, PMA) with dispersoids such as insulating Al 2O 3, Al 2(SO 4) 3·16H 2O and (NH 4) 10W 12O 41·2H 2O are prepared for use as possible solid-state electrolytes in batteries. Bulk electrical conductivity as a function of composition is reported. Rechargeable solid-state proton batteries are fabricated and characterized. A cell with the configuration Zn+ZnSO 4·7H 2O+MH x|PMA+APT|PbO 2+V 2O 5+C+E gives an open circuit voltage of 1.5 V and can run for >850 h at a current drain of 2.4 μA cm -2. The cell can be recharged without much loss up to 18-20 cycles.

  13. Study of gadolinia-doped ceria solid electrolyte surface by XPS

    SciTech Connect

    Datta, Pradyot Majewski, Peter; Aldinger, Fritz

    2009-02-15

    Gadolinia-doped ceria (CGO) is an important material to be used as electrolyte for solid oxide fuel cell for intermediate temperature operation. Ceria doped with 10 mol% gadolinia (Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}) was prepared by conventional solid state synthesis and found to be single phase by room temperature X-ray diffraction (XRD). The chemical states of the surface of the prepared sample were analyzed by X-ray photoelectron spectroscopy (XPS). Though Gd was present in its characteristic chemical state, Ce was found in both Ce{sup 4+} and Ce{sup 3+} states. Presence of Ce{sup 3+} state was ascribed to the differential yield of oxygen atoms in the sputtering process.

  14. A mathematical model of the solid-polymer-electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Bernardi, Dawn M.; Verbrugge, Mark W.

    1992-09-01

    A mathematical model of the solid-polymer-electrolyte fuel cell is presented and applied to investigate factors that limit cell performance and elucidate the mechanism of species transport in the complex network of gas, liquid, and solid phases of the cell. Calculations of cell polarization behavior compare favorably with existing experimental data. For most practical electral thicknesses, model results indicate that the volume fraction of the cathode available for gas transport must exceed 20 percent in order to avoid unacceptably low cell-limiting current densities. It is shown that membrane dehydration can also pose limitations on operating current density. Circumvention of this problem by appropriate membrane and electrode design and efficient water-management schemes is discussed. It is found that for a broad range of practical current densities there are no external water requirements because the water produced at the cathode is sufficient to satisfy the water requirement of the membrane.

  15. Reshaping Lithium Plating/Stripping Behavior via Bifunctional Polymer Electrolyte for Room-Temperature Solid Li Metal Batteries.

    PubMed

    Zeng, Xian-Xiang; Yin, Ya-Xia; Li, Nian-Wu; Du, Wen-Cheng; Guo, Yu-Guo; Wan, Li-Jun

    2016-12-14

    High-energy rechargeable Li metal batteries are hindered by dendrite growth due to the use of a liquid electrolyte. Solid polymer electrolytes, as promising candidates to solve the above issue, are expected to own high Li ion conductivity without sacrificing mechanical strength, which is still a big challenge to realize. In this study, a bifunctional solid polymer electrolyte exactly having these two merits is proposed with an interpenetrating network of poly(ether-acrylate) (ipn-PEA) and realized via photopolymerization of ion-conductive poly(ethylene oxide) and branched acrylate. The ipn-PEA electrolyte with facile processing capability integrates high mechanical strength (ca. 12 GPa) with high room-temperature ionic conductance (0.22 mS cm(-1)), and significantly promotes uniform Li plating/stripping. Li metal full cells assembled with ipn-PEA electrolyte and cathodes within 4.5 V vs Li(+)/Li operate effectively at a rate of 5 C and cycle stably at a rate of 1 C at room temperature. Because of its fabrication simplicity and compelling characteristics, the bifunctional ipn-PEA electrolyte reshapes the feasibility of room-temperature solid-state Li metal batteries.

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

    NASA Technical Reports Server (NTRS)

    Baldwin, Richard S.; Bennett, William R.

    2007-01-01

    In fiscal year 2000, The National Aeronautics and Space Administration (NASA) and the Air Force Research Laboratory (AFRL) established a collaborative effort to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The ultimate objective of this development program, which was referred to as the Polymer Energy Rechargeable System (PERS), was to establish a world-class technology capability and U.S. leadership in polymer-based battery technology for aerospace applications. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. Out of a total of 38 proposals received in response to a NASA Research Announcement (NRA) solicitation, 18 proposals (13 contracts and 5 grants) were selected for initial award to address these technical challenges. Brief summaries of technical approaches, results and accomplishments of the PERS Program development efforts are presented. With Agency support provided through FY 2004, the PERS Program efforts were concluded in 2005, as internal reorganizations and funding cuts resulted in shifting programmatic priorities within NASA. Technically, the PERS Program participants explored, to various degrees over the lifetime of the formal program, a variety of conceptual approaches for developing and demonstrating performance of a viable advanced solid polymer electrolyte possessing the desired attributes, as well as several participants addressing all components of an integrated cell configuration. Programmatically, the NASA PERS Program was very successful, even though the very challenging technical goals for achieving a viable solid polymer electrolyte material or

  17. Hot pressed K+ ion conducting solid polymer electrolytes: synthesis, ion conduction and polymeric battery fabrication

    NASA Astrophysics Data System (ADS)

    Chandra, Angesh

    2016-07-01

    Synthesis and ion transport studies of hot pressed K+ ion conducting solid polymer electrolytes (SPEs): (1 - x) PEO: x KBr, where 0 < x < 50 in wt%, are reported. The solvent-free/hot-press method is used for synthesis of the present SPEs. The two orders of conductivity enhancement achieved after the polymer-salt complexation in SPE composition: (70:30) with conductivity ( σ) 5.01 × 10-7 S cm-1 from the room temperature conductivity measurements. Materials characterization and polymer-salt complexations of present SPEs have been explained with the help of various techniques viz. X-ray diffraction, Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy technique. To explain the ion conduction in the present SPEs, temperature dependent ionic conductivity ( σ), ionic mobility ( μ), mobile ion concentration ( n), ionic transference number ( t ion ) and ionic drift velocity ( v d ) have been calculated with the help of various experimental techniques. A solid state polymer battery is also fabricated by using the present SPE as an electrolyte and have been calculated their important cell parameters at room temperature.

  18. Solid oxide fuel cell electrolytes produced via very low pressure suspension plasma spray and electrophoretic deposition

    NASA Astrophysics Data System (ADS)

    Fleetwood, James D.

    Solid oxide fuel cells (SOFCs) are a promising element of comprehensive energy policies due to their direct mechanism for converting the oxidization of fuel, such as hydrogen, into electrical energy. Both very low pressure plasma spray and electrophoretic deposition allow working with high melting temperature SOFC suspension based feedstock on complex surfaces, such as in non-planar SOFC designs. Dense, thin electrolytes of ideal composition for SOFCs can be fabricated with each of these processes, while compositional control is achieved with dissolved dopant compounds that are incorporated into the coating during deposition. In the work reported, sub-micron 8 mole % Y2O3-ZrO2 (YSZ) and gadolinia-doped ceria (GDC), powders, including those in suspension with scandium-nitrate dopants, were deposited on NiO-YSZ anodes, via very low pressure suspension plasma spray (VLPSPS) at Sandia National Laboratories' Thermal Spray Research Laboratory and electrophoretic deposition (EPD) at Purdue University. Plasma spray was carried out in a chamber held at 320 - 1300 Pa, with the plasma composed of argon, hydrogen, and helium. EPD was characterized utilizing constant current deposition at 10 mm electrode separation, with deposits sintered from 1300 -- 1500 °C for 2 hours. The role of suspension constituents in EPD was analyzed based on a parametric study of powder loading, powder specific surface area, polyvinyl butyral (PVB) content, polyethyleneimine (PEI) content, and acetic acid content. Increasing PVB content and reduction of particle specific surface area were found to eliminate the formation of cracks when drying. PEI and acetic acid content were used to control suspension stability and the adhesion of deposits. Additionally, EPD was used to fabricate YSZ/GDC bilayer electrolyte systems. The resultant YSZ electrolytes were 2-27 microns thick and up to 97% dense. Electrolyte performance as part of a SOFC system with screen printed LSCF cathodes was evaluated with peak

  19. Flexible thin-film battery based on graphene-oxide embedded in solid polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Kammoun, M.; Berg, S.; Ardebili, H.

    2015-10-01

    Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending.Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method

  20. 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.

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

    PubMed Central

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

    2016-01-01

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

  2. Graphene-Analogues Boron Nitride Nanosheets Confining Ionic Liquids: A High-Performance Quasi-Liquid Solid Electrolyte.

    PubMed

    Li, Mingtao; Zhu, Wenshuai; Zhang, Pengfei; Chao, Yanhong; He, Qian; Yang, Bolun; Li, Huaming; Borisevich, Albinab; Dai, Sheng

    2016-07-01

    Solid electrolytes are one of the most promising electrolyte systems for safe lithium batteries, but the low ionic conductivity of these electrolytes seriously hinders the development of efficient lithium batteries. Here, a novel class of graphene-analogues boron nitride (g-BN) nanosheets confining an ultrahigh concentration of ionic liquids (ILs) in an interlayer and out-of-layer chamber to give rise to a quasi-liquid solid electrolyte (QLSE) is reported. The electron-insulated g-BN nanosheet host with a large specific surface area can confine ILs as much as 10 times of the host's weight to afford high ionic conductivity (3.85 × 10(-3) S cm(-1) at 25 °C, even 2.32 × 10(-4) S cm(-1) at -20 °C), which is close to that of the corresponding bulk IL electrolytes. The high ionic conductivity of QLSE is attributed to the enormous absorption for ILs and the confining effect of g-BN to form the ordered lithium ion transport channels in an interlayer and out-of-layer of g-BN. Furthermore, the electrolyte displays outstanding electrochemical properties and battery performance. In principle, this work enables a wider tunability, further opening up a new field for the fabrication of the next-generation QLSE based on layered nanomaterials in energy conversion devices.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes.

    PubMed

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-24

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g(-1)carbon at 20 μA cm(-2). Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g(-1)carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g(-1)carbon at 20 μA cm(-2) and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage.

  5. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes

    NASA Astrophysics Data System (ADS)

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-01

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g‑1carbon at 20 μA cm‑2. Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g‑1carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g‑1carbon at 20 μA cm‑2 and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage.

  6. A Rechargeable Li-Air Fuel Cell Battery Based on Garnet Solid Electrolytes

    PubMed Central

    Sun, Jiyang; Zhao, Ning; Li, Yiqiu; Guo, Xiangxin; Feng, Xuefei; Liu, Xiaosong; Liu, Zhi; Cui, Guanglei; Zheng, Hao; Gu, Lin; Li, Hong

    2017-01-01

    Non-aqueous Li-air batteries have been intensively studied in the past few years for their theoretically super-high energy density. However, they cannot operate properly in real air because they contain highly unstable and volatile electrolytes. Here, we report the fabrication of solid-state Li-air batteries using garnet (i.e., Li6.4La3Zr1.4Ta0.6O12, LLZTO) ceramic disks with high density and ionic conductivity as the electrolytes and composite cathodes consisting of garnet powder, Li salts (LiTFSI) and active carbon. These batteries run in real air based on the formation and decomposition at least partially of Li2CO3. Batteries with LiTFSI mixed with polyimide (PI:LiTFSI) as a binder show rechargeability at 200 °C with a specific capacity of 2184 mAh g−1carbon at 20 μA cm−2. Replacement of PI:LiTFSI with LiTFSI dissolved in polypropylene carbonate (PPC:LiTFSI) reduces interfacial resistance, and the resulting batteries show a greatly increased discharge capacity of approximately 20300 mAh g−1carbon and cycle 50 times while maintaining a cutoff capacity of 1000 mAh g−1carbon at 20 μA cm−2 and 80 °C. These results demonstrate that the use of LLZTO ceramic electrolytes enables operation of the Li-air battery in real air at medium temperatures, leading to a novel type of Li-air fuel cell battery for energy storage. PMID:28117359

  7. Energetics of Intermediate Temperature Solid Oxide Fuel Cell Electrolytes: Singly and Doubly doped Ceria Systems

    NASA Astrophysics Data System (ADS)

    Buyukkilic, Salih

    Solid oxide fuel cells (SOFCs) have potential to convert chemical energy directly to electrical energy with high efficiency, with only water vapor as a by-product. However, the requirement of extremely high operating temperatures (~1000 °C) limits the use of SOFCs to only in large scale stationary applications. In order to make SOFCs a viable energy solution, enormous effort has been focused on lowering the operating temperatures below 700 °C. A low temperature operation would reduce manufacturing costs by slowing component degradation, lessening thermal mismatch problems, and sharply reducing costs of operation. In order to optimize SOFC applications, it is critical to understand the thermodynamic stabilities of electrolytes since they directly influence device stability, sustainability and performance. Rare-earth doped ceria electrolytes have emerged as promising materials for SOFC applications due to their high ionic conductivity at the intermediate temperatures (500--700 °C). However there is a fundamental lack of understanding regarding their structure, thermodynamic stability and properties. Therefore, the enthalpies of formation from constituent oxides and ionic conductivities were determined to investigate a relationship between the stability, composition, structural defects and ionic conductivity in rare earth doped ceria systems. For singly doped ceria electrolytes, we investigated the solid solution phase of bulk Ce1-xLnxO2-0.5x where Ln = Sm and Nd (0 ≤ x ≤ 0.30) and analyzed their enthalpies of formation, mixing and association, and bulk ionic conductivities while considering cation size mismatch and defect associations. It was shown that for ambient temperatures in the dilute dopant region, the positive heat of formation reaches a maximum as the system becomes increasingly less stable due to size mismatch. In concentrated region, stabilization to a certain solubility limit was observed probably due to the defect association of trivalent cations

  8. Nanocomposite polymer electrolyte based on Poly(ethylene oxide) and solid super acid for lithium polymer battery

    NASA Astrophysics Data System (ADS)

    Xi, Jingyu; Tang, Xiaozhen

    2004-07-01

    This Letter reports a novel PEO-based nanocomposite polymer electrolyte by using solid super acid SO 42-/ZrO 2 as filler. XRD, DSC, and FT-IR results prove the strong Lewis acid-base interactions between SO 42-/ZrO 2 and PEO chains. The addition of SO 42-/ZrO 2 can enhance the ionic conductivity and the lithium ion transference number of the electrolyte. The highest room temperature ionic conductivity of 2.1 × 10 -5 S cm -1 is obtained for the sample PEO 12-LiClO 4-7%SO 42-/ZrO 2. The excellent performances such as good compatibility with lithium electrode, and broad electrochemical stability window suggest that PEO-LiClO 4-SO 42-/ZrO 2 nanocomposite electrolyte can be used as electrolyte materials for lithium polymer batteries.

  9. Transport properties of the solid polymer electrolyte system P(EO){sub n}LiTFSI

    SciTech Connect

    Edman, L.; Doeff, M.M.; Ferry, A.; Kerr, J.; De Jonghe, L.C.

    2000-04-20

    Values for the lithium ion transference number ({tau}{sub +}{sup 0}) are reported for the solid polymer electrolyte system poly(ethylene oxide) (PEO) complexed with Li(CF{sub 3}SO{sub 2}){sub 2}N (LiTFSI). {tau}{sub +}{sup 0} ranges from 0.17 {+-} 0.17 to 0.60 {+-} 0.03 in the salt concentration (c) region of 742 to 2,982 mol/m{sup 3} at 85 C. The concentration dependence of {tau}{sub +}{sup 0} and the molar ionic conductivity ({Lambda}) are shown to be in good agreement with a free volume approach over the salt-rich composition range investigated. The present {tau}{sub +}{sup 0} results were obtained using an electrochemical technique based on concentrated solution theory. This experimentally straightforward method is herein demonstrated to give accurate results for a highly concentrated SPE system, without relying on any dubious simplifications regarding the state of the electrolyte.

  10. Some laws governing the electrosynthesis of organic compounds with a solid polymetric electrolyte

    SciTech Connect

    Rodionova, N.A.; Avrutskaya, I.A.; Fioshin, M. Ya.; Khrizolitova, M.A.

    1986-01-01

    The electrosynthesis of organic compounds with a solid polymetric electrolyte (SPE) makes it possible to carry out the process in the absence of a supporting electrolyte. This facilitates the recovery of the desired product, eliminates the inorganic waste products, and allows a small interelectrode distance, and the absence of the accumulation of gases lowers the voltage in the cell. Some laws governing syntheses of SPE were studied in the example cases of the electrochemical reduction of 2,2,6,6-tetramethyl-4-oxopiperidine to 2,2,6,6-tetramethyl-4-hydroxy-piperidine, the reduction of triacetonamine oxime and triacetonamine azine to 2,2,6,6-tetramethyl-4- aminopiperidine and the oxidation of isobutanol to isobutyric acid. The electrolysis with an SPE was carried out under galvanostatic conditions in an electrolyzer of the filter-press type with forced circulation of the catholyte and anolyte. Low reaction rates are found to be characteristic of all the compounds investigated when the electrolysis is carried out with an SPE.

  11. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus

    DOEpatents

    Zaromb, Solomon

    1994-01-01

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

  12. Humidity-resistant ambient-temperature solid-electrolyte amperometric sensing apparatus and methods

    DOEpatents

    Zaromb, Solomon

    2001-01-01

    Apparatus and methods for detecting selected chemical compounds in air or other gas streams at room or ambient temperature includes a liquid-free humidity-resistant amperometric sensor comprising a sensing electrode and a counter and reference electrode separated by a solid electrolyte. The sensing electrode preferably contains a noble metal, such as Pt black. The electrolyte is water-free, non-hygroscopic, and substantially water-insoluble, and has a room temperature ionic conductivity .gtoreq.10.sup.-4 (ohm-cm).sup.-1, and preferably .gtoreq.0.01 (ohm-cm).sup.-1. The conductivity may be due predominantly to Ag+ ions, as in Ag.sub.2 WO.sub.4.4AgI, or to F- ions, as in Ce.sub.0.95 Ca.sub.0.05 F.sub.2.95. Electrical contacts serve to connect the electrodes to potentiostating and detecting circuitry which controls the potential of the sensing electrode relative to the reference electrode, detects the signal generated by the sensor, and indicates the detected signal.

  13. Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Ticianelli, E. A.; Derouin, C. R.; Redondo, A.

    1987-01-01

    The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

  14. Low-temperature ceria-electrolyte solid oxide fuel cells for efficient methanol oxidation

    NASA Astrophysics Data System (ADS)

    Meng, Xie; Zhan, Zhongliang; Liu, Xuejiao; Wu, Hao; Wang, Shaorong; Wen, Tinglian

    Low temperature anode-supported solid oxide fuel cells with thin films of samarium-doped ceria (SDC) as electrolytes, graded porous Ni-SDC anodes and composite La 0.6Sr 0.4Co 0.2Fe 0.8O 3 (LSCF)-SDC cathodes are fabricated and tested with both hydrogen and methanol fuels. Power densities achieved with hydrogen are between 0.56 W cm -2 at 500 °C and 1.09 W cm -2 at 600 °C, and with methanol between 0.26 W cm -2 at 500 °C and 0.82 W cm -2 at 600 °C. The difference in the cell performance can be attributed to variation in the interfacial polarization resistance due to different fuel oxidation kinetics, e.g., 0.21 Ω cm 2 for methanol versus 0.10 Ω cm 2 for hydrogen at 600 °C. Further analysis suggests that the leakage current densities as high as 0.80 A cm -2 at 600 °C and 0.11 A cm -2 at 500 °C, resulting from the mixed electronic and ionic conductivity in the SDC electrolyte and thus reducing the fuel efficiency, can nonetheless help remove any carbon deposit and thereby ensure stable and coking-free operation of low temperature SOFCs in methanol fuels.

  15. Constrasting conductance/viscosity relations in liquid states of vitreous and polymer solid electrolytes. Technical report

    SciTech Connect

    McLin, M.; Angell, C.A.

    1987-11-01

    In order to contrast conductivity mechanisms in fast-ion glassy and rubbery polymer electrolytes, the liquid states of two prototypical cases were studied. Viscosity and conductivity measurements were performed on molten (as opposed to glassy) (AgCl) 0.35 (Ag(I)) 0.45 (CsCl) 0.20 and on solutions of sodium triflate in low-molecular-weight PPG (as opposed to high mw, 1,000,000 rubbery solid PPG - called PPO). Both types of system show non-Arrhenius viscosity with divergent behavior near T(g). The energetics of the conductivity processes, however, are very different. This is emphasized by reduced temperature scale (T/T(g)) plotting of (temperature-dependent) activation energies. For the polymer salt systems, as for normal molten-salt systems and aqueous solutions, conductance and viscosity energetics are comparable - the processes are coupled. Reduced-temperature plots of polymer solutions and glass-forming aqueous-solution data show the relative importance of T(g) and ion-association factors in limiting polymer-electrolyte performance.

  16. Flexible thin-film battery based on graphene-oxide embedded in solid polymer electrolyte.

    PubMed

    Kammoun, M; Berg, S; Ardebili, H

    2015-11-07

    Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm(-2) and an energy density of 4.8 mW h cm(-3). The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending.

  17. Effect of Eutectic Concentration on Conductivity in PEO:LiX Based Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Zhan, Pengfei; Ganapatibhotla, Lalitha; Maranas, Janna

    Polyethylene oxide (PEO) and lithium salt based solid polymer electrolytes (SPEs) have been widely proposed as a substitution for the liquid electrolyte in Li-ion batteries. As salt concentration varies, these systems demonstrate rich phase behavior. Conductivity as a function of salt concentration has been measured for decades and various concentration dependences have been observed. A PEO:LiX mixture can have one or two conductivity maximums, while some mixtures with salt of high ionic strength will have higher conductivity as the salt concentration decrease. The factors that affect the conductivity are specific for each sample. The universal factor that affects conductivity is still not clear. In this work, we measured the conductivity of a series of PEO:LiX mixtures and statistical analysis shows conductivity is affected by the concentration difference from the eutectic concentration (Δc). The correlation with Δc is stronger than the correlation with glass transition temperature. We believe that at the eutectic concentration, during the solidification process, unique structures can form which aid conduction. Currently at Dow Chemical.

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

    PubMed

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

    2014-09-24

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

  19. 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

  20. 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.

  1. Morphology and conductivity study of solid electrolyte Li{sub 3}PO{sub 4}

    SciTech Connect

    Prayogi, Lugas Dwi Faisal, Muhamad; Kartini, Evvy Honggowiranto, Wagiyo; Supardi

    2016-02-08

    The comparison between two different methods of synthesize of solid electrolyte Li{sub 3}PO{sub 4} as precursor material for developing lithium ion battery, has been performed. The first method is to synthesize Li{sub 3}PO{sub 4} prepared by wet chemical reaction from LiOH and H{sub 3}PO{sub 4} which provide facile, abundant available resource, low cost, and low toxicity. The second method is solid state reaction prepared by Li{sub 2}CO{sub 3} and NH{sub 4}H{sub 2}PO{sub 4.} In addition, the possible morphology identification of comparison between two different methods will also be discussed. The composition, morphology, and additional identification phase and another compound of Li{sub 3}PO{sub 4} powder products from two different reaction are characterized by SEM, EDS, and EIS. The Li{sub 3}PO{sub 4} powder produced from wet reaction and solid state reaction have an average diameter of 0.834 – 7.81 µm and 2.15 – 17.3 µm, respectively. The density of Li{sub 3}PO{sub 4} prepared by wet chemical reaction is 2.238 gr/cm{sup 3}, little bit lower than the sample prepared by solid state reaction which density is 2.3560 gr/cm{sup 3}. The EIS measurement result shows that the conductivity of Li{sub 3}PO{sub 4} is 1.7 x 10{sup −9} S.cm{sup −1} for wet chemical reaction and 1.8 x 10{sup −10} S.cm{sup −1} for solid state reaction. The conductivity of Li{sub 3}PO{sub 4} is not quite different between those two samples even though they were prepared by different method of synthesize.

  2. Thermodynamics of solid electrolytes and related oxide ceramics based on the fluorite structure

    SciTech Connect

    Navrotsky, Alexandra

    2010-01-01

    Oxides based on the fluorite structure are important as electrolytes in solid oxide fuel cells, thermal barrier coatings, gate dielectrics, catalysts, and nuclear materials. Though the parent fluorite structure is simple, the substitution of trivalent for tetravalent cations, coupled with the presence of charge-balancing oxygen vacancies, leads to a wealth of short-range and long-range ordered structures and complex thermodynamic properties. The location of vacancies and the nature of clusters affect the energetics of mixing in rare earth doped zirconia, hafnia, ceria, urania, and thoria, with systematic trends in energetics as a function of cation radius. High temperature oxide melt solution calorimetry has provided direct measurement of formation enthalpies of these refractory materials. Surface and interfacial energies have also been measured in yttria stabilized zirconia (YSZ) nanomaterials. Other ionic conductors having perovskite, apatite, and mellilite structures are discussed briefly.

  3. Development of solid electrolytes for water electrolysis at intermediate temperatures. Task 3 report; Annual report

    SciTech Connect

    Linkous, C.A.; Anderson, R.; Kopitzke, R.W.

    1995-12-01

    This project is an attempt to synthesize and fabricate proton exchange membranes for hydrogen production via water electrolysis that can take advantage of the better kinetic and thermodynamic conditions that exist at higher temperatures. Current PEM technology is limited to the 125--150 C range. Based on previous work evaluating thermohydrolytic stability, some 5 families of polymers were chosen as viable candidates: polyether ketones, polyether sulfones, fluorinated polyimides, polybenzimidazoles, and polyphenyl quinoxalines. Several of these have been converted into ionomers via sulfonation and fashioned into membranes for evaluation. In particular, the sulfonated polyetheretherketone, or SPEEK, was tested for water uptake, thermo-conductimetric analysis, and performance as the solid electrolyte material in an electrolysis cell. Results comparable to commercial perfluorocarbon sulfonates were obtained.

  4. Table 2.4. Cell voltages with solid state electrolyte systems

    NASA Astrophysics Data System (ADS)

    Holze, R.

    This document is part of Volume 9 `Electrochemistry', Subvolume A, of Landolt-Börnstein - Group IV `Physical Chemistry'. The document lists normal voltages of cells with solid state electrolyte systems. The cells are composed of the following materials: silver (Ag), aluminium (Al), barium (Ba), bismuth (Bi), carbon (C), cadmium (Cd), cobalt (Co), chromium (Cr), cesium (Cs), copper (Cu), iron (Fe), germanium (Ge), hafnium (Hf), iridium (Ir), potassium (K), lanthanum (La), lithium (Li), magnesium (Mg), manganese (Mn), molybdenum (Mo), nitrogen (N), natrium (Na), niobium (Nb), neodymium (Nd), nickel (Ni), lead (Pb), palladium (Pd), rhodium (Rh), ruthenium (Ru), antimony (Sb), samarium (Sm), tin (Sn), strontium (Sr), tantalum (Ta), tellurium (Te), thorium (Th), thallium (Tl), uranium (U), yttrium (Y), zinc (Zn), zirconium (Zr). The compositions of the cells are given along with, where available, the temperatures of mesurements of the voltages.

  5. Development status of solid polymer electrolyte water electrolysis for manned spacecraft life support systems

    NASA Technical Reports Server (NTRS)

    Nuttall, L. J.; Titterington, W. A.

    1974-01-01

    Details of the design and system verification test results are presented for a six-man-rated oxygen generation system. The system configuration incorporates components and instrumentation for computer-controlled operation with automatic start-up/shutdown sequencing, fault detection and isolation, and with self-contained sensors and controls for automatic safe emergency shutdown. All fluid and electrical components, sensors, and electronic controls are designed to be easily maintainable under zero-gravity conditions. On-board component spares are utilized in the system concept to sustain long-term operation (six months minimum) in a manned spacecraft application. The system is centered on a 27-cell solid polymer electrolyte water electrolysis module which, combined with the associated system components and controls, forms a total system envelope 40 in. high, 40 in. wide, and 30 in. deep.

  6. Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

    DOEpatents

    Richardson, Thomas J.; Ross, Philip N.

    1999-01-01

    A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85.degree. C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1.times.10.sup.-8 cm.sup.2 /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

  7. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface.

    PubMed

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-07-15

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica.

  8. Method of producing ceramic distribution members for solid state electrolyte cells

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1995-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes, The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  9. Ceramic distribution members for solid state electrolyte cells and method of producing

    NASA Technical Reports Server (NTRS)

    Clark, Douglas J. (Inventor); Galica, Leo M. (Inventor); Losey, Robert W. (Inventor); Suitor, Jerry W. (Inventor)

    1993-01-01

    A solid state electrolyte cells apparatus and method of producing is disclosed. The apparatus can be used for separating oxygen from an oxygen-containing feedstock or as a fuel cell for reacting fluids. Cells can be stacked so that fluids can be introduced and removed from the apparatus through ceramic distribution members having ports designed for distributing the fluids in parallel flow to and from each cell. The distribution members can also serve as electrodes to membranes or as membrane members between electrodes. The distribution member design does not contain any horizontal internal ports which allows the member to be thin. A method of tape casting in combination with an embossing method allows intricate radial ribs and bosses to be formed on each distribution member. The bosses serve as seals for the ports and allow the distribution members to be made without any horizontal internal ports.

  10. Solid polymer electrolyte water electrolysis system development. [to generate oxygen for manned space station applications

    NASA Technical Reports Server (NTRS)

    1975-01-01

    Solid polymer electrolyte technology used in a water electrolysis system (WES) to generate oxygen and hydrogen for manned space station applications was investigated. A four-man rated, low pressure breadboard water electrolysis system with the necessary instrumentation and controls was fabricated and tested. A six man rated, high pressure, high temperature, advanced preprototype WES was developed. This configuration included the design and development of an advanced water electrolysis module, capable of operation at 400 psig and 200 F, and a dynamic phase separator/pump in place of a passive phase separator design. Evaluation of this system demonstrated the goal of safe, unattended automated operation at high pressure and high temperature with an accumulated gas generation time of over 1000 hours.

  11. Enhanced lithium ion conductivity in lithium lanthanum titanate solid electrolyte nanowires prepared by electrospinning

    NASA Astrophysics Data System (ADS)

    Yang, Ting; Li, Ying; Chan, Candace K.

    2015-08-01

    Solid electrolytes have great potential to address the safety issues of Li-ion batteries, but better synthesis methods are still required for ceramics such as lithium lanthanum titanate (LLTO) since current techniques require high-temperature calcination for long times. Here we report a new approach that utilizes electrospinning to prepare phase-pure polycrystalline LLTO nanowires with well-crystallized tetragonal structure after only 3 h calcination at 1000 °C. Pellets prepared from the electrospun LLTO nanowires had higher density, less void space, and higher Li+ conductivity compared to those comprised of LLTO prepared with conventional sol-gel methods. This work demonstrates the potential that electrospinning can provide towards improving the properties of sol-gel derived ceramics.

  12. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    NASA Astrophysics Data System (ADS)

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-07-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01-1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica.

  13. Characterization of NASICON-type Na solid electrolyte ceramics by impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Kazakevičius, E.; Kežionis, A.; Žukauskaitė, L.; Barré, M.; Šalkus, T.; Orliukas, A.

    2014-08-01

    Na solid electrolytes are cheaper than the ones of Li and could be of interest to apply in secondary batteries and gas sensors. In the present work, the NASICON-type Na1.3Ti1.7Al0.3(PO4)3 compound has been synthesized by Pechini method and the phase purity of the compound was confirmed by XRD. Ceramics of the compound were prepared in several different sintering temperatures and the morphology of the samples was examined by SEM. The investigation of the electrical properties was performed in 10 Hz to 3 ṡ 109 Hz and 300-500 K frequency and temperature ranges by means of impedance spectroscopy. The impedance spectra were analyzed and observed dispersions were related to microstructure of the ceramics.

  14. Nanostructured Gd-CeO2 electrolyte for solid oxide fuel cell by aqueous tape casting

    NASA Astrophysics Data System (ADS)

    Akbari-Fakhrabadi, A.; Mangalaraja, R. V.; Sanhueza, Felipe A.; Avila, Ricardo E.; Ananthakumar, S.; Chan, S. H.

    2012-11-01

    Gadolinia-doped ceria (Ce0.9Gd0.1O1.95, GDC) electrolyte was fabricated by aqueous-based tape casting method for solid oxide fuel cells (SOFCs). The ceramic powder prepared by combustion synthesis was used with poly acrylic acid (PAA), poly vinyl alcohol (PVA), poly ethylene glycol (PEG), Octanol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylate and double distilled water as dispersant, binder, plasticizer, defoamer, surfactant and solvent respectively, to prepare stable GDC slurry. The conditions for preparing stable GDC slurries were studied and optimized by sedimentation, zeta potential and viscosity measurements. Green tapes with smooth surface, flexibility, thickness in the range of 0.35-0.4 mm and 45% relative green density were prepared. Conventional and flash sintering techniques were used and compared for densification which demonstrated the possibility of surpassing sintering at high temperatures and retarding related grain growth.

  15. Fast Na/+/-ion transport in skeleton structures. [solid electrolyte applications

    NASA Technical Reports Server (NTRS)

    Goodenough, J. B.; Hong, H. Y.-P.; Kafalas, J. A.

    1976-01-01

    The skeleton structures considered in the investigations consist of a rigid subarray with an interconnected interstitial space in which ions move in three dimensions. The classes of skeleton structures investigated include the Im3 phase of high-pressure KSbO3, the defect-pyrochlore structure illustrated by RbMgAlF6, and the carnegieite structure of high-temperature NaAlSiO4. A description is given of the results obtained in transport measurements involving dense polycrystalline ceramic disks. Results obtained in the case of the Na(+)-ion transport in Na3Zr2PSi2O12 appear particularly promising concerning the possible use of such substances in solid-electrolyte applications.

  16. The thermal stability of sodium beta''-Alumina solid electrolyte ceramic in AMTEC cells

    NASA Astrophysics Data System (ADS)

    Williams, Roger M.; Ryan, Margaret A.; Homer, Margie L.; Lara, Liana; Manatt, Ken; Shields, Virgil; Cortez, Roger H.; Kulleck, James

    1999-01-01

    A critical component of alkali metal thermal-to electric converter (AMTEC) devices for long duration space missions is the beta''-alumina solid electrolyte ceramic (BASE), for which there exists no substitute. The temperature and environmental conditions under which BASE remains stable control operational parameters of AMTEC devices. We have used mass loss experiments in vacuum to 1573K to characterize the kinetics of BASE decomposition, and conductivity and exchange current measurements in sodium vapor filled exposure cells to 1223K to investigate changes in the BASE which affect its ionic conductivity. There is no clear evidence of direct thermal decomposition of BASE below 1273K, although limited soda loss may occur. Reactive metals such as Mn or Cr can react with BASE at temperatures at least as low as 1223K.

  17. Performance and modelling of a direct methanol solid polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Scott, K.; Taama, W.; Cruickshank, J.

    The performance and modelling of a direct methanol fuel cell based on a solid polymer electrolyte membrane (SPE) is reported. Two sizes of cell are used: a small cell with an area of 9 cm 2 and a large single cell with an area of 250 cm 2. The fuel cell utilises a vapourised methanol fuel at a porous carbon/Pt-Ru catalyst electrode. The performance of the fuel cell is affected by the cross-over of methanol from the anode to the cathode through the polymer membrane and this behaviour is modelled. To evaluate cell performance, mathematical models are constructed which describe mass transport in the porous electrode structures and the potential and concentration distributions in the electrode regions. These models are used to predict the cell voltage and current density response of the fuel cell.

  18. Electrolytes at Solid-Water Interfaces: Theoretical Studies for Practical Applications

    SciTech Connect

    Striolo, Alberto

    2013-09-23

    The goal of this research program was to determine how a solid substrate affects structure and dynamics of aqueous electrolyte solutions. From fundamental observations, we seek to improve practical applications. Of particular interest at the project inset were carbon nanotube separation, electric double layer capacitors, and water desalination. As time progresses, we became interested in sub-surface water transport and fate, and in hydraulic fracturing. We employed an arsenal of techniques based on atomistic molecular dynamics simulations. We validated our methods using experimental data, to propose practical improvements. Some experiments were conducted in house. We established valuable collaborations with experienced scientists at National Laboratories to provide information not attainable with our in-house resources.

  19. Lithium phosphorus oxynitride solid-state thin-film electrolyte deposited and modified by bias sputtering and low temperature annealing

    SciTech Connect

    Chiu, K.-F.; Chen, C. C.; Lin, K. M.; Lo, C. C.; Lin, H. C.; Ho, W.-H.; Jiang, C. S.

    2010-07-15

    Amorphous lithium phosphorus oxynitride (LiPON) solid-state thin-film electrolyte has been deposited and characterized. The thin films were prepared by rf magnetron sputtering under various substrate biases. By fabricating under different substrate biases and applying low temperature annealing (473 K), the properties of the LiPON thin-film electrolytes and the electrolyte/cathode interfaces were modified. The ionic conductivity as high as 9.4x10{sup -4} S m{sup -1} can be obtained by depositing at optimal bias. The performances of the consequently fabricated SnO{sub 2}/LiPON/LiMn{sub 2}O{sub 4} all-solid-state lithium ion thin-film batteries were improved using the bias sputtering technique, due to the enhanced the ionic conductivity and uniform interface.

  20. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    SciTech Connect

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-05-30

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  1. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    NASA Astrophysics Data System (ADS)

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; Han, Lili; Grillon, Nathanael; Guy-Bouyssou, Delphine; Bouyssou, Emilien; Proust, Marina; Meng, Ying Shirley

    2016-08-01

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte - electrode interfaces will be critical to improve performance. In this study, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grew in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. The stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.

  2. Plasma membranes modified by plasma treatment or deposition as solid electrolytes for potential application in solid alkaline fuel cells.

    PubMed

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-07-30

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane.

  3. Solid Polymer Electrolytes Based on Functionalized Tannic Acids from Natural Resources for All-Solid-State Lithium-Ion Batteries.

    PubMed

    Shim, Jimin; Bae, Ki Yoon; Kim, Hee Joong; Lee, Jin Hong; Kim, Dong-Gyun; Yoon, Woo Young; Lee, Jong-Chan

    2015-12-21

    Solid polymer electrolytes (SPEs) for all-solid-state lithium-ion batteries are prepared by simple one-pot polymerization induced by ultraviolet (UV) light using poly(ethylene glycol) methyl ether methacrylate (PEGMA) as an ion-conducting monomeric unit and tannic acid (TA)-based crosslinking agent and plasticizer. The crosslinking agent and plasticizer based on natural resources are obtained from the reaction of TA with glycidyl methacrylate and glycidyl poly(ethylene glycol), respectively. Dimensionally stable free-standing SPE having a large ionic conductivity of 5.6×10(-4)  Scm(-1) at room temperature can be obtained by the polymerization of PEGMA into P(PEGMA) with a very small amount (0.1 wt %) of the crosslinking agent and 2.0 wt % of the plasticizer. The ionic conductivity value of SPE with a crosslinked structure is one order of magnitude larger than that of linear P(PEGMA) in the waxy state.

  4. Plasma Membranes Modified by Plasma Treatment or Deposition as Solid Electrolytes for Potential Application in Solid Alkaline Fuel Cells

    PubMed Central

    Reinholdt, Marc; Ilie, Alina; Roualdès, Stéphanie; Frugier, Jérémy; Schieda, Mauricio; Coutanceau, Christophe; Martemianov, Serguei; Flaud, Valérie; Beche, Eric; Durand, Jean

    2012-01-01

    In the highly competitive market of fuel cells, solid alkaline fuel cells using liquid fuel (such as cheap, non-toxic and non-valorized glycerol) and not requiring noble metal as catalyst seem quite promising. One of the main hurdles for emergence of such a technology is the development of a hydroxide-conducting membrane characterized by both high conductivity and low fuel permeability. Plasma treatments can enable to positively tune the main fuel cell membrane requirements. In this work, commercial ADP-Morgane® fluorinated polymer membranes and a new brand of cross-linked poly(aryl-ether) polymer membranes, named AMELI-32®, both containing quaternary ammonium functionalities, have been modified by argon plasma treatment or triallylamine-based plasma deposit. Under the concomitant etching/cross-linking/oxidation effects inherent to the plasma modification, transport properties (ionic exchange capacity, water uptake, ionic conductivity and fuel retention) of membranes have been improved. Consequently, using plasma modified ADP-Morgane® membrane as electrolyte in a solid alkaline fuel cell operating with glycerol as fuel has allowed increasing the maximum power density by a factor 3 when compared to the untreated membrane. PMID:24958295

  5. Local electrical and dielectric properties of nanocrystalline solid oxide fuel cell electrolytes

    NASA Astrophysics Data System (ADS)

    Perry, Nicola Helen

    Reducing the operating temperature of solid oxide fuel cells (SOFCs), to improve durability and lower cost, requires an increase in the low temperature oxygen-ion conductivity of the electrolyte. This work investigates whether the electrolyte conductivity could be increased by decreasing the grain size into the nanoscale. Bulk electrolytes - cubic yttria-stabilized zirconia (YSZ, with 8mol% Y2O3), tetragonal zirconia polycrystal (TZP, with 3mol% Y2O3), and Sr- and Mg- co-doped LaGaO3 (LSGM) - were fabricated with grain sizes ranging from 10nm to 3mum, using commercial or sol-gel-derived nanopowders and various sintering techniques. Local grain boundary and grain core conductivities and dielectric constants were analyzed over a range of temperatures and atmospheres using AC-impedance spectroscopy and our novel nano-Grain Composite Model, and interpreted in terms of grain-size dependent defect chemistry (e.g. space charge models, local thermodynamics, and impurity/ acceptor segregation). All three oxides exhibited qualitatively similar electrical/ dielectric behavior. Their single crystal/ grain core dielectric constants exhibited an upturn with temperature, which was attributed to the onset of dipolar relaxation. Grain boundary dielectric constants were consistently higher than grain core dielectric constants at the nanoscale. n-GCM-derived electrical grain boundary half-widths agreed well with measured acceptor dopant segregation widths at grain boundaries. The local grain boundary conductivity was consistently increased in nanocrystalline vs. microcrystalline samples, although the mechanisms responsible for this behavior differed in each material. Grain core conductivity did not change with grain size in each case. Despite the increase in local grain boundary conductivity at the nanoscale, the total conductivity decreased monotonically with decreasing grain size in all three electrolytes; the grain boundaries remain barriers to transport (relative to grain cores

  6. High-temperature solid-state dye-sensitized solar cells based on organic ionic plastic crystal electrolytes.

    PubMed

    Li, Qing; Zhao, Jie; Sun, Baoquan; Lin, Bencai; Qiu, Lihua; Zhang, Yueguang; Chen, Xiaojian; Lu, Jianmei; Yan, Feng

    2012-02-14

    Organic ionic plastic crystal, 1-ethyl-1-methyl pyrrolidinium iodide (P(12) I), is employed as the solid-state electrolytes for dye-sensitized solar cells. The fabricated solid-state devices show an overall power conversion efficiency of ~5.8% under AM 1.5 radiation (50 mW/cm(2) ) and excellent long-term stability at 80 °C.

  7. Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

    2016-02-01

    The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

  8. Methods for using novel cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    DOEpatents

    Jacobson, Allan J.; Wang, Shuangyan; Kim, Gun Tae

    2016-01-12

    Methods using novel cathode, electrolyte and oxygen separation materials operating at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes include oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

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

    DOE PAGES

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

    2015-08-06

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

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

    NASA Technical Reports Server (NTRS)

    Porter, F. J., Jr.

    1972-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  12. All solid-state redox supercapacitors based on supramolecular 1,5-diaminoanthraquinone oligomeric electrode and polymeric electrolytes

    NASA Astrophysics Data System (ADS)

    Hashmi, S. A.; Suematsu, Shunzo; Naoi, Katsuhiko

    Supramolecular conducting oligomeric 1,5-diaminoanthraquinone (DAAQ)-based all solid-state redox supercapacitors have been fabricated with the solid polymer electrolyte, poly vinyl alcohol (PVA)-H 3PO 4 blend and polymeric gel electrolyte poly methyl methacrylate (PMMA)-ethylene carbonate (EC)-propylene carbonate (PC)-tetra ethyl ammonium perchlorate (TEAClO 4) system. The films of gel electrolyte of the optimized composition PMMA (35 wt.%)-EC:PC (1:1 v/v)-1 M TEAClO 4 and polymer electrolyte PVA-H 3PO 4 (50:50 w/w) blend exhibited high ionic conductivity (10 -4 to 10 -3 S cm -1 at room temperature) with good mechanical strength, suitable for application in electrochemical supercapacitors. The capacitors have been characterized using a.c. impedance spectroscopy, linear sweep voltammetry and prolonged cyclic test. The maximum capacitance value of 3.7-5.4 mF cm -2 (equivalent to single electrode capacitance 125-184 F g -1 of DAAQ electrode) has been observed for the PMMA-gel electrolyte based capacitor. This corresponds to the energy density 92-135 Wh kg -1. System based on the proton-conducting PVA-H 3PO 4 polymer blend, however has relatively lower capacitance of 1.1-4.0 mF cm -2 (equivalent to single electrode capacitance of 36-136 F g -1).

  13. Conducting gel electrolytes with microporous structures for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Yuan, Shuangshuang; Tang, Qunwei; He, Benlin; Yu, Liangmin

    2015-01-01

    Conducting gel electrolytes from poly(acrylic acid)-cetyltrimethylammonium bromide/polyaniline (PAA-CTAB/PANi) and poly(acrylic acid)-cetyltrimethylammonium bromide/polypyrrole (PAA-CTAB/PPy) are synthesized under driving forces of both osmotic pressure and capillary force within microporous PAA-CTAB matrix. The as-synthesized PAA-CTAB/PANi or PAA-CTAB/PPy can extend the reduction reaction of triiodides from gel electrolyte/Pt counter electrode interface to both interface and three-dimensional framework of conducting gel electrolyte due to the electrical conduction of PANi or PPy toward reflux electrons (electrons from external circuit to Pt counter electrode). The enhanced kinetics for triiodides → iodide conversion is promising in elevating photovoltaic performances of quasi-solid-state dye-sensitized solar cells (DSSCs). Driving forces by both osmotic pressure across PAA-CTAB matrix and capillary force presenting in micropores can elevate the loading of PANi or PPy incorporated liquid electrolyte in per unit volume, leading to further enhancement in charge transfer and electrocatalytic activity. The total power conversion efficiencies of 7.11% and 6.39% are recorded in the solar cells with PAA-CTAB/PANi and PAA-CTAB/PPy electrolytes under one sun irradiation, respectively, whereas it is 6.07% for the cell device with pure PAA-CTAB gel electrolyte. Electrical and electrochemical characterizations reveal that the electrical conduction and electrocatalytic performances have been significantly enhanced by incorporating electrical conducting PANi or PPy into microporous PAA-CTAB matrix. The concept opens a new approach of fabricating efficient polymer gel electrolytes for robust quasi-solid-state DSSC applications.

  14. Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

    DOEpatents

    Kuo, Lewis J. H.; Singh, Prabhakar; Ruka, Roswell J.; Vasilow, Theodore R.; Bratton, Raymond J.

    1997-01-01

    A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators.

  15. Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

    DOEpatents

    Kuo, L.J.H.; Singh, P.; Ruka, R.J.; Vasilow, T.R.; Bratton, R.J.

    1997-11-11

    A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators. 4 figs.

  16. Ion transport in polycarbonate based solid polymer electrolytes: experimental and computational investigations.

    PubMed

    Sun, Bing; Mindemark, Jonas; Morozov, Evgeny V; Costa, Luciano T; Bergman, Martin; Johansson, Patrik; Fang, Yuan; Furó, István; Brandell, Daniel

    2016-04-14

    Among the alternative host materials for solid polymer electrolytes (SPEs), polycarbonates have recently shown promising functionality in all-solid-state lithium batteries from ambient to elevated temperatures. While the computational and experimental investigations of ion conduction in conventional polyethers have been extensive, the ion transport in polycarbonates has been much less studied. The present work investigates the ionic transport behavior in SPEs based on poly(trimethylene carbonate) (PTMC) and its co-polymer with ε-caprolactone (CL) via both experimental and computational approaches. FTIR spectra indicated a preferential local coordination between Li(+) and ester carbonyl oxygen atoms in the P(TMC20CL80) co-polymer SPE. Diffusion NMR revealed that the co-polymer SPE also displays higher ion mobilities than PTMC. For both systems, locally oriented polymer domains, a few hundred nanometers in size and with limited connections between them, were inferred from the NMR spin relaxation and diffusion data. Potentiostatic polarization experiments revealed notably higher cationic transference numbers in the polycarbonate based SPEs as compared to conventional polyether based SPEs. In addition, MD simulations provided atomic-scale insight into the structure-dynamics properties, including confirmation of a preferential Li(+)-carbonyl oxygen atom coordination, with a preference in coordination to the ester based monomers. A coupling of the Li-ion dynamics to the polymer chain dynamics was indicated by both simulations and experiments.

  17. One-pot preparation of new copolymer electrolytes with tunable network structure for all-solid-state lithium battery

    NASA Astrophysics Data System (ADS)

    Chen, Bo; Xu, Qiang; Huang, Zhen; Zhao, Yanran; Chen, Shaojie; Xu, Xiaoxiong

    2016-11-01

    A new class of copolymer electrolytes with tunable network structure is successfully designed and prepared via a facile one-pot reaction. The trimethylolpropane triglycidyl ether (TMPEG) is cross-linked with poly (ethylene glycol) diamine (NPEG) to create well-defined solid network polymer electrolyte (SNPE). The network structure could be tuned by changing the molar ratio of TMPEG and NPEG or the molecular weight of NPEG. The effects of molecular weight of NPEG and molar ratio of EO/Li+ on the ionic conductivity are systematically investigated. The optimal electrolyte TMPEG-NPEG4K[2:1]-16:1 presents a maximum conductivity of 1.10 × 10-4 S cm-1 under 30 °C, and an 18-fold ionic conductivity enhancement in that of PEO-based electrolyte. Furthermore, it also exhibits wide electrochemical window (0-5.4 V), excellent compatibility with metallic Li, and superior mechanical properties. The all-solid-state lithium batteries LiFePO4/Li are assembled with TMPEG-NPEG4K[2:1]-16:1 electrolyte, and present good cycling and rate performance under 60 °C. The initial discharge specific capacities of the batteries are 161.7 mAh g-1 at 0.2 C and 132.7 mAh g-1 at 1 C, and the capacity retention ratio can be retained at 90.6% and 90.5% after 100 cycles. This new copolymer electrolyte may become a promising candidate for applications in all-solid-state lithium battery.

  18. Absorbency and conductivity of quasi-solid-state polymer electrolytes for dye-sensitized solar cells: A characterization review

    NASA Astrophysics Data System (ADS)

    Mohamad, Ahmad Azmin

    2016-10-01

    The application of quasi-solid state electrolytes for dye-sensitized solar cells opens up an interesting research field to explore, which is evident from the increasing amount of publications on this topic. Since 2010, significant progress has been made with new and more complicated quasi-solid-states materials being produced. The optimization of new materials requires specific characterizations. This review presents a comprehensive overview and recent progress of characterization methods for studying quasi-solid-state electrolytes. Emphasis is then placed on the absorbency and conductivity characterizations. Each characterization will be reviewed according to the objective, experimental set-up, summary of important outcomes, and a few case studies worth discussing. Finally, strategies for future characterizations and developments are described.

  19. A synthesis of crystalline Li7P3S11 solid electrolyte from 1,2-dimethoxyethane solvent

    NASA Astrophysics Data System (ADS)

    Ito, Seitaro; Nakakita, Moeka; Aihara, Yuichi; Uehara, Takahiro; Machida, Nobuya

    2014-12-01

    A crystalline solid electrolyte, Li7P3S11, was synthesized by a liquid-phase reaction of Li2S and P2S5 in an organic solvent. A precursor, which was a mixture of solvated Li3PS4 and Li4P2S7, was prepared by mixing Li2S and P2S5 powders in 1,2-dimethoxyethane (DME) solvent. After a vacuum drying of the precursor, the crystalline phase of Li7P3S11 was obtained by heat treatment at 250 °C for 1 h in Ar atmosphere. The Li7P3S11 sample showed high ionic conductivity of 2.7 × 10-4 S cm-1 at room temperature. The liquid-phase synthesis of the solid electrolyte has advantages for mass-production of all-solid-state batteries.

  20. Ionic Liquid Electrolytes for Li–Air Batteries: Lithium Metal Cycling

    PubMed Central

    Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

    2014-01-01

    In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li–air cells. PMID:24815072

  1. Ionic liquid electrolytes for Li-air batteries: lithium metal cycling.

    PubMed

    Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

    2014-05-08

    In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li-air cells.

  2. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

    PubMed

    Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

    2012-02-17

    All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

  3. Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

    NASA Astrophysics Data System (ADS)

    Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

    2017-01-01

    A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm‑1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

  4. Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

    PubMed Central

    Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

    2017-01-01

    A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

  5. A system using solid ceramic oxygen electrolyte cells to measure oxygen fugacities in gas-mixing systems

    NASA Technical Reports Server (NTRS)

    Williams, R. J.; Mullins, O.

    1976-01-01

    Details are given for the construction and operation of a 101.3 kN/sq m (1 atmosphere) redox control system. A solid ceramic oxygen electrolyte cell is used to monitor the oxygen fugacity in the furnace. The system consists of a vertical quench, gas mixing furnace with heads designed for mounting the electrolyte cell and with facilities for inserting and removing the samples. The system also contains the high input impedance electronics necessary for measurements, a simplified version of a gas mixing apparatus, and devices for experiments under controlled rates of change relative to temperature and redox state. The calibration and maintenance of the system are discussed.

  6. Enhanced molecular dynamics for simulating porous interphase layers in batteries.

    SciTech Connect

    Zimmerman, Jonathan A.; Wong, Bryan Matthew; Jones, Reese E.; Templeton, Jeremy Alan; Lee, Jonathan

    2009-10-01

    Understanding charge transport processes at a molecular level using computational techniques is currently hindered by a lack of appropriate models for incorporating anistropic electric fields in molecular dynamics (MD) simulations. An important technological example is ion transport through solid-electrolyte interphase (SEI) layers that form in many common types of batteries. These layers regulate the rate at which electro-chemical reactions occur, affecting power, safety, and reliability. In this work, we develop a model for incorporating electric fields in MD using an atomistic-to-continuum framework. This framework provides the mathematical and algorithmic infrastructure to couple finite element (FE) representations of continuous data with atomic data. In this application, the electric potential is represented on a FE mesh and is calculated from a Poisson equation with source terms determined by the distribution of the atomic charges. Boundary conditions can be imposed naturally using the FE description of the potential, which then propagates to each atom through modified forces. The method is verified using simulations where analytical or theoretical solutions are known. Calculations of salt water solutions in complex domains are performed to understand how ions are attracted to charged surfaces in the presence of electric fields and interfering media.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  8. In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO2 Lithium Batteries

    PubMed Central

    Chai, Jingchao; Ma, Jun; Wang, Jia; Liu, Xiaochen; Liu, Haisheng; Zhang, Jianjun; Chen, Liquan

    2016-01-01

    Nowadays it is extremely urgent to seek high performance solid polymer electrolyte that possesses both interfacial stability toward lithium/graphitic anodes and high voltage cathodes for high energy density solid state batteries. Inspired by the positive interfacial effect of vinylene carbonate additive on solid electrolyte interface, a novel poly (vinylene carbonate) based solid polymer electrolyte is presented via a facile in situ polymerization process in this paper. It is manifested that poly (vinylene carbonate) based solid polymer electrolyte possess a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 9.82 × 10−5 S cm−1 at 50 °C. Moreover, it is demonstrated that high voltage LiCoO2/Li batteries using this solid polymer electrolyte display stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristic. It is believed that poly (vinylene carbonate) based electrolyte can be a very promising solid polymer electrolyte candidate for high energy density lithium batteries. PMID:28251055

  9. In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO2 Lithium Batteries.

    PubMed

    Chai, Jingchao; Liu, Zhihong; Ma, Jun; Wang, Jia; Liu, Xiaochen; Liu, Haisheng; Zhang, Jianjun; Cui, Guanglei; Chen, Liquan

    2017-02-01

    Nowadays it is extremely urgent to seek high performance solid polymer electrolyte that possesses both interfacial stability toward lithium/graphitic anodes and high voltage cathodes for high energy density solid state batteries. Inspired by the positive interfacial effect of vinylene carbonate additive on solid electrolyte interface, a novel poly (vinylene carbonate) based solid polymer electrolyte is presented via a facile in situ polymerization process in this paper. It is manifested that poly (vinylene carbonate) based solid polymer electrolyte possess a superior electrochemical stability window up to 4.5 V versus Li/Li(+) and considerable ionic conductivity of 9.82 × 10(-5) S cm(-1) at 50 °C. Moreover, it is demonstrated that high voltage LiCoO2/Li batteries using this solid polymer electrolyte display stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristic. It is believed that poly (vinylene carbonate) based electrolyte can be a very promising solid polymer electrolyte candidate for high energy density lithium batteries.

  10. Ultrafast laser induced breakdown spectroscopy of electrode/electrolyte interfaces

    NASA Astrophysics Data System (ADS)

    Zorba, Vassilia; Syzdek, Jaroslaw; Mao, Xianglei; Russo, Richard E.; Kostecki, Robert

    2012-06-01

    Direct chemical analysis of electrode/electrolyte interfaces can provide critical information on surface phenomena that define and control the performance of Li-based battery systems. In this work, we introduce the use of ex situ femtosecond laser induced breakdown spectroscopy to probe compositional variations within the solid electrolyte interphase (SEI) layer. Nanometer-scale depth resolution was achieved for elemental and molecular depth profiling of SEI layers formed on highly oriented pyrolytic graphite electrodes in an organic carbonate-based electrolyte. This work demonstrates the unique ability of ultrafast laser spectroscopy as a highly versatile, light element-sensitive technique for direct chemical analysis of interfacial layers in electrochemical energy storage systems.

  11. 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.

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

    NASA Technical Reports Server (NTRS)

    Srinivasan, Supramaniam; Manko, David J.; Enayatullah, Mohammad; Appleby, A. John

    1989-01-01

    High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

  13. Kinetic factors determining conducting filament formation in solid polymer electrolyte based planar devices

    NASA Astrophysics Data System (ADS)

    Krishnan, Karthik; Aono, Masakazu; Tsuruoka, Tohru

    2016-07-01

    Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength, and the reduction sites for precipitation. Different filament formations, resulting from unidirectional and dendritic growth behaviours, can be controlled by tuning specified parameters, which in turn improves the stability and performance of SPE-based devices.Resistive switching characteristics and conducting filament formation dynamics in solid polymer electrolyte (SPE) based planar-type atomic switches, with opposing active Ag and inert Pt electrodes, have been investigated by optimizing the device configuration and experimental parameters such as the gap distance between the electrodes, the salt inclusion in the polymer matrix, and the compliance current applied in current-voltage measurements. The high ionic conductivities of SPE enabled us to make scanning electron microscopy observations of the filament formation processes in the sub-micrometer to micrometer ranges. It was found that switching behaviour and filament growth morphology depend strongly on several kinetic factors, such as the redox reaction rate at the electrode-polymer interfaces, ion mobility in the polymer matrix, electric field strength

  14. A lightweight solid polymer electrolyte fuel cell with stack power density of 3 kW/lb (7 kW/kg)

    NASA Astrophysics Data System (ADS)

    Appleby, A. John

    The objectives of the solid polymer electrolyte fuel cell project are: (1) Investigations of physico-chemical properties of various solid polymer electrolyte electrode kinetics at Pt/solid polymer electrolyte interfaces; (2) Optimization of low and high Pt-loading gas diffusion electrode conditions, structures, membrane bonding to obtain most effective electrocatalyst membrane interface and hence attain maximum fuel cell performance; and (3) Mathematical modeling of electrochemical, mass transfer and heat generation characteristics associated with cell operation to optimize fuel cell thermal and water management.

  15. Alkaline direct ethanol fuel cell performance using alkali-impregnated polyvinyl alcohol/functionalized carbon nano-tube solid electrolytes

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Yi; Lin, Jia-Shiun; Pan, Wen-Han; Shih, Chao-Ming; Liu, Ying-Ling; Lue, Shingjiang Jessie

    2016-01-01

    This study investigates the application of a polyvinyl alcohol (PVA)/functionalized carbon nano-tubes (m-CNTs) composite in alkaline direct ethanol fuel cells (ADEFC). The m-CNTs are functionalized with PVA using the ozone mediation method, and the PVA composite containing the modified CNTs is prepared. Adding m-CNT into the PVA matrix enhances the alkaline uptake and the ionic conductivity of the KOH-doped electrolyte. Meanwhile, the m-CNT-containing membrane exhibited a lower swelling ratio and suppressed ethanol permeability compared to the pristine PVA film. The optimal condition for the ADEFC is determined to be under operation at an anode feed of 3 M ethanol in a 5 M KOH solution (at a flow rate of 5 cm3 min-1) with a cathode feed of moisturized oxygen (with a flow rate of 100 cm3 min-1) and the KOH-doped PVA/m-CNT electrolyte. We achieved a peak power density value of 65 mW cm-2 at 60 °C, which is the highest among the ADEFC literature data and several times higher than the proton-exchange direct ethanol fuel cells using sulfonated membrane electrolytes. Therefore, the KOH-doped PVA/m-CNT electrolyte is a suitable solid electrolyte for ADEFCs and has potential for commercialization in alkaline fuel cell applications.

  16. Potential modulation of equilibrium and excitation phenomena at the electrolyte-solid interface

    SciTech Connect

    Furtak, T.E.

    1991-10-01

    This progress report covers the work accomplished from the beginning of Sept. 1990, through Sept. 1991. This includes the final portion of the last funding period as well as the first 7 months of the new period. During this time we have pursued our goal of studying the role of the interfacial potential difference in determining the ground and excited electronic sates of the electrolyte-solid system. Ours is program designed to provide fundamental information about this complicated environment. We seek to improve the techniques with which electrochemical interfaces can be studied and thereby observe details which have never before been measured. We are primarily concerned with optical techniques, but have also integrated conventional and non-conventional supplementary methods. We have developed the technique of optical second harmonic generation into a spectroscopy by performing the experiment with a wide range of nearly continuous incident photon energies. Through this advantage we have performed detailed tests of the interfacial potential as derived through local density functional methods in the jellium limit. Our data show that the theory is reasonably satisfactory when the surface is electron deficient. However, when the surface is negatively charged (electron excess) significant discrepancies are evident. At least part of this deviation has been explained by transitions involving potential modulated surface states. This project has helped clarify some important questions concerning the nonlinear optical properties of metals, as well as lay he ground work for future applications aimed at monitoring adsorption phenomena with optical second harmonic reflectance spectroscopy.

  17. Electrode and solid electrolyte thin films for secondary lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Chen, C. H.; Kelder, E. M.; Schoonman, J.

    Electrostatic spray deposition (ESD) was employed to prepare thin layers of Li 1.2Mn 2O 4 (nominal composition) and BPO 4:0.035Li 2O for all-solid-state thin film lithium-ion batteries. The relationships between layer morphologies and deposition conditions such as solvent composition of the precursor solutions and substrate temperature were investigated. It was found that a low substrate temperature and/or high boiling point of the solvent may lead to a relatively dense structure. Reticular porous structures are formed, if films were deposited at 250°C and a mixture of 85 vol.% butyl carbitol and 15 vol.% ethanol was used as the solvent. The Li 1.2Mn 2O 4 layers, formed in the 250-400°C temperature range, were amorphous or micro-crystalline. After annealing beyond 600 °C, they could be crystallized into a spinel-structured material. Glassy BPO 4:0.035Li 2O layers could fill the pores of porous Li 1.2Mn 2O 4 layers to form a dense intermediate electrolyte layer. Thin-film rocking-chair batteries, Li 1.2Mn 2O 4|BPO 4:0.035Li 2O|Li 1.2Mn 2O 4|Al, were prepared and revealed an open-circuit voltage of about 1.2 V after charging.

  18. Ion conducting polymers as solid electrolytes. Final report, 1985-1986

    SciTech Connect

    Semancik, J.D.

    1986-05-28

    Electrically conducting polymers have recently been the subject of much interest. In particular, their potential as electrolytes in solid-state batteries has gained the attention of the U.S. Navy. Current ion-conducting polymers have conductivities too low by a factor of ten at operational temperatures. In order to be able to obtain suitable conductivities in these polymers, a thorough understanding of the mechanisms governing ion motion in them must be attained. The processes involved in the ion conduction of one particular polymer, poly(propylene oxide) or PPO, were studied in this research. Samples were prepared using an ion-implantation procedure developed as part of the project as well as by the traditional chemical complexing technique involving alkali-metal salt doping. The samples produced were analyzed using both differential scanning calorimetry and audio-frequency complex impedance measurements. Results indicate that the polarity of the salts has a major effect upon the activation volume and the glass transition of PPO. As a result of these effects, it seems that nonpolar anions may aid in increasing the cationic transport number of the polymer. More importantly, the first direct numerical evidence of a connection between the large-scale segmental motions of the polymer chains and the chains and the conductivity has been established.

  19. Studies on the Properties of Plasticizer and Lithium Salt on PMMA-based Solid Polymer Electrolytes

    SciTech Connect

    Chew, K. W.; Tan, C. G.; Osman, Z.

    2010-03-11

    The effects of plasticizer and lithium salt on PMMA-based solid polymer electrolyte have been investigated. In current project, three system samples consisted of pure poly(methyl methacrylate (PMMA) system, plasticized poly(methyl methacrylate)(PMMA-EC) system and the LiCF{sub 3}SO{sub 3} salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system have been prepared using solution casting technique. The conductivities of the films from each system are characterized by impedance spectroscopy and infrared spectrum. With the addition of plasticizer, results show improvement on the ionic conductivity value where the value of 6.25x10{sup -10} Scm{sup -1} is obtained. This may be due to the nature of plasticizer that softens the polymer and hence enhanced the ionic transportation across the polymer. The room temperature conductivity for the highest conducting sample in the ([PMMA-EC]-LiCF{sub 3}SO{sub 3}) system is 1.36x10{sup -5} Scm{sup -1}. Fourier Transform Infrared Spectroscopy (FTIR) indicates complexation between the polymer and the plasticizer and the polymer, the plasticizer and the salts, and the result of XRD further supports the observation.

  20. Order-disorder transitions in gadolinium zirconate: A potential electrolyte material in solid oxide fuel cells

    SciTech Connect

    Meilicke, S.; Haile, S.

    1995-12-31

    Rare-earth, yttrium, and calcium doped zirconates are the materials of choice for electrolytes in solid oxide fuel cells. The dopant in these materials serves not only to stabilized the cubic phase of zirconia, but also to introduce anion defects that presumably increase the ionic conductivity. In order to understand the relationships between anion defect distribution, thermal history and ionic conductivity, the structural properties of gadolinium zirconate, Gd{sub 2}Zr{sub 2}O{sub 7}, have been examined via high-temperature x-ray powder diffraction. Gadolinium zirconate is an ideal material for such a structure-property-processing study: it shows ordering of defects at low temperatures, taking on a pyrochlore structure, and disordering at elevated temperature, taking on a defect fluorite structure. Diffraction experiments, performed as functions of time and temperature, confirmed the transition temperature to lie between 1,500 and 1,550 C. They also revealed that the transformation takes place most rapidly just below the transition temperature, indicating that the ordering process is kinetically constrained at low temperatures. Moreover, x-ray data collected at room temperature from quenched samples were found to be as useful, if not more so, than those collected in situ at high temperature. The latter are affected by thermal scattering, severely compromising data quality.

  1. Atomically resolved three-dimensional structures of electrolyte aqueous solutions near a solid surface

    PubMed Central

    Martin-Jimenez, Daniel; Chacon, Enrique; Tarazona, Pedro; Garcia, Ricardo

    2016-01-01

    Interfacial liquid layers play a central role in a variety of phenomena ranging from friction to molecular recognition. Liquids near a solid surface form an interfacial layer where the molecular structure is different from that of the bulk. Here we report atomic resolution three-dimensional images of electrolyte solutions near a mica surface that demonstrate the existence of three types of interfacial structures. At low concentrations (0.01–1 M), cations are adsorbed onto the mica. The cation layer is topped by a few hydration layers. At higher concentrations, the interfacial layer extends several nanometres into the liquid. It involves the alternation of cation and anion planes. Fluid Density Functional calculations show that water molecules are a critical factor for stabilizing the structure of the interfacial layer. The interfacial layer stabilizes a crystal-like structure compatible with liquid-like ion and solvent mobilities. At saturation, some ions precipitate and small crystals are formed on the mica. PMID:27416784

  2. Design and test status for life support applications of SPE oxygen generation systems. [Solid Polymer Electrolyte

    NASA Technical Reports Server (NTRS)

    Titterington, W. A.; Erickson, A. C.

    1975-01-01

    An advanced six-man rated oxygen generation system has been fabricated and tested as part of a NASA/JSC technology development program for a long lived, manned spacecraft life support system. Details of the design and tests results are presented. The system is based on the Solid Polymer Electrolyte (SPE) water electrolysis technology and its nominal operating conditions are 2760 kN/sq m (400 psia) and 355 K (180 F) with an electrolysis module current density capability up to 350 mA/sq cm (326 ASF). The system is centered on a 13-cell SPE water electrolysis module having a single cell active area of 214 sq cm (33 sq in) and it incorporates instrumentation and controls for single pushbutton automatic startup/shutdown, component fault detection and isolation, and self-contained sensors and controls for automatic safe emergency shutdown. The system has been tested in both the orbital cyclic and continuous mode of operation. Various parametric tests have been completed to define the system capability for potential application in spacecraft environmental systems.

  3. The dynamic-state effects of sodium ion contamination on the solid polymer electrolyte water electrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Linsong; Jie, Xiao; Shao, Zhi-Gang; Wang, Xunying; Yi, Baolian

    2013-11-01

    Na+ is a likely intrinsic impurity in water and is a potential cation impurity in the solid polymer electrolyte water electrolysis. In this paper, the dynamic-state effect of low concentration of Na+ is studied by adding Na+ into the deionized water fed in the SPE water electrolyser. The dynamic variation of cell voltage results show that the cell performance degraded more severely in the presence of Na+ impurity by anode poisoning than by cathode poisoning. The severity and poisoning rate of the cell depend on the Na+ concentration, water flow rate and cell temperature. However, the current density does not impact the extent of the cell voltage increase. In the meantime, an external reference electrode is used to measure the anode and cathode potentials. The performance degradation is mainly ascribed to the increase in cathode overpotential by anode poisoning. EIS measurements show that the performance difference primarily comes from the kinetics loss rather than the ohmic loss. The decrease of available protons in the three phase boundaries may lead to the increase in charge transfer resistance. The electron probe microanalysis tests show that Na+ remains in CCM even recovered with deionized water, which results in only partially recovered cell performance.

  4. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte

    NASA Astrophysics Data System (ADS)

    Dutta, Dipak; Nagapradeep, N.; Zhu, Haijin; Forsyth, Maria; Verma, Sandeep; Bhattacharyya, Aninda J.

    2016-04-01

    Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it’s in-built supply of Li+-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10‑7 to 10‑3 Ω‑1 cm‑1) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80–100 °C, from a dual Li+ and H+ (<100 °C) to a pure Li+ conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries.

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

    SciTech Connect

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

    2013-11-27

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

  6. Lithium battery with solid polymer electrolyte based on comb-like copolymers

    NASA Astrophysics Data System (ADS)

    Daigle, Jean-Christophe; Vijh, Ashok; Hovington, Pierre; Gagnon, Catherine; Hamel-Pâquet, Julie; Verreault, Serge; Turcotte, Nancy; Clément, Daniel; Guerfi, Abdelbast; Zaghib, Karim

    2015-04-01

    In this paper we report on the synthesis of comb-like copolymers as solid polymer electrolytes (SPE). The synthesis involved anionic polymerization of styrene (St) and 4-vinylanisole (VA) as the followed by grafting of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization (ATRP). The comb-like copolymer's structure was analyzed by Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The membranes were made by solvent casting and the morphologies were analyzed by atomic forces microscopy (AFM) and scanning electron microscopy (SEM). We observed that a nano and micro phase separation occurs which improves ionic conductivity. The ionic conductivities were determined by AC Impedance, which showed that the SPEs have good conductivities (10-5 Scm-1) at room temperature owing to the negligible values (<10 kJ mol-1) of the activation energies for conductivity. The batteries with these polymers exhibit a capacity of 146 mAh g-1 at C/24, and no evidence of degradation after intense cycling was observed. However, poor cycle life was observed at C/6 and C/3, which is a consequence of several factors. We partially explain that behavior by arguing that whereas PEO lightly "solvates" Li+ thus slowing Li-ion mobility, and PEGMA chains "solvate" Li ions too strongly, trapping and inhibiting their mobility.

  7. A new composite cathode for intermediate temperature solid oxide fuel cells with zirconia-based electrolytes

    NASA Astrophysics Data System (ADS)

    Zhang, Cuijuan; Huang, Kevin

    2017-02-01

    Improving the electrocatalytic activity of electrode materials is vitally important to achieve practically meaningful performance for intermediate temperature solid oxide fuel cells (IT-SOFCs). The present work develops a composite cathode consisting of an electronic conductor Sr-doped LaMnO3 (LSM) and an ionic conductor Y- and Ce- co-doped Bi2O3 (BYC7). BYC7 is an excellent oxide-ion conductor, exhibiting a high and stable ionic conductivity of 0.008 S cm-1 at 500 °C. The polarization resistance of LSM-BYC7 cathode in a symmetrical cell with doped ZrO2 as electrolyte varies from 5.76 at 500 °C to 0.25 Ω cm2 at 650 °C. The surface diffusion and charge transfer at the triple phase boundaries are the rate determining steps based on the dependence of polarization resistance on partial pressure of oxygen. The maximum power density of a ZrO2-based anode-supported cell with LSM-BYC7 composite cathode is 56.4, 154.6, 327.9, and 451.0 mW cm-2 at 500, 550, 600, and 650 °C respectively. AC impedance analysis reveals that the performance of IT-SOFC prepared in this study is actually limited by the anode, not by LSM-BYC7 cathode.

  8. Thermodynamic stability of Na 2ZrO 3 using the solid electrolyte galvanic cell technique

    NASA Astrophysics Data System (ADS)

    Subasri, R.; Mathews, T.; Swaminathan, K.; Sreedharan, O. M.

    2002-02-01

    The sodium potential in the test electrode (a) Pt,O 2,Na 2ZrO 3,ZrO 2 was measured by using the emf technique employing Na-β ″-alumina as the solid electrolyte in conjunction with (b) Pt,O 2,Al 2O 3,NaAl 11O 17, (c) Pt,O 2,Na 2MoO 4,Na 2Mo 2O 7 and (d) Pt,Na 2CO 3,CO 2,O 2 as the reference electrodes over the ranges 880-1045, 700-800 and 850-940 K, respectively. The emf results between electrodes (b) and (c) were utilized for internal consistency checks. From the results on cells formed between (a) and (b) and those on (a) and (c), the standard Gibbs energy of formation, ΔfGo (kJ/mol) of Na 2ZrO 3 was determined to be -1699.4+0.3652 T (K) valid over the temperature range 700-1045 K. The break in the emf data at 1045 K was corroborated by independent TG/DTA measurements carried out on Na 2ZrO 3 which exhibited an endotherm at 1055 K indicative of a phase transition in Na 2ZrO 3.

  9. N7-(carboxymethyl)guanine-Lithium Crystalline Complex: A Bioinspired Solid Electrolyte

    PubMed Central

    Dutta, Dipak; Nagapradeep, N.; Zhu, Haijin; Forsyth, Maria; Verma, Sandeep; Bhattacharyya, Aninda J.

    2016-01-01

    Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it’s in-built supply of Li+-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10−7 to 10−3 Ω−1 cm−1) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80–100 °C, from a dual Li+ and H+ (<100 °C) to a pure Li+ conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries. PMID:27091631

  10. Global Failure Criteria for Positive/Electrolyte/Negative Structure of Planar Solid Oxide Fuel Cell

    SciTech Connect

    Liu, Wenning N.; Sun, Xin; Khaleel, Mohammad A.; Qu, Jianmin

    2009-07-15

    Due to mismatch of the coefficients of thermal expansion of various layers in the positive/electrolyte/negative (PEN) structures of solid oxide fuel cells (SOFC), thermal stresses and warpage on the PEN are unavoidable due to the temperature changes from the stress-free sintering temperature to room temperature during the PEN manufacturing process. In the meantime, additional mechanical stresses will also be created by mechanical flattening during the stack assembly process. In order to ensure the structural integrity of the cell and stack of SOFC, it is necessary to develop failure criteria for SOFC PEN structures based on the initial flaws occurred during cell sintering and stack assembly. In this paper, the global relationship between the critical energy release rate and critical curvature and maximum displacement of the warped cells caused by the temperature changes as well as mechanical flattening process is established so that possible failure of SOFC PEN structures may be predicted deterministically by the measurement of the curvature and displacement of the warped cells.

  11. Performance/design formulation for a solid polymer based acid electrolyte hydrogen/air fuel cell

    NASA Astrophysics Data System (ADS)

    Sandhu, S. S.; Fellner, J. P.

    Mathematical development of preliminary performance/design equations for a hydrogen/air, solid polymer acid electrolyte based fuel cell is presented. The development is based on the principles of transport phenomena, intrinsic electrochemical kinetics, and classical thermodynamics. The developed formulation is intended to quantitatively describe the mass fraction profiles of the chemical species, hydrogen and oxygen, in the cell anode and cathode diffusion and electrocatalytic reaction layers as a function of the distance in the proton transport direction at an axial distance parallel to the cell anode or cathode channel flow. Given the cell geometry, chemical species and charge transport, and intrinsic electrochemical kinetic parameters, the developed formulation can be employed to compute the species local mass fluxes and predict the cell anode and cathode cell overvoltages for a desired geometric current density. The presented single cell performance predictive formulation has also been linked to the formulation needed to predict the performance of a stack of a number of identical PEMFCs connected in series.

  12. Modelling of temperature distribution in a solid polymer electrolyte fuel cell stack

    NASA Astrophysics Data System (ADS)

    Maggio, G.; Recupero, V.; Mantegazza, C.

    The production of electricity in a fuel cell system is associated with the production of an equivalent amount of thermal energy, both for large size power plants and for transportation applications. The heat released by the cells must be removed by a cooling system, characterized by its small size and weight, which must be able to assure uniform work conditions and reduce performance losses. Based upon realistic assumptions, a mathematical model has been developed to determine the temperature and current density distribution in a solid polymer electrolyte fuel cell (SPEFC) stack as a function of operating conditions and stack geometry. The model represents a useful tool to identify operating conditions, such as to have an optimal longitudinal and axial temperature profile, so allowing the design of cooling system and bipolar plates. In this paper, the model has been applied to determine the temperature profile of an experimental SPEFC stack. The model is validated by comparing model results with experimental measurements; simulated and experimental results agree satisfactorily.

  13. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    NASA Astrophysics Data System (ADS)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  14. Mobility enhancement of SnO2 nanowire transistors gated with a nanogranular SiO2 solid electrolyte.

    PubMed

    Sun, Jia; Huang, Wenlong; Qian, Chuan; Yang, Junliang; Gao, Yongli

    2014-01-21

    Field-effect transistors (FETs) based on semiconducting nanowires are the most fundamental electronic elements for exploring charge transport as well as possible applications in functional nanoelectronics. Here, we report the effect of different gate dielectrics on the electrical performance of SnO2 nanowire FETs. By using solid-electrolytes with large electric-double-layer (EDL) capacitance as gate dielectrics, both low-voltage operation and high gating efficiency can be obtained. Electrical transport measurements indicate that the nanowire FETs gated by solid-electrolytes show improved electrical performances in terms of on-current, sub-threshold swing, and mobility, in comparison to those gated by traditional thermally grown dielectrics. The observed performance improvement is possibly due to the reduction of the contact-resistance and the Schottky barrier at the semiconductor/metal junctions.

  15. Development of bulk-type all-solid-state lithium-sulfur battery using LiBH{sub 4} electrolyte

    SciTech Connect

    Unemoto, Atsushi Ikeshoji, Tamio; Yasaku, Syun; Matsuo, Motoaki; Nogami, Genki; Tazawa, Masaru; Taniguchi, Mitsugu; Orimo, Shin-ichi

    2014-08-25

    Stable battery operation of a bulk-type all-solid-state lithium-sulfur battery was demonstrated by using a LiBH{sub 4} electrolyte. The electrochemical activity of insulating elemental sulfur as the positive electrode was enhanced by the mutual dispersion of elemental sulfur and carbon in the composite powders. Subsequently, a tight interface between the sulfur-carbon composite and the LiBH{sub 4} powders was manifested only by cold-pressing owing to the highly deformable nature of the LiBH{sub 4} electrolyte. The high reducing ability of LiBH{sub 4} allows using the use of a Li negative electrode that enhances the energy density. The results demonstrate the interface modification of insulating sulfur and the architecture of an all-solid-state Li-S battery configuration with high energy density.

  16. Solid state double layer capacitor based on a polyether polymer electrolyte blend and nanostructured carbon black electrode composites

    NASA Astrophysics Data System (ADS)

    Lavall, Rodrigo L.; Borges, Raquel S.; Calado, Hállen D. R.; Welter, Cezar; Trigueiro, João P. C.; Rieumont, Jacques; Neves, Bernardo R. A.; Silva, Glaura G.

    An all solid double layer capacitor was assembled by using poly(ethylene oxide)/poly(propylene glycol)- b-poly(ethylene glycol)- b-poly(propylene glycol)-bis(2-aminopropyl ether) blend (PEO-NPPP) and LiClO 4 as polymer electrolyte layer and PEO-NPPP-carbon black (CB) as electrode film. High molecular weight PEO and the block copolymer NPPP with molecular mass of 2000 Da were employed, which means that the design is safe from the point of view of solvent or plasticizer leakage and thus, a separator is not necessary. Highly conductive with large surface area nanostructured carbon black was dispersed in the polymer blend to produce the electrode composite. The electrolyte and electrode multilayers prepared by spray were studied by differential scanning calorimetry, atomic force microscopy (AFM) and impedance spectroscopy. The ionic conductivity as a function of temperature was fitted with the Williams-Landel-Ferry equation, which indicates a conductivity mechanism typical of solid polymer electrolyte. AFM images of the nanocomposite electrode showed carbon black particles of approximately 60 nm in size well distributed in a semicrystalline and porous polymer blend coating. The solid double layer capacitor with 10 wt.% CB was designed with final thickness of approximately 130 μm and delivered a capacitance of 17 F g -1 with a cyclability of more than 1000 cycles. These characteristics make possible the construction of a miniature device in complete solid state which will avoid electrolyte leakage and present a performance superior to other similar electric double layer capacitors (EDLCs) presented in literature, as assessed in specific capacitance by total carbon mass.

  17. Transport Properties Of PbI2 Doped Silver Oxysalt Based Amorphous Solid Electrolytes

    NASA Astrophysics Data System (ADS)

    Shrisanjaykumar Jayswal, Manishkumar

    Solid electrolytes are a class of materials that conduct electricity by means of motion of ions like Ag+, Na+, Li +, Cu+, H+, F-, O -2 etc. in solid phase. The host materials include crystalline, polycrystalline, glasses, polymers and composites. Ion conducting glasses are one of the most sought after solid electrolytes that are useful in various electrochemical applications like solid state batteries, gas sensors, supercapacitors, electrochromic devices, to name a few. Since the discovery of fast silver ion transport in silver oxyhalide glasses at the end of the 1960s, many glasses showing large ionic conductivity up to 10-4 10-2 S/cm at room temperature have been developed, chiefly silver and copper ion conductors. The silver ion conducting glasses owe their high ionic conductivity mainly to stabilized alpha-AgI. AgI, as we know, undergoes a structural phase transition from wurtzite (beta phase) at room temperature to body centered cubic (alpha phase) structure at temperatures higher than 146 °C. The alpha-AgI possesses approximately six order of higher ionic conductivity than beta-AgI. The high ionic conductivity of alpha-AgI is attributed to its molten sublattice type of structure, which facilitates easy Ag+ ion migration, like a liquid. And hence, several attempts have been made to stabilize it at room temperature in crystalline as well as non-crystalline hosts like oxide and non-oxide glasses. Recently, in order to stabilize AgI in glasses, instead of directly doping it, indirect routes have also been explored. Where, a metal iodide salt along with silver oxide or silver phosphate is taken and an exchange reaction permitted by Hard and Soft, Acid and Base (HSAB) principle occurs between the two and AgI and metal oxide form in the glass forming melt. Work done in the present thesis has been organized in seven chapters as follows: Chapter 1: A review and background information of different solid electrolyte materials and their development is presented. Along

  18. A highly stable sodium solid-state electrolyte based on a dodeca/deca-borate equimolar mixture.

    PubMed

    Duchêne, L; Kühnel, R-S; Rentsch, D; Remhof, A; Hagemann, H; Battaglia, C

    2017-03-27

    Na2(B12H12)0.5(B10H10)0.5, a new solid-state sodium electrolyte is shown to offer high Na(+) conductivity of 0.9 mS cm(-1) at 20 °C, excellent thermal stability up to 300 °C, and a large electrochemical stability window of 3 V including stability towards sodium metal anodes, all essential prerequisites for a stable room-temperature 3 V all-solid-state sodium-ion battery.

  19. Oxygen vacancy diffusion across cathode/electrolyte interface in solid oxide fuel cells: An electrochemical phase-field model

    NASA Astrophysics Data System (ADS)

    Hong, Liang; Hu, Jia-Mian; Gerdes, Kirk; Chen, Long-Qing

    2015-08-01

    An electrochemical phase-field model is developed to study electronic and ionic transport across the cathode/electrolyte interface in solid oxide fuel cells. The influences of local current density and interfacial electrochemical reactions on the transport behaviors are incorporated. This model reproduces two electrochemical features. Nernst equation is satisfied through the thermodynamic equilibriums of the electron and oxygen vacancy. The distributions of charged species around the interface induce charge double layer. Moreover, we verify the nonlinear current/overpotential relationship. This model facilitates the exploration of problems in solid oxide fuel cells, which are associated with transport of species and electrochemical reactions at high operating temperature.

  20. Advanced electrolyte/additive for lithium-ion batteries with silicon anode

    SciTech Connect

    Zhang, Shuo; He, Meinan; Su, Chi-Cheung; Zhang, Zhengcheng

    2016-08-01

    State-of-the-art lithium-ion batteries (LIBs) are based on a lithium transition metal oxide cathode, a graphite anode and a nonaqueous carbonate electrolyte. To further increase the energy and power density of LIBs, silicon anodes have been intensively explored due to their high theoretical capacity, low operation potential, and low cost. However, the main challenges for Si anode are the large volume change during lithiation/delithiation process and the instability of the solid-electrolyte-interphase associated with this process. Recently, significant progress has been achieved via advanced material fabrication technologies and rational electrolyte design in terms of improving the Coulombic efficiency and capacity retention. In this paper, new developments in advanced electrolyte and additive for LIBs with Si anode were systematically reviewed, and perspectives over future research were suggested.

  1. Alkyl Pyrocarbonate Electrolyte Additives for Performance Enhancement of Li Ion Cells

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

    2000-01-01

    Lithium ion rechargeable batteries are being developed for various aerospace applications under a NASA-DoD Interagency program. These applications require further improvements in several areas, specifically in the cycle life for LEO and GEO satellites and in the low temperature performance for the Mars Lander and Rover missions. Accordingly, we have been pursuing research studies to achieve improvement in the low temperature performance, long cycle life and active life of Li ion cells. The studies are mainly focused on electrolytes, to identify newer formulations of new electrolyte additives to enhance Li permeability (at low temperatures) and stability towards the electrode. The latter approach is particularly aimed at the formation suitable SEI (solid electrolyte interphase) on carbon electrodes. In this paper, we report the beneficial effect of using alkyl pyrocarbonates as electrolyte additives to improve the low temperature performance of Li ion cells.

  2. A new solid polymer electrolyte incorporating Li10GeP2S12 into a polyethylene oxide matrix for all-solid-state lithium batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Yanran; Wu, Chuan; Peng, Gang; Chen, Xiaotian; Yao, Xiayin; Bai, Ying; Wu, Feng; Chen, Shaojie; Xu, Xiaoxiong

    2016-01-01

    Li10GeP2S12 (LGPS) is incorporated into polyethylene oxide (PEO) matrix to fabricate composite solid polymer electrolyte (SPE) membranes. The lithium ion conductivities of as-prepared composite membranes are evaluated, and the optimal composite membrane exhibits a maximum ionic conductivity of 1.21 × 10-3 S cm-1 at 80 °C and an electrochemical window of 0-5.7 V. The phase transition behaviors for electrolytes are characterized by DSC, and the possible reasons for their enhanced ionic conductivities are discussed. The LGPS microparticles, acting as active fillers incorporation into the PEO matrix, have a positive effect on the ionic conductivity, lithium ion transference number and electrochemical stabilities. In addition, two kinds of all-solid-state lithium batteries (LiFeO4/SPE/Li and LiCoO2/SPE/Li) are fabricated to demonstrate the good compatibility between this new SPE membrane and different electrodes. And the LiFePO4/Li battery exhibits fascinating electrochemical performance with high capacity retention (92.5% after 50 cycles at 60 °C) and attractive capacities of 158, 148, 138 and 99 mAh g-1 at current rates of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C, respectively. It is demonstrated that this new composite SPE should be a promising electrolyte applied in solid state batteries based on lithium metal electrode.

  3. All-solid state supercapacitors operating at 3.5 V by using ionic liquid based polymer electrolytes

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    All-solid state supercapacitors (SCs) using Ionic Liquid based Polymer Electrolyte (IL-b-PE) and activated carbon were assembled and characterized electrochemically. IL-b-PE consisted of a binary blend of a polymeric ionic liquid (PIL), poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (pDADMATFSI), and their corresponding ionic liquid (IL), N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR14TFSI) in a ratio of 40:60,w/w respectively. Assembling of supercapacitors simply consists of facing two impregnated electrodes without the need of additional separator. Several all-solid state SCs with impregnation ratios (IL-b-PE mass/active material mass) ranging from 5 to 18 were characterized. An all-solid state SC with impregnation ratio of 7 showed the best performance with specific capacitance (Cam) and real energy (Ereal) of 100 F g-1 and 32 Wh kg-1, respectively. After increasing temperatures to 60 °C, the performance of SCs further improved exhibiting Ereal values of 42 Wh kg-1 at 1 mA cm-2. These figures of merit are only slightly lower than those obtained for convectional SCs using pure PYR14TFS and much higher as compared with other solid SCs based on conventional polymer electrolytes. This is mainly due to the high electrochemical stability of this IL-b-PE that allows these solid SCs to operate at maximum voltages as high as 3.5 V for the first time.

  4. Method for producing electricity from a fuel cell having solid-oxide ionic electrolyte

    DOEpatents

    Mason, David M.

    1984-01-01

    Stabilized quadrivalent cation oxide electrolytes are employed in fuel cells at elevated temperatures with a carbon and/or hydrogen containing fuel anode and an oxygen cathode. The fuel cell is operated at elevated temperatures with conductive metallic coatings as electrodes and desirably having the electrolyte surface blackened. Of particular interest as the quadrivalent oxide is zirconia.

  5. A New Miniaturized Inkjet Printed Solid State Electrolyte Sensor for Applications in Life Support Systems - First Results

    NASA Astrophysics Data System (ADS)

    Hill, Christine; Stefanos Fasoulas, -; Eberhart, Martin; Berndt, Felix

    New generations of integrated closed loop systems will combine life support systems (incl. biological components) and energy systems such as fuel cell and electrolysis systems. Those systems and their test beds also contain complex safety sensor monitoring systems. Especially in fuel cells and electrolysis systems, the hydrogen and oxygen flows and exchange into other areas due to diffusion processes or leaks need to be monitored. Knowledge of predominant gas concentrations at all times is essential to avoid explosive gas mixtures. Solid state electrolyte sensors are promising for use as safety sensors. They have already been developed and produced at various institutes, but the power consumption for heating an existing solid state electrolyte sensor element still lies between 1 to 1.5 W and the operational readiness still takes about 20 to 30 s. This is partially due to the current manufacturing process for the solid state electrolyte sensor elements that is based on screen printing technology. However this technology has strong limitations in flexibility of the layout and re-designs. It is therefore suitable for mass production, but not for a flexible development and the production of specific individual sensors, e.g. for space applications. Moreover a disadvantage is the relatively high material consumption, especially in combination with the sensors need of expensive noble metal and ceramic pastes, which leads to a high sensor unit price. The Inkjet technology however opens up completely new possibilities in terms of dimensions, geometries, structures, morphologies and materials of sensors. This new approach is capable of printing finer high-resolution layers without the necessity of meshes or masks for patterning. Using the Inkjet technology a design change is possible at any time on the CAD screen. Moreover the ink is only deposited where it is needed. Custom made sensors, as they are currently demanded in space sensor applications, are thus realized simply

  6. Study on the LLT solid electrolyte thin film with LiPON interlayer intervening between LLT and electrodes

    NASA Astrophysics Data System (ADS)

    Lee, Jong min; Kim, Soo ho; Tak, Yongsug; Yoon, Young Soo

    In this study, a lithium lanthanum titanate (LLT) thin film electrolyte was prepared by RF magnetron sputtering, in order to assess its potential use in solid state thin film batteries. Even though the LLT has high ionic conductivity, it cannot be used alone as a thin film electrolyte since it is chemically unstable when it comes into contact with Li metal and it has a high electronic conductivity. Lithium phosphorous oxynitride (LiPON) is stable when in contact with Li and has an extremely low electronic conductivity. We expected that the LiPON/LLT/LiPON structure would make it possible to use a LLT thin film as a thin film solid electrolyte. In order to prepare this structure, a LiPON thin film was also deposited by RF magnetron sputtering and was deposited for various times (30, 60, 90 and 120 min), in order to determine the optimum thickness ratio between LLT and LiPON. In linear sweep voltammetry measurements, the current hardly flowed in the potential range from 0 to 5.5 V in the blocking electrode and ac impedance was measured for measuring the resistance at LiPON/LLT/LiPON. When only the LLT thin film was deposited, a current of scores of mA flowed in the operating potential range, but when an interlayer of LiPON thin film was deposited for more than 30 min on both sides of the LLT thin film, the current was less than 1 μA. Ionic conductivities of 1.11, 0.82 and 0.48 × 10 -7 S cm -1 were observed for the deposition times of the LiPON thin film of 60, 90 and 120 min, respectively. This result suggests that the LiPON/LLT/LiPON structure might be able to be used as a thin film solid electrolyte if its ionic conductivity could be improved.

  7. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    PubMed Central

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-01-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1−xCaxAlO3−δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at −300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles. PMID:27886278

  8. A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

    NASA Astrophysics Data System (ADS)

    Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

    2016-11-01

    NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1‑xCaxAlO3‑δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400–500 °C. The response current value at ‑300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

  9. Towards safer sodium-ion batteries via organic solvent/ionic liquid based hybrid electrolytes

    NASA Astrophysics Data System (ADS)

    Monti, Damien; Ponrouch, Alexandre; Palacín, M. Rosa; Johansson, Patrik

    2016-08-01

    Hybrid electrolytes aimed at application in sodium-ion batteries (SIB) consisting of an organic solvent mixture (EC:PC) and different ionic liquids (ILs); EMImTFSI, BMImTFSI, and Pyr13TFSI, and with the NaTFSI salt providing the Na+ charge carriers have here been extensively studied. The physico-chemical and electrochemical characterisation includes ionic conductivity, viscosity, density, cation coordination and solvation, various safety measures, and electrochemical stability window (ESW). Hybrid electrolytes with 10-50% of IL content were found to have ionic conductivities on par with comparable organic solvent based electrolytes, but with highly enhanced safety properties. A systematic Raman spectroscopy study of the cation coordination and solvation before and after electrolyte safety tests by ignition suggest that IL cations and TFSI remain stable when ignited while organic solvents are consumed. Finally, the solid electrolyte interphase (SEI) formed when using hybrid electrolytes has both better mechanical and electrochemical stability than the SEI derived from pure IL based electrolytes. For a half-cell with a hard carbon (HC) electrode and a hybrid electrolyte with a composition of 0.8 m NaTFSI in EC0.45:PC0.45:Pyr13TFSI0.10 encouraging results were obtained for IL based electrolytes - ca. 182 mAhg-1 at C/10 over 40 cycles.

  10. Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

    DOE PAGES

    Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; ...

    2016-05-30

    All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

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

    PubMed

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

    2013-05-01

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

  12. Nanoporous palladium anode for direct ethanol solid oxide fuel cells with nanoscale proton-conducting ceramic electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Yong; Wong, Lai Mun; Xie, Hanlin; Wang, Shijie; Su, Pei-Chen

    2017-02-01

    In this work, we demonstrate the operation of micro-solid oxide fuel cells (μ-SOFCs) with nanoscale proton-conducting Y-BaZrO3 (BZY) electrolyte to avoid the fuel crossover problem for direct ethanol fuel cells (DEFCs). The μ-SOFCs are operated with the direct utilisation of ethanol vapour as a fuel and Pd as anode at the temperature range of 300-400 °C. The nanoporous Pd anode is achieved by DC sputtering at high Ar pressure of 80 mTorr. The Pd-anode/BYZ-electrolyte/Pt-cathode cell show peak power densities of 72.4 mW/cm2 using hydrogen and 15.3 mW/cm2 using ethanol at 400 °C. No obvious carbon deposition is seen from XPS analysis after fuel cell test with ethanol fuel.

  13. Synthesis and characterization of hot pressed ion conducting solid polymer electrolytes: (1 - x) PEO: x NaClO4

    NASA Astrophysics Data System (ADS)

    Chandra, Angesh; Chandra, Archana; Thakur, Kiran

    2015-02-01

    Synthesis and ion transport characterization of hot-pressed poly(ethylene oxide) PEO-based solid polymer electrolytes (SPEs): (1 - x) PEO: x NaClO4, where 0 < x < 50 wt.%, are reported. The composition: (70PEO: 30NaClO4) with ionic conductivity (σ) ~ 7.07 × 10-7 S cm-1 shows the highest conducting composition and this have been referred to as optimum conducting composition (OCC). Materials characterization and thermal behavior of the present SPEs have been done with the help of XRD, FTIR, SEM, DSC and TG analysis. To determine the activation energy, temperature dependent ionic conductivity (σ) of different compositions has been measured. Ionic nature of the SPEs has been explained with the help of ionic transference number (tion) measurements. Finally, the thin film polymer battery is also fabricated using the SPE OCC as electrolyte and calculated their cell parameters at room temperature.

  14. Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

    SciTech Connect

    Park, Joong Sun; An, Jihwan; Lee, Min Hwan; Prinz, Friedrich B.; Lee, Wonyoung

    2015-11-01

    In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created with yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.

  15. 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.

  16. About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

    PubMed

    Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

    2016-10-12

    The reactivity of mixtures of high voltage spinel cathode materials Li2NiMn3O8, Li2FeMn3O8, and LiCoMnO4 cosintered with Li1.5Al0.5Ti1.5(PO4)3 and Li6.6La3Zr1.6Ta0.4O12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li6.6La3Zr1.6Ta0.4O12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li2MnO3 and then decompose to form stable and often insulating phases such as La2Zr2O7, La2O3, La3TaO7, TiO2, and LaMnO3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li1.5Al0.5Ti1.5(PO4)3 mixtures, the Mn tends to oxidize to MnO2 or Mn2O3, supplying lithium to the electrolyte for the formation of Li3PO4 and metal phosphates such as AlPO4 and LiMPO4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

  17. Polymer Models of Interphase Chromosomes

    NASA Astrophysics Data System (ADS)

    Martin, Joshua; Kondev, Jané; Bressen, Debra; Haber, James

    2006-03-01

    Experiments during interphase, the growth phase of the cell cycle in eukaryotic cells, have shown that parts of chromosomes are tethered to the nuclear periphery[1]. Using a simple polymer model of interphase chromosomes that includes tethering, we compute the probability distribution for the distance between two marked points on the chromosome. These calculations are inspired by recent experiments with two or more fluorescent markers placed along the chromosome[2]. We demonstrate how experiments of this kind, in conjunction with simpe polymer models, can be used to systematically dissect the spatial organization of interphase chromosomes in the nucleus of living cells. This comparison of theory with experiments has lead to the conclusion that the structure of chromosome III in yeast is consistent with a 10nm-fiber model of chromatin. [1]Wallace F. Marshall. Current Biology, 12, 2002. [2] Kerstin Bystricky, Patrick Heun, Lutz Gehlen, Jörg Langowski and Susan M. Gasser. PNAS, 101(47) 2004

  18. Investigations on the electrochemical decomposition of the electrolyte additive vinylene carbonate in Li metal half cells and lithium ion full cells

    NASA Astrophysics Data System (ADS)

    Qian, Yunxian; Schultz, Carola; Niehoff, Philip; Schwieters, Timo; Nowak, Sascha; Schappacher, Falko M.; Winter, Martin

    2016-11-01

    In this study, the decomposition of vinylene carbonate (VC) additive and its effect on the aging behavior is investigated in Li metal half cells and lithium ion full cells. Four electrolyte systems, the reference electrolyte with three VC additive amounts, i.e., 1, 5 and 10 vol% are examined with commercial LiNi1/3Mn1/3Co1/3O2 (NMC 111) cathode material and mesophase carbon microbeads (MCMB) anode material. The thickness changes of the cathode electrolyte interphase (CEI) and of the solid electrolyte interphase (SEI) after 5 constant current cycles at 0.1C and 200 constant current/constant voltage (potential) cycles at 1C are investigated for cells containing different amounts of VC. With the help of X-ray photoelectron spectroscopy (XPS) and high-performance liquid chromatography (HPLC), a correlation between CEI thickness change and electrolyte decomposition is figured out. The addition of VC leads to a thin CEI layer and a high capacity retention in a lithium metal half cell. A strong dependence of the performance on the VC concentration is found for half cells that results from the continuous consumption of electrolyte and the electrolyte additive at the Li metal counter electrode. In contrast, for full cells, even 1 vol% of VC helps to form both a stable CEI and SEI, while a larger amount of VC increases the CEI thickness, electric contact loss and the internal resistance.

  19. Sensor-actuator coupled device for active tracheal tube using solid polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    Ihara, Tadashi; Nakamura, Taro; Mukai, Toshiharu; Asaka, Kinji

    2007-04-01

    A sensor-actuator coupled device was developed using solid polymer electrolyte membrane (SPM) as an active tracheal tube for ventilator. Active tracheal tube is a novel type of tube for ventilator that removes patient's phlegm automatically upon sensing the narrowing of trachea by phlegm. This type of active tube is extremely useful in clinical settings as currently the sole measure to remove phlegm from patient's tube is to do it manually by a nurse every few hours. As SPM works both as a sensor and an actuator, an effective compact device was developed. SPM based sensor-actuator coupled device was fabricated with modified gold plating method. Prepared SPM was fixed as an array on a plastic pipe of diameter 22 mm and was connected to a ventilator circuit and driven by a ventilator with a volume control ventilation (VCV) mode. SPM was connected both to a sensing unit and an actuation unit. Generated voltage developed by the membrane with the setting of the maximum pressure from 5 cmH IIO to 20 cmH IIO was in order of several hundred μV. SPM sensor demonstrated a biphasic response to the ventilator flow. The sensor data showed nearly linearly proportional voltage development to the intra-tracheal pressure. The sensed signal was filtered and digitized with an A/D converting unit on a PC board. A real time operating program was used to detect the sensed signal that indicates the narrowing of trachea. The program then activated a driving signal to control the actuation of the membrane. The signal was sent to a D/A converting unit. The output of the D/A unit was sent to an amplifier and the galvanostat unit which drives the membrane with constant current regardless of the change in the load. It was demonstrated that the sensor-actuator unit detects the narrowing of trachea within several hundreds milli-seconds and responds by actuating the same membrane with the driving voltage of 3-4 V and driving current of several hundred milli-ampere for each membrane. SPM array

  20. Aging of solidified/stabilized electrolytic manganese solid waste with accelerated carbonation and aging inhibition.

    PubMed

    Du, Bing; Zhou, Changbo; Dan, Zhigang; Zhao, Zhiyuan; Peng, Xianjia; Liu, Jianguo; Duan, Ning

    2016-12-01

    High concentrations of soluble Mn in electrolytic manganese solid waste (EMSW) in soil cause the severe contamination in China. Calcium oxide and magnesium oxide-dominated stabilizers are suitable for the solidification/stabilization (s/s) of EMSW. However, the long-term performance of s/s using those two types of stabilizer is problematic. The aim of this study was to develop an accelerated aging method to simulate the long-term natural carbonation of solidified/stabilized EMSW. The joint use of accelerated carbonation, leaching test, mineralogical analysis, and microstructural observation was applied to assess the long-term performance of the s/s EMSW system. On an accelerated carbonation test for solidified/stabilized EMSW, an increase in Mn leaching from 13.6 to 408 mg/kg and a 1.5-2.3 decrease in pH was achieved by using CaO-dominated stabilizers, while an increase in manganese (Mn) from 30 to 266 mg/kg and a decrease in pH of 0.17-0.68 was seen using MgO-dominated stabilizers. CaO+Na3PO4 and CaO+CaCO3 were exceptions in that the leaching value of soluble Mn was lower after carbonation. Mineralogical analysis showed that rhodochrosite in the carbonated s/s system was generated not only from the reduction of hausmannite but also from the reversible reaction between Mn(OH)2 and MnCO3. Carbonation destroyed the tight particle structure resulting in a porous and loose structure. As for s/s EMSW treated by MgO-dominated stabilizers, carbonation affected the agglomerating structure and mineralogical composition by increasing magnesium (Mg) migration, thereby forming hydromagnesite that had weak binding ability and a nested porous shape. Therefore, carbonation by itself does not cause deterioration to s/s products of the soluble Mn but does have significant effects on the microstructure and mineralogical composition. It is recommended to add Na3PO4 or CaCO3 into a single CaO stabilized EMSW system to prevent aging of the system, allow formation of Mn phosphate

  1. Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

    PubMed Central

    Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

    2015-01-01

    Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC). PMID:26218470

  2. 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.

  3. 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

  4. Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells.

    PubMed

    Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

    2015-07-28

    Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC).

  5. Molten salt electrolyte separator

    DOEpatents

    Kaun, Thomas D.

    1996-01-01

    A molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication.

  6. Fabrication of ultrathin solid electrolyte membranes of β-Li3PS4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

    SciTech Connect

    Wang, Hui; Hood, Zachary D.; Xia, Younan; Liang, Chengdu

    2016-04-25

    All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li3PS4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreased to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li3PS4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.

  7. Structural, electrical conductivity and dielectric behavior of Na2SO4–LDT composite solid electrolyte

    PubMed Central

    Iqbal, Mohd Z.; Rafiuddin

    2015-01-01

    A series of composite materials of general molecular formula (1 − x) Na2SO4 − (x) LDT was prepared by solid state reaction method. The phase structure and functionalization of these materials were defined by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) respectively. Differential thermal analysis (DTA) revealed that the hump of phase transition at 250 °C has decreased while its thermal stability was enhanced. Scanning electron microscopy signifies the presence of improved rigid surfaces and interphases that are accountable for the high ionic conduction due to dispersion of LDT particles in the composite systems. Arrhenius plots of the conductance show the maximum conductivity, σ = 4.56 × 10−4 S cm−1 at 500 °C for the x = 0.4 composition with the lowest activation energy 0.34 eV in the temperature range of 573–773 K. The value of dielectric constant was decreased with increasing frequency and follows the usual trend. PMID:26843979

  8. Effect of Plasticizers on Methyl Cellulose-Based Alkaline Solid Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Rosli, N. H. A.; Harun, N. I.; Taib, M. F. M.; Saaid, S. I. Y.; Kudin, T. I. T.; Ali, A. M. M.; Yahya, M. Z. A.

    2010-07-01

    A preliminary investigation of biopolymer electrolytes based on methyl cellulose (MC), potassium hydroxide (KOH), and various plasticizing additives are described in this presentation. The electrolyte films with the composition of KOH between 5 and 50 wt.% (with respect to MC), were prepared by the solution cast technique. The biopolymer was first dissolved in distilled water with controlled amount of the KOH. The homogenous solutions obtained were evaporated in vacuum oven at constant temperature (40 °C) to form thin films. The room temperature ionic conductivity of the solvent free electrolytes films were characterized using impedance spectroscopy technique. In general, the unplasticized KOH based electrolytes were found to show moderate ionic conductivity up to 5.64×10-6 S/cm. Upon the addition of plasticizers PC and EC the conductivity rises to 6.70×10×6 and up to 3.58×10-3 respectively. However, the addition of propylene carbonate (PC) and ethylene carbonate (EC) as a plasticizing additive lowered the mechanical stability. To control mechanical stability, the addition of such plasticizers is limited the suitability use of the electrolytes.

  9. Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

    2017-02-01

    A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

  10. 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.

  11. 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.

  12. Exploring electrolyte organization in supercapacitor electrodes with solid-state NMR

    NASA Astrophysics Data System (ADS)

    Deschamps, Michaël; Gilbert, Edouard; Azais, Philippe; Raymundo-Piñero, Encarnación; Ammar, Mohammed Ramzi; Simon, Patrick; Massiot, Dominique; Béguin, François

    2013-04-01

    Supercapacitors are electrochemical energy-storage devices that exploit the electrostatic interaction between high-surface-area nanoporous electrodes and electrolyte ions. Insight into the molecular mechanisms at work inside supercapacitor carbon electrodes is obtained with 13C and 11B ex situ magic-angle spinning nuclear magnetic resonance (MAS-NMR). In activated carbons soaked with an electrolyte solution, two distinct adsorption sites are detected by NMR, both undergoing chemical exchange with the free electrolyte molecules. On charging, anions are substituted by cations in the negative carbon electrode and cations by anions in the positive electrode, and their proportions in each electrode are quantified by NMR. Moreover, acetonitrile molecules are expelled from the adsorption sites at the negative electrode alone. Two nanoporous carbon materials were tested, with different nanotexture orders (using Raman and 13C MAS-NMR spectroscopies), and the more disordered carbon shows a better capacitance and a better tolerance to high voltages.

  13. Investigations on Poly (ethylene oxide) (PEO) - blend based solid polymer electrolytes for sodium ion batteries

    NASA Astrophysics Data System (ADS)

    Koduru, H. K.; Iliev, M. T.; Kondamareddy, K. K.; Karashanova, D.; Vlakhov, T.; Zhao, X.-Z.; Scaramuzza, N.

    2016-10-01

    Polymer blend electrolytes based on Polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP), complexed with NaIO4 salt and Graphene oxide (GO) are investigated in the present report. The electrolytes are prepared by a facile solution cast technique. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) are employed to study the influence of ion-polymer interactions on the micro structural properties of blend electrolytes. Measurements of electrical conductivity of the blend polymer complexes have been performed by using complex impedance spectroscopy in the frequency range 1 Hz - 1 MHz and within the temperature range 303 K - 343 K.A study on electrical conductivity properties of GO doped ‘salt complexed electrolyte’ systems is presented.

  14. Study, selection, and preparation of solid cationic conductors. [characteristics of solid electrolytes for rechargeable high energy and high power density batteries

    NASA Technical Reports Server (NTRS)

    Roth, W. L.; Muller, O.

    1974-01-01

    Crystal chemical principles and transport theory have been used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. Structures with 1-, 2-, and 3-dimensional channels were synthesized and screened by nuclear magnetic resonance, dielectric loss, and conductivity. There is significant conductivity at room temperature in some of the materials but none attain a level that is comparable to beta-alumina. Microwave and fast pulse methods were developed to measure conductivity in powders and in small crystals.

  15. Effect of random p-n junctions on quasi-solid-state dye-sensitized solar cells with polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Cui, Jiarui; Yang, Ying; Yi, Pengfei; Guo, Xueyi

    2014-12-01

    In this paper, the effect of p-n junction additives via blending p-type semiconductors (NiO and CuI) with n-type TiO2 in polymer electrolyte on quasi-solid-state DSSCs is studied. The conduction mechanism of DSSCs modified with random p-n junctions has been investigated by FTIR, SEM, UV-Vis and electrochemical analysis. The results indicate that the CuI-TiO2 p-n blend modified polymer electrolyte reaches the maximum ionic conductivity of 6.44 mS cm-1, which is almost twice over than that of pure-TiO2 modified one. From photovoltaic study, it is found that introducing CuI-TiO2 and NiO-TiO2 p-n blends in polymer electrolyte can obviously improve electron recombination and light-to-electric conversion efficiency of DSSCs. The conversion efficiency of CuI-TiO2 p-n blend modified DSSC is 3.34%, which is much higher than that of pure TiO2 modified device (1.76%). It is also demonstrated that the photovoltaic properties of DSSCs directly depends on the ratio of p-type CuI and n-type TiO2 in the p-n blends and the optimal conversion efficiency of 4.27% is obtained at CuI:TiO2 ratio of 4:1.

  16. Polypropylene oil as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

    NASA Astrophysics Data System (ADS)

    Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

    2017-03-01

    The research focusses on converting polypropylene oil as pyrolysis product of polypropylene plastic into an electricity. The converter was a direct liquid fuel-solid oxide fuel cell (SOFC) with cerium oxide based material as electrolyte. The polypropylene vapor flowed into fuel cell, in the anode side and undergo oxidation reaction, meanwhile, the Oxygen in atmosphere reduced into oxygen ion at cathode. The fuel cell test was conducted at 400 - 600 °C. According to GC-MS analysis, the polypropylene oil consist of C8 to C27 hydrocarbon chain. The XRD analysis result shows that Na2CO3 did not change the crystal structure of SDC even increases the electrical conductivity. The maximum power density is 0.079 mW.cm-2 at 773 K. The open circuite voltage is 0.77 volt. Chemical stability test by analysing the single cell at before and after fuel cell test found that ionic migration occured during fuel cell operation. It is supported by the change of elemental composition in the point position of electrolyte and at the electrolyte-electrode interface

  17. 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.

  18. Extracting local surface charges and charge regulation behavior from atomic force microscopy measurements at heterogeneous solid-electrolyte interfaces

    NASA Astrophysics Data System (ADS)

    Zhao, Cunlu; Ebeling, Daniel; Siretanu, Igor; van den Ende, Dirk; Mugele, Frieder

    2015-10-01

    We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.

  19. Optimization of a quasi-solid-state dye-sensitized solar cell employing a nanocrystal-polymer composite electrolyte modified with water and ethanol.

    PubMed

    Yang, Ying; Zhou, Cong-Hua; Xu, Sheng; Zhang, Jing; Wu, Su-Juan; Hu, Hao; Chen, Bo-Lei; Tai, Qi-Dong; Sun, Zheng-Hua; Liu, Wei; Zhao, Xing-Zhong

    2009-03-11

    A quasi-solid-state dye-sensitized solar cell employing a poly(ethylene oxide)-poly(vinylidene fluoride) (PEO-PVDF)/TiO2 gel electrolyte modified by various concentrations of water and ethanol is described. It is shown that the introduction of water and ethanol prevents the crystallization of the polymer matrix, and enhances the free I(-)/I(3)(-) concentration and the networks for ion transportation in the electrolyte, thus leading to an improvement in conductivity. A high energy conversion efficiency of about 5.8% is achieved by controlling the additive concentration in the electrolyte. Optimization of the additive-modified electrolyte performance has been obtained by studying the cross-linking behavior of water and ethanol with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC) and viscosity measurements, and the electrical conduction behavior of the electrolyte with impedance spectra measurements.

  20. Co-existence of LiI and KI in filler-free, quasi-solid-state electrolyte for efficient and stable dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Agarwala, S.; Thummalakunta, L. N. S. A.; Cook, C. A.; Peh, C. K. N.; Wong, A. S. W.; Ke, L.; Ho, G. W.

    A quasi-solid-state electrolyte employing a poly (ethylene oxide)/LiI system without a filler is evaluated. The electrolyte is optimized for various potassium iodide (KI) concentrations. The electrolyte containing 14.5 wt.% KI exhibits the highest conductivity (3.0 × 10 -3 S cm -1). An efficiency of 4.5% is achieved using this composition of the electrolyte. It is shown that the introduction of KI in a conventional PEO/I 2/LiI electrolyte system prevents the crystallization of the polymer matrix and enhances the ionic conductivity. The energy conversion efficiency of the device is further enhanced to 5.8% by incorporating a light-scattering layer.

  1. Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

    NASA Technical Reports Server (NTRS)

    Isenberg, Arnold O.; Cusick, Robert J.

    1988-01-01

    The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

  2. Conduction mechanisms in concentrated LiI-polyethylene oxide-Al{sub 2}O{sub 3}-based solid electrolytes

    SciTech Connect

    Golodnitsky, D.; Ardel, G.; Strauss, E.; Peled, E.; Lareah, Y.; Rosenberg, Y.

    1997-10-01

    The ionic conductivity of concentrated LiI-polyethylene oxide P(EO){sub n} high surface area oxide composite polymer electrolytes has been investigated. Two different Arrhenius dependences for concentrated composite polymer electrolytes (CPEs) have been identified. The first one is characterized by an inflection point at about 80 C, and the second, by a conductivity jump. The authors have suggested that in CPEs, where 3solid phase is major contributor to the overall ionic conductivity at temperatures above, but close to the melting point of the eutectic (T{sub m}solid electrolytes (CSEs, n{le}3), is about 40% of that for CPEs. The authors believe that the preferred conduction path in even more concentrated CPEs, which are defined as CSEs, is interfacial conduction. Differential scanning calorimetry, scanning electron microscopy, and X-ray data, presented here, are evidence supporting the view. The effects of several parameters including type and content of oxide matrix, Li salt to ethylene oxide ratio, copolymers, and solvents on polymer electrolyte conductivity (especially at T >T{sub k}orT{sub jump}) and on Ea have been studied (T{sub jump}=temperature of the conductivity jump). The addition of small quantities of ethylene carbonate, poly(methyl methacrylate), and polyacrylonitrile were found to be beneficial while poly(methyl acrylate), poly(butyl acrylate), and poly(vinylidene fluoride) additions made the polymer electrolyte stiffer and less conductive. MgO, Al{sub 2}O{sub 3}, and potassium aluminosilicate muscovite mica based CSEs have similar conductivity. Results clearly demonstrated the depression of CPE crystallinity by addition of fine Al{sub 2}O{sub 3} powder, ethylene carbonate, and poly(ethylene glycol) dimethyl ether, in agreement with the conductivity enhancement of the CPE.

  3. Crystalline Li(sub 3)PO(sub 4)/SiO(sub 4) solid solutions as an electrolyte for film batteries using sputtered cathode layers

    NASA Technical Reports Server (NTRS)

    Whitacre, J. F.; West, W. C.

    2003-01-01

    Crystalline solid solutions of 1:1 Li3PO4/SiO4 were synthesized and tested electrochemically using thin film, physical vapor deposited electrodes. After cathode deposition, the electrolyte/cathode structures were annealed at 700 degrees Celsius for 2 hours, a process that resulted in cathode crystallization without encouraging deleterious interfacial reactions. Results indicate that the electrolyte functioned well in this configuration.

  4. Functionally Graded Bismuth Oxide/Zirconia Bilayer Electrolytes for High-Performance Intermediate-Temperature Solid Oxide Fuel Cells (IT-SOFCs).

    PubMed

    Joh, Dong Woo; Park, Jeong Hwa; Kim, Doyeub; Wachsman, Eric D; Lee, Kang Taek

    2017-03-15

    A functionally graded Bi1.6Er0.4O3 (ESB)/Y0.16Zr0.84O1.92 (YSZ) bilayer electrolyte is successfully developed via a cost-effective screen printing process using nanoscale ESB powders on the tape-cast NiO-YSZ anode support. Because of the highly enhanced oxygen incorporation process at the cathode/electrolyte interface, a novel bilayer solid oxide fuel cell (SOFC) yields extremely high power density of ∼2.1 W cm(-2) at 700 °C, which is a 2.4 times increase compared to that of the YSZ single electrolyte SOFC.

  5. Alkali-Resistant Quasi-Solid-State Electrolyte for Stretchable Supercapacitors.

    PubMed

    Tang, Qianqiu; Wang, Wenqiang; Wang, Gengchao

    2016-10-05

    Research on stretchable energy-storage devices has been motivated by elastic electronics, and considerable research efforts have been devoted to the development of stretchable electrodes. However, stretchable electrolytes, another critical component in stretchable devices, have earned quite little attention, especially the alkali-resistant ones. Here, we reported a novel stretchable alkali-resistant electrolyte made of a polyolefin elastomer porous membrane supported potassium hydroxide-potassium polyacrylate (POE@KOH-PAAK). The as-prepared electrolyte shows a negligible plastic deformation even after 1000 stretching cycles at a strain of 150% as well as a high conductivity of 0.14 S cm(-1). It also exhibits excellent alkali resistance, which shows no obvious degradation of the mechanical performance after immersion in 2 M KOH for up to 2 weeks. To demonstrate its good properties, a high-performance stretchable supercapacitor is assembled using a carbon-nanotube-film-supported NiCo2O4 (CNT@NiCo2O4) as the cathode and Fe2O3 (CNT@Fe2O3) as the anode, proving great application promise of the stretchable alkali-resistant electrolyte in stretchable energy-storage devices.

  6. Estimation of energy density of Li-S batteries with liquid and solid electrolytes

    NASA Astrophysics Data System (ADS)

    Li, Chunmei; Zhang, Heng; Otaegui, Laida; Singh, Gurpreet; Armand, Michel; Rodriguez-Martinez, Lide M.

    2016-09-01

    With the exponential growth of technology in mobile devices and the rapid expansion of electric vehicles into the market, it appears that the energy density of the state-of-the-art Li-ion batteries (LIBs) cannot satisfy the practical requirements. Sulfur has been one of the best cathode material choices due to its high charge storage (1675 mAh g-1), natural abundance and easy accessibility. In this paper, calculations are performed for different cell design parameters such as the active material loading, the amount/thickness of electrolyte, the sulfur utilization, etc. to predict the energy density of Li-S cells based on liquid, polymeric and ceramic electrolytes. It demonstrates that Li-S battery is most likely to be competitive in gravimetric energy density, but not volumetric energy density, with current technology, when comparing with LIBs. Furthermore, the cells with polymer and thin ceramic electrolytes show promising potential in terms of high gravimetric energy density, especially the cells with the polymer electrolyte. This estimation study of Li-S energy density can be used as a good guidance for controlling the key design parameters in order to get desirable energy density at cell-level.

  7. Excellent stability of a lithium-ion-conducting solid electrolyte upon reversible Li+/H+ exchange in aqueous solutions

    DOE PAGES

    Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu; ...

    2014-10-21

    Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long-term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li-stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchangedmore » even under a high exchange rate of 63.6%. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. Furthermore, these observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries.« less

  8. 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.

  9. 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.

  10. Ionic Borate-Based Covalent Organic Frameworks: Lightweight Porous Materials for Lithium-Stable Solid State Electrolytes

    SciTech Connect

    Black, Hayden T.; Harrison, Katharine Lee

    2016-10-01

    The synthesis and characterization of the first polyelectrolyte of intrinsic microporosity (PEIM) is described. The novel material was synthesized via reaction between the nitrile group in the polymer backbone and n-butyl lithium, effectively anchoring an imine anion to the porous framework while introducing a mobile lithium counterion. The PEIM was characterized by 13C, 1H, and 7Li NMR experiments, revealing quantitative conversion of the nitrile functionality to the anionic imine. Variable temperature 7Li NMR analysis of the dry PEIM and the electrolyteswollen PEIM revealed that lithium ion transport within the dry PEIM was largely due to interchain hopping of the Li+ ions, and that the mobility of polymer associated Li+ was reduced after swelling in electrolyte solution. Meanwhile, the swollen PEIM supported efficient transport of dissolved Li+ within the expanded pores. These results are discussed in the context of developing novel solid or solid-like lithium ion electrolytes using the new PEIM material.

  11. STABLE HIGH CONDUCTIVITY BILAYERED ELECTROLYTES FOR LOW TEMPERATURE SOLID OXIDE FUEL CELLS

    SciTech Connect

    Eric D. Wachsman; Keith L. Duncan

    2002-09-30

    A bilayer electrolyte consisting of acceptor-doped ceria (on the fuel/reducing side) and cubic-stabilized bismuth oxide (on the oxidizing side) was developed. The bilayer electrolyte that was developed showed significant improvement in open-circuit potential versus a typical ceria based SOFC. Moreover, the OCP of the bilayer cells increased as the thickness of the bismuth oxide layer increased relative to the ceria layer. Thereby, verifying the bilayer concept. Although, because of the absence of a suitable cathode (a problem we are still working assiduously to solve), we were unable to obtain power density curves, our modeling work predicts a reduction in electrolyte area specific resistance of two orders of magnitude over cubic-stabilized zirconia and projects a maximum power density of 9 W/m{sup 2} at 800 C and 0.09 W/m{sup 2} at 500 C. Towards the development of the bilayer electrolyte other significant strides were made. Among these were, first, the development of a, bismuth oxide based, oxide ion conductor with the highest conductivity (0.56 S/cm at 800 C and 0.043 S/cm at 500 C) known to date. Second, a physical model of the defect transport mechanisms and the driving forces for the ordering phenomena in bismuth oxide and other fluorite systems was developed. Third, a model for point defect transport in oxide mixed ionic-electronic conductors was developed, without the typical assumption of a uniform distribution of ions and including the effect of variable loads on the transport properties of an SOFC (with either a single or bilayer electrolyte).

  12. A High Temperature Electrochemical Energy Storage System Based on Sodium Beta-Alumina Solid Electrolyte (Base)

    SciTech Connect

    Anil Virkar

    2008-03-31

    This report summarizes the work done during the period September 1, 2005 and March 31, 2008. Work was conducted in the following areas: (1) Fabrication of sodium beta{double_prime} alumina solid electrolyte (BASE) using a vapor phase process. (2) Mechanistic studies on the conversion of {alpha}-alumina + zirconia into beta{double_prime}-alumina + zirconia by the vapor phase process. (3) Characterization of BASE by X-ray diffraction, SEM, and conductivity measurements. (4) Design, construction and electrochemical testing of a symmetric cell containing BASE as the electrolyte and NaCl + ZnCl{sub 2} as the electrodes. (5) Design, construction, and electrochemical evaluation of Na/BASE/ZnCl{sub 2} electrochemical cells. (6) Stability studies in ZnCl{sub 2}, SnCl{sub 2}, and SnI{sub 4} (7) Design, assembly and testing of planar stacks. (8) Investigation of the effect of porous surface layers on BASE on cell resistance. The conventional process for the fabrication of sodium ion conducting beta{double_prime}-alumina involves calcination of {alpha}-alumina + Na{sub 2}CO{sub 3} + LiNO{sub 3} at 1250 C, followed by sintering powder compacts in sealed containers (platinum or MgO) at {approx}1600 C. The novel vapor phase process involves first sintering a mixture of {alpha}-alumina + yttria-stabilized zirconia (YSZ) into a dense ceramic followed by exposure to soda vapor at {approx}1450 C to convert {alpha}-alumina into beta{double_prime}-alumina. The vapor phase process leads to a high strength BASE, which is also resistant to moisture attack, unlike BASE made by the conventional process. The PI is the lead inventor of the process. Discs and tubes of BASE were fabricated in the present work. In the conventional process, sintering of BASE is accomplished by a transient liquid phase mechanism wherein the liquid phase contains NaAlO{sub 2}. Some NaAlO{sub 2} continues to remain at grain boundaries; and is the root cause of its water sensitivity. In the vapor phase process, Na

  13. In situ gelation of Al(III)-4-tert-butylpyridine based metal-organic gel electrolyte for efficient quasi-solid-state dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Dong, Yu-Jie; Rao, Hua-Shang; Cao, Yang; Chen, Hong-Yan; Kuang, Dai-Bin; Su, Cheng-Yong

    2017-03-01

    A novel Al(III)-4-tert-butylpyridine (TBP) gel electrolyte is successfully achieved by a simple and facile in situ gelation method and applied as quasi-solid-state electrolyte for dye-sensitized solar cells (DSSCs). Through directly adding Al3+ into the TBP solution, the induced hydrolysis of Al3+ and the coordination interaction between Al3+ and TBP facilitates the formation of metal-organic gels(MOGs), in which such bi-functional TBP molecules will act as both gelators and active additives to tailor the performance of electrolytes. In addition, the gel electrolytes can largely preserve the properties of liquid electrolyte and penetrate well into the TiO2 photoanode film. Both Al3+ and TBP in the gel electrolytes affect the performance of cells. The Jsc of gel electrolytes decrease with the increasing concentration of gelators due to the enhanced strength and viscosity of the gel electrolytes, while the competition between Al3+ and TBP causes conduction band edge shift and electron recombination, leading to a variation of Voc. Herein, by tuning the molar ratio of Al3+/TBP, an impressive conversion efficiency of 8.25% is obtained, indicating a promising protocol of preparing MOGs not only to achieve high performance in solar cells, but also opens up extended scopes in other energy-related fields such as catalysis.

  14. Development of Bipolar All-solid-state Lithium Battery Based on Quasi-solid-state Electrolyte Containing Tetraglyme-LiTFSA Equimolar Complex

    PubMed Central

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-01-01

    The development of high energy–density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V. PMID:25746860

  15. Development of bipolar all-solid-state lithium battery based on quasi-solid-state electrolyte containing tetraglyme-LiTFSA equimolar complex.

    PubMed

    Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

    2015-03-09

    The development of high energy-density lithium-ion secondary batteries as storage batteries in vehicles is attracting increasing attention. In this study, high-voltage bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex were prepared, and the performance of the device was evaluated. Via the successful production of double-layered and triple-layered high-voltage devices, it was confirmed that these stacked batteries operated properly without any internal short-circuits of a single cell within the package: Their plateau potentials (6.7 and 10.0 V, respectively) were two and three times that (3.4 V) of the single-layered device, respectively. Further, the double-layered device showed a capacity retention of 99% on the 200th cycle at 0.5 C, which is an indication of good cycling properties. These results suggest that bipolar stacked batteries with a quasi-solid-state electrolyte containing a Li-Glyme complex could readily produce a high voltage of 10 V.

  16. Oxygen reduction and evolution in an ionic liquid ([BMP][TFSA]) based electrolyte: A model study of the cathode reactions in Mg-air batteries

    NASA Astrophysics Data System (ADS)

    Law, Y. T.; Schnaidt, J.; Brimaud, S.; Behm, R. J.

    2016-11-01

    Aiming at a molecular scale understanding of the cathode processes in an Mg-air battery, we have investigated the oxygen reduction (ORR) and oxygen evolution (OER) reactions under well-defined conditions, using an ionic liquid (butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide, [BMP][TFSA]) based electrolyte and polycrystalline Au and glassy carbon, respectively, as model electrodes. Electrochemical measurements performed under enforced electrolyte flow provide information on the electrochemical and electrocatalytic properties of these electrodes, in particular on the reversibility of the ORR/OER both in the absence and in the presence of Mg2+ in the electrolyte, and on the build-up of a reaction inhibiting passivation layer (solid-electrolyte interphase). Further information on the nature of the deposits and their dependence both on the electrode material and on the potential cycling conditions is derived from scanning electron microscopy/energy dispersive X-ray spectroscopy and from X-ray photoelectron spectroscopy measurements performed ex situ after the electrochemical measurements. Consequences of these results on the understanding of the ORR/OER under these conditions and in particular of the nature and role of the solid-electrolyte interphase layer formed during potential cycling and their relevance for the operation of Mg-air batteries are discussed.

  17. Anhydrous state proton and lithium ion conducting solid polymer electrolytes based on sulfonated bisphenol-A-poly(arylene ethers)

    NASA Astrophysics Data System (ADS)

    Guha Thakurta, Soma

    Sulfonated polymer based solid polymer electrolytes (SPEs) have received considerable interest in recent years because of their wide variety of applications particularly in fuel cells, batteries, supercapacitors, and electrochromic devices. The present research was focused on three interrelated subtopics. First, two different bisphenol-A-poly(arylene ethers), polyetherimide (PEI) and polysulfone (PSU) were sulfonated by a post sulfonation method to various degrees of sulfonation, and their thermal and mechanical properties were examined. The effects of poly(arylene ether) chemical structure, reaction time, concentration, and types of sulfonating agents on sulfonation reaction were investigated. It was found that deactivation of bisphenol A unit caused by the electron withdrawing imide, retarded the sulfonation of PEI compared to PSU. Sulfonation conducted with a high concentration of sulfonating agent and/or prolonged reaction time exhibited evidence of degradation at the isopropylidene unit. The degradation occurred through the same mechanistic pathway with the two different sulfonating agents, chlorosulfonic acid (CSA) and trimethylsilyl chlorosulfonate (TMSCS). The degradation was faster with CSA than its silyl ester, TMSCS, and was evident even at low acid concentration. Second, novel anhydrous proton conducting solid polymer electrolytes (SPEs) were prepared by the incorporation of 1H-1,2,4-triazole (Taz) as a proton solvent in sulfonated polyetherimide (SPEI) matrix. The size, shape, and state of dispersion (crystal morphology) of triazole crystals in SPEI were examined as a function of degree of sulfonation and triazole concentration. Increasing sulfonic acid content caused reduction of triazole crystallite size, hence the depression of melting temperature and their uniform distribution throughout the sulfonated polymer matrix. The increased rate of structure diffusion within the smaller size crystals due to the improved molecular mobility contributed

  18. Photointercalating Semiconductor/Solid Electrolyte Junctions for Storage and Chemical Detection. Phase 2.

    DTIC Science & Technology

    1988-05-31

    Typical thermal gradients used were between 750C and 8000 C. Crystal growth occurred over 25 days. In all 4cases the relatively large crystals obtained...mixture together with 5mg 12/ml of the quartz transport tube volume. This was performed in a three temperature zone furnace. Typical thermal gradients...character- isti, s of single crystal n-HfS 2 in liquid non-aqueous electrolyte (acetonitrile containing O.1M tetrabutylammonium hexafluorophosphate

  19. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    DOE PAGES

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; ...

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  20. Dynamics of Ion-Gating 2D Crystals Using a Solid Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Hua-Min; Bourdon, Buchanan; Lin, Yu-Chuan; Robinson, Joshua; Seabaugh, Alan; Fullerton, Susan; CenterLow Energy Systems Technology (Least) Team

    2015-03-01

    Ion-gating can significantly increase the static carrier density of graphene due to the formation of an electric double layer (EDL); however, the dynamics of ion-gating have not been extensively reported. A comprehensive understanding of ion dynamics is important because it establishes the timescales required to achieve EDL equilibrium, and directly affects the operating speed of devices and circuits employing electrolytic gates. Here, ion dynamics are measured on epitaxial graphene Hall-bar devices that are electrolytically gated with polyethylene oxide and lithium perchlorate. The time constants for EDL formation and dissipation are measured as a function of temperature. The measured formation time is slower than the dissipation time, because ion diffusion resulting from a concentration gradient must be opposed during EDL formation. These results quantitatively agree with COMSOL multiphysics simulations. EDL dissipation follows a stretched exponential decay described by the Kohlrausch-Williams-Watts (KWW) equation. The temperature-dependent relaxation times extracted from the KWW fit follow the Vogel-Fulcher-Tammann (VFT) temperature dependence. At temperatures approaching the glass transition temperature of the electrolyte, the relaxation times exceed several hours, demonstrating the long timescales over which the EDL can persist in the absence of a gate bias.