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.

The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering

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

Wei, Xialu; Rechtin, Jack; Olevsky, Eugene

Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries (ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals that the functionally graded structure can eliminate themore » delamination effect at the electrode–electrolyte interface and, therefore, retains better performance.« less

The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering

DOE PAGES

Wei, Xialu; Rechtin, Jack; Olevsky, Eugene

2017-09-14

Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries (ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals that the functionally graded structure can eliminate themore » delamination effect at the electrode–electrolyte interface and, therefore, retains better performance.« less

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.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

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

1998-03-17

A solid electrolytic capacitor is described 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. 2 figs.

Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes.

PubMed

Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan; Wu, Qi-Hui; Tang, Shuai; Yan, Jia-Wei; Zheng, Ming-Sen; Wu, De-Yin; Fan, Chun-Hai; Hu, Wei-Qiang; Chen, Zhao-Bin; Fang, Yuan; Zhang, Qing-Hong; Dong, Quan-Feng; Mao, Bing-Wei

2018-04-09

Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm -2 with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.

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 → 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. We consider the passivation layer, called “solid electrolyte interphasemore » (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 Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

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 Office of Scientific and Technical Information (OSTI.GOV)

Li, Yunsong; Leung, Kevin; Qi, Yue

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. We consider the passivation layer, called “solid electrolyte interphasemore » (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 Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

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

Solid polymer MEMS-based fuel cells

DOEpatents

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

2008-04-22

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

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

Electrocatalytic cermet gas detector/sensor

DOEpatents

Vogt, Michael C.; Shoemarker, Erika L.; Fraioli, deceased, Anthony V.

1995-01-01

An electrocatalytic device for sensing gases. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte.

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. It was found that the solid electrolyte films became discolored within seconds after they were placed in contact with the cathodes - a result of facile diffusion of iodine through the solid electrolyte material (see figure).

Solid oxide electrochemical cell fabrication process

DOEpatents

Dollard, Walter J.; Folser, George R.; Pal, Uday B.; Singhal, Subhash C.

1992-01-01

A method to form an electrochemical cell (12) is characterized by the steps of thermal spraying stabilized zirconia over a doped lanthanum manganite air electrode tube (14) to provide an electrolyte layer (15), coating conductive particles over the electrolyte, pressurizing the outside of the electrolyte layer, feeding halide vapors of yttrium and zirconium to the outside of the electrolyte layer and feeding a source of oxygen to the inside of the electrolyte layer, heating to cause oxygen reaction with the halide vapors to close electrolyte pores if there are any and to form a metal oxide coating on and between the particles and provide a fuel electrode (16).

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

Electrocatalytic cermet gas detector/sensor

DOEpatents

Vogt, M.C.; Shoemarker, E.L.; Fraioli, A.V.

1995-07-04

An electrocatalytic device for sensing gases is described. The gas sensing device includes a substrate layer, a reference electrode disposed on the substrate layer comprised of a nonstoichiometric chemical compound enabling oxygen diffusion therethrough, a lower reference electrode coupled to the reference electrode, a solid electrolyte coupled to the lower reference electrode and an upper catalytically active electrode coupled to the solid electrolyte. 41 figs.

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 (Li 3.7Si). We attribute this breathing to the continual consumption of electrolyte with cycling.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, Joseph E.

1987-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

Role of additives in formation of solid-electrolyte interfaces on carbon electrodes and their effect on high-voltage stability.

PubMed

Qu, Weiguo; Dorjpalam, Enkhtuvshin; Rajagopalan, Ramakrishnan; Randall, Clive A

2014-04-01

The in situ modification of a lithium hexafluorophosphate-based electrolyte using a molybdenum oxide catalyst and small amount of water (1 vol %) yields hydrolysis products such as mono-, di-, and alkylfluorophosphates. The electrochemical stability of ultrahigh-purity, high-surface-area carbon electrodes derived from polyfurfuryl alcohol was tested using the modified electrolyte. Favorable modification of the solid electrolyte interface (SEI) layer on the activated carbon electrode increased the cyclable electrochemical voltage window (4.8-1.2 V vs. Li/Li(+)). The chemical modification of the SEI layer induced by electrolyte additives was characterized by using X-ray photoelectron spectroscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, John P.; Young, John E.

1984-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween, and each interconnect wall consists of thin layers of the cathode and anode materials sandwiching a thin layer of interconnect material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick.

Design, fabrication and characterization of a double layer solid oxide fuel cell (DLFC)

NASA Astrophysics Data System (ADS)

Wang, Guangjun; Wu, Xiangying; Cai, Yixiao; Ji, Yuan; Yaqub, Azra; Zhu, Bin

2016-11-01

A double layer solid oxide fuel cell (DLSOFC) without using the electrolyte (layer) has been designed by integrating advantages of positive electrode material of lithium ion battery(LiNi0.8Co0.15Al0.05O2) and oxygen-permeable membranes material (trace amount cobalt incorporated terbium doped ceria, TDC + Co) based on the semiconductor physics principle. Instead of using an electrolyte layer, the depletion layer between the anode and cathode served as an electronic insulator to block the electrons but to maintain the electrolyte function for ionic transport. Thus the device with two layers can realize the function of SOFC and at the same time avoids the electronic short circuiting problem. Such novel DLFC showed good performance at low temperatures, for instance, a maximum power density of 230 mWcm-2 was achieved at 500 °C. The working principle of the new device is presented.

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

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

Electrocatalytic cermet sensor

DOEpatents

Shoemaker, E.L.; Vogt, M.C.

1998-06-30

A sensor is described for O{sub 2} and CO{sub 2} gases. The gas sensor includes a plurality of layers driven by a cyclic voltage to generate a unique plot characteristic of the gas in contact with the sensor. The plurality of layers includes an alumina substrate, a reference electrode source of anions, a lower electrical reference electrode of Pt coupled to the reference source of anions, a solid electrolyte containing tungsten and coupled to the lower reference electrode, a buffer layer for preventing flow of Pt ions into the solid electrolyte and an upper catalytically active Pt electrode coupled to the buffer layer. 16 figs.

Electrocatalytic cermet sensor

DOEpatents

Shoemaker, Erika L.; Vogt, Michael C.

1998-01-01

A sensor for O.sub.2 and CO.sub.2 gases. The gas sensor includes a plurality of layers driven by a cyclic voltage to generate a unique plot characteristic of the gas in contact with the sensor. The plurality of layers includes an alumina substrate, a reference electrode source of anions, a lower electrical reference electrode of Pt coupled to the reference source of anions, a solid electrolyte containing tungsten and coupled to the lower reference electrode, a buffer layer for preventing flow of Pt ions into the solid electrolyte and an upper catalytically active Pt electrode coupled to the buffer layer.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, J.P.; Young, J.E.

1983-10-12

A solid oxide fuel cell is described for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick.

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

DTIC Science & Technology

2010-05-12

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

Solid electroytes for CNT-based actuators

NASA Astrophysics Data System (ADS)

Riemenschneider, Johannes; Geier, Sebastian; Mahrholz, Thorsten; Mosch, Jürgen; Monner, Hans Peter; Sinapius, Michael

2009-03-01

Actuators based on carbon nanotubes (CNT) have the potential to generate high forces at very low voltages. The density of the raw material is just 1330 kg/m3, which makes them well applicable for lightweight applications. Moreover, active strains of up to 1% can be achieved - due to the CNTs dimensional changes on charge injection. Therefore the nanotubes have to be arranged and electrically wired like electrodes of a capacitor. In previous works the system's response of the Nanotubes comprising a liquid electrolyte was studied in detail. The major challenge is to repeat such experiments with solid electrolytes, which is a prerequisite for structural integration. In this paper a method is proposed which makes sure the expansion is not based on thermal expansion. This is done by analysing the electrical system response. As thermal expansion is dominated by ohmic resistance the CNT based actuators show a strong capacitive behavior. This behavior is referable to the constitution of the electrochemical double layer around the nanotubes, which causes the tubes to expand. Also a novel test setup is described, which guarantees that the displacement which is measured will not be caused by bending of a bimorph but due to expansion of a single layer of nanotubes. This paper also presents experimental results demonstrating both, the method of electrical characterization of CNT based actuators with implemented solid electrolytes and the novel test setup which is used to measure the needed data. The actuators which were characterized are hybrids of CNT and the solid electrolyte NAFION which is supplying the ions needed to constitute the electrochemical double layer. The manufacturing, processing of these actuators and also some first experimental results are shown. Unfortunately, the results are not as clear as those for liquid electrolytes, which depend on the hybrid character of the analyzed devices. In the liquid electrolyte based case the CNTs are the only source of stiffness, whereas in the solid electrolyte case electrodes and electrolyte contribute to the overall stiffness and damping as well. Since the introduction of solid electrolytes is a major stumbling block in the development of such actuators, this work is of particular importance.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, J.E.

1985-05-20

Disclosed is a solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output. The cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

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.

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.

Slurry spin coating of thin film yttria stabilized zirconia/gadolinia doped ceria bi-layer electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Kim, Hyun Joong; Kim, Manjin; Neoh, Ke Chean; Han, Gwon Deok; Bae, Kiho; Shin, Jong Mok; Kim, Gyu-Tae; Shim, Joon Hyung

2016-09-01

Thin ceramic bi-layered membrane comprising yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC) is fabricated by the cost-effective slurry spin coating technique, and it is evaluated as an electrolyte of solid oxide fuel cells (SOFCs). It is demonstrated that the slurry spin coating method is capable of fabricating porous ceramic films by adjusting the content of ethyl-cellulose binders in the source slurry. The porous GDC layer deposited by spin coating under an optimal condition functions satisfactorily as a cathode-electrolyte interlayer in the test SOFC stack. A 2-μm-thick electrolyte membrane of the spin-coated YSZ/GDC bi-layer is successfully deposited as a dense and stable film directly on a porous NiO-YSZ anode support without any interlayers, and the SOFC produces power output over 200 mW cm-2 at 600 °C, with an open circuit voltage close to 1 V. Electrochemical impedance spectra analysis is conducted to evaluate the performance of the fuel cell components in relation with the microstructure of the spin-coated layers.

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

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

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the formation of solid-electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and other electrolyte components are still unclear. Here, we report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach involving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li 2S, LiF, Li 2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and electrolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS 5) fouling process. In conclusion, these new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

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

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

DOE PAGES

Nandasiri, Manjula I.; Camacho-Forero, Luis E.; Schwarz, Ashleigh M.; ...

2017-05-03

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the formation of solid-electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and other electrolyte components are still unclear. Here, we report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach involving AIMD modelingmore » and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li 2S, LiF, Li 2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and electrolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS 5) fouling process. In conclusion, these new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.« less

Formation of thin walled ceramic solid oxide fuel cells

DOEpatents

Claar, Terry D.; Busch, Donald E.; Picciolo, John J.

1989-01-01

To reduce thermal stress and improve bonding in a high temperature monolithic solid oxide fuel cell (SOFC), intermediate layers are provided between the SOFC's electrodes and electrolyte which are of different compositions. The intermediate layers are comprised of a blend of some of the materials used in the electrode and electrolyte compositions. Particle size is controlled to reduce problems involving differential shrinkage rates of the various layers when the entire structure is fired at a single temperature, while pore formers are provided in the electrolyte layers to be removed during firing for the formation of desired pores in the electrode layers. Each layer includes a binder in the form of a thermosetting acrylic which during initial processing is cured to provide a self-supporting structure with the ceramic components in the green state. A self-supporting corrugated structure is thus formed prior to firing, which the organic components of the binder and plasticizer removed during firing to provide a high strength, high temperature resistant ceramic structure of low weight and density.

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

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

Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.

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-ionmore » 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); approximate to 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.« less

Electrolyte volume effects on electrochemical performance and solid electrolyte interphase in Si-graphite/NMC lithium-ion pouch cells

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2017-05-15

This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate with 10 wt.% fluoroethylene carbonate. Single layer pouch cells (100 mAh) were constructed with 15 wt.% Si-graphite/LiNi 0.5Mn 0.3CO 0.2O 2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendritesmore » are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. As a result, solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is non-uniform after cycling.« less

Lithium Dendrite Suppression and Enhanced Interfacial Compatibility Enabled by an Ex Situ SEI on Li Anode for LAGP-Based All-Solid-State Batteries.

PubMed

Hou, Guangmei; Ma, Xiaoxin; Sun, Qidi; Ai, Qing; Xu, Xiaoyan; Chen, Lina; Li, Deping; Chen, Jinghua; Zhong, Hai; Li, Yang; Xu, Zhibin; Si, Pengchao; Feng, Jinkui; Zhang, Lin; Ding, Fei; Ci, Lijie

2018-06-06

The electrode-electrolyte interface stability is a critical factor influencing cycle performance of All-solid-state lithium batteries (ASSLBs). Here, we propose a LiF- and Li 3 N-enriched artificial solid state electrolyte interphase (SEI) protective layer on metallic lithium (Li). The SEI layer can stabilize metallic Li anode and improve the interface compatibility at the Li anode side in ASSLBs. We also developed a Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 -poly(ethylene oxide) (LAGP-PEO) concrete structured composite solid electrolyte. The symmetric Li/LAGP-PEO/Li cells with SEI-protected Li anodes have been stably cycled with small polarization at a current density of 0.05 mA cm -2 at 50 °C for nearly 400 h. ASSLB-based on SEI-protected Li anode, LAGP-PEO electrolyte, and LiFePO 4 (LFP) cathode exhibits excellent cyclic stability with an initial discharge capacity of 147.2 mA h g -1 and a retention of 96% after 200 cycles.

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

PubMed Central

Liu, Yayuan; Lin, Dingchang; Jin, Yang; Liu, Kai; Tao, Xinyong; Zhang, Qiuhong; Zhang, Xiaokun; Cui, Yi

2017-01-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellent adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g−1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm−2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature. PMID:29062894

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

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

Liu, Yayuan; Lin, Dingchang; Jin, Yang

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Jin, Yang; ...

2017-10-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Electrode-Electrolyte Interfaces in Lithium-Sulfur Batteries with Liquid or Inorganic Solid Electrolytes.

PubMed

Yu, Xingwen; Manthiram, Arumugam

2017-11-21

Electrode-electrolyte interfacial properties play a vital role in the cycling performance of lithium-sulfur (Li-S) batteries. The issues at an electrode-electrolyte interface include electrochemical and chemical reactions occurring at the interface, formation mechanism of interfacial layers, compositional/structural characteristics of the interfacial layers, ionic transport across the interface, and thermodynamic and kinetic behaviors at the interface. Understanding the above critical issues is paramount for the development of strategies to enhance the overall performance of Li-S batteries. Liquid electrolytes commonly used in Li-S batteries bear resemblance to those employed in traditional lithium-ion batteries, which are generally composed of a lithium salt dissolved in a solvent matrix. However, due to a series of unique features associated with sulfur or polysulfides, ether-based solvents are generally employed in Li-S batteries rather than simply adopting the carbonate-type solvents that are generally used in the traditional Li + -ion batteries. In addition, the electrolytes of Li-S batteries usually comprise an important additive, LiNO 3 . The unique electrolyte components of Li-S batteries do not allow us to directly take the interfacial theories of the traditional Li + -ion batteries and apply them to Li-S batteries. On the other hand, during charging/discharging a Li-S battery, the dissolved polysulfide species migrate through the battery separator and react with the Li anode, which magnifies the complexity of the interfacial problems of Li-S batteries. However, current Li-S battery development paths have primarily been energized by advances in sulfur cathodes. Insight into the electrode-electrolyte interfacial behaviors has relatively been overshadowed. In this Account, we first examine the state-of-the-art contributions in understanding the solid-electrolyte interphase (SEI) formed on the Li-metal anode and sulfur cathode in conventional liquid-electrolyte Li-S batteries and how the resulting chemical and physical properties of the SEI affect the overall battery performance. A few strategies recently proposed for improving the stability of SEI are briefly summarized. Solid Li + -ion conductive electrolytes have been attempted for the development of Li-S batteries to eliminate the polysulfide shuttle issues. One approach is based on a concept of "all-solid-state Li-S battery," in which all the cell components are in the solid state. Another approach is based on a "hybrid-electrolyte Li-S battery" concept, in which the solid electrolyte plays roles both as a Li + -ion conductor for the electrochemical reaction and as a separator to prevent polysulfide shuttle. However, these endeavors with the solid electrolyte are not able to provide an overall satisfactory cell performance. In addition to the low ionic conductivity of solid-state electrolytes, a critical issue lies in the poor interfacial properties between the electrode and the solid electrolyte. This Account provides a survey of the relevant research progress in understanding and manipulating the interfaces of electrode and solid electrolytes in both the "all-solid-state Li-S batteries" and the "hybrid-electrolyte Li-S batteries". A recently proposed "semi-solid-state Li-S battery" concept is also briefly discussed. Finally, future research and development directions in all the above areas are suggested.

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

PubMed Central

Li, Yutao; Zhou, Weidong; Chen, Xi; Lü, Xujie; Cui, Zhiming; Xin, Sen; Xue, Leigang; Jia, Quanxi; Goodenough, John B.

2016-01-01

A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life. PMID:27821751

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

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

Lu, Dongping; Tao, Jinhui; Yan, Pengfei

2017-02-10

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, inmore » which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.« less

Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

NASA Astrophysics Data System (ADS)

Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

2018-03-01

Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

High performance cermet electrodes

DOEpatents

Isenberg, Arnold O.; Zymboly, Gregory E.

1986-01-01

Disclosed is a method of increasing the operating cell voltage of a solid oxide electrochemical cell having metal electrode particles in contact with an oxygen-transporting ceramic electrolyte. The metal electrode is heated with the cell, and oxygen is passed through the oxygen-transporting ceramic electrolyte to the surface of the metal electrode particles so that the metal electrode particles are oxidized to form a metal oxide layer between the metal electrode particles and the electrolyte. The metal oxide layer is then reduced to form porous metal between the metal electrode particles and the ceramic electrolyte.

Surface-protected LiCoO2 with ultrathin solid oxide electrolyte film for high-voltage lithium ion batteries and lithium polymer batteries

NASA Astrophysics Data System (ADS)

Yang, Qi; Huang, Jie; Li, Yejing; Wang, Yi; Qiu, Jiliang; Zhang, Jienan; Yu, Huigen; Yu, Xiqian; Li, Hong; Chen, Liquan

2018-06-01

Surface modification of LiCoO2 with the ultrathin film of solid state electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) has been realized by a new and facile solution-based method. The coated LiCoO2 reveals enhanced structural and electrochemical stability at high voltage (4.5 V vs Li+/Li) in half-cell with liquid electrolyte. Transmission electron microscopy (TEM) images show that a dense LATP coating layer is covered on the surface of LiCoO2 uniformly with thickness of less than 20 nm. The LATP coating layer is proven to be able to prevent the direct contact between the cathode and the electrolyte effectively and thus to suppress the side reactions of liquid electrolyte with LiCoO2 surface at high charging voltage. As a result, dissolution of Co3+ has been largely suppressed over prolonged cycling as indicated by the X-ray photoelectron spectroscopy (XPS) measurements. Due to this surface passivating feature, the electrochemical performance of 0.5 wt% LATP modified LiCoO2 has also been evaluated in an all solid lithium battery with poly(ethylene oxide)-based polymer electrolyte. The cell exhibits 93% discharge capacity retention of the initial discharge capacity after 50 cycles at the charging cut-off voltage of 4.2 V, suggesting that the LATP coating layer is effective to suppress the oxidation of PEO at high voltage.

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

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

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan

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 coupledmore » 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.« less

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.

Solid state oxygen sensor

DOEpatents

Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

1996-01-01

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

Artificially-built solid electrolyte interphase via surface-bonded vinylene carbonate derivative on graphite by molecular layer deposition

NASA Astrophysics Data System (ADS)

Chae, Seulki; Lee, Jeong Beom; Lee, Jae Gil; Lee, Tae-jin; Soon, Jiyong; Ryu, Ji Heon; Lee, Jin Seok; Oh, Seung M.

2017-12-01

Vinylene carbonate (VC) is attached in a ring-opened form on a graphite surface by molecular layer deposition (MLD) method, and its role as a solid electrolyte interphase (SEI) former is studied. When VC is added into the electrolyte solution of a graphite/LiNi0.5Mn1.5O4 (LNMO) full-cell, it is reductively decomposed to form an effective SEI on the graphite electrode. However, VC in the electrolyte solution has serious adverse effects due to its poor stability against electrochemical oxidation on the LNMO positive electrode. A excessive acid generation as a result of VC oxidation is observed, causing metal dissolution from the LNMO electrode. The dissolved metal ions are plated on the graphite electrode to destroy the SEI layer, eventually causing serious capacity fading and poor Coulombic efficiency. The VC derivative on the graphite surface also forms an effective SEI layer on the graphite negative electrode via reductive decomposition. The detrimental effects on the LNMO positive electrode, however, can be avoided because the bonded VC derivative on the graphite surface cannot move to the LNMO electrode. Consequently, the graphite/LNMO full-cell fabricated with the VC-attached graphite outperforms the cells without VC or with VC in the electrolyte, in terms of Coulombic efficiency and capacity retention.

Fabrication of low-temperature solid oxide fuel cells with a nanothin protective layer by atomic layer deposition

PubMed Central

2013-01-01

Anode aluminum oxide-supported thin-film fuel cells having a sub-500-nm-thick bilayered electrolyte comprising a gadolinium-doped ceria (GDC) layer and an yttria-stabilized zirconia (YSZ) layer were fabricated and electrochemically characterized in order to investigate the effect of the YSZ protective layer. The highly dense and thin YSZ layer acted as a blockage against electron and oxygen permeation between the anode and GDC electrolyte. Dense GDC and YSZ thin films were fabricated using radio frequency sputtering and atomic layer deposition techniques, respectively. The resulting bilayered thin-film fuel cell generated a significantly higher open circuit voltage of approximately 1.07 V compared with a thin-film fuel cell with a single-layered GDC electrolyte (approximately 0.3 V). PMID:23342963

Characterization of metal-supported axial injection plasma sprayed solid oxide fuel cells with aqueous suspension plasma sprayed electrolyte layers

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

A method for manufacturing metal-supported SOFCs with atmospheric plasma spraying (APS) is presented, making use of aqueous suspension feedstock for the electrolyte layer and dry powder feedstock for the anode and cathode layers. The cathode layer was deposited first directly onto a metal support, in order to minimize contact resistance, and to allow the introduction of added porosity. The electrolyte layers produced by suspension plasma spraying (SPS) were characterized in terms of thickness, permeability, and microstructure, and the impact of substrate morphology on electrolyte properties was investigated. Fuel cells produced by APS were electrochemically tested at temperatures ranging from 650 to 750 °C. The substrate morphology had little effect on open circuit voltage, but substrates with finer porosity resulted in lower kinetic losses in the fuel cell polarization.

High power density proton exchange membrane fuel cells

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

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

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte

DOE PAGES

Pearse, Alexander J.; Schmitt, Thomas E.; Fuller, Elliot J.; ...

2017-04-10

Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiO tBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li 2PO 2N between 250 and 300°C. The P/N ratio of the films is always 1, indicative of a particular polymorph ofmore » LiPON which closely resembles a polyphosphazene. Films grown at 300°C have an ionic conductivity of (6.51 ± 0.36)×10 -7 S/cm at 35°C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li +. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO 2 as the cathode and Si as the anode operating at up to 1 mA/cm 2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<40nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.« less

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

Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.

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

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2016-04-09

An in-depth review is presented on the science of lithium-ion battery (LIB) solid electrolyte interphase (SEI) formation on the graphite anode, including structure, morphology, chemical composition, electrochemistry, formation mechanism, and LIB formation cycling. During initial operation of LIBs, the SEI layer forms on the graphite surfaces, the most commonly used anode material, due to side reactions with the electrolyte solvent/salt at low electro-reduction potentials. It is accepted that the SEI layer is essential to the long-term performance of LIBs, and it also has an impact on its initial capacity loss, self-discharge characteristics, cycle life, rate capability, and safety. While themore » presence of the anode SEI layer is vital, it is difficult to control its formation and growth, as the chemical composition, morphology, and stability depend on several factors. These factors include the type of graphite, electrolyte composition, electrochemical conditions, and cell temperature. Thus, SEI layer formation and electrochemical stability over long-term operation should be a primary topic of future investigation in the development of LIB technology. We review the progression of knowledge gained about the anode SEI, from its discovery in 1979 to the current state of understanding, and covers its formation process, differences in the chemical and structural makeup when cell materials and components are varied, methods of characterization, and associated reactions with the liquid electrolyte phase. It also discusses the relationship of the SEI layer to the LIB formation step, which involves both electrolyte wetting and subsequent slow charge-discharge cycles to grow the SEI.« less

Direct liquid-feed fuel cell with membrane electrolyte and manufacturing thereof

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1999-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Improvements in interfacing of the catalyst layer and the membrane and activating catalyst materials are disclosed.

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

Kazyak, Eric; Chen, Kuan-Hung; Wood, Kevin N.

Lithium solid electrolytes are a promising platform for achieving high energy density, long-lasting, and safe rechargeable batteries, which could have widespread societal impact. In particular, the ceramic oxide garnet Li7La3Zr2O12 (LLZO) has been shown to be a promising electrolyte due to its stability and high ionic conductivity. Two major challenges for commercialization are manufacturing of thin layers and creating stable, low-impedance, interfaces with both anode and cathode materials. Atomic Layer Deposition (ALD) has recently been shown as a potential method for depositing both solid electrolytes and interfacial layers to improve the stability and performance at electrode-electrolyte interfaces in battery systems.more » Herein we present the first reported ALD process for LLZO, demonstrating the ability to tune composition within the amorphous film and anneal to achieve the desired cubic garnet phase. Formation of the cubic phase was observed at temperatures as low as 555°C, significantly lower than is required for bulk processing. Additionally, challenges associated with achieving a dense garnet phase due to substrate reactivity, morphology changes and Li loss under the necessary high temperature annealing are quantified via in situ synchrotron diffraction.« less

Methods for using atomic layer deposition to produce a film for solid state electrolytes and protective electrode coatings for lithium batteries

DOEpatents

Elam, Jeffrey W.; Meng, Xiangbo

2018-03-13

A method for using atomic layer deposition to produce a film configured for use in an anode, cathode, or solid state electrolyte of a lithium-ion battery or a lithium-sulfur battery. The method includes repeating a cycle for a predetermined number of times in an inert atmosphere. The cycle includes exposing a substrate to a first precursor, purging the substrate with inert gas, exposing the substrate to a second precursor, and purging the substrate with inert gas. The film is a metal sulfide.

Solid state oxygen sensor

DOEpatents

Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

1996-08-06

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, A.F.; Makowiecki, D.M.; Rambach, G.D.; Randich, E.

1998-05-19

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated. 8 figs.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1999-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Hybrid deposition of thin film solid oxide fuel cells and electrolyzers

DOEpatents

Jankowski, Alan F.; Makowiecki, Daniel M.; Rambach, Glenn D.; Randich, Erik

1998-01-01

The use of vapor deposition techniques enables synthesis of the basic components of a solid oxide fuel cell (SOFC); namely, the electrolyte layer, the two electrodes, and the electrolyte-electrode interfaces. Such vapor deposition techniques provide solutions to each of the three critical steps of material synthesis to produce a thin film solid oxide fuel cell (TFSOFC). The electrolyte is formed by reactive deposition of essentially any ion conducting oxide, such as defect free, yttria stabilized zirconia (YSZ) by planar magnetron sputtering. The electrodes are formed from ceramic powders sputter coated with an appropriate metal and sintered to a porous compact. The electrolyte-electrode interface is formed by chemical vapor deposition of zirconia compounds onto the porous electrodes to provide a dense, smooth surface on which to continue the growth of the defect-free electrolyte, whereby a single fuel cell or multiple cells may be fabricated.

Addressing the Interface Issues in All-Solid-State Bulk-Type Lithium Ion Battery via an All-Composite Approach.

PubMed

Chen, Ru-Jun; Zhang, Yi-Bo; Liu, Ting; Xu, Bing-Qing; Lin, Yuan-Hua; Nan, Ce-Wen; Shen, Yang

2017-03-22

All-solid-state bulk-type lithium ion batteries (LIBs) are considered ultimate solutions to the safety issues associated with conventional LIBs using flammable liquid electrolyte. The development of bulk-type all-solid-state LIBs has been hindered by the low loading of active cathode materials, hence low specific surface capacity, and by the high interface resistance, which results in low rate and cyclic performance. In this contribution, we propose and demonstrate a synergistic all-composite approach to fabricating flexible all-solid-state LIBs. PEO-based composite cathode layers (filled with LiFePO 4 particles) of ∼300 μm in thickness and composite electrolyte layers (filled with Al-LLZTO particles) are stacked layer-by-layer with lithium foils as negative layer and hot-pressed into a monolithic all-solid-state LIB. The flexible LIB delivers a high specific discharge capacity of 155 mAh/g, which corresponds to an ultrahigh surface capacity of 10.8 mAh/cm 2 , exhibits excellent capacity retention up to at least 10 cycles and could work properly under harsh operating conditions such as bending or being sectioned into pieces. The all-composite approach is favorable for improving both mesoscopic and microscopic interfaces inside the all-solid-state LIB and may provide a new toolbox for design and fabrication of all-solid-state LIBs.

Developing Battery Computer Aided Engineering Tools for Military Vehicles

DTIC Science & Technology

2013-12-01

Task 1.b Modeling Bullet penetration. The purpose of Task 1.a was to extend the chemical kinetics models of CoO2 cathodes developed under CAEBAT to...lithium- ion batteries. The new finite element model captures swelling/shrinking in cathodes /anodes due to thermal expansion and lithium intercalation...Solid Electrolyte Interphase (SEI) layer decomposition 80 2 Anode — electrolyte 100 3 Cathode — electrolyte 130 4 Electrolyte decomposition 180

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Direct deposit of catalyst on the membrane of direct feed fuel cells

NASA Technical Reports Server (NTRS)

Chun, William (Inventor); Narayanan, Sekharipuram R. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor); Linke, Juergen (Inventor)

2001-01-01

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2006-10-10

Low-cost, mechanically strong, highly electronically conductive porous substrates and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures provide solid state electrochemical device substrates of novel composition and techniques for forming thin electrode/membrane/electrolyte coatings on the novel or more conventional substrates. In particular, in one aspect the invention provides techniques for co-firing of device substrate (often an electrode) with an electrolyte or membrane layer to form densified electrolyte/membrane films 5 to 20 microns thick. In another aspect, densified electrolyte/membrane films 5 to 20 microns thick may be formed on a pre-sintered substrate by a constrained sintering process. In some cases, the substrate may be a porous metal, alloy, or non-nickel cermet incorporating one or more of the transition metals Cr, Fe and Cu, or alloys thereof.

Effect of water on solid electrolyte interphase formation in Li-ion batteries

NASA Astrophysics Data System (ADS)

Saito, M.; Fujita, M.; Aoki, Y.; Yoshikawa, M.; Yasuda, K.; Ishigami, R.; Nakata, Y.

2016-03-01

Time-of-flight-elastic recoil detection analysis (TOF-ERDA) with 20 MeV Cu ions has been applied to measure the depth profiles of solid electrolyte interphase (SEI) layers on the negative electrode of lithium ion batteries (LIB). In order to obtain quantitative depth profiles, the detector efficiency was first assessed, and the test highlighted a strong mass and energy dependence of the recoiled particles, especially H and He. Subsequently, we prepared LIB cells with different water contents in the electrolyte, and subjected them to different charge-discharge cycle tests. TOF-ERDA, X-ray photoelectron spectrometry (XPS), gas chromatography (GC), ion chromatography (IC), and 1H nuclear magnetic resonance (1H NMR) were applied to characterize the SEI region of the negative electrode. The results showed that the SEI layer is formed after 300 cycle tests, and a 500 ppm water concentration in the electrolyte does not appear to cause significant differences in the elemental and organic content of the SEI.

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

PubMed Central

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

2015-01-01

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

Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage

DOEpatents

Farmer, Joseph C.; Kaschmitter, James; Pierce, Steve

2017-06-06

A method for producing a multi-layer bipolar coated cell according to one embodiment includes applying a first active cathode material above a substrate to form a first cathode; applying a first solid-phase ionically-conductive electrolyte material above the first cathode to form a first electrode separation layer; applying a first active anode material above the first electrode separation layer to form a first anode; applying an electrically conductive barrier layer above the first anode; applying a second active cathode material above the anode material to form a second cathode; applying a second solid-phase ionically-conductive electrolyte material above the second cathode to form a second electrode separation layer; applying a second active anode material above the second electrode separation layer to form a second anode; and applying a metal material above the second anode to form a metal coating section. In another embodiment, the anode is formed prior to the cathode. Cells are also disclosed.

A review of electrolyte materials and compositions for electrochemical supercapacitors.

PubMed

Zhong, Cheng; Deng, Yida; Hu, Wenbin; Qiao, Jinli; Zhang, Lei; Zhang, Jiujun

2015-11-07

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

All-solid-state Li-ion batteries based on ceramic solid electrolyte materials are a promising next-generation energy storage technology with high energy density and enhanced cycle life. The poor interfacial conductance is one of the key limitations in enabling all-solid-state Li-ion batteries. However, the origin of this poor conductance has not been understood, and there is limited knowledge about the solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries. In this paper, we performed first principles calculations to evaluate the thermodynamics of the interfaces between solid electrolyte and electrode materials and to identify the chemical and electrochemical stabilities of these interfaces. Our computation results revealmore » that many solid electrolyte–electrode interfaces have limited chemical and electrochemical stability, and that the formation of interphase layers is thermodynamically favorable at these interfaces. These formed interphase layers with different properties significantly affect the electrochemical performance of all-solid-state Li-ion batteries. The mechanisms of applying interfacial coating layers to stabilize the interface and to reduce interfacial resistance are illustrated by our computation. This study demonstrates a computational scheme to evaluate the chemical and electrochemical stability of heterogeneous solid interfaces. Finally, the enhanced understanding of the interfacial phenomena provides the strategies of interface engineering to improve performances of all-solid-state Li-ion batteries.« less

Stability study of cermet-supported solid oxide fuel cells with bi-layered electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Gazzarri, Javier; Robertson, Mark; Decès-Petit, Cyrille; Kesler, Olivera

Performance and stability of five cermet-supported button-type solid oxide fuel cells featuring a bi-layered electrolyte (SSZ/SDC), an SSC cathode, and a Ni-SSZ anode, were analyzed using polarization curves, impedance spectroscopy, and post-mortem SEM observation. The cell performance degradation at 650 °C in H 2/air both with and without DC bias conditions was manifested primarily as an increase in polarization resistance, approximately at a rate of 2.3 mΩ cm 2 h -1 at OCV, suggesting a decrease in electrochemical kinetics as the main phenomenon responsible for the performance decay. In addition, the initial series resistance was about ten times higher than the calculated resistance corresponding to the electrolyte, reflecting a possible inter-reaction between the electrolyte layers that occurred during the sintering stage. In situ and ex situ sintered cathodes showed no obvious difference in cell performance or decay rate. The stability of the cells with and without electrical load was also investigated and no significant influence of DC bias was recorded. Based on the experimental results presented, we preliminarily attribute the performance degradation to electrochemical and microstructural degradation of the cathode.

Properties of nanostructured undoped ZrO{sub 2} thin film electrolytes by plasma enhanced atomic layer deposition for thin film solid oxide fuel cells

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

Cho, Gu Young; Noh, Seungtak; Lee, Yoon Ho

2016-01-15

Nanostructured ZrO{sub 2} thin films were prepared by thermal atomic layer deposition (ALD) and by plasma-enhanced atomic layer deposition (PEALD). The effects of the deposition conditions of temperature, reactant, plasma power, and duration upon the physical and chemical properties of ZrO{sub 2} films were investigated. The ZrO{sub 2} films by PEALD were polycrystalline and had low contamination, rough surfaces, and relatively large grains. Increasing the plasma power and duration led to a clear polycrystalline structure with relatively large grains due to the additional energy imparted by the plasma. After characterization, the films were incorporated as electrolytes in thin film solidmore » oxide fuel cells, and the performance was measured at 500 °C. Despite similar structure and cathode morphology of the cells studied, the thin film solid oxide fuel cell with the ZrO{sub 2} thin film electrolyte by the thermal ALD at 250 °C exhibited the highest power density (38 mW/cm{sup 2}) because of the lowest average grain size at cathode/electrolyte interface.« less

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D.; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

2017-01-01

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries. PMID:28435874

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

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

Fu, Kun; Gong, Yunhui; Liu, Boyang

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

DOE PAGES

Fu, Kun; Gong, Yunhui; Liu, Boyang; ...

2017-04-07

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

Structures And Fabrication Techniques For Solid State Electrochemical Devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-12-27

Provided are low-cost, mechanically strong, highly electronically conductive porous substrates and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical device substrates of novel composition and techniques for forming thin electrode/membrane/electrolyte coatings on the novel or more conventional substrates. In particular, in one embodiment the invention provides techniques for co-firing of device substrate (often an electrode) with an electrolyte or membrane layer to form densified electrolyte/membrane films 5 to 20 microns thick. In another embodiment, densified electrolyte/membrane films 5 to 20 microns thick may be formed on a pre-sintered substrate by a constrained sintering process. In some cases, the substrate may be a porous metal, alloy, or non-nickel cermet incorporating one or more of the transition metals Cr, Fe, Cu and Ag, or alloys thereof.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2003-08-12

Provided are low-cost, mechanically strong, highly electronically conductive porous substrates and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical device substrates of novel composition and techniques for forming thin electrode/membrane/electrolyte coatings on the novel or more conventional substrates. In particular, in one embodiment the invention provides techniques for co-firing of device substrate (often an electrode) with an electrolyte or membrane layer to form densified electrolyte/membrane films 5 to 20 microns thick. In another embodiment, densified electrolyte/membrane films 5 to 20 microns thick may be formed on a pre-sintered substrate by a constrained sintering process. In some cases, the substrate may be a porous metal, alloy, or non-nickel cermet incorporating one or more of the transition metals Cr, Fe, Cu and Ag, or alloys thereof.

Higher Efficiency for Quasi-Solid State Dye Sensitized Solar Cells Under Low Light Irradiance

NASA Astrophysics Data System (ADS)

Desilva, Ajith; Bandara, T. M. W. J.; Fernado, H. D. N. S.; Fernando, P. S. L.; Dissanayake, M. A. K. L.; Jayasundara, W. J. M. J. S. R.; Furlani, M.; Mellander, B.-E.

2014-03-01

Dye-sensitized solar cells (DSSCs), lower cost solar energy conversion devices are alternative green energy source. The liquid based electrolyte DSSCs have higher efficiencies with many practical issues while the quasi-solid-state DSSCs resolve the key problems but efficiencies are relatively low. Polyacrylonitrile (PAN) based gel polymer electrolytes were fabricated as DSSCs by incorporating ethylene carbonate and propylene carbonate plasticizers and tetrapropylammonium iodide salt. A thin layer of electrolyte was sandwiched between the TiO2 anode (sensitized with N719 dye) and the Pt counter electrode. The electrolyte had an ionic conductivity of 2.6 mS/cm at 25 degrees of Celsius. DSSCs incorporating this gel electrolyte revealed Vsc circuit, Jsc, fill factor (FF) and efficiency values of 0.71 V, 11.8 mA, 51 percent and 4.2 percent respectively under 1 sun irradiation. The efficiency of the cell increased with decreasing solar irradiance achieving up to 10 percent efficiency and 80 percent FF at low irradiance values. This work uncovers that quasi-solid state DSSCs can reach efficiencies close to that of liquid electrolytes based cells.

Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

Electrochemical performance of metal-supported plasma sprayed (PS) solid oxide fuel cells (SOFCs) was tested for three nominal electrolyte thicknesses and three electrolyte fabrication conditions to determine the effects of electrolyte thickness and microstructure on open circuit voltage (OCV) and series resistance (R s). The measured OCV values were approximately 90% of the Nernst voltages, and electrolyte area specific resistances below 0.1 Ω cm 2 were obtained at 750 °C for electrolyte thicknesses below 20 μm. Least-squares fitting was used to estimate the contributions to R s of the YSZ bulk material, its microstructure, and the contact resistance between the current collectors and the cells. It was found that the 96% dense electrolyte layers produced from high plasma gas flow rate conditions had the lowest permeation rates, the highest OCV values, and the smallest electrolyte-related voltage losses. Optimal electrolyte thicknesses were determined for each electrolyte microstructure that would result in the lowest combination of OCV loss and voltage loss due to series resistance for operating voltages of 0.8 V and 0.7 V.

Method of making a cermet fuel electrode containing an inert additive

DOEpatents

Jensen, R.R.

1992-08-25

An electrode is attached to a solid electrolyte material by: (1) mixing a metallic nickel component and 1 wt% to 10 wt% of yttria stabilized zirconia having particle diameters up to 3 micrometers with an organic binder solution to form a slurry, (2) applying the slurry to a solid zirconia electrolyte material, (3) heating the slurry to drive off the organic binder and form a porous layer of metallic nickel substantially surrounded and separated by the zirconia particles, and (4) electro-chemical vapor depositing a skeletal structure between and around the metallic nickel and the zirconia particles where the metallic nickel components do not substantially sinter to each other, yet the layer remains porous. 4 figs.

Method of making a cermet fuel electrode containing an inert additive

DOEpatents

Jensen, Russel R.

1992-01-01

An electrode is attached to a solid electrolyte material by: (1) mixing a metallic nickel component and 1 wt% to 10 wt% of yttria stabilized zirconia having particle diameters up to 3 micrometers with an organic binder solution to form a slurry, (2) applying the slurry to a solid zirconia electrolyte material, (3) heating the slurry to drive off the organic binder and form a porous layer of metallic nickel substantially surrounded and separated by the zirconia particles, and (4) electro-chemical vapor depositing a skeletal structure between and around the metallic nickel and the zirconia particles where the metallic nickel components do not substantially sinter to each other, yet the layer remains porous.

The influence of the carbonate species on LiNi0.8Co0.15Al0.05O2 surfaces for all-solid-state lithium ion battery performance

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Fujiki, Satoshi; Aihara, Yuichi; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

2014-12-01

The influence of selected carbonate species on LiNi0.8Co0.15Al0.05O2 (NCA) surface for all-solid-state lithium-ion battery (ASSB) with a sulfide based solid electrolyte was studied for its electrochemical properties, structural stabilities, and surface characteristics. The rated discharge performance improved with the reduction of the carbonate concentration on the NCA surface due to the decrease of the interface resistance. The species and coordination of the adsorbed carbonates on the NCA surface were analyzed by diffuse reflectance Fourier transformed infrared (DRIFT) spectroscopy. The coordination of the adsorbed carbonate anion was determined based on the degree of splitting of the ν3(CO) stretching vibrations. It is found that the surface carbonate species exists in an unidentate coordination on the surface. They react with the sulfide electrolyte to form an irreversible passivation layer. This layer obstructs the charge transfer process at the cathode/electrolyte interface, and results in the rise of the interface resistance and drop of the rated discharge capability.

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers

PubMed Central

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-01-01

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180o. PMID:26846891

Strong Photo-Amplification Effects in Flexible Organic Capacitors with Small Molecular Solid-State Electrolyte Layers Sandwiched between Photo-Sensitive Conjugated Polymer Nanolayers.

PubMed

Lee, Hyena; Kim, Jungnam; Kim, Hwajeong; Kim, Youngkyoo

2016-02-05

We demonstrate strong photo-amplification effects in flexible organic capacitors which consist of small molecular solid-state electrolyte layers sandwiched between light-sensitive conjugated polymer nanolayers. The small molecular electrolyte layers were prepared from aqueous solutions of tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (ALQSA3), while poly(3-hexylthiophene) (P3HT) was employed as the light-sensitive polymer nanolayer that is spin-coated on the indium-tin oxide (ITO)-coated poly(ethylene terephthalate) (PET) film substrates. The resulting capacitors feature a multilayer device structure of PET/ITO/P3HT/ALQSA3/P3HT/ITO/PET, which were mechanically robust due to good adhesion between the ALQSA3 layers and the P3HT nanolayers. Results showed that the specific capacitance was increased by ca. 3-fold when a white light was illuminated to the flexible organic multilayer capacitors. In particular, the capacity of charge storage was remarkably (ca. 250-fold) enhanced by a white light illumination in the potentiostatic charge/discharge operation, and the photo-amplification functions were well maintained even after bending for 300 times at a bending angle of 180(°).

Electrolyte-stimulated biphasic dissolution profile and stability enhancement for tablets containing drug-polyelectrolyte complexes.

PubMed

Kindermann, Christoph; Matthée, Karin; Sievert, Frank; Breitkreutz, Jörg

2012-10-01

Recently introduced drug-polyelectrolyte complexes prepared by hot-melt extrusion should be processed to solid dosage forms with tailor-made release properties. Their potential of stability enhancement should be investigated. Milled hot-melt extruded naproxen-EUDRAGIT® E PO polyelectrolyte complexes were subsequently processed to double-layer tablets with varying complex loadings on a rotary-die press. Physicochemical interactions were studied under ICH guideline conditions and using the Gordon-Taylor equation. Sorption and desorption were determined to investigate the influence of moisture and temperature on the complex and related to stability tests under accelerated conditions. Naproxen release from the drug-polyelectrolyte complex is triggered by electrolyte concentration. Depending on the complex loading, phosphate buffer pH 6.8 stimulated a biphasic dissolution profile of the produced double-layer tablets: immediate release from the first layer with 65% loading and prolonged release from the second layer within 24 h (98.5% loading). XRPD patterns proved pseudopolymorphism for tablets containing the pure drug under common storage conditions whereas the drug-complex was stable in the amorphous state. Drug-polyelectrolyte complexes enable tailor-made dissolution profiles of solid dosage forms by electrolyte stimulation and increase stability under common storage conditions.

Atomic layer deposition of lithium phosphates as solid-state electrolytes for all-solid-state microbatteries

NASA Astrophysics Data System (ADS)

Wang, Biqiong; Liu, Jian; Sun, Qian; Li, Ruying; Sham, Tsun-Kong; Sun, Xueliang

2014-12-01

Atomic layer deposition (ALD) has been shown as a powerful technique to build three-dimensional (3D) all-solid-state microbattery, because of its unique advantages in fabricating uniform and pinhole-free thin films in 3D structures. The development of solid-state electrolyte by ALD is a crucial step to achieve the fabrication of 3D all-solid-state microbattery by ALD. In this work, lithium phosphate solid-state electrolytes were grown by ALD at four different temperatures (250, 275, 300, and 325 °C) using two precursors (lithium tert-butoxide and trimethylphosphate). A linear dependence of film thickness on ALD cycle number was observed and uniform growth was achieved at all four temperatures. The growth rate was 0.57, 0.66, 0.69, and 0.72 Å/cycle at deposition temperatures of 250, 275, 300, and 325 °C, respectively. Furthermore, x-ray photoelectron spectroscopy confirmed the compositions and chemical structures of lithium phosphates deposited by ALD. Moreover, the lithium phosphate thin films deposited at 300 °C presented the highest ionic conductivity of 1.73 × 10-8 S cm-1 at 323 K with ˜0.51 eV activation energy based on the electrochemical impedance spectroscopy. The ionic conductivity was calculated to be 3.3 × 10-8 S cm-1 at 26 °C (299 K).

Method of forming a plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Spengler, Charles J.; Folser, George R.; Vora, Shailesh D.; Kuo, Lewis; Richards, Von L.

1995-01-01

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO.sub.3 particles doped with an element selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by plasma spraying doped LaCrO.sub.3 powder, preferably compensated with chromium as Cr.sub.2 O.sub.3 and/or dopant element, preferably by plasma arc spraying; and, (C) heating the doped and compensated LaCrO.sub.3 layer to about 1100.degree. C. to 1300.degree. C. to provide a dense, substantially gas-tight, substantially hydration-free, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the unselected portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell.

Method of forming a plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Spengler, C.J.; Folser, G.R.; Vora, S.D.; Kuo, L.; Richards, V.L.

1995-06-20

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO{sub 3} particles doped with an element selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by plasma spraying doped LaCrO{sub 3} powder, preferably compensated with chromium as Cr{sub 2}O{sub 3} and/or dopant element, preferably by plasma arc spraying; and, (C) heating the doped and compensated LaCrO{sub 3} layer to about 1100 C to 1300 C to provide a dense, substantially gas-tight, substantially hydration-free, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the unselected portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 6 figs.

Tris(trimethylsilyl) Phosphite as an Efficient Electrolyte Additive To Improve the Surface Stability of Graphite Anodes.

PubMed

Yim, Taeeun; Han, Young-Kyu

2017-09-27

Tris(trimethylsilyl) phosphite (TMSP) has received considerable attention as a functional additive for various cathode materials in lithium-ion batteries, but the effect of TMSP on the surface stability of a graphite anode has not been studied. Herein, we demonstrate that TMSP serves as an effective solid electrolyte interphase (SEI)-forming additive for graphite anodes in lithium-ion batteries (LIBs). TMSP forms SEI layers by chemical reactions between TMSP and a reductively decomposed ethylene carbonate (EC) anion, which is strikingly different from the widely known mechanism of the SEI-forming additives. TMSP is stable under cathodic polarization, but it reacts chemically with radical anion intermediates derived from the electrochemical reduction of the carbonate solvents to generate a stable SEI layer. These TMSP-derived SEI layers improve the interfacial stability of the graphite anode, resulting in a retention of 96.8% and a high Coulombic efficiency of 95.2%. We suggest the use of TMSP as a functional additive that effectively stabilizes solid electrolyte interfaces of both the anode and cathode in lithium-ion batteries.

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

2017-05-22

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 the 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 material. The effect of the 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 an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-gel for gating graphene transistors.

PubMed

Kim, Beom Joon; Um, Soong Ho; Song, Woo Chul; Kim, Yong Ho; Kang, Moon Sung; Cho, Jeong Ho

2014-05-14

Water, the primary electrolyte in biology, attracts significant interest as an electrolyte-type dielectric material for transistors compatible with biological systems. Unfortunately, the fluidic nature and low ionic conductivity of water prevents its practical usage in such applications. Here, we describe the development of a solid state, megahertz-operating, water-based gate dielectric system for operating graphene transistors. The new electrolyte systems were prepared by dissolving metal-substituted DNA polyelectrolytes into water. The addition of these biocompatible polyelectrolytes induced hydrogelation to provide solid-state integrity to the system. They also enhanced the ionic conductivities of the electrolytes, which in turn led to the quick formation of an electric double layer at the graphene/electrolyte interface that is beneficial for modulating currents in graphene transistors at high frequencies. At the optimized conditions, the Na-DNA water-gel-gated flexible transistors and inverters were operated at frequencies above 1 MHz and 100 kHz, respectively.

Designing a Novel Polymer Electrolyte for Improving the Electrode/Electrolyte Interface in Flexible All-Solid-State Electrical Double-Layer Capacitors.

PubMed

Wang, Jeng-An; Lu, Yi-Ting; Lin, Sheng-Chi; Wang, Yu-Sheng; Ma, Chen-Chi M; Hu, Chi-Chang

2018-05-30

A novel copolymer, polyurethane-poly(acrylic acid) (PAA), is successfully synthesized from poly(acrylic acid) (PAA) backbone cross-linked with waterborne polyurethane (WPU). This sticky polymer, which is neutralized with 1 M KOH and then soaked in 1 M KOH (denoted as WPU-PAAK-K), provides an ionic conductivity greater than 10 -2 S cm -1 and acts as a gel electrolyte perfectly improving the electrode/electrolyte interfaces in a flexible all-solid-state electrical double-layer capacitor (EDLC). The PAA backbone chains in the copolymer increase the amount of carboxyl groups and promote the segmental motion. The carboxyl groups enhance the water-uptake capacity, which facilitates the ion transport and promotes the ionic conductivity. The cross-linked agent, WPU chains, effectively maintains the rich water content and provides mechanical stickiness to bind two electrodes together. An acid-treated carbon paper (denoted as ACP) combining with such a gel polymer electrolyte demonstrates excellent capacitive behavior with a high areal capacitance of 211.6 mF cm -2 at 10 mV s -1 . A full cell consisting of ACP/WPU-PAAK-K/ACP displays a low equivalent series resistance of 0.44 Ω from the electrochemical impedance spectroscopic results. An all-solid-state ACP/WPU-PAAK-K/ACP EDLC provides an areal specific capacitance of 94.6 mF cm -2 at 1 mA cm -2 . This device under 180° bending shows a capacitance retention over 90%, revealing its remarkable flexibility.

High power density solid oxide fuel cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2004-10-12

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O (LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

Performance of intermediate temperature (600-800 °C) solid oxide fuel cell based on Sr and Mg doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

The solid electrolyte chosen for this investigation was La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSGM). To select appropriate electrode materials from a group of possible candidate materials, AC complex impedance spectroscopy studies were conducted between 600 and 800 °C on symmetrical cells that employed the LSGM electrolyte. Based on the results of the investigation, LSGM electrolyte supported solid oxide fuel cells (SOFCs) were fabricated with La 0.6Sr 0.4Co 0.8Fe 0.2O 3-La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSCF-LSGM) composite cathode and nickel-Ce 0.6La 0.4O 2 (Ni-LDC) composite anode having a barrier layer of Ce 0.6La 0.4O 2 (LDC) between the LSGM electrolyte and the Ni-LDC anode. Electrical performances of these cells were determined and the electrode polarization behavior as a function of cell current was modeled between 600 and 800 °C.

Sustainable Interfaces between Si Anodes and Garnet Electrolytes for Room-Temperature Solid-State Batteries.

PubMed

Chen, Cheng; Li, Quan; Li, Yiqiu; Cui, Zhonghui; Guo, Xiangxin; Li, Hong

2018-01-17

Solid-state batteries (SSBs) have seen a resurgence of research interests in recent years for their potential to offer high energy density and excellent safety far beyond current commercialized lithium-ion batteries. The compatibility of Si anodes and Ta-doped Li 7 La 3 Zr 2 O 12 (Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 , LLZTO) solid electrolytes and the stability of the Si anode have been investigated. It is found that Si layer anodes thinner than 180 nm can maintain good contact with the LLZTO plate electrolytes, leading the Li/LLZTO/Si cells to exhibit excellent cycling performance with a capacity retention over 85% after 100 cycles. As the Si layer thickness is increased to larger than 300 nm, the capacity retention of Li/LLZTO/Si cells becomes 77% after 100 cycles. When the thickness is close to 900 nm, the cells can cycle only for a limited number of times because of the destructive volume change at the interfaces. Because of the sustainable Si/LLZTO interfaces with the Si layer anodes with a thickness of 180 nm, full cells with the LiFePO 4 cathodes show discharge capacities of 120 mA h g -1 for LiFePO 4 and 2200 mA h g -1 for the Si anodes at room temperature. They cycle 100 times with a capacity retention of 72%. These results indicate that the combination between the Si anodes and the garnet electrolytes is a promising strategy for constructing high-performance SSBs.

Method for Making a Fuel Cell

NASA Technical Reports Server (NTRS)

Cable, Thomas L. (Inventor); Setlock, John A. (Inventor); Farmer, Serene C. (Inventor)

2014-01-01

The invention is a novel solid oxide fuel cell (SOFC) stack comprising individual bi-electrode supported fuel cells in which an electrolyte layer is supported between porous electrodes. The porous electrodes may be made from graded pore ceramic tape that has been created by the freeze cast method followed by freeze-drying. Each piece of graded pore tape later becomes a graded pore electrode scaffold that, subsequent to sintering, is made into either an anode or a cathode. The electrode scaffold comprising the anode includes a layer of liquid metal. The pores of the electrode scaffolds gradually increase in diameter as the layer extends away from the electrolyte layer. As a result of this diameter increase, any forces that would tend to pull the liquid metal away from the electrolyte are reduced while maintaining a diffusion path for the fuel. Advantageously, the fuel cell of the invention may utilize a hydrocarbon fuel without pre-processing to remove sulfur.

Fabrication and Characterization of Functionally Graded Cathodes for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Simonet, J.; Kapelski, G.; Bouvard, D.

2008-02-01

Solid oxide fuel cells are multi-layered designed. The most prevalent structure is an anode supported cell with a thick porous layer of nickel oxide NiO and yttrium stabilized zirconia (YSZ) composite acting as an anode, a thin dense layer of YSZ as an electrolyte, a composite thin porous layer of lanthanum strontium manganate LSM and YSZ and a current collector layer of porous LSM. Regular operating temperature is 1000 °C. The industrial development requires designing cathodes with acceptable electrochemical and mechanical properties at a lower temperature, typically between 700 and 800 °C. A solution consists in designing composite bulk cathodes with more numerous electro-chemical reaction sites. This requirement could be met by grading the composition of the cathode in increasing the YSZ volume fraction near the electrolyte and the LSM volume fraction near the current collector layer so that the repartition of reaction sites and the interfacial adhesion between the cathode and electrolyte layers are optimal. The fabrication of graded composite cathode has been investigated using a sedimentation process that consists of preparing a suspension containing the powder mixture and allowing the particles to fall by gravity upon a substrate. Different composite cathodes with continuous composition gradient have been obtained by sedimentation of LSM and YSZ powder mixture upon a dense YSZ substrate and subsequent firing. Their compositions and microstructures have been analysed with Scanning Electron Microscope (SEM) and Electron Dispersive Spectrometry (EDS).

In Situ STEM-EELS observation of nanoscale interfacial phenomena in all-solid-state batteries

DOE PAGES

Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei; ...

2016-05-03

Behaviors of functional interfaces are crucial factors in the performance and safety of energy storage and conversion devices. Indeed, solid electrode–solid electrolyte interfacial impedance is now considered the main limiting factor in all-solid-state batteries rather than low ionic conductivity of the solid electrolyte. In this paper, we present a new approach to conducting in situ scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) in order to uncover the unique interfacial phenomena related to lithium ion transport and its corresponding charge transfer. Our approach allowed quantitative spectroscopic characterization of a galvanostatically biased electrochemical system under in situmore » conditions. Using a LiCoO 2/LiPON/Si thin film battery, an unexpected structurally disordered interfacial layer between LiCoO 2 cathode and LiPON electrolyte was discovered to be inherent to this interface without cycling. During in situ charging, spectroscopic characterization revealed that this interfacial layer evolved to form highly oxidized Co ions species along with lithium oxide and lithium peroxide species. These findings suggest that the mechanism of interfacial impedance at the LiCoO 2/LiPON interface is caused by chemical changes rather than space charge effects. Finally, insights gained from this technique will shed light on important challenges of interfaces in all-solid-state energy storage and conversion systems and facilitate improved engineering of devices operated far from equilibrium.« less

Performance of strontium- and magnesium-doped lanthanum gallate electrolyte with lanthanum-doped ceria as a buffer layer for IT-SOFCs

NASA Astrophysics Data System (ADS)

Lee, Dokyol; Han, Ju-Hyeong; Kim, Eun-Gu; Song, Rak-Hyun; Shin, Dong-Ryul

La 0.8Sr 0.2Ga 0.8Mg 0.2O 2.8 (LSGM8080) powder, showing the highest electrical conductivity among LSGMs of various compositions, is synthesized using the glycine nitrate process (GNP) and used as the electrolyte for an intermediate-temperature solid oxide fuel cell (IT-SOFC). The LDC (Ce 0.55La 0.45O 1.775) powder is synthesized by a solid-state reaction and employed as the material for a buffer layer to prevent the reaction between the anode and electrolyte materials. The LDC also serves as the skeleton material for the anode. An anode-supported single cell with an active area of 1 cm 2 is constructed for performance evaluation. A single-cell test is performed at 750 and 800 °C. The maximum power density of the cell 459 and 664 mW cm -2 at 750 and 800 °C, respectively.

High ion conductive Sb2O5-doped β-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Xie, Dongjiu; Chen, Shaojie; Zhang, Zhihua; Ren, Jie; Yao, Lili; Wu, Linbin; Yao, Xiayin; Xu, Xiaoxiong

2018-06-01

The combination of high conductivity and good stability against Li is not easy to achieve for solid electrolytes, hindering the development of high energy solid-state batteries. In this study, doped electrolytes of Li3P1-xSbxS4-2.5xO2.5x are successfully prepared via the high energy ball milling and subsequent heat treatment. Plenty of techniques like XRD, Raman, SEM, EDS and TEM are utilized to characterize the crystal structures, particle sizes, and morphologies of the glass-ceramic electrolytes. Among them, the Li3P0.98Sb0.02S3.95O0.05 (x = 0.02) exhibits the highest ionic conductivity (∼1.08 mS cm-1) at room temperature with an excellent stability against lithium. In addition, all-solid-state lithium batteries are assembled with LiCoO2 as cathode, Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 as the bi-layer electrolyte, and lithium as anode. The constructed solid-state batteries delivers a high initial discharge capacity of 133 mAh g-1 at 0.1C in the range of 3.0-4.3 V vs. Li/Li+ at room temperature, and shows a capacity retention of 78.6% after 50 cycles. Most importantly, the all-solid-state lithium batteries with the Li10GeP2S12/Li3P0.98Sb0.02S3.95O0.05 electrolyte can be workable even at -10 °C. This study provides a promising electrolyte with the improved conductivity and stability against Li for the application of all-solid-state lithium batteries.

Co-extrusion of electrolyte/anode functional layer/anode triple-layer ceramic hollow fibres for micro-tubular solid oxide fuel cells-electrochemical performance study

NASA Astrophysics Data System (ADS)

Li, Tao; Wu, Zhentao; Li, K.

2015-01-01

In this study, the effects of an anode functional layer (AFL) with controlled thickness on physical and electrochemical properties of a micro-tubular SOFC have been systematically studied. A series of electrolyte/AFL/anode triple-layer hollow fibres with controllable AFL thicknesses (16.9-52.7 μm) have been fabricated via a single-step phase-inversion assisted co-extrusion technique. Both robustness of the cell and gas-tightness of the electrolyte layer are considerably improved by introducing the AFL of this type. The fracture force of the sample with the thickest AFL (9.67 N) almost doubles when compared to the electrolyte/anode dual-layer counterpart (5.24 N). Gas-tightness of the electrolyte layer is also considerably increased as AFL contributes to better-matched sintering behaviours between different components. Moreover, the formation of an AFL simultaneously with electrolyte and anode significantly improves the cell performances. The sample with the thinnest AFL (approximately 16.9 μm, 6% of the total anode thickness) leads to a 30% (from 0.89 to 1.21 W cm-2) increase in maximum power density, due to increased triple-phase boundaries (TPB). However, further increase in TPB from a thicker AFL is less effective for improving the cell performance, due to the substantially increased fuel diffusion resistance and subsequently higher concentration polarization. This indicates that the control over the AFL thickness is critically important in avoiding offsetting the benefits of extended TPB and consequently decreased cell performances.

Fast formation cycling for lithium ion batteries

DOE PAGES

An, Seong Jin; Li, Jianlin; Du, Zhijia; ...

2017-01-09

The formation process for lithium ion batteries typically takes several days or more, and it is necessary for providing a stable solid electrolyte interphase on the anode (at low potentials vs. Li/Li +) for preventing irreversible consumption of electrolyte and lithium ions. An analogous layer known as the cathode electrolyte interphase layer forms at the cathode at high potentials vs. Li/Li +. However, several days, or even up to a week, of these processes result in either lower LIB production rates or a prohibitively large size of charging-discharging equipment and space (i.e. excessive capital cost). In this study, a fastmore » and effective electrolyte interphase formation protocol is proposed and compared with an Oak Ridge National Laboratory baseline protocol. Graphite, NMC 532, and 1.2 M LiPF 6 in ethylene carbonate: diethyl carbonate were used as anodes, cathodes, and electrolytes, respectively. Finally, results from electrochemical impedance spectroscopy show the new protocol reduced surface film (electrolyte interphase) resistances, and 1300 aging cycles show an improvement in capacity retention.« less

High performance solid-state electric double layer capacitor from redox mediated gel polymer electrolyte and renewable tamarind fruit shell derived porous carbon.

PubMed

Senthilkumar, S T; Selvan, R Kalai; Melo, J S; Sanjeeviraja, C

2013-11-13

The activated carbon was derived from tamarind fruit shell and utilized as electrodes in a solid state electrochemical double layer capacitor (SSEDLC). The fabricated SSEDLC with PVA (polyvinyl alcohol)/H2SO4 gel electrolyte delivered high specific capacitance and energy density of 412 F g(-1) and 9.166 W h kg(-1), respectively, at 1.56 A g(-1). Subsequently, Na2MoO4 (sodium molybdate) added PVA/H2SO4 gel electrolyte was also prepared and applied for SSEDLC, to improve the performance. Surprisingly, 57.2% of specific capacitance (648 F g(-1)) and of energy density (14.4 Wh kg(-1)) was increased while introducing Na2MoO4 as the redox mediator in PVA/H2SO4 gel electrolyte. This improved performance is owed to the redox reaction between Mo(VI)/Mo(V) and Mo(VI)/Mo(IV) redox couples in Na2MoO4/PVA/H2SO4 gel electrolyte. Similarly, the fabricated device shows the excellent capacitance retention of 93% for over 3000 cycles. The present work suggests that the Na2MoO4 added PVA/H2SO4 gel is a potential electrolyte to improve the performance instead of pristine PVA/H2SO4 gel electrolyte. Based on the overall performance, it is strongly believed that the combination of tamarind fruit shell derived activated carbon and Na2MoO4/PVA/H2SO4 gel electrolyte is more attractive in the near future for high performance SSEDLCs.

Ionic liquids as electrolytes for Li-ion batteries-An overview of electrochemical studies

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

The paper reviews properties of room temperature ionic liquids (RTILs) as electrolytes for lithium and lithium-ion batteries. It has been shown that the formation of the solid electrolyte interface (SEI) on the anode surface is critical to the correct operation of secondary lithium-ion batteries, including those working with ionic liquids as electrolytes. The SEI layer may be formed by electrochemical transformation of (i) a molecular additive, (ii) RTIL cations or (iii) RTIL anions. Such properties of RTIL electrolytes as viscosity, conductivity, vapour pressure and lithium-ion transport numbers are also discussed from the point of view of their influence on battery performance.

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, N.Q.; Horne, C.R.

1994-03-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array. 10 figures.

Method of fabricating a monolithic solid oxide fuel cell

DOEpatents

Minh, Nguyen Q.; Horne, Craig R.

1994-01-01

In a two-step densifying process of making a monolithic solid oxide fuel cell, a limited number of anode-electrolyte-cathode cells separated by an interconnect layer are formed and partially densified. Subsequently, the partially densified cells are stacked and further densified to form a monolithic array.

Method of Fabrication of High Power Density Solid Oxide Fuel Cells

DOEpatents

Pham, Ai Quoc; Glass, Robert S.

2008-09-09

A method for producing ultra-high power density solid oxide fuel cells (SOFCs). The method involves the formation of a multilayer structure cells wherein a buffer layer of doped-ceria is deposited intermediate a zirconia electrolyte and a cobalt iron based electrode using a colloidal spray deposition (CSD) technique. For example, a cobalt iron based cathode composed of (La,Sr)(Co,Fe)O(LSCF) may be deposited on a zirconia electrolyte via a buffer layer of doped-ceria deposited by the CSD technique. The thus formed SOFC have a power density of 1400 mW/cm.sup.2 at 600.degree. C. and 900 mW/cm.sup.2 at 700.degree. C. which constitutes a 2-3 times increased in power density over conventionally produced SOFCs.

Sodium ion transport mechanisms in antiperovskite electrolytes Na 3OBr and Na 4OI 2: An in Situ neutron diffraction study

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

Zhu, Jinlong; Wang, Yonggang; Li, Shuai

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-stat battery. In this work, the sodium ionic transport pathways of the parent compound Na 3OBr, as well as the modified layered antiperovskite Na 4OI 2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na 3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions ho within and among oxygen octahedra, and Br - ions are not involved in the tetragonal Namore » 4OI 2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. In conclusion, the transport of sodium ions along the c axis is assisted by I - ions.« less

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

NASA Astrophysics Data System (ADS)

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

2006-03-01

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

Sodium ion transport mechanisms in antiperovskite electrolytes Na 3OBr and Na 4OI 2: An in Situ neutron diffraction study

DOE PAGES

Zhu, Jinlong; Wang, Yonggang; Li, Shuai; ...

2016-06-02

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-stat battery. In this work, the sodium ionic transport pathways of the parent compound Na 3OBr, as well as the modified layered antiperovskite Na 4OI 2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na 3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions ho within and among oxygen octahedra, and Br - ions are not involved in the tetragonal Namore » 4OI 2 antiperovskite, Na ions, which connect octahedra in the ab plane, have the lowest activation energy barrier. In conclusion, the transport of sodium ions along the c axis is assisted by I - ions.« less

Carbon Dioxide Gas Sensors and Method of Manufacturing and Using Same

NASA Technical Reports Server (NTRS)

Hunter, Gary W. (Inventor); Xu, Jennifer C. (Inventor)

2014-01-01

A gas sensor comprises a substrate layer; a pair of interdigitated metal electrodes, said electrodes include upper surfaces, the electrodes selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, Os, and their alloys. A first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON and.beta.''-Alumina. A second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of the electrodes and the first solid electrolyte. The metal carbonates selected from the group consisting of the following ions Na.sup.+, K.sup.+, Li.sup.+, Ag.sup.+, H.sup.+, Pb.sup.2+, Sr.sup.2+, Ba.sup.2+, and any combination thereof. An extra layer of metal oxide selected from the group consisting of SnO.sub.2, In.sub.2O.sub.3, TiO.sub.2, WO.sub.3, ZnO, Fe.sub.2O.sub.3, ITO, CdO, U.sub.3O.sub.8, Ta.sub.2O.sub.5, BaO, MoO.sub.2, MoO.sub.3, V.sub.2O.sub.5, Nb.sub.2O.sub.5, CuO, Cr.sub.2O.sub.3, La.sub.2O.sub.3, RuO.sub.3, RuO.sub.2, ReO.sub.2, ReO.sub.3, Ag.sub.2O, CoO, Cu.sub.2O, SnO, NiO, Pr.sub.2O.sub.3, BaO, PdO.sub.2, HfO.sub.3, HfO.sub.3 or other metal oxide and their mixtures residing above and in engagement with the second electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

High-temperature solid electrolyte interphases (SEI) in graphite electrodes

NASA Astrophysics Data System (ADS)

Rodrigues, Marco-Tulio F.; Sayed, Farheen N.; Gullapalli, Hemtej; Ajayan, Pulickel M.

2018-03-01

Thermal fragility of the solid electrolyte interphase (SEI) is a major source of performance decay in graphite anodes, and efforts to overcome the issues offered by extreme environments to Li-ion batteries have had limited success. Here, we demonstrate that the SEI can be extensively reinforced by carrying the formation cycles at elevated temperatures. Under these conditions, decomposition of the ionic liquid present in the electrolyte favored the formation of a thicker and more protective layer. Cells in which the solid electrolyte interphase was cast at 90 °C were significantly less prone to self-discharge when exposed to high temperature, with no obvious damages to the formed SEI. This additional resilience was accomplished at the expense of rate capability, as charge transfer became growingly inefficient in these systems. At slower rates, however, cells that underwent SEI formation at 90 °C presented superior performances, as a result of improved Li+ transport through the SEI, and optimal wetting of graphite by the electrolyte. This work analyzes different graphite hosts and ionic liquids, showing that this effect is more pervasive than anticipated, and offering the unique perspective that, for certain systems, temperature can actually be an asset for passivation.

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

High performance red phosphorus electrode in ionic liquid-based electrolyte for Na-ion batteries

NASA Astrophysics Data System (ADS)

Dahbi, Mouad; Fukunishi, Mika; Horiba, Tatsuo; Yabuuchi, Naoaki; Yasuno, Satoshi; Komaba, Shinichi

2017-09-01

Electrochemical performance of the red phosphorus electrode was examined in ionic-liquid electrolyte, 0.25 mol dm-3 sodium bisfluorosulfonylamide (NaFSA) dissolved N-methyl-N-propylpyridinium-bisfluorosulfonylamide (MPPFSA), at room temperature. We compared its electrochemical performance to conventional EC/PC/DEC, EC/DEC, and PC solutions containing 1 mol dm-3 NaPF6. The electrode in NaFSA/MPPFSA demonstrated a reversible capacity of 1480 mAh g-1 and excellent capacity retention of 93% over 80 cycles, which is much better than those in the conventional electrolytes. The difference in capacity retention for the electrolytes correlates to the different solid electrolyte interphase (SEI) layer formed on the phosphorus electrode. To understand the SEI formation in NaFSA/MPPFSA and its evolution during cycling, we investigate the surface layer of the red phosphorus electrodes with hard X-ray photoelectron spectroscopy (HAXPES) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). A detailed analysis of HAXPES spectra demonstrates that SEI layer consists of major inorganic and minor organic species, originating from decomposition of MPP+ and FSA-. Homogenous surface layer is formed during the first cycle in NaFSA/MPPFSA while in alkyl carbonate ester electrolytes, continuous growth of surface film up to the 20th cycle is observed. Possibility of red phosphorous electrode for battery applications with pure ionic liquid is discussed.

Materials system for intermediate temperature solid oxide fuel cells based on doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan

2005-07-01

The objective of this work was to identify a materials system for intermediate temperature solid oxide fuel cells (IT-SOFCs). Towards this goal, alternating current complex impedance spectroscopy was employed as a tool to study electrode polarization effects in symmetrical cells employing strontium and magnesium doped lanthanum gallate (LSGM) electrolyte. Several cathode materials were investigated including strontium doped lanthanum manganite (LSM), Strontium and iron doped lanthanum cobaltate (LSCF), LSM-LSGM, and LSCF-LSGM composites. Investigated Anode materials included nickel-gadolinium or lanthanum doped cerium oxide (Ni-GDC, or Ni-LDC) composites. The ohmic and the polarization resistances of the symmetrical cells were obtained as a function of temperature, time, thickness, and the composition of the electrodes. Based on these studies, the single phase LSM electrode had the highest polarization resistance among the cathode materials. The mixed-conducting LSCF electrode had polarization resistance orders of magnitude lower than that of the LSM-LSGM composite electrodes. Although incorporating LSGM in the LSCF electrode did not reduce the cell polarization resistance significantly, it could reduce the thermal expansion coefficient mismatch between the LSCF electrodes and LSGM electrolyte. Moreover, the polarization resistance of the LSCF electrode decreased asymptotically as the electrode thickness was increased thus suggesting that the electrode thickness needed not be thicker than this asymptotic limit. On the anode side of the IT-SOFC, Ni reacted with LSGM electrolyte, and lanthanum diffusion occurred from the LSGM electrolyte to the GDC barrier layer, which was between the LSGM electrolyte and the Ni-composite anode. However, LDC served as an effective barrier layer. Ni-LDC (70 v% Ni) anode had the largest polarization resistance, while all other anode materials, i.e. Ni-LDC (50 v% Ni), Ni-GDC (70 v% NO, and Ni-GDC (50 v% Ni), had similar polarization resistances. Ni-LDC (50 v% NO was selected to be the anode for the LSGM electrolyte with a thin LDC barrier layer. Finally, the performance of complete LSGM electrolyte-supported IT-SOFCs with the selected cathode (LSCF-LSGM) and anode (Ni-LDC) materials coupled with the LDC barrier layer was evaluated at 600--800°C. The simulated cell performance of the anode-supported cell based on LSGM electrolyte was promising.

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

NASA Astrophysics Data System (ADS)

Divya, Velpula; Sangaranarayanan, M. V.

2018-04-01

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

Influence of Electrode Design and Contacting Layers on Performance of Electrolyte Supported SOFC/SOEC Single Cells.

PubMed

Kusnezoff, Mihails; Trofimenko, Nikolai; Müller, Martin; Michaelis, Alexander

2016-11-08

The solid oxide cell is a basis for highly efficient and reversible electrochemical energy conversion. A single cell based on a planar electrolyte substrate as support (ESC) is often utilized for SOFC/SOEC stack manufacturing and fulfills necessary requirements for application in small, medium and large scale fuel cell and electrolysis systems. Thickness of the electrolyte substrate, and its ionic conductivity limits the power density of the ESC. To improve the performance of this cell type in SOFC/SOEC mode, alternative fuel electrodes, on the basis of Ni/CGO as well as electrolytes with reduced thickness, have been applied. Furthermore, different interlayers on the air side have been tested to avoid the electrode delamination and to reduce the cell degradation in electrolysis mode. Finally, the influence of the contacting layer on cell performance, especially for cells with an ultrathin electrolyte and thin electrode layers, has been investigated. It has been found that Ni/CGO outperform traditional Ni/8YSZ electrodes and the introduction of a ScSZ interlayer substantially reduces the degradation rate of ESC in electrolysis mode. Furthermore, it was demonstrated that, for thin electrodes, the application of contacting layers with good conductivity and adhesion to current collectors improves performance significantly.

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.

Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

NASA Astrophysics Data System (ADS)

Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

2017-02-01

In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

Component-/structure-dependent elasticity of solid electrolyte interphase layer in Li-ion batteries: Experimental and computational studies

NASA Astrophysics Data System (ADS)

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

2015-03-01

The mechanical instability of the Solid Electrolyte Interphase (SEI) layer in lithium ion (Li-ion) batteries causes significant side reactions resulting in Li-ion consumption and cell impedance rise by forming further SEI layers, which eventually leads to battery capacity fade and power fade. In this paper, the composition-/structure-dependent elasticity of the SEI layer is investigated via Atomic Force Microscopy (AFM) measurements coupled with X-ray Photoelectron Spectroscopy (XPS) analysis, and atomistic calculations. It is observed that the inner layer is stiffer than the outer layer. The measured Young's moduli are mostly in the range of 0.2-4.5 GPa, while some values above 80 GPa are also observed. This wide variation of the observed elastic modulus is elucidated by atomistic calculations with a focus on chemical and structural analysis. The numerical analysis shows the Young's moduli range from 2.4 GPa to 58.1 GPa in the order of the polymeric, organic, and amorphous inorganic components. The crystalline inorganic component (LiF) shows the highest value (135.3 GPa) among the SEI species. This quantitative observation on the elasticity of individual components of the SEI layer must be essential to analyzing the mechanical behavior of the SEI layer and to optimizing and controlling it.

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.

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.

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.

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid-solution range. The solid-solution range, which is reduced at higher current by the rate of transfer of the working ion across electrode/electrolyte interfaces and within a host, limits the amount of charge per electrode formula unit that can be transferred over the time Δt = Δt(I). Moreover, the difference between energies of the LUMO and the HOMO of the electrolyte, i.e., electrolyte window, determines the maximum voltage for a long shelf and cycle life. The maximum stable voltage with an aqueous electrolyte is 1.5 V; the Li-ion rechargeable battery uses an organic electrolyte with a larger window, which increase the density of stored energy for a given Δt. Anode or cathode electrochemical potentials outside the electrolyte window can increase V, but they require formation of a passivating surface layer that must be permeable to Li(+) and capable of adapting rapidly to the changing electrode surface area as the electrode changes volume during cycling. A passivating surface layer adds to the impedance of the Li(+) transfer across the electrode/electrolyte interface and lowers the cycle life of a battery cell. Moreover, formation of a passivation layer on the anode robs Li from the cathode irreversibly on an initial charge, further lowering the reversible Δt. These problems plus the cost of quality control of manufacturing plague development of Li-ion rechargeable batteries that can compete with the internal combustion engine for powering electric cars and that can provide the needed low-cost storage of electrical energy generated by renewable wind and/or solar energy. Chemists are contributing to incremental improvements of the conventional strategy by investigating and controlling electrode passivation layers, improving the rate of Li(+) transfer across electrode/electrolyte interfaces, identifying electrolytes with larger windows while retaining a Li(+) conductivity σ(Li) > 10(-3) S cm(-1), synthesizing electrode morphologies that reduce the size of the active particles while pinning them on current collectors of large surface area accessible by the electrolyte, lowering the cost of cell fabrication, designing displacement-reaction anodes of higher capacity that allow a safe, fast charge, and designing alternative cathode hosts. However, new strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions (e.g. sulfur) by liquid cathodes that may contain flow-through redox molecules, or by catalysts for air cathodes; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively. Opportunities exist for the chemist to bring together oxide and polymer or graphene chemistry in imaginative morphologies.

The thermomechanical stability of micro-solid oxide fuel cells fabricated on anodized aluminum oxide membranes

NASA Astrophysics Data System (ADS)

Kwon, Chang-Woo; Lee, Jae-Il; Kim, Ki-Bum; Lee, Hae-Weon; Lee, Jong-Ho; Son, Ji-Won

2012-07-01

The thermomechanical stability of micro-solid oxide fuel cells (micro-SOFCs) fabricated on an anodized aluminum oxide (AAO) membrane template is investigated. The full structure consists of the following layers: AAO membrane (600 nm)/Pt anode/YSZ electrolyte (900 nm)/porous Pt cathode. The utilization of a 600-nm-thick AAO membrane significantly improves the thermomechanical stability due to its well-known honeycomb-shaped nanopore structure. Moreover, the Pt anode layer deposited in between the AAO membrane and the YSZ electrolyte preserves its integrity in terms of maintaining the triple-phase boundary (TPB) and electrical conductivity during high-temperature operation. Both of these results guarantee thermomechanical stability of the micro-SOFC and extend the cell lifetime, which is one of the most critical issues in the fabrication of freestanding membrane-type micro-SOFCs.

Solid oxide fuel cell cathode with oxygen-reducing layer

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

Surdoval, Wayne A.; Berry, David A.; Shultz, Travis

The disclosure provides a SOFC comprised of an electrolyte, anode, and cathode, where the cathode comprises an MIEC and an oxygen-reducing layer. The oxygen-reducing layer is in contact with the MIEC, and the MIEC is generally between and separating the oxygen-reducing layer and the electrolyte. The oxygen-reducing layer is comprised of single element oxides, single element carbonates, or mixtures thereof, and has a thickness of less than about 30 nm. In a particular embodiment, the thickness is less than 5 nm. In another embodiment, the thickness is about 3 monolayers or less. The oxygen-reducing layer may be a continuous filmmore » or a discontinuous film with various coverage ratios. The oxygen-reducing layer at the thicknesses described may be generated on the MIEC surface using means known in the art such as, for example, ALD processes.« less

Solvothermal synthesis of gallium-indium-zinc-oxide nanoparticles for electrolyte-gated transistors.

PubMed

Santos, Lídia; Nunes, Daniela; Calmeiro, Tomás; Branquinho, Rita; Salgueiro, Daniela; Barquinha, Pedro; Pereira, Luís; Martins, Rodrigo; Fortunato, Elvira

2015-01-14

Solution-processed field-effect transistors are strategic building blocks when considering low-cost sustainable flexible electronics. Nevertheless, some challenges (e.g., processing temperature, reliability, reproducibility in large areas, and cost effectiveness) are requirements that must be surpassed in order to achieve high-performance transistors. The present work reports electrolyte-gated transistors using as channel layer gallium-indium-zinc-oxide nanoparticles produced by solvothermal synthesis combined with a solid-state electrolyte based on aqueous dispersions of vinyl acetate stabilized with cellulose derivatives, acrylic acid ester in styrene and lithium perchlorate. The devices fabricated using this approach display a ION/IOFF up to 1 × 10(6), threshold voltage (VTh) of 0.3-1.9 V, and mobility up to 1 cm(2)/(V s), as a function of gallium-indium-zinc-oxide ink formulation and two different annealing temperatures. These results validates the usage of electrolyte-gated transistors as a viable and promising alternative for nanoparticle based semiconductor devices as the electrolyte improves the interface and promotes a more efficient step coverage of the channel layer, reducing the operating voltage when compared with conventional dielectrics gating. Moreover, it is shown that by controlling the applied gate potential, the operation mechanism of the electrolyte-gated transistors can be modified from electric double layer to electrochemical doping.

Development of wide temperature electrolyte for graphite/ LiNiMnCoO2 Li-ion cells: High throughput screening

NASA Astrophysics Data System (ADS)

Kafle, Janak; Harris, Joshua; Chang, Jeremy; Koshina, Joe; Boone, David; Qu, Deyang

2018-07-01

In this report, we demonstrate that the low temperature power capability of a Li-ion battery can be substantially improved not by adding commercially unavailable additives into the electrolyte, but by rational design of the composition of the most commonly used solvents. Through the detail analysis with electrochemical impedance spectroscopy, the formation of a homogenous solid electrolyte interface (SEI) layer on the carbon anode surface is found to be critical to ensure the performance of a Li-ion battery in a wide temperature range. The post mortem analysis of the negative electrode by XPS revealed that all the electrolyte compositions form similar compounds in the solid electrolyte interphase. However, the electrolytes which give higher capacities at low temperature showed higher percentage of LiF and lower percentage of carbon containing species such as lithium carbonate and lithium ethylene di-carbonate. The electrolyte compositions where cyclic carbonates make up less than 25% of the total solvent showed increased low temperature performance. The solvent composition with higher percentage of linear short chain carbonates showed an improved low temperature performance. The high temperature performances were similar in almost all the combinations.

Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility.

PubMed

Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Rüdiger-A

2018-06-22

High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi 2 (PO 4 ) 3 anode and Li 3 V 2 (PO 4 ) 3 cathode composite layers on a densely sintered Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chemical and mechanical matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery utilized a phosphate backbone in combination with tailored morphology of the electrode materials to ensure good interfacial matching for a durable mechanical stability. Moreover, the operating voltage range of the active materials matches with the intrinsic electrochemical window of the electrolyte which resulted in high electrochemical stability. A highly competitive discharge capacity of 63.5 mAh g -1 at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The analysis of interfacial charge transfer kinetics confirmed the structural and electrical properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance analysis with subsequent distribution of relaxation times analysis. Moreover, the prepared solid-state battery could be processed and operated in air atmosphere owing to the low oxygen sensitivity of the phosphate materials. The analysis of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.

Use of Tween Polymer To Enhance the Compatibility of the Li/Electrolyte Interface for the High-Performance and High-Safety Quasi-Solid-State Lithium-Sulfur Battery.

PubMed

Liu, Jie; Qian, Tao; Wang, Mengfan; Zhou, Jinqiu; Xu, Na; Yan, Chenglin

2018-06-07

Lithium metal batteries have attracted increasing attention recently due to their particular advantages in energy density. However, as for their practical application, the development of solid-state lithium metal batteries is restricted because of the poor Li/electrolyte interface, low Li-ion conductivity, and irregular growth of Li dendrites. To address the above issues, we herein report a high Li-ion conductivity and compatible polymeric interfacial layer by grafting tween-20 on active lithium metal. Sequential oxyethylene groups in tween-grafted Li (TG-Li) improve the ion conductivity and the compatibility of the Li/electrolyte interface, which enables low overpotentials and stable performance over 1000 cycles. Consequently, the poly(ethylene oxide)-based solid-state lithium-sulfur battery with TG-Li exhibits a high reversible capacity of 1051.2 mA h g -1 at 0.2 C (1 C = 1675 mA h g -1 ) and excellent stability for 500 cycles at 2 C. The decreasing concentration of the sulfur atom with increasing Ar + sputtering depth indicates that the polymer interfacial layer works well in suppressing polysulfide reduction to Li 2 S/Li 2 S 2 on the metallic Li surface even after long-term cycling.

Thick solid electrolyte interphases grown on silicon nanocone anodes during slow cycling and their negative effects on the performance of Li-ion batteries.

PubMed

Luo, Fei; Chu, Geng; Xia, Xiaoxiang; Liu, Bonan; Zheng, Jieyun; Li, Junjie; Li, Hong; Gu, Changzhi; Chen, Liquan

2015-05-07

Thickness, homogeneity and coverage of the surface passivation layer on Si anodes for Li-ion batteries have decisive influences on their cyclic performance and coulombic efficiency, but related information is difficult to obtain, especially during cycling. In this work, a well-defined silicon nanocone (SNC) on silicon wafer sample has been fabricated as a model electrode in lithium ion batteries to investigate the growth of surface species on the SNC electrode during cycling using ex situ scanning electronic microscopy. It is observed that an extra 5 μm thick layer covers the top of the SNCs after 25 cycles at 0.1 C. This top layer has been proven to be a solid electrolyte interphase (SEI) layer by designing a solid lithium battery. It is noticed that the SEI layer is much thinner at a high rate of 1 C. The cyclic performance of the SNCs at 1 C looks much better than that of the same electrode at 0.1 C in the half cell. Our findings clearly demonstrate that the formation of the thick SEI on the naked nanostructured Si anode during low rate cycling is a serious problem for practical applications. An in depth understanding of this problem may provide valuable guidance in designing Si-based anode materials.

Water at silica/liquid water interfaces investigated by DFT-MD simulations

NASA Astrophysics Data System (ADS)

Gaigeot, Marie-Pierre

This talk is dedicated to probing the microscopic structural organization of water at silica/liquid water interfaces including electrolytes by first principles DFT-based molecular dynamics simulations (DFT-MD). We will present our very recent DFT-MD simulations of electrolytic (KCl, NaCl, NaI) silica/liquid water interfaces in order to unravel the intertwined structural properties of water and electrolytes at the crystalline quartz/liquid water and amorphous silica/liquid water interfaces. DFT-MD simulations provide direct knowledge of the structural organization of water and the H-Bond network formed between the water molecules within the different water layers above the silica surface. One can furthermore extract vibrational signatures of the water molecules within the interfacial layers from the DFT-MD simulations, especially non-linear SFG (Sum Frequency generation) signatures that are active at solid/liquid interfaces. The strength of the simulated spectra is that a detailed analysis of the signatures in terms of the water/water H-Bond networks formed within the interfacial water layers and in terms of the water/silica or water/electrolytes H-Bond networks can be given. Comparisons of SFG spectra between quartz/water/electrolytes and amorphous silica/water/electrolytes interfaces allow us to definitely conclude on how the structural arrangements of liquid water at these electrolytic interfaces modulate the final spectroscopic signatures. Invited speaker.

Electro-convective versus electroosmotic instability in concentration polarization.

PubMed

Rubinstein, Isaak; Zaltzman, Boris

2007-10-31

Electro-convection is reviewed as a mechanism of mixing in the diffusion layer of a strong electrolyte adjacent to a charge-selective solid, such as an ion exchange (electrodialysis) membrane or an electrode. Two types of electro-convection in strong electrolytes may be distinguished: bulk electro-convection, due to the action of the electric field upon the residual space charge of a quasi-electro-neutral bulk solution, and convection induced by electroosmotic slip, due to electric forces acting in the thin electric double layer of either quasi-equilibrium or non-equilibrium type near the solid/liquid interface. According to recent studies, the latter appears to be the likely source of mixing in the diffusion layer, leading to 'over-limiting' conductance in electrodialysis. Electro-convection near a planar uniform charge selective solid/liquid interface sets on as a result of hydrodynamic instability of one-dimensional steady state electric conduction through such an interface. We compare the results of linear stability analysis obtained for instabilities of this kind appearing in the full electro-convective and limiting non-equilibrium electroosmotic formulations. The short- and long-wave aspects of these instabilities are discussed along with the wave number selection principles.

Method and closing pores in a thermally sprayed doped lanthanum chromite interconnection layer

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1995-01-01

A dense, substantially gas-tight electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an air electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO.sub.3 particles doped with an element or elements selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by thermal spraying doped LaCrO.sub.3 particles, either by plasma arc spraying or flame spraying; (C) depositing a mixture of CaO and Cr.sub.2 O.sub.3 on the surface of the thermally sprayed layer; and (D) heating the doped LaCrO.sub.3 layer coated with CaO and Cr.sub.2 O.sub.3 surface deposit at from about 1000.degree. C. to 1200.degree. C. to substantially close the pores, at least at a surface, of the thermally sprayed doped LaCrO.sub.3 layer. The result is a dense, substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the nonselected portion of the air electrode. A fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell, for example for generation of electrical power.

Method and closing pores in a thermally sprayed doped lanthanum chromite interconnection layer

DOEpatents

Singh, P.; Ruka, R.J.

1995-02-14

A dense, substantially gas-tight electrically conductive interconnection layer is formed on an air electrode structure of an electrochemical cell by (A) providing an air electrode surface; (B) forming on a selected portion of the electrode surface, a layer of doped LaCrO{sub 3} particles doped with an element or elements selected from Ca, Sr, Ba, Mg, Co, Ni, Al and mixtures thereof by thermal spraying doped LaCrO{sub 3} particles, either by plasma arc spraying or flame spraying; (C) depositing a mixture of CaO and Cr{sub 2}O{sub 3} on the surface of the thermally sprayed layer; and (D) heating the doped LaCrO{sub 3} layer coated with CaO and Cr{sub 2}O{sub 3} surface deposit at from about 1,000 C to 1,200 C to substantially close the pores, at least at a surface, of the thermally sprayed doped LaCrO{sub 3} layer. The result is a dense, substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode surface. A solid electrolyte layer can be applied to the nonselected portion of the air electrode. A fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell, for example for generation of electrical power. 5 figs.

All-solid-state reduced graphene oxide supercapacitor with large volumetric capacitance and ultralong stability prepared by electrophoretic deposition method.

PubMed

Wang, Mei; Duong, Le Dai; Mai, Nguyen Thi; Kim, Sanghoon; Kim, Youngjun; Seo, Heewon; Kim, Ye Chan; Jang, Woojin; Lee, Youngkwan; Suhr, Jonghwan; Nam, Jae-Do

2015-01-21

Portable energy storage devices have gained special attention due to the growing demand for portable electronics. Herein, an all-solid-state supercapacitor is successfully fabricated based on a poly(vinyl alcohol)-H3PO4 (PVA-H3PO4) polymer electrolyte and a reduced graphene oxide (RGO) membrane electrode prepared by electrophoretic deposition (EPD). The RGO electrode fabricated by EPD contains an in-plane layer-by-layer alignment and a moderate porosity that accommodate the electrolyte ions. The all-solid-state RGO supercapacitor is thoroughly tested to give high specific volumetric capacitance (108 F cm(-3)) and excellent energy and power densities (7.5 Wh cm(-3) and 2.9 W cm(-3), respectively). In addition, the all-solid-state RGO supercapacitor exhibits an ultralong lifetime for as long as 180 days (335 000 cycles), which is an ultrahigh cycling capability for a solid-state supercapacitor. The RGO is also tested for being used as a transparent supercapacitor electrode demonstrating its possible use in various transparent optoelectronic devices. Due to the facile scale-up capability of the EPD process and RGO dispersion, the developed all-solid-state supercapacitor is highly applicable to large-area portable energy storage devices.

Static and hydrodynamic studies of the conformation of adsorbed macromolecules at the solid/liquid interface

NASA Astrophysics Data System (ADS)

Yavorsky, D. P.

1981-08-01

The structure of an adsorbed macromolecular layer at the solid/liquid interface under both stationary and flow conditions is examined. The conformation of adsorbed bovine serum albumin (BSA) is deduced from the thickness of surface layers formed on the pore walls of track etched (mica) membranes. Changes in membrane permeability due to protein adsorption are related directly to a net reduction in pore size or an equivalent adsorbed layer thickness. Complementary permeability measurements using electrolyte conduction, tracer diffusion, and pressure driven flow have verified the unique structural qualities of the track etched membrane and collectively demonstrate an ability to determine bare pore size with an accuracy of + or - 2A. The average static thickness of an adsorbed BSA layer, as derived from electrolyte conduction and tracer diffusion, was 43 + or - 3A independent of pore size. In comparison with the known BSA solution dimensions, this measured thickness is consistent with a monolayer of structurally unperturbed protein molecules each oriented in a "side-on" position. Pronounced conformational changes in adsorbed BSA layers were observed under conditions of shear flow. Electrostatic interactions were also shown to significantly affect adsorbed protein conformation through changes in solution ionic strength and surface charge.

Nb and Pd co-doped La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ as a stable, high performance electrode for barrier-layer-free Y2O3-ZrO2 electrolyte of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Chen, Kongfa; He, Shuai; Li, Na; Cheng, Yi; Ai, Na; Chen, Minle; Rickard, William D. A.; Zhang, Teng; Jiang, San Ping

2018-02-01

La0.6Sr0.2Co0.2Fe0.8O3-δ (LSCF) is the most intensively investigated high performance cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), but strontium segregation and migration at the electrode/electrolyte interface is a critical issue limiting the electrocatalytic activity and stability of LSCF based cathodes. Herein, we report a Nb and Pd co-doped LSCF (La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ, LSCFNPd) perovskite as stable and active cathode on a barrier-layer-free anode-supported yttria-stabilized zirconia (YSZ) electrolyte cell using direct assembly method without pre-sintering at high temperatures. The cell exhibits a peak power density of 1.3 W cm-2 at 750 °C and excellent stability with no degradation during polarization at 500 mA cm-2 and 750 °C for 175 h. Microscopic and spectroscopic analysis show that the electrochemical polarization promotes the formation of electrode/electrolyte interface in operando and exsolution of Pd/PdO nanoparticles. The Nb doping in the B-site of LSCF significantly reduces the Sr surface segregation, enhancing the stability of the cathode, while the exsoluted Pd/PdO nanoparticles increases the electrocatalytic activity for the oxygen reduction reaction. The present study opens up a new route for the development of cobaltite-based perovskite cathodes with high activity and stability for barrier-layer-free YSZ electrolyte based IT-SOFCs.

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.

Non-Faradaic Li + Migration and Chemical Coordination across Solid-State Battery Interfaces

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

Gittleson, Forrest S.; El Gabaly, Farid

Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at critical electrode–electrolyte interfaces have proven successful, yet interfacial chemistry and its impact on cell function remains poorly understood. Using X-ray photoelectron spectroscopy combined with electrochemical techniques, we elucidate chemical coordination near the LiCoO 2–LIPON interface, providing experimental validation of space-charge separation. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chemistry of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li+ ions from the electrode to themore » electrolyte, which reduces reversible cathodic capacity by ~15%. Inserting a thin, ion-conducting LiNbO 3 interlayer between the electrode and electrolyte, however, can reduce space-charge separation, mitigate the loss of Li+ from LiCoO 2, and return cathodic capacity to its theoretical value. This work illustrates the importance of interfacial chemistry in understanding and improving solid-state batteries.« less

Morphological evolution of carbon nanofibers encapsulating SnCo alloys and its effect on growth of the solid electrolyte interphase layer.

PubMed

Shin, Jungwoo; Ryu, Won-Hee; Park, Kyu-Sung; Kim, Il-Doo

2013-08-27

Two distinctive one-dimensional (1-D) carbon nanofibers (CNFs) encapsulating irregularly and homogeneously segregated SnCo nanoparticles were synthesized via electrospinning of polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) polymers containing Sn-Co acetate precursors and subsequent calcination in reducing atmosphere. CNFs synthesized with PVP, which undergoes structural degradation of the polymer during carbonization processes, exhibited irregular segregation of heterogeneous alloy particles composed of SnCo, Co3Sn2, and SnO with a size distribution of 30-100 nm. Large and exposed multiphase SnCo particles in PVP-driven amorphous CNFs (SnCo/PVP-CNFs) kept decomposing liquid electrolyte and were partly detached from CNFs during cycling, leading to a capacity fading at the earlier cycles. The closer study of solid electrolyte interphase (SEI) layers formed on the CNFs reveals that the gradual growth of fiber radius due to continuous increment of SEI layer thickness led to capacity fading. In contrast, SnCo particles in PAN-driven CNFs (SnCo/PAN-CNFs) showed dramatically reduced crystallite sizes (<10 nm) of single phase SnCo nanoparticles which were entirely embedded in dense, semicrystalline, and highly conducting 1-D carbon matrix. The growth of SEI layer was limited and saturated during cycling. As a result, SnCo/PAN-CNFs showed much improved cyclability (97.9% capacity retention) and lower SEI layer thickness (86 nm) after 100 cycles compared to SnCo/PVP-CNFs (capacity retention, 71.9%; SEI layer thickness, 593 nm). This work verifies that the thermal behavior of carbon precursor is highly responsible for the growth mechanism of SEI layer accompanied with particles detachment and cyclability of alloy particle embedded CNFs.

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, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li3PO4 has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li3PO4 has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H3PO4. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li3PO4, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li3PO4 was around 10-8 S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li3PO4 for lithium ion battery will give more added values to the researches and national industry.

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

PubMed

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

Atomic Layer Deposition of the Solid Electrolyte LiPON

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

Kozen, Alexander C.; Pearse, Alexander J.; Lin, Chuan -Fu

We demonstrate an atomic layer deposition (ALD) process for the solid electrolyte lithium phosphorousoxynitride (LiPON) using lithium tert-butoxide (LiO tBu), H 2O, trimethylphosphate (TMP), and plasma N 2 ( PN 2) as precursors. We use in-situ spectroscopic ellipsometry to determine growth rates for process optimization to design a rational, quaternary precursor ALD process where only certain substrate–precursor chemical reactions are favorable. We demonstrate via in-situ XPS tunable nitrogen incorporation into the films by variation of the PN 2 dose and find that ALD films over approximately 4.5% nitrogen are amorphous, whereas LiPON ALD films with less than 4.5% nitrogen aremore » polycrystalline. Lastly, we characterize the ionic conductivity of the ALD films as a function of nitrogen content and demonstrate their functionality on a model battery electrode—a Si anode on a Cu current collector.« less

Atomic Layer Deposition of the Solid Electrolyte LiPON

DOE PAGES

Kozen, Alexander C.; Pearse, Alexander J.; Lin, Chuan -Fu; ...

2015-07-09

We demonstrate an atomic layer deposition (ALD) process for the solid electrolyte lithium phosphorousoxynitride (LiPON) using lithium tert-butoxide (LiO tBu), H 2O, trimethylphosphate (TMP), and plasma N 2 ( PN 2) as precursors. We use in-situ spectroscopic ellipsometry to determine growth rates for process optimization to design a rational, quaternary precursor ALD process where only certain substrate–precursor chemical reactions are favorable. We demonstrate via in-situ XPS tunable nitrogen incorporation into the films by variation of the PN 2 dose and find that ALD films over approximately 4.5% nitrogen are amorphous, whereas LiPON ALD films with less than 4.5% nitrogen aremore » polycrystalline. Lastly, we characterize the ionic conductivity of the ALD films as a function of nitrogen content and demonstrate their functionality on a model battery electrode—a Si anode on a Cu current collector.« less

A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes.

PubMed

Li, Nian-Wu; Shi, Yang; Yin, Ya-Xia; Zeng, Xian-Xiang; Li, Jin-Yi; Li, Cong-Ju; Wan, Li-Jun; Wen, Rui; Guo, Yu-Guo

2018-02-05

Lithium (Li) metal is a promising anode material for high-energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self-adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA-Li/LiPAA-Li symmetrical cell. The innovative strategy of self-adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid oxide fuel cell having compound cross flow gas patterns

DOEpatents

Fraioli, A.V.

1983-10-12

A core construction for a fuel cell is disclosed having both parallel and cross flow passageways for the fuel and the oxidant gases. Each core passageway is defined by electrolyte and interconnect walls. Each electrolyte wall consists of cathode and anode materials sandwiching an electrolyte material. Each interconnect wall is formed as a sheet of inert support material having therein spaced small plugs of interconnect material, where cathode and anode materials are formed as layers on opposite sides of each sheet and are electrically connected together by the interconnect material plugs. Each interconnect wall in a wavy shape is connected along spaced generally parallel line-like contact areas between corresponding spaced pairs of generally parallel electrolyte walls, operable to define one tier of generally parallel flow passageways for the fuel and oxidant gases. Alternate tiers are arranged to have the passageways disposed normal to one another. Solid mechanical connection of the interconnect walls of adjacent tiers to the opposite sides of the common electrolyte wall therebetween is only at spaced point-like contact areas, 90 where the previously mentioned line-like contact areas cross one another.

Solid oxide fuel cell having compound cross flow gas patterns

DOEpatents

Fraioli, Anthony V.

1985-01-01

A core construction for a fuel cell is disclosed having both parallel and cross flow passageways for the fuel and the oxidant gases. Each core passageway is defined by electrolyte and interconnect walls. Each electrolyte wall consists of cathode and anode materials sandwiching an electrolyte material. Each interconnect wall is formed as a sheet of inert support material having therein spaced small plugs of interconnect material, where cathode and anode materials are formed as layers on opposite sides of each sheet and are electrically connected together by the interconnect material plugs. Each interconnect wall in a wavy shape is connected along spaced generally parallel line-like contact areas between corresponding spaced pairs of generally parallel electrolyte walls, operable to define one tier of generally parallel flow passageways for the fuel and oxidant gases. Alternate tiers are arranged to have the passageways disposed normal to one another. Solid mechanical connection of the interconnect walls of adjacent tiers to the opposite sides of the common electrolyte wall therebetween is only at spaced point-like contact areas, 90 where the previously mentioned line-like contact areas cross one another.

In situ analytical techniques for battery interface analysis.

PubMed

Tripathi, Alok M; Su, Wei-Nien; Hwang, Bing Joe

2018-02-05

Lithium-ion batteries, simply known as lithium batteries, are distinct among high energy density charge-storage devices. The power delivery of batteries depends upon the electrochemical performances and the stability of the electrode, electrolytes and their interface. Interfacial phenomena of the electrode/electrolyte involve lithium dendrite formation, electrolyte degradation and gas evolution, and a semi-solid protective layer formation at the electrode-electrolyte interface, also known as the solid-electrolyte interface (SEI). The SEI protects electrodes from further exfoliation or corrosion and suppresses lithium dendrite formation, which are crucial needs for enhancing the cell performance. This review covers the compositional, structural and morphological aspects of SEI, both artificially and naturally formed, and metallic dendrites using in situ/in operando cells and various in situ analytical tools. Critical challenges and the historical legacy in the development of in situ/in operando electrochemical cells with some reports on state-of-the-art progress are particularly highlighted. The present compilation pinpoints the emerging research opportunities in advancing this field and concludes on the future directions and strategies for in situ/in operando analysis.

Flow produced by a free-moving floating magnet driven electromagnetically

NASA Astrophysics Data System (ADS)

Piedra, Saúl; Román, Joel; Figueroa, Aldo; Cuevas, Sergio

2018-04-01

The flow generated by a free-moving magnet floating in a thin electrolyte layer is studied experimentally and numerically. The magnet is dragged by a traveling vortex dipole produced by a Lorentz force created when a uniform dc current injected in the electrolyte interacts with the magnetic field of the same magnet. The problem represents a typical case of fluid-solid interaction but with a localized electromagnetic force promoting the motion. Classical wake flow structures are observed when the applied current varies in the range of 0.2 to 10 A. Velocity fields at the surface of the electrolyte are obtained for different flow conditions through particle image velocimetry. Quasi-two-dimensional numerical simulations, based on the immersed boundary technique that incorporates the fluid-solid interaction, reproduce satisfactorily the dynamics observed in the experiments.

Glassy materials for lithium batteries: electrochemical properties and devices performances

NASA Astrophysics Data System (ADS)

Duclot, Michel; Souquet, Jean-Louis

Amorphous or glassy materials may be used as electrolyte or electrode materials for lithium primary or secondary batteries. A first generation proceeded from classical coin cells in which the organic electrolyte was replaced by a high lithium conductive glassy electrolyte. The solid components were assembled under isostatic pressure. The main advantages of such cells are a good storage stability and ability to operate until 200°C. Nevertheless, the high resistivity of the glassy electrolyte below room temperature and a limited depth for charge and discharge cycles makes these cells not competitive compared to conventional lithium-ion batteries. More promising, are the thin films solid state microbatteries realised by successive depositions of electrodes and electrolyte. The low resistance of the electrolyte amorphous layer allows cycling at temperatures as low as -10°C. The total thickness of thin film batteries, including packaging is less than 100 μm. A capacity of about 100 μAh cm -2 with over 10 4 charge-discharge cycles at 90% in depth of discharge is well suited for energy independent smart cards or intelligent labels, which represent for these devices a large and unrivalled market.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2012-10-09

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Structures and fabrication techniques for solid state electrochemical devices

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2008-04-01

Porous substrates and associated structures for solid-state electrochemical devices, such as solid-oxide fuel cells (SOFCs), are low-cost, mechanically strong and highly electronically conductive. Some preferred structures have a thin layer of an electrocatalytically active material (e.g., Ni--YSZ) coating a porous high-strength alloy support (e.g., SS-430) to form a porous SOFC fuel electrode. Electrode/electrolyte structures can be formed by co-firing or constrained sintering processes.

Engineering the Membrane/Electrode Interface To Improve the Performance of Solid-State Supercapacitors.

PubMed

Huang, Chun; Zhang, Jin; Snaith, Henry J; Grant, Patrick S

2016-08-17

This paper investigates the effect of adding a 450 nm layer based on porous TiO2 at the interface between a 4.5 μm carbon/TiO2 nanoparticle-based electrode and a polymer electrolyte membrane as a route to improve energy storage performance in solid-state supercapacitors. Electrochemical characterization showed that adding the interface layer reduced charge transfer resistance, promoted more efficient ion transfer across the interface, and significantly improved charge/discharge dynamics in a solid-state supercapacitor, resulting in an increased areal capacitance from 45.3 to 111.1 mF cm(-2) per electrode at 0.4 mA cm(-2).

Inorganic-Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode.

PubMed

Zhao, Yang; Goncharova, Lyudmila V; Zhang, Qian; Kaghazchi, Payam; Sun, Qian; Lushington, Andrew; Wang, Biqiong; Li, Ruying; Sun, Xueliang

2017-09-13

Metallic Na anode is considered as a promising alternative candidate for Na ion batteries (NIBs) and Na metal batteries (NMBs) due to its high specific capacity, and low potential. However, the unstable solid electrolyte interphase layer caused by serious corrosion and reaction in electrolyte will lead to big challenges, including dendrite growth, low Coulombic efficiency and even safety issues. In this paper, we first demonstrate the inorganic-organic coating via advanced molecular layer deposition (alucone) as a protective layer for metallic Na anode. By protecting Na anode with controllable alucone layer, the dendrites and mossy Na formation have been effectively suppressed and the lifetime has been significantly improved. Moreover, the molecular layer deposition alucone coating shows better performances than the atomic layer deposition Al 2 O 3 coating. The novel design of molecular layer deposition protected Na metal anode may bring in new opportunities to the realization of the next-generation high energy-density NIBs and NMBs.

Preparation of functional layers for anode-supported solid oxide fuel cells by the reverse roll coating process

NASA Astrophysics Data System (ADS)

Mücke, R.; Büchler, O.; Bram, M.; Leonide, A.; Ivers-Tiffée, E.; Buchkremer, H. P.

The roll coating technique represents a novel method for applying functional layers to solid oxide fuel cells (SOFCs). This fast process is already used for mass production in other branches of industry and offers a high degree of automation. It was utilized for coating specially developed anode (NiO + 8YSZ, 8YSZ: 8 mol% yttria-stabilized zirconia) and electrolyte (8YSZ) suspensions on green and pre-sintered tape-cast anode supports (NiO + 8YSZ). The layers formed were co-fired in a single step at 1400 °C for 5 h. As a result, the electrolyte exhibited a thickness of 14-18 μm and sufficient gas tightness. Complete cells with a screen-printed and sintered La 0.65Sr 0.3MnO 3- δ (LSM)/8YSZ cathode yielded a current density of 0.9-1.1 A cm -2 at 800 °C and 0.7 V, which is lower than the performance of non-co-fired slip-cast or screen-printed Jülich standard cells with thinner anode and electrolyte layers. The contribution of the cell components to the total area-specific resistance (ASR) was calculated by analyzing the distribution function of the relaxation times (DRTs) of measured electrochemical impedance spectra (EIS) and indicates the potential improvement in the cell performance achievable by reducing the thickness of the roll-coated layers. The results show that the anode-supported planar half-cells can be fabricated cost-effectively by combining roll coating with subsequent co-firing.

Fabrication of Semi-quasi Solid DSSC using Spiro Material as Hole Transport Material

NASA Astrophysics Data System (ADS)

Safriani, L.; Primawati, W. P.; Mulyana, C.; Susilawati, T.; Aprilia, A.

2017-05-01

Dye Sensitized Solar Cells (DSSC) has been emerging a promising development in recent years. DSSC is a low-cost solar cell belonging to the third generation of solar cells. However, the conversion efficiency of DSSC is still far behind compared to silicon based solar cells. To produce long stability of DSSC, the used of solid state electrolyte is recommended instead of liquid electrolyte, though solid state DSSC also has problem relating to a lack of pore-filling hole transport material into mesoporous TiO2. In this work an attempt to improve performance of DSSC has been done by adding hole transport material into mesoporous TiO2 layer and optimizing fabrication method. In the first part of the work, we used low Tg material spiro-TAD and spiro-TPD as hole transport material with mosalyte and hybrid polymer as gel electrolyte to obtain a semi-quasi solid DSSC. In the second part, we modified fabrication method by annealing process before spin-coated spiro material into dye-coated TiO2 substrate. Current-voltage measurement of semi-quasi solid DSSC was performed using halogen lamp. We found that the used of spiro-TPD as hole transport give the best power conversion efficiency η = 2.03% of semi-quasi solid DSSC.

Atomic layer deposition of ultrathin blocking layer for low-temperature solid oxide fuel cell on nanoporous substrate

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

Yu, Wonjong; Cho, Gu Young; Noh, Seungtak

2015-01-15

An ultrathin yttria-stabilized zirconia (YSZ) blocking layer deposited by atomic layer deposition (ALD) was utilized for improving the performance and reliability of low-temperature solid oxide fuel cells (SOFCs) supported by an anodic aluminum oxide substrate. Physical vapor-deposited YSZ and gadolinia-doped ceria (GDC) electrolyte layers were deposited by a sputtering method. The ultrathin ALD YSZ blocking layer was inserted between the YSZ and GDC sputtered layers. To investigate the effects of an inserted ultrathin ALD blocking layer, SOFCs with and without an ultrathin ALD blocking layer were electrochemically characterized. The open circuit voltage (1.14 V) of the ALD blocking-layered SOFC was visiblymore » higher than that (1.05 V) of the other cell. Furthermore, the ALD blocking layer augmented the power density and improved the reproducibility.« less

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

PubMed Central

Lochala, Joshua A.; Kwok, Alexander; Deng, Zhiqun Daniel

2017-01-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1–1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges. PMID:28852621

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

DOE PAGES

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander; ...

2017-03-31

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications.

PubMed

Zheng, Jianming; Lochala, Joshua A; Kwok, Alexander; Deng, Zhiqun Daniel; Xiao, Jie

2017-08-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

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

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

PubMed Central

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; Yano, Junko; Hussain, Zahid; Liu, Zhi; Crumlin, Ethan J.

2016-01-01

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzing the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential. PMID:27576762

Direct ethanol solid oxide fuel cell operating in gradual internal reforming

NASA Astrophysics Data System (ADS)

Nobrega, S. D.; Galesco, M. V.; Girona, K.; de Florio, D. Z.; Steil, M. C.; Georges, S.; Fonseca, F. C.

2012-09-01

An electrolyte supported solid oxide fuel cell (SOFC) using standard electrodes, doped-lanthanum manganite cathode and Ni-cermet anode, was operated with direct (anhydrous) ethanol for more than 100 h, delivering essentially the same power output as running on hydrogen. A ceria-based layer provides the catalytic activity for the gradual internal reforming, which uses the steam formed by the electrochemical oxidation of hydrogen for the decomposition of ethanol. Such a concept opens up the way for multi-fuel SOFCs using standard components and a catalytic layer.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, J.D.

1993-11-09

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of standard polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, J.D.

1995-03-07

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, John D.

1993-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, John D.

1996-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, John D.

1995-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

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

Zhu, Jinlong; Wang, Yonggang; Li, Shuai

Na-rich antiperovskites are recently developed solid electrolytes with enhanced sodium ionic conductivity and show promising functionality as a novel solid electrolyte in an all solid-state battery. In this work, the sodium ionic transport pathways of the parent compound Na3OBr, as well as the modified layered antiperovskite Na4OI2, were studied and compared through temperature dependent neutron diffraction combined with the maximum entropy method. In the cubic Na3OBr antiperovskite, the nuclear density distribution maps at 500 K indicate that sodium ions hop within and among oxygen octahedra, and Br- ions are not involved. In the tetragonal Na4OI2 antiperovskite, Na ions, which connectmore » octahedra in the ab plane, have the lowest activation energy barrier. The transport of sodium ions along the c axis is assisted by I- ions.« less

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries.

PubMed

Gomez-Ballesteros, Jose L; Balbuena, Perla B

2017-07-20

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this work, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6 ) and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2 H 4 + CO 3 2- ) take place near the film/electrolyte and film/anode interfaces. Reaction products incorporate into the structure of the film and create a new kind of solid-electrolyte interphase layer.

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries

DOE PAGES

Gomez-Ballesteros, Jose L.; Balbuena, Perla B.

2017-07-07

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this paper, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6), and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2H 4 + CO 3 2-) take place near the film/electrolyte and film/anode interfaces. Finally,more » reactions products incorporate to the structure of the film and create a new kind of solid-electrolyte interphase layer.« less

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

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

Kartini, Evvy; Manawan, Maykel

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 stillmore » 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, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li{sub 3}PO{sub 4} has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li{sub 3}PO{sub 4} has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H{sub 3}PO{sub 4}. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li{sub 3}PO{sub 4}, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li{sub 3}PO{sub 4} was around 10{sup −8} S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li{sub 3}PO{sub 4} for lithium ion battery will give more added values to the researches and national industry.« less

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, J.C.; Singh, P.

1989-08-29

A dense, electronically conductive interconnection layer is bonded onto a porous, tubular, electronically conductive air electrode structure, optionally supported by a ceramic support, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface, without the use of pressure, particles of LaCrO[sub 3] doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300 C to 1,550 C, without the application of pressure, to provide a dense, sintered, interconnection material bonded to the air electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO[sub 3]. A solid electrolyte layer can be applied to the uncovered portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 4 figs.

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, Jeffrey C.; Singh, Prabhakar

1989-01-01

A dense, electronically conductive interconnection layer 26 is bonded onto a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface 24, without the use of pressure, particles of LaCrO.sub.3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300.degree. C. to 1,550.degree. C., without the application of pressure, to provide a dense, sintered, interconnection material 26 bonded to the air electrode 16, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO.sub.3. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

The effect of diamond-like carbon coating on LiNi0.8Co0.15Al0.05O2 particles for all solid-state lithium-ion batteries based on Li2S-P2S5 glass-ceramics

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Aihara, Yuichi; Ito, Seitaro; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

2016-05-01

There have been several reports on improvements of the performance of all solid-state battery using lithium metal oxide coatings on the cathode active material. However, the mechanism of the performance improvement remains unclear. To better understand the effect of the surface coating, we studied the impact of diamond-like carbon (DLC) coating on LiNi0.8Co0.15Al0.05O2 (NCA) by chemical vapor deposition (CVD). The DLC coated NCA showed good cycle ability and rate performance. This result is further supported by reduction of the interfacial resistance of the cathode and electrolyte observed in impedance spectroscopy. The DLC layer was analyzed by transmission electron microscopy electron energy loss spectroscopy (TEM-EELS). After 100 cycles the sample was analyzed by X-ray photo spectroscopy (XPS), and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). These analyses showed that the thickness of the coating layer was around 4 nm on average, acting to hinder the side reactions between the cathode particle and the solid electrolyte. The results of this study will provide useful insights for understanding the nature of the buffer layer for the cathode materials.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Post-test characterization of a solid oxide fuel cell stack operated for more than 30,000 hours: The cell

NASA Astrophysics Data System (ADS)

Menzler, Norbert H.; Sebold, Doris; Guillon, Olivier

2018-01-01

A four-layer solid oxide fuel cell stack with planar anode-supported cells was operated galvanostatically at 700 °C and 0.5Acm-2 for nearly 35,000 h. One of the four planes started to degrade more rapidly after ∼28,000 h and finally more progressively after ∼33,000 h. The stack was then shut down and a post-test analysis was carefully performed. The cell was characterized with respect to cathodic impurities and clarification of the reason(s) for failure. Wet chemical analysis revealed very low chromium incorporation into the cathode. However, SEM and TEM observations on polished and fractured surfaces showed catastrophic failure in the degraded layer. The cathode-barrier-electrolyte cell layer system delaminated from the entire cell over large areas. The source of delamination was the formation of a porous, sponge-like secondary phase consisting of zirconia, yttria and manganese (oxide). Large secondary phase islands grew from the electrolyte-anode interface towards the anode and cracked the bonding between both layers. The manganese originated from the contact or protection layers used on the air side. This stack result shows that volatile species - in this case manganese - should be avoided, especially when long-term applications are envisaged.

Electrode and method of interconnection sintering on an electrode of an electrochemical cell

DOEpatents

Ruka, R.J.; Kuo, L.J.H.

1994-01-11

An electrode structure is made by applying a base layer of doped LaCrO[sub 3] particles on a portion of an electrode and then coating the particles with a top layer composition such as CaO+Al[sub 2]O[sub 3], SrO+Al[sub 2]O[sub 3], or BaO+Al[sub 2]O[sub 3], and then heating the composition for a time effective to melt the composition and allow it to fill any open porosity in the base layer of doped LaCrO[sub 3] to form an interconnection, after which solid oxide electrolyte can be applied to the remaining portion of the electrode and the electrolyte can be covered with a cermet exterior electrode. 2 figures.

Electrode and method of interconnection sintering on an electrode of an electrochemical cell

DOEpatents

Ruka, Roswell J.; Kuo, Lewis J. H.

1994-01-01

An electrode structure (10) is made by applying a base layer of doped LaCrO.sub.3 particles on a portion of an electrode (16) and then coating the particles with a top layer composition such as CaO+Al.sub.2 O.sub.3, SrO+Al.sub.2 O.sub.3, or BaO+Al.sub.2 O.sub.3, and then heating the composition for a time effective to melt the composition and allow it to fill any open porosity in the base layer of doped LaCrO.sub.3 to form an interconnection (26), after which solid oxide electrolyte (18) can be applied to the remaining portion of the electrode (16) and the electrolyte (18) can be covered with a cermet exterior electrode (20).

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

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

Zhu, Jinlong; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li 3OX (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 Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

Enhanced ionic conductivity with Li 7O 2Br 3 phase in Li 3OBr anti-perovskite solid electrolyte

DOE PAGES

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

2016-09-07

Cubic anti-perovskites with general formula Li 3OX (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 Li 3OBr and layered Li 7O 2Br 3, by solid state reaction routes. The results indicate that with the phase fraction of Li 7O 2Br 3 increasingmore » to 44 wt. %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li 3OBr. Formation energy calculations revealed the meta-stable nature of Li 7O 2Br 3, which supports the great difficulty in producing phase-pure Li 7O 2Br 3 at ambient pressure. Here, methods of obtaining phase-pure Li 7O 2Br 3 will continue to be explored, including both high pressure and metathesis techniques.« less

Flexible interfaces between Si anodes and composite electrolytes consisting of poly(propylene carbonates) and garnets for solid-state batteries

NASA Astrophysics Data System (ADS)

Huo, Hanyu; Sun, Jiyang; chen, Cheng; Meng, Xianglu; He, Minghui; Zhao, Ning; Guo, Xiangxin

2018-04-01

Flexible interfaces between Si anodes and composite electrolytes consisting of poly(propylene carbonates) (PPCs) and garnets have been fabricated. The solid polymer electrolytes (SPEs) of PPC/garnet/LiTFSI show the conductivity of 4.2 × 10-4 S cm-1 at room temperature. Their combination with the Si layer anodes allows great alleviation of internal stress resulting from the large volume variation during lithiation and delithiation process of Si anodes. As a result, the Si/SPE/Li cells exhibit 2520 mAh g-1, 2260 mAh g-1, 1902 mAh g-1, 1342 mAh g-1 at 0.1 C, 0.2 C, 0.5 C, and 1 C, respectively. Furthermore, with such compatible and stable interfaces of Si/SPE and the LiFePO4 cathodes in solid-state batteries, the specific capacity of 2296 mAh g-1 in terms of Si is obtained, which remains 82.6% after 100 cycles at room temperature and 0.1 C. The results here indicate that constructing of flexible interfaces between Si anodes and SPEs is a promising strategy to develop high performance solid-state batteries.

Electrochemical Stability of Li 10GeP 2S 12 and Li 7La 3Zr 2O 12 Solid Electrolytes

DOE PAGES

Han, Fudong; Zhu, Yizhou; He, Xingfeng; ...

2016-01-21

The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, J.D.

1996-08-20

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface. 3 figs.

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

None

Broad Funding Opportunity Announcement Project: Led by MIT professor Donald Sadoway, the Electroville project team is creating a community-scale electricity storage device using new materials and a battery design inspired by the aluminum production process known as smelting. A conventional battery includes a liquid electrolyte and a solid separator between its 2 solid electrodes. MIT’s battery contains liquid metal electrodes and a molten salt electrolyte. Because metals and salt don’t mix, these 3 liquids of different densities naturally separate into layers, eliminating the need for a solid separator. This efficient design significantly reduces packaging materials, which reduces cost and allowsmore » more space for storing energy than conventional batteries offer. MIT’s battery also uses cheap, earth-abundant, domestically available materials and is more scalable. By using all liquids, the design can also easily be resized according to the changing needs of local communities.« less

Driving mechanisms of ionic polymer actuators having electric double layer capacitor structures.

PubMed

Imaizumi, Satoru; Kato, Yuichi; Kokubo, Hisashi; Watanabe, Masayoshi

2012-04-26

Two solid polymer electrolytes, composed of a polyether-segmented polyurethaneurea (PEUU) and either a lithium salt (lithium bis(trifluoromethanesulfonyl)amide: Li[NTf2]) or a nonvolatile ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide: [C2mim][NTf2]), were prepared in order to utilize them as ionic polymer actuators. These salts were preferentially dissolved in the polyether phases. The ionic transport mechanism of the polyethers was discussed in terms of the diffusion coefficients and ionic transference numbers of the incorporated ions, which were estimated by means of pulsed-field gradient spin-echo (PGSE) NMR. There was a distinct difference in the ionic transport properties of each polymer electrolyte owing to the difference in the magnitude of interactions between the cations and the polyether. The anionic diffusion coefficient was much faster than that of the cation in the polyether/Li[NTf2] electrolyte, whereas the cation diffused faster than the anion in the polyether/[C2mim][NTf2] electrolyte. Ionic polymer actuators, which have a solid-state electric-double-layer-capacitor (EDLC) structure, were prepared using these polymer electrolyte membranes and ubiquitous carbon materials such as activated carbon and acetylene black. On the basis of the difference in the motional direction of each actuator against applied voltages, a simple model of the actuation mechanisms was proposed by taking the difference in ionic transport properties into consideration. This model discriminated the behavior of the actuators in terms of the products of transference numbers and ionic volumes. The experimentally observed behavior of the actuators was successfully explained by this model.

A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes

NASA Astrophysics Data System (ADS)

Liu, Nian; Lu, Zhenda; Zhao, Jie; McDowell, Matthew T.; Lee, Hyun-Wook; Zhao, Wenting; Cui, Yi

2014-03-01

Silicon is an attractive material for anodes in energy storage devices, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li-O2 and Li-S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (~300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode-electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm-3), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm-2).

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.

Demonstration of an electrochemical liquid cell for operando transmission electron microscopy observation of the lithiation/delithiation behavior of Si nanowire battery anodes.

PubMed

Gu, Meng; Parent, Lucas R; Mehdi, B Layla; Unocic, Raymond R; McDowell, Matthew T; Sacci, Robert L; Xu, Wu; Connell, Justin Grant; Xu, Pinghong; Abellan, Patricia; Chen, Xilin; Zhang, Yaohui; Perea, Daniel E; Evans, James E; Lauhon, Lincoln J; Zhang, Ji-Guang; Liu, Jun; Browning, Nigel D; Cui, Yi; Arslan, Ilke; Wang, Chong-Min

2013-01-01

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

All-Solid-State Batteries with Thick Electrode Configurations.

PubMed

Kato, Yuki; Shiotani, Shinya; Morita, Keisuke; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji

2018-02-01

We report the preparation of thick electrode all-solid-state lithium-ion cells in which a large geometric capacity of 15.7 mAh cm -2 was achieved at room temperature using a 600 μm-thick cathode layer. The effect of ionic conductivity on the discharge performance was then examined using two different materials for the solid electrolyte. Furthermore, important morphological information regarding the tortuosity factor was electrochemically extracted from the capacity-current data. The effect of tortuosity on cell performance was also quantitatively discussed.

Scattering-layer-induced energy storage function in polymer-based quasi-solid-state dye-sensitized solar cells.

PubMed

Zhang, Xi; Jiang, Hongrui

2015-03-09

Photo-self-charging cells (PSCs) are compact devices with dual functions of photoelectric conversion and energy storage. By introducing a scattering layer in polymer-based quasi-solid-state dye-sensitized solar cells, two-electrode PSCs with highly compact structure were obtained. The charge storage function stems from the formed ion channel network in the scattering layer/polymer electrolyte system. Both the photoelectric conversion and the energy storage functions are integrated in only the photoelectrode of such PSCs. This design of PSC could continuously output power as a solar cell with considerable efficiency after being photo-charged. Such PSCs could be applied in highly-compact mini power devices.

Electric shielding films for biased TEM samples and their application to in situ electron holography.

PubMed

Nomura, Yuki; Yamamoto, Kazuo; Hirayama, Tsukasa; Saitoh, Koh

2018-06-01

We developed a novel sample preparation method for transmission electron microscopy (TEM) to suppress superfluous electric fields leaked from biased TEM samples. In this method, a thin TEM sample is first coated with an insulating amorphous aluminum oxide (AlOx) film with a thickness of about 20 nm. Then, the sample is coated with a conductive amorphous carbon film with a thickness of about 10 nm, and the film is grounded. This technique was applied to a model sample of a metal electrode/Li-ion-conductive-solid-electrolyte/metal electrode for biasing electron holography. We found that AlOx film with a thickness of 10 nm has a large withstand voltage of about 8 V and that double layers of AlOx and carbon act as a 'nano-shield' to suppress 99% of the electric fields outside of the sample. We also found an asymmetry potential distribution between high and low potential electrodes in biased solid-electrolyte, indicating different accumulation behaviors of lithium-ions (Li+) and lithium-ion vacancies (VLi-) in the biased solid-electrolyte.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications.

PubMed

Huang, Chun; Zhang, Jin; Young, Neil P; Snaith, Henry J; Grant, Patrick S

2016-05-10

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices.

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

DTIC Science & Technology

1999-05-05

stabilized zirconia but are equally applicable to components, have been developed. Halogen com- other oxide electrolytes. pounds such as ZrCl4 and YC13...substrates. They used ZrCl4 and an oxygen source reactant. EVD is a two-step YC13 vapor mixtures as the metal compound sources process. The first step...thin zirconia layers on ited film. In this step oxygen ions formed on the porous alumina substrates. ZrCl4 and YC13 vapor water vapor side of the

Foaming in simulated radioactive waste.

PubMed

Bindal, S K; Nikolov, A D; Wasan, D T; Lambert, D P; Koopman, D C

2001-10-01

Radioactive waste treatment process usually involves concentration of radionuclides before waste can be immobilized by storing it in stable solid form. Foaming is observed at various stages of waste processing like SRAT (sludge receipt and adjustment tank) and melter operations. This kind of foaming greatly limits the process efficiency. The foam encountered can be characterized as a three-phase foam that incorporates finely divided solids (colloidal particles). The solid particles stabilize foaminess in two ways: by adsorption of biphilic particles at the surfaces of foam lamella and by layering of particles trapped inside the foam lamella. During bubble generation and rise, solid particles organize themselves into a layered structure due to confinement inside the foam lamella, and this structure provides a barrier against the coalescence of the bubbles, thereby causing foaming. Our novel capillary force balance apparatus was used to examine the particle-particle interactions, which affect particle layer formation in the foam lamella. Moreover, foaminess shows a maximum with increasing solid particle concentration. To explain the maximum in foaminess, a study was carried out on the simulated sludge, a non-radioactive simulant of the radioactive waste sludge at SRS, to identify the parameters that affect the foaming in a system characterized by the absence of surface-active agents. This three-phase foam does not show any foam stability unlike surfactant-stabilized foam. The parameters investigated were solid particle concentration, heating flux, and electrolyte concentration. The maximum in foaminess was found to be a net result of two countereffects that arise due to particle-particle interactions: structural stabilization and depletion destabilization. It was found that higher electrolyte concentration causes a reduction in foaminess and leads to a smaller bubble size. Higher heating fluxes lead to greater foaminess due to an increased rate of foam lamella generation in the sludge system.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, Kenneth Orville

1998-01-01

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

Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, M. C.; Hwang, C.; Krause, F. C.; Soler, J.; West, W. C.; Ratnakumar, B. V.; Amine, K.

2012-01-01

A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

MEMS-based thin-film fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2003-10-28

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

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

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

Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo

The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ionmore » and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.« less

A monolithic functional film of nanotubes/cellulose/ionic liquid for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Basiricò, Lucia; Lanzara, Giulia

2014-12-01

A novel monolithic, pre-fabricated, fully functional film made of a nanostructured free-standing layer is presented for a new and competitive class of easy-to-assemble flexible supercapacitors whose design is in-between the all solid state and the traditional liquid electrolyte. The film is made of two vertically aligned multi-walled carbon nanotube (VANT) electrodes that store ions, embedded-in, and monolithically interspaced by a solution of microcrystalline cellulose in a room temperature ionic liquid (RTIL) electrolyte (1-ethyl-3-methylimidazolium acetate-EMIM Ac). The fine tuning of VANTs length and electrolyte/cellulose amount leads, in a sole and continuous block, to ions storage and physical separation between the electrodes without the need of the additional separator layer that is typically used in supercapacitors. Thus, physical discontinuities that can induce disturbances to ions mobility, are fully eliminated significantly reducing the equivalent series resistance and increasing the knee frequency, hence outclassing the best supercapacitors based on VANTs and non-aqueous electrolytes. The excellent electrochemical response can also be addressed to the chosen electrolyte that, not only has the advantage of leading to a significantly simpler and more affordable fabrication procedure, but has higher ionic conductivity, lower viscosity and higher ions mobility than other electrolytes capable of dissolving cellulose.

Process to produce lithium-polymer batteries

DOEpatents

MacFadden, K.O.

1998-06-30

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

An amperometric NO2 sensor based on La10Si5NbO27.5 electrolyte and nano-structured CuO sensing electrode.

PubMed

Wang, Ling; Han, Bingxu; Dai, Lei; Zhou, Huizhu; Li, Yuehua; Wu, Yinlin; Zhu, Jing

2013-11-15

A novel amperometric-type NO2 sensor based on La10Si5NbO27.5 (LSNO) electrolyte and nano-structured CuO sensing electrode was fabricated and tested. A bilayer LSNO electrolyte including both a dense layer and a porous layer was prepared by conventional solid state reaction method and screen-printing technology. The nano-structured CuO sensing electrode was in situ fabricated in LSNO porous layer by impregnating method. The composition and microstructure of the sample were characterized by XRD and SEM, respectively. The results showed that the CuO particles with diameters range of 200-500 nm were homogeneously dispersed on the LSNO backbone in porous layer. The sensor exhibited well sensing characteristics to NO2. The response current was almost linear to NO2 concentration in the range of 25-500 ppm at 600-800 °C. With increase of operating temperature, the sensitivity increased and reached 297 nA/ppm at 800 °C. The response currents toward NO2 were slightly affected by coexistent O2 (0-21 vol%) and CO2 (0-5 vol%). Copyright © 2013 Elsevier B.V. All rights reserved.

Methods of flash sintering

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

Raj, Rishi; Cologna, Marco; Francis, John S.

2016-05-10

This disclosure provides methods of flash sintering and compositions created by these methods. Methods for sintering multilayered bodies are provided in which a sintered body is produced in less than one minute. In one aspect, each layer is of a different composition, and may be constituted wholly from a ceramic or from a combination of ceramic and metallic particles. When the body includes a layer of an anode composition, a layer of an electrolyte composition and a layer of a cathode composition, the sintered body can be used to produce a solid oxide fuel cell.

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

DOE PAGES

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

2016-10-31

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

Unravelling the electrochemical double layer by direct probing of the solid/liquid interface

DOE PAGES

Favaro, Marco; Jeong, Beomgyun; Ross, Philip N.; ...

2016-08-31

The electrochemical double layer plays a critical role in electrochemical processes. Whilst there have been many theoretical models predicting structural and electrical organization of the electrochemical double layer, the experimental verification of these models has been challenging due to the limitations of available experimental techniques. The induced potential drop in the electrolyte has never been directly observed and verified experimentally, to the best of our knowledge. In this study, we report the direct probing of the potential drop as well as the potential of zero charge by means of ambient pressure X-ray photoelectron spectroscopy performed under polarization conditions. By analyzingmore » the spectra of the solvent (water) and a spectator neutral molecule with numerical simulations of the electric field, we discern the shape of the electrochemical double layer profile. In addition, we determine how the electrochemical double layer changes as a function of both the electrolyte concentration and applied potential.« less

Enhanced charging capability of lithium metal batteries based on lithium bis(trifluoromethanesulfonyl)imide-lithium bis(oxalato)borate dual-salt electrolytes

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

Xiang, Hongfa; Shi, Pengcheng; Bhattacharya, Priyanka

2016-06-01

Rechargeable lithium (Li) metal batteries with conventional LiPF6-carbonate electrolytes have been reported to fail quickly at charging current densities of about 1.0 mA cm-2 and above. In this work, we demonstrate the rapid charging capability of the Li||LiNi0.8Co0.15Al0.05O2 (NCA) cells enabled by a dual-salt electrolyte of LiTFSI-LiBOB in a carbonate solvent mixture. It is found that the thickness of solid electrolyte interphase (SEI) layer on Li metal anode largely increases with increasing charging current density. However, the cells using the LiTFSI-LiBOB dual-salt electrolyte significantly outperforms those using the LiPF6 electrolyte at high charging current densities. At the charging current densitymore » of 1.50 mA cm-2, the Li||NCA cells with the dual-salt electrolyte can still deliver a discharge capacity of 131 mAh g-1 and a capacity retention of 80% after 100 cycles, while those with the LiPF6 electrolyte start to show fast capacity fading after the 30th cycle and only exhibit a low capacity of 25 mAh g-1 and a low retention of 15% after 100 cycles. The reasons for the good chargeability and cycling stability of the cells using LiTFSI-LiBOB dual-salt electrolyte can be attributed to the good film-formation ability of the electrolyte on lithium metal anode and the highly conductive nature of the sulfur-rich interphase layer.« less

Electrophoretic deposition of bi-layered LSM/LSM-YSZ cathodes for solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Itagaki, Yoshiteru; Watanabe, Shinji; Yamaji, Tsuyoshi; Asamoto, Makiko; Yahiro, Hidenori; Sadaoka, Yoshihiko

2012-09-01

Bi-layered cathodes with the LSM/LSM-YSZ structure for solid oxide fuel cells were successfully formed on the carbon-sputtered surface of a YSZ sheet by electrophoretic deposition (EPD). The thicknesses of the first layer of LSM-YSZ (LY) and the second layer of La0.8Sr0.2MnO3 (LSM) could be controlled by adjusting the deposition time in the EPD process. The cathodic properties of the bi-layered structures were superior to those of the mono-layered structures, and were dependent on the thickness of each layer. Decreasing the thickness of the first layer and increasing that of the second layer tended to reduce both polarization and ohmic resistances. The optimal thickness of the first layer at the operating temperature of 600 °C was 4 μm, suggesting that an effective three-phase boundary was extended from the interface between the electrolyte and cathode film to around 4 μm thickness.

Method of doping interconnections for electrochemical cells

DOEpatents

Pal, Uday B.; Singhal, Subhash C.; Moon, David M.; Folser, George R.

1990-01-01

A dense, electronically conductive interconnection layer 26 is bonded on a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) forming a layer of oxide particles of at least one of the metals Ca, Sr, Co, Ba or Mg on a part 24 of a first surface of the air electrode 16, (B) heating the electrode structure, (C) applying a halide vapor containing at least lanthanum halide and chromium halide to the first surface and applying a source of oxygen to a second opposite surface of the air electrode so that they contact at said first surface, to cause a reaction of the oxygen and halide and cause a dense lanthanum-chromium oxide structure to grow, from the first electrode surface, between and around the oxide particles, where the metal oxide particles get incoporated into the lanthanum-chromium oxide structure as it grows thicker with time, and the metal ions in the oxide particles diffuse into the bulk of the lanthamum-chromium oxide structure, to provide a dense, top, interconnection layer 26 on top of the air electrode 16. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

The effect of fluoroethylene carbonate additive content on the formation of the solid-electrolyte interphase and capacity fade of Li-ion full-cell employing nano Si-graphene composite anodes

NASA Astrophysics Data System (ADS)

Bordes, Arnaud; Eom, KwangSup; Fuller, Thomas F.

2014-07-01

When fluoroethylene carbonate (FEC) is added to the ethylene carbonate (EC)-diethyl carbonate (DEC) electrolyte, the capacity and cyclability of full-cells employing Si-graphene anode and lithium nickel cobalt aluminum oxide cathode (NCA) cathode are improved due to formation of a thin (30-50 nm) SEI layer with low ionic resistance (∼2 ohm cm2) on the surface of Si-graphene anode. These properties are confirmed with electrochemical impedance spectroscopy and a cross-sectional image analysis using Focused Ion Beam (FIB)-SEM. Approximately 5 wt.% FEC in EC:DEC (1:1 wt.%) shows the highest capacity and most stability. This high capacity and low capacity fade is attributed to a more stable SEI layer containing less CH2OCO2Li, Li2CO3 and LiF compounds, which consume cyclable Li. Additionally, a greater amount of polycarbonate (PC), which is known to form a more robust passivation layer, thus reducing further reduction of electrolyte, is confirmed with X-ray photoelectron spectroscopy (XPS).

3D-Printing Electrolytes for Solid-State Batteries.

PubMed

McOwen, Dennis W; Xu, Shaomao; Gong, Yunhui; Wen, Yang; Godbey, Griffin L; Gritton, Jack E; Hamann, Tanner R; Dai, Jiaqi; Hitz, Gregory T; Hu, Liangbing; Wachsman, Eric D

2018-05-01

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li 7 La 3 Zr 2 O 12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling Solid-Electrolyte-Interphase Layer by Coating P-Type Semiconductor NiOx on Li4Ti5O12 for High-Energy-Density Lithium-Ion Batteries.

PubMed

Jo, Mi Ru; Lee, Gi-Hyeok; Kang, Yong-Mook

2015-12-23

Li4Ti5O12 is a promising anode material for rechargeable lithium batteries due to its well-known zero strain and superb kinetic properties. However, Li4Ti5O12 shows low energy density above 1 V vs Li(+)/Li. In order to improve the energy density of Li4Ti5O12, its low-voltage intercalation behavior beyond Li7Ti5O12 has been demonstrated. In this approach, the extended voltage window is accompanied by the decomposition of liquid electrolyte below 1 V, which would lead to an excessive formation of solid electrolyte interphase (SEI) films. We demonstrate an effective method to improve electrochemical performance of Li4Ti5O12 in a wide working voltage range by coating Li4Ti5O12 powder with p-type semiconductor NiOx. Ex situ XRD, XPS, and FTIR results show that the NiOx coating suppresses electrochemical reduction reactions of the organic SEI components to Li2CO3, thereby promoting reversibility of the charge/discharge process. The NiOx coating layer offers a stable SEI film for enhanced rate capability and cyclability.

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

Studying Degradation in Lithium-Ion Batteries by Depth Profiling with Lithium-Nuclear Reaction Analysis

NASA Astrophysics Data System (ADS)

Schulz, Adam

Lithium ion batteries (LIBs) are secondary (rechargeable) energy storage devices that lose the ability to store charge, or degrade, with time. This charge capacity loss stems from unwanted reactions such as the continual growth of the solid electrolyte interphase (SEI) layer on the negative carbonaceous electrode. Parasitic reactions consume mobile lithium, the byproducts of which deposit as SEI layer. Introducing various electrolyte additives and coatings on the positive electrode reduce the rate of SEI growth and lead to improved calendar lifetimes of LIBs respectively. There has been substantial work both electrochemically monitoring and computationally modeling the development of the SEI layer. Additionally, a plethora of spectroscopic techniques have been employed in an attempt to characterize the components of the SEI layer. Despite lithium being the charge carrier in LIBs, depth profiles of lithium in the SEI are few. Moreover, accurate depth profiles relating capacity loss to lithium in the SEI are virtually non-existent. Better quantification of immobilized lithium would lead to improved understanding of the mechanisms of capacity loss and allow for computational and electrochemical models dependent on true materials states. A method by which to prepare low variability, high energy density electrochemical cells for depth profiling with the non-destructive technique, lithium nuclear reaction analysis (Li-NRA), is presented here. Due to the unique and largely non-destructive nature of Li-NRA we are able to perform repeated measurement on the same sample and evaluate the variability of the technique. By using low variability electrochemical cells along with this precise spectroscopic technique, we are able to confidently report trends of lithium concentration while controlling variables such as charge state, age and electrolyte composition. Conversion of gamma intensity versus beam energy, rendered by NRA, to Li concentration as a function of depth requires calibration and modeling of the nuclear stopping power of the substrate (electrode material). A methodology to accurately convert characteristic gamma intensity versus beam energy raw data to Li % as a function of depth is presented. Depth profiles are performed on the electrodes of commercial LIBs charged to different states of charge and aged to different states of health. In-lab created Li-ion cells are prepared with different electrolytes and then depth profiled by Li-NRA. It was found lithium accumulates within the solid electrolyte interphase (SEI) layer with the square root of time, consistent with previous reports. When vinylene carbonate (VC) is introduced to electrolyte lithium accumulates at a rapidly reduced rate as compared to cells containing ethylene carbonte (EC). Additionally, lithium concentration within the positive electrode surface was observed to decrease linearly with time independent of electrolyte tested. Future experiments to be conducted to finish the work and the underpinnings of a materials based capacity loss model are proposed.

Achieving Ultrahigh Energy Density and Long Durability in a Flexible Rechargeable Quasi-Solid-State Zn-MnO2 Battery.

PubMed

Zeng, Yinxiang; Zhang, Xiyue; Meng, Yue; Yu, Minghao; Yi, Jianan; Wu, Yiqiang; Lu, Xihong; Tong, Yexiang

2017-07-01

Advanced flexible batteries with high energy density and long cycle life are an important research target. Herein, the first paradigm of a high-performance and stable flexible rechargeable quasi-solid-state Zn-MnO 2 battery is constructed by engineering MnO 2 electrodes and gel electrolyte. Benefiting from a poly(3,4-ethylenedioxythiophene) (PEDOT) buffer layer and a Mn 2+ -based neutral electrolyte, the fabricated Zn-MnO 2 @PEDOT battery presents a remarkable capacity of 366.6 mA h g -1 and good cycling performance (83.7% after 300 cycles) in aqueous electrolyte. More importantly, when using PVA/ZnCl 2 /MnSO 4 gel as electrolyte, the as-fabricated quasi-solid-state Zn-MnO 2 @PEDOT battery remains highly rechargeable, maintaining more than 77.7% of its initial capacity and nearly 100% Coulombic efficiency after 300 cycles. Moreover, this flexible quasi-solid-state Zn-MnO 2 battery achieves an admirable energy density of 504.9 W h kg -1 (33.95 mW h cm -3 ), together with a peak power density of 8.6 kW kg -1 , substantially higher than most recently reported flexible energy-storage devices. With the merits of impressive energy density and durability, this highly flexible rechargeable Zn-MnO 2 battery opens new opportunities for powering portable and wearable electronics. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of forming a dense, high temperature electronically conductive composite layer on a porous ceramic substrate

DOEpatents

Isenberg, A.O.

1992-04-21

An electrochemical device, containing a solid oxide electrolyte material and an electrically conductive composite layer, has the composite layer attached by: (A) applying a layer of LaCrO[sub 3], YCrO[sub 3] or LaMnO[sub 3] particles, on a portion of a porous ceramic substrate, (B) heating to sinter bond the particles to the substrate, (C) depositing a dense filler structure between the doped particles, (D) shaving off the top of the particles, and (E) applying an electronically conductive layer over the particles as a contact. 7 figs.

Study of storage capacity in various carbon/graphene-based solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Subramaniam, C. K.; Boopalan, G.

2014-09-01

Solid-state electrochemical double-layer capacitor (SEDLC) forms excellent energy storage device for high-power applications. They are highly reliable, with no electrolyte leaks, and can be packaged to suit various applications. The electrode material can be activated carbon to graphene. These can have a range of particle size, surface area, pore size and pore distribution for charge storage. The emphasis will be to optimize the graphene to carbon blend in the electrodes which would provide appreciable storage density of the SEDLC. We can use perfluorosulfonic acid polymer as the solid electrolyte in the SEDLC assembly. They have high ionic conductivity, good thermal stability, and mechanical strength. They also have excellent long-term chemical stability. Carbon is widely used for many practical applications, especially for the adsorption of ions and molecules, as it is possible to synthesize one-, two- or three-dimensional (1-, 2-, or 3-D) carbons. Some of the problems in activated carbon like varying micro or mesopores, poor ion mobility due to varying pore distribution, low electrical conductivity, can be overcome using graphene and blends of graphene with carbon of the right pore dimension and distribution. Graphene in various structural nomenclatures have been used by various groups for charge storage. Graphene nanoplates (GNP), with narrow mesopore distributions have been effectively used for SEDLCs. SEDLCs assembled with GNP and blends of GNP with Vulcan XC and solid polymer electrolyte like Nafion show exceptional performance. The cyclic voltammetric studies show that they support high scan rates with substantial smaller capacitance drop as we increase scan rates. Optimization of the electrode structure in terms of blend percentage, binder content and interface character in the frequency and time domain provides excellent insight into the double-layer interface.

Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes

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

Kalaga, Kaushik; Shkrob, Ilya A.; Haasch, Richard T.

In this study, Auger electron spectroscopy (AES) combined with ion sputtering profilometry, Xray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) have been used in a complementary fashion to examine chemical and microstructural changes in graphite (Gr) and silicon/graphite (Si/Gr) blends contained in the negative electrodes of lithium-ion cells. We demonstrate how AES can be used to characterize morphology of the solid-electrolyte interphase (SEI) deposits in such heterogeneous media, complementing well-established methods, such as XPS and SEM. In this way we demonstrate that the SEI does not consist of uniformly thick layers on the graphite and silicon; the thickness ofmore » the SEI layers in cycle-life aged electrodes follows an exponential distribution with a mean of ca. 13 nm for the graphite and ca. 20-25 nm for the silicon nanoparticles (with a crystalline core of 50-70 nm in diameter). Furthermore, a “sticky-sphere” model, in which Si nanoparticles are covered with a layer of polymer binder (that is replaced by the SEI during cycling) of variable thickness is introduced to account for the features observed.« less

Auger Electrons as Probes for Composite Micro- and Nano- structured Materials: Application to Solid Electrolyte Interphases in Graphite and Silicon-Graphite Electrodes

DOE PAGES

Kalaga, Kaushik; Shkrob, Ilya A.; Haasch, Richard T.; ...

2017-10-05

In this study, Auger electron spectroscopy (AES) combined with ion sputtering profilometry, Xray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) have been used in a complementary fashion to examine chemical and microstructural changes in graphite (Gr) and silicon/graphite (Si/Gr) blends contained in the negative electrodes of lithium-ion cells. We demonstrate how AES can be used to characterize morphology of the solid-electrolyte interphase (SEI) deposits in such heterogeneous media, complementing well-established methods, such as XPS and SEM. In this way we demonstrate that the SEI does not consist of uniformly thick layers on the graphite and silicon; the thickness ofmore » the SEI layers in cycle-life aged electrodes follows an exponential distribution with a mean of ca. 13 nm for the graphite and ca. 20-25 nm for the silicon nanoparticles (with a crystalline core of 50-70 nm in diameter). Furthermore, a “sticky-sphere” model, in which Si nanoparticles are covered with a layer of polymer binder (that is replaced by the SEI during cycling) of variable thickness is introduced to account for the features observed.« less

Materiais a base de oxidos com estrutura do tipo perovskite e compositos como anodos de PCES: Propriedades Funcionais e Comportamento Eletroquimico em Celulas com Eletrolitos Solidos a Base de Galatos e Silicatos

NASA Astrophysics Data System (ADS)

Kolotygin, Vladislav

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-delta (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27-based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-delta.

Towards high-energy and durable lithium-ion batteries via atomic layer deposition: elegantly atomic-scale material design and surface modification

NASA Astrophysics Data System (ADS)

Meng, Xiangbo

2015-01-01

Targeted at fueling future transportation and sustaining smart grids, lithium-ion batteries (LIBs) are undergoing intensive investigation for improved durability and energy density. Atomic layer deposition (ALD), enabling uniform and conformal nanofilms, has recently made possible many new advances for superior LIBs. The progress was summarized by Liu and Sun in their latest review [1], offering many insightful views, covering the design of nanostructured battery components (i.e., electrodes and solid electrolytes), and nanoscale modification of electrode/electrolyte interfaces. This work well informs peers of interesting research conducted and it will also further help boost the applications of ALD in next-generation LIBs and other advanced battery technologies.

Electrolyte Structure near Electrode Interfaces in Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lordi, Vincenzo; Ong, Mitchell; Verners, Osvalds; van Duin, Adri; Draeger, Erik; Pask, John

2014-03-01

The performance of lithium-ion secondary batteries (LIBs) is strongly tied to electrochemistry and ionic transport near the electrode-electrolyte interface. Changes in ion solvation near the interface affect ion conductivity and also are associated with the formation and evolution of solid-electrolyte interphase (SEI) layers, which impede transport but also passivate the interface. Thus, understanding these effects is critical to optimizing battery performance. Here we present molecular dynamics (MD) simulations of typical organic liquid LIB electrolytes in contact with graphite electrodes to understand differences in molecular structure and solvation near the interface compared to the bulk electrolyte. Results for different graphite terminations are presented. We compare the results of density-functional based MD to the empirical reactive forcefield ReaxFF and the non-reactive, non-polarizable COMPASS forcefield. Notable differences in the predictive power of each of these techniques are discussed. Prepared by LLNL under Contract DE-AC52-07NA27344.

Water Transport in the Micro Porous Layer and Gas Diffusion Layer of a Polymer Electrolyte Fuel Cell

NASA Astrophysics Data System (ADS)

Qin, C.; Hassanizadeh, S. M.

2015-12-01

In this work, a recently developed dynamic pore-network model is presented [1]. The model explicitly solves for both water pressure and capillary pressure. A semi-implicit scheme is used in updating water saturation in each pore body, which considerably increases the numerical stability at low capillary number values. Furthermore, a multiple-time-step algorithm is introduced to reduce the computational effort. A number of case studies of water transport in the micro porous layer (MPL) and gas diffusion layer (GDL) are conducted. We illustrate the role of MPL in reducing water flooding in the GDL. Also, the dynamic water transport through the MPL-GDL interface is explored in detail. This information is essential to the reduced continua model (RCM), which was developed for multiphase flow through thin porous layers [2, 3]. C.Z. Qin, Water transport in the gas diffusion layer of a polymer electrolyte fuel cell: dynamic pore-network modeling, J Electrochimical. Soci., 162, F1036-F1046, 2015. C.Z. Qin and S.M. Hassanizadeh, Multiphase flow through multilayers of thin porous media: general balance equations and constitutive relationships for a solid-gas-liquid three-phase system, Int. J. Heat Mass Transfer, 70, 693-708, 2014. C.Z. Qin and S.M. Hassanizadeh, A new approach to modeling water flooding in a polymer electrolyte fuel cell, Int. J. Hydrogen Energy, 40, 3348-3358, 2015.

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.

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

PubMed

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

2017-10-25

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

A bifunctional electrolyte additive for separator wetting and dendrite suppression in lithium metal batteries

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

Zheng, Hao; Xie, Yong; Xiang, Hongfa

Reformulation of electrolyte systems and improvement of separator wettability are vital to electrochemical performances of rechargeable lithium (Li) metal batteries, especially for suppressing Li dendrites. In this work we report a bifunctional electrolyte additive that improves separator wettability and suppresses Li dendrite growth in LMBs. A triblock polyether (Pluronic P123) was introduced as an additive into a commonly used carbonate-based electrolyte. It was found that addition of 0.2~1% (by weight) P123 into the electrolyte could effectively enhance the wettability of polyethylene separator. More importantly, the adsorption of P123 on Li metal surface can act as an artificial solid electrolyte interphasemore » layer and contribute to suppress the growth of Li dendrites. A smooth and dendritic-free morphology can be achieved in the electrolyte with 0.2% P123. The Li||Li symmetric cells with the 0.2% P123 containing electrolyte exhibit a relatively stable cycling stability at high current densities of 1.0 and 3.0 mA cm-2.« less

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices.A high contact resistance between the active materials and the current collector, a low ionic conductivity of the gel electrolyte, and an impenetrable electrode structure are the three major barriers which greatly limit the capacitance of MnO2 in solid state supercapacitors. As a potential solution to these problems, in this work we report a novel electrode for solid state supercapacitors, based on a ternary system composed of hierarchical MnO2 spheres as the active material, macroporous Ni foam as gel penetrable skeletons and an ordered mesoporous carbon (OMC) membrane as the charge-transport accelerating layer. By employing butyl-3-methylimidazolium chloride (BMIMCl) modified gels as the ionic conducting electrolyte, the utilization efficiency of MnO2 on the specific capacitance was enhanced up to 88% of the theoretical value, delivering a volumetric capacitance of 81 F cm-3, which is the highest value among MnO2 based solid state supercapacitors. Moreover, such a flexible device exhibits exceptional volumetric energy and power density (6.6 Wh L-1 and 549 W L-1, based on the whole device volume) combined with a small capacity loss of 8.5% after 6000 cycles under twisting. These encouraging findings unambiguously overcome the energy bottleneck of MnO2 in solid state supercapacitors, and open up a new application of macro/mesoporous materials in flexible devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr02215d

In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ross, Philip N.; ...

2015-12-11

The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF 6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials wheremore » electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC 2H 5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.« less

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

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

Soto, Fernando A.; Yan, Pengfei; Engelhard, Mark H.

Solid-electrolyte interphase (SEI) with controllable properties are highly desirable to improve battery performance. In this paper, we use a combined experimental and simulation approach to study the SEI formation on hard carbon in Li and Na-ion batteries. We show that with proper additives, stable SEI can be formed on hard carbon by pre-cycling the electrode materials in Li or Na-ion electrolyte. Detailed mechanistic studies suggest that the ion transport in the SEI layer is kinetically controlled and can be tuned by the applied voltage. Selective Na and Li-ion SEI membranes are produced using the Na or Li-ion based electrolytes respectively.more » The large Na ion SEI allows easy transport of Li ions, while the small Li ion SEI shuts off the Na-ion transport. Na-ion storage can be manipulated by tuning the SEI with film-forming electrolyte additives or preforming a SEI on the electrodes’ surface. The Na specific capacity can be controlled to <25 mAh/g, ~1/10 of the normal capacity (250 mAh/g). Unusual selective/preferential transport of Li-ion is demonstrated by preforming a SEI on the electrode’s surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion selective conductors using electrochemical approaches in the future.« less

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

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 withmore » 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.« less

Determination of the Solid Electrolyte Interphase Structure Grown on a Silicon Electrode Using a Fluoroethylene Carbonate Additive

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

Veith, Gabriel M.; Doucet, Mathieu; Sacci, Robert L.

2017-07-24

In this work we explore how an electrolyte additive (fluorinated ethylene carbonate – FEC) mediates the thickness and composition of the solid electrolyte interphase formed over a silicon anode in situ as a function of state-of-charge and cycle. We show the FEC condenses on the surface at open circuit voltage then is reduced to C-O containing polymeric species around 0.9 V (vs. Li/Li +). The resulting film is about 50 Å thick. Upon lithiation the SEI thickens to 70 Å and becomes more organic-like. With delithiation the SEI thins by 13 Å and becomes more inorganic in nature, consistent withmore » the formation of LiF. This thickening/thinning is reversible with cycling and shows the SEI is a dynamic structure. We compare the SEI chemistry and thickness to 280 Å thick SEI layers produced without FEC and provide a mechanism for SEI formation using FEC additives.« less

Hybrid solid polymer electrolyte from diapers as separator for electrochemical double layer capacitor (EDLC)

NASA Astrophysics Data System (ADS)

Hashim, Mohd Azman; Yatim, Nadhrah Md.; Mahmud, Nor Azura Che; Sazali, Nur Ezniera Shafieza; Hamdan, Ellisah; Yahya, Mohd Adib; Ngah, Che Wan Zanariah Che Wan; Suhaimi, Syahida

2018-06-01

EDLC was fabricated using hybrid solid polymer electrolyte from PVA-diapers and an activated carbon powder as electrode by using solution casting method. For comparison, four types of EDLC cells were constructed and tested. It was found that an EDLC with a PVA-diapers (60:40) polymer electrolyte exhibited much higher capacitance and longer cycle-life. The electrocapacitive properties of the supercapacitor (P50HD50, P60HD40, P70HD30 and P80HD20) were done using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge discharge (GCD). Results from these analysis showed that P60HD40 cell had recorded excellent rate capability and highest Csp value of 179 F g-1 (EIS), 50 F g-1 (CV), 328 F g-1 (GCD) respectively. Futher, results from ESR (GCD) analysis showed that P60HD40 composition of PVA/H3PO4 liquid electroyte gave a lower value of 88.05 Ω in the supercapacitor cell compared with another cells.

Suppression of Dendritic Lithium Growth by in Situ Formation of a Chemically Stable and Mechanically Strong Solid Electrolyte Interphase.

PubMed

Wan, Guojia; Guo, Feihu; Li, Hui; Cao, Yuliang; Ai, Xinping; Qian, Jiangfeng; Li, Yangxing; Yang, Hanxi

2018-01-10

The growth and proliferation of Li dendrites during repeated Li cycling has long been a crucial issue that hinders the development of secondary Li-metal batteries. Building a stable and robust solid state electrolyte interphase (SEI) on the Li-anode surface is regarded as a promising strategy to overcome the dendrite issues. In this work, we report a simple strategy to engineer the interface chemistry of Li-metal anodes by using tiny amounts of dimethyl sulfate (DMS, C 2 H 6 SO 4 ) as the SEI-forming additive. With the preferential reduction of DMS, an SEI layer composed of Li 2 S/Li 2 O forms on the Li surface. This inorganic SEI layer features high structural modulus and low interfacial resistant, enabling a dense and dendrite-free Li deposition as evidenced by scanning electron microscopy, atomic force microscopy, and in situ optical images. In addition, this SEI layer can prevent the deposited Li from direct contact with corrosive electrolytes, thus rendering an improved cycling stability of Li anodes with an average Coulombic efficiency of 97% for up to 150 cycles. When the DMS additive is introduced into a Li/NCM full cell, the cycle life of Li-metal batteries can be also improved significantly. This work demonstrates a feasible route to suppress Li dendrite growth by designing appropriate film-forming additives to regulate the interfacial properties of the SEI layer, and also the sulfonyl-based derivatives revealed in this work represent a large variety of new film-forming molecules, providing a broad selectivity for constructing high efficiency and cycle-stable Li anodes to address the intrinsic problems of rechargeable Li-metal batteries.

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene-modified mesoscopic carbon-counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Han, Hongwei

2013-01-01

A monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene-modified mesoscopic carbon-counter electrode is developed. A TiO2-working electrode layer, ZrO2 spacer layer, and carbon counter electrode layer were constructed on a single conducting glass substrate by screen printing. The quasi-solid-state polymer gel electrolyte employed a polymer composite as the gelator, and effectively infiltrated the porous layers. Fabricated with normal carbon-counter electrode (NC-CE) containing graphite and carbon black, the DSSC had a power conversion efficiency (PCE) of 5.09% with the fill factor of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE was modified with graphene sheets, the PCE and fill factor were enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Aiping; Kadam, Sanket; Li, Hong; Shi, Siqi; Qi, Yue

2018-03-01

A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li+ transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multi-scale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications

PubMed Central

Huang, Chun; Zhang, Jin; Young, Neil P.; Snaith, Henry J.; Grant, Patrick S.

2016-01-01

Supercapacitors are in demand for short-term electrical charge and discharge applications. Unlike conventional supercapacitors, solid-state versions have no liquid electrolyte and do not require robust, rigid packaging for containment. Consequently they can be thinner, lighter and more flexible. However, solid-state supercapacitors suffer from lower power density and where new materials have been developed to improve performance, there remains a gap between promising laboratory results that usually require nano-structured materials and fine-scale processing approaches, and current manufacturing technology that operates at large scale. We demonstrate a new, scalable capability to produce discrete, multi-layered electrodes with a different material and/or morphology in each layer, and where each layer plays a different, critical role in enhancing the dynamics of charge/discharge. This layered structure allows efficient utilisation of each material and enables conservative use of hard-to-obtain materials. The layered electrode shows amongst the highest combinations of energy and power densities for solid-state supercapacitors. Our functional design and spray manufacturing approach to heterogeneous electrodes provide a new way forward for improved energy storage devices. PMID:27161379

Permeability and Microstructure of Suspension Plasma-Sprayed YSZ Electrolytes for SOFCs on Various Substrates

NASA Astrophysics Data System (ADS)

Marr, Michael; Kesler, Olivera

2012-12-01

Yttria-stabilized zirconia electrolyte coatings for solid oxide fuel cells were deposited by suspension plasma spraying using a range of spray conditions and a variety of substrates, including finely structured porous stainless steel disks and cathode layers on stainless steel supports. Electrolyte permeability values and trends were found to be highly dependent on which substrate was used. The most gas-tight electrolyte coatings were those deposited directly on the porous metal disks. With this substrate, permeability was reduced by increasing the torch power and reducing the stand-off distance to produce dense coating microstructures. On the substrates with cathodes, electrolyte permeability was reduced by increasing the stand-off distance, which reduced the formation of segmentation cracks and regions of aligned and concentrated porosity. The formation mechanisms of the various permeability-related coating features are discussed and strategies for reducing permeability are presented. The dependences of electrolyte deposition efficiency and surface roughness on process conditions and substrate properties are also presented.

Hollow Few-Layer Graphene-Based Structures from Parafilm Waste for Flexible Transparent Supercapacitors and Oil Spill Cleanup.

PubMed

Nguyen, Duc Dung; Hsieh, Ping-Yen; Tsai, Meng-Ting; Lee, Chi-Young; Tai, Nyan-Hwa; To, Bao Dong; Vu, Duc Tu; Hsu, Chia Chen

2017-11-22

We report a versatile strategy to exploit parafilm waste as a carbon precursor for fabrication of freestanding, hollow few-layer graphene fiber mesh (HFGM) structures without use of any gaseous carriers/promoters via an annealing route. The freestanding HFGMs possess good mechanical flexibility, tailorable transparency, and high electrical conductivity, consequently qualifying them as promising electrochemical electrodes. Because of the hollow spaces, electrolyte ions can easily access into and contact with interior surfaces of the graphene fibers, accordingly increasing electrode/electrolyte interfacial area. As expected, solid-state supercapacitors based on the HFGMs exhibit a considerable enhancement in specific capacitance (20-30 fold) as compared to those employing chemical vapor deposition compact graphene films. Moreover, the parafilm waste is found to be beneficial for one-step fabrication of nanocarbon/few-layer graphene composite meshes with superior electrochemical performance, outstanding superhydrophobic property, good self-cleaning ability, and great promise for oil spill cleanup.

Continuous process to produce lithium-polymer batteries

DOEpatents

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

1998-01-01

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

A new percolation model for composite solid electrolytes and dispersed ionic conductors

NASA Astrophysics Data System (ADS)

Risyad Hasyim, Muhammad; Lanagan, Michael T.

2018-02-01

Composite solid electrolytes (CSEs) including conductor/insulator composites known as dispersed ionic conductors (DICs) have motivated the development of novel percolation models that describe their conductivity. Despite the long history, existing models lack in one or more key areas: (1) rigorous foundation for their physical theory, (2) explanation for non-universal conductor-insulator transition, (3) classification of DICs, and (4) extension to frequency-domain. This work describes a frequency-domain effective medium approximation (EMA) of a bond percolation model for CSEs. The EMA is derived entirely from Maxwell’s equations and contains basic microstructure parameters. The model was applied successfully to several composite systems from literature. Simulations and fitting of literature data address these key areas and illustrate the interplay between space charge layer properties and bulk microstructure.

Facilitated ion transport in all-solid-state flexible supercapacitors.

PubMed

Choi, Bong Gill; Hong, Jinkee; Hong, Won Hi; Hammond, Paula T; Park, HoSeok

2011-09-27

The realization of highly flexible and all-solid-state energy-storage devices strongly depends on both the electrical properties and mechanical integrity of the constitutive materials and the controlled assembly of electrode and solid electrolyte. Herein we report the preparation of all-solid-state flexible supercapacitors (SCs) through the easy assembly of functionalized reduced graphene oxide (f-RGO) thin films (as electrode) and solvent-cast Nafion electrolyte membranes (as electrolyte and separator). In particular, the f-RGO-based SCs (f-RGO-SCs) showed a 2-fold higher specific capacitance (118.5 F/g at 1 A/g) and rate capability (90% retention at 30 A/g) compared to those of all-solid-state graphene SCs (62.3 F/g at 1A/g and 48% retention at 30 A/g). As proven by the 4-fold faster relaxation of the f-RGO-SCs than that of the RGO-SCs and more capacitive behavior of the former at the low-frequency region, these results were attributed to the facilitated ionic transport at the electrical double layer by means of the interfacial engineering of RGO by Nafion. Moreover, the superiority of all-solid-state flexible f-RGO-SCs was demonstrated by the good performance durability under the 1000 cycles of charging and discharging due to the mechanical integrity as a consequence of the interconnected networking structures. Therefore, this research provides new insight into the rational design and fabrication of all-solid-state flexible energy-storage devices as well as the fundamental understanding of ion and charge transport at the interface. © 2011 American Chemical Society

Spreading of Electrolyte Drops on Charged Surfaces: Electric Double Layer Effects on Drop Dynamics

NASA Astrophysics Data System (ADS)

Bae, Kyeong; Sinha, Shayandev; Chen, Guang; Das, Siddhartha

2015-11-01

Drop spreading is one of the most fundamental topics of wetting. Here we study the spreading of electrolyte drops on charged surfaces. The electrolyte solution in contact with the charged solid triggers the formation of an electric double layer (EDL). We develop a theory to analyze how the EDL affects the drop spreading. The drop dynamics is studied by probing the EDL effects on the temporal evolution of the contact angle and the base radius (r). The EDL effects are found to hasten the spreading behaviour - this is commensurate to the EDL effects causing a ``philic'' tendency in the drops (i.e., drops attaining a contact angle smaller than its equilibrium value), as revealed by some of our recent papers. We also develop scaling laws to illustrate the manner in which the EDL effects make the r versus time (t) variation deviate from the well known r ~tn variation, thereby pinpointing the attainment of different EDL-mediated spreading regimes.

Monolithic quasi-solid-state dye-sensitized solar cells based on graphene modified mesoscopic carbon counter electrodes

NASA Astrophysics Data System (ADS)

Rong, Yaoguang; Li, Xiong; Liu, Guanghui; Wang, Heng; Ku, Zhiliang; Xu, Mi; Liu, Linfeng; Hu, Min; Yang, Ying; Han, Hongwei

2013-03-01

We have developed a monolithic quasi-solid-state dye-sensitized solar cell (DSSC) based on graphene modified mesoscopic carbon counter electrode (GC-CE), which offers a promising prospect for commercial applications. Based on the design of a triple layer structure, the TiO2 working electrode layer, ZrO2 spacer layer and carbon counter electrode (CE) layer are constructed on a single conducting glass substrate by screen-printing. The quasi-solid-state polymer gel electrolyte employs a polymer composite as the gelator and could effectively infiltrate into the porous layers. Fabricated with normal carbon counter electrode (NC-CE) containing graphite and carbon black, the device shows a power conversion efficiency (PCE) of 5.09% with the fill factor (FF) of 0.63 at 100 mW cm-2 AM1.5 illumination. When the NC-CE is modified with graphene sheets, the PCE and FF could be enhanced to 6.27% and 0.71, respectively. This improvement indicates excellent conductivity and high electrocatalytic activity of the graphene sheets, which have been considered as a promising platinum-free electrode material for DSSCs.

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

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

Crowe, Adam J.; Bartlett, Bart M., E-mail: bartmb@umich.edu

2016-10-15

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recentmore » advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.« less

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

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

Liu, Gao; Wang, Dongdong

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

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

DOEpatents

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

2015-05-05

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

Method of forming a dense, high temperature electronically conductive composite layer on a porous ceramic substrate

DOEpatents

Isenberg, Arnold O.

1992-01-01

An electrochemical device, containing a solid oxide electrolyte material and an electrically conductive composite layer, has the composite layer attached by: (A) applying a layer of LaCrO.sub.3, YCrO.sub.3 or LaMnO.sub.3 particles (32), on a portion of a porous ceramic substrate (30), (B) heating to sinter bond the particles to the substrate, (C) depositing a dense filler structure (34) between the doped particles (32), (D) shaving off the top of the particles, and (E) applying an electronically conductive layer over the particles (32) as a contact.

Continuous process to produce lithium-polymer batteries

DOEpatents

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

1998-05-12

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

Fuel cell generator containing a gas sealing means

DOEpatents

Makiel, J.M.

1987-02-03

A high temperature solid electrolyte electrochemical generator is made, operating with flowing fuel gas and oxidant gas, the generator having a thermal insulation layer, and a sealing means contacting or contained within the insulation, where the sealing means is effective to control the contact of the various gases utilized in the generator. 5 figs.

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

Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

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

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

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

2016-07-06

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

Solid 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.

DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

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

M. S. Sohal; J. E. O'Brien; C. M. Stoots

2012-02-01

Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL's test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

DEGRADATION ISSUES IN SOLID OXIDE CELLS DURING HIGH TEMPERATURE ELECTROLYSIS

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

J. E. O'Brien; C. M. Stoots; V. I. Sharma

2010-06-01

Idaho National Laboratory (INL) is performing high-temperature electrolysis research to generate hydrogen using solid oxide electrolysis cells (SOECs). The project goals are to address the technical and degradation issues associated with the SOECs. This paper provides a summary of various ongoing INL and INL sponsored activities aimed at addressing SOEC degradation. These activities include stack testing, post-test examination, degradation modeling, and a list of issues that need to be addressed in future. Major degradation issues relating to solid oxide fuel cells (SOFC) are relatively better understood than those for SOECs. Some of the degradation mechanisms in SOFCs include contact problemsmore » between adjacent cell components, microstructural deterioration (coarsening) of the porous electrodes, and blocking of the reaction sites within the electrodes. Contact problems include delamination of an electrode from the electrolyte, growth of a poorly (electronically) conducting oxide layer between the metallic interconnect plates and the electrodes, and lack of contact between the interconnect and the electrode. INL’s test results on high temperature electrolysis (HTE) using solid oxide cells do not provide a clear evidence whether different events lead to similar or drastically different electrochemical degradation mechanisms. Post-test examination of the solid oxide electrolysis cells showed that the hydrogen electrode and interconnect get partially oxidized and become non-conductive. This is most likely caused by the hydrogen stream composition and flow rate during cool down. The oxygen electrode side of the stacks seemed to be responsible for the observed degradation due to large areas of electrode delamination. Based on the oxygen electrode appearance, the degradation of these stacks was largely controlled by the oxygen electrode delamination rate. University of Utah (Virkar) has developed a SOEC model based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. This model is under continued development. It shows that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, within the electrolyte. The chemical potential within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just under the oxygen electrode (anode)/electrolyte interface, leading to electrode delamination. This theory is being further refined and tested by introducing some electronic conduction in the electrolyte.« less

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.

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.

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.

Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

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

Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo

2015-06-24

Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmissionmore » electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.« less

Li + Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li 3 OCl Electrolyte

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

Stegmaier, Saskia; Voss, Johannes; Reuter, Karsten

In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode.more » With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less

Li + Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li 3 OCl Electrolyte

DOE PAGES

Stegmaier, Saskia; Voss, Johannes; Reuter, Karsten; ...

2017-04-26

In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode.more » With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less

Structure and Li+ ion transport in a mixed carbonate/LiPF6 electrolyte near graphite electrode surfaces: a molecular dynamics study.

PubMed

Boyer, Mathew J; Vilčiauskas, Linas; Hwang, Gyeong S

2016-10-12

Electrolyte and electrode materials used in lithium-ion batteries have been studied separately to a great extent, however the structural and dynamical properties of the electrolyte-electrode interface still remain largely unexplored despite its critical role in governing battery performance. Using molecular dynamics simulations, we examine the structural reorganization of solvent molecules (cyclic ethylene carbonate : linear dimethyl carbonate 1 : 1 molar ratio doped with 1 M LiPF 6 ) in the vicinity of graphite electrodes with varying surface charge densities (σ). The interfacial structure is found to be sensitive to the molecular geometry and polarity of each solvent molecule as well as the surface structure and charge distribution of the negative electrode. We also evaluated the potential difference across the electrolyte-electrode interface, which exhibits a nearly linear variation with respect to σ up until the onset of Li + ion accumulation onto the graphite edges from the electrolyte. In addition, well-tempered metadynamics simulations are employed to predict the free-energy barriers to Li + ion transport through the relatively dense interfacial layer, along with analysis of the Li + solvation sheath structure. Quantitative analysis of the molecular arrangements at the electrolyte-electrode interface will help better understand and describe electrolyte decomposition, especially in the early stages of solid-electrolyte-interphase (SEI) formation. Moreover, the computational framework presented in this work offers a means to explore the effects of solvent composition, electrode surface modification, and operating temperature on the interfacial structure and properties, which may further assist in efforts to engineer the electrolyte-electrode interface leading to a SEI layer that optimizes battery performance.

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

PubMed

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

2016-06-09

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

Space charge induced surface stresses: implications in ceria and other ionic solids.

PubMed

Sheldon, Brian W; Shenoy, Vivek B

2011-05-27

Volume changes associated with point defects in space charge layers can produce strains that substantially alter thermodynamic equilibrium near surfaces in ionic solids. For example, near-surface compressive stresses exceeding -10 GPa are predicted for ceria. The magnitude of this effect is consistent with anomalous lattice parameter increases that occur in ceria nanoparticles. These stresses should significantly alter defect concentrations and key transport properties in a wide range of materials (e.g., ceria electrolytes in fuel cells). © 2011 American Physical Society

Enhanced ionic conductivity with Li{sub 7}O{sub 2}Br{sub 3} phase in Li{sub 3}OBr anti-perovskite solid electrolyte

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

Zhu, Jinlong, E-mail: jlzhu04@physics.unlv.edu, E-mail: yusheng.zhao@unlv.edu, E-mail: zhaoys@sustc.edu.cn; Li, Shuai; Zhang, Yi

Cubic anti-perovskites with general formula Li{sub 3}OX (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 Li{sub 3}OBr and layered Li{sub 7}O{sub 2}Br{sub 3,} by solid state reaction routes. The results indicate that with the phase fraction of Li{sub 7}O{sub 2}Br{sub 3} increasing to 44 wt.more » %, the ionic conductivity increased by more than one order of magnitude compared with pure phase Li{sub 3}OBr. Formation energy calculations revealed the meta-stable nature of Li{sub 7}O{sub 2}Br{sub 3}, which supports the great difficulty in producing phase-pure Li{sub 7}O{sub 2}Br{sub 3} at ambient pressure. Methods of obtaining phase-pure Li{sub 7}O{sub 2}Br{sub 3} will continue to be explored, including both high pressure and metathesis techniques.« less

Production of an ion-exchange membrane-catalytic electrode bonded material for electrolytic cells

NASA Technical Reports Server (NTRS)

Takenaka, H.; Torikai, E.

1986-01-01

A good bond is achieved by placing a metal salt in solution on one side of a membrane and a reducing agent on the other side so that the reducing agent penetrates the membrane and reduces the metal. Thus, a solution containing Pt, Rh, etc., is placed on one side of the membrane and a reducing agent such as NaBH, is placed on the other side. The bonded metal layer obtained is superior in catalytic activity and is suitable as an electrode in a cell such as for solid polymer electrolyte water electrolysis.

Eco-friendly Energy Storage System: Seawater and Ionic Liquid Electrolyte.

PubMed

Kim, Jae-Kwang; Mueller, Franziska; Kim, Hyojin; Jeong, Sangsik; Park, Jeong-Sun; Passerini, Stefano; Kim, Youngsik

2016-01-08

As existing battery technologies struggle to meet the requirements for widespread use in the field of large-scale energy storage, novel concepts are urgently needed concerning batteries that have high energy densities, low costs, and high levels of safety. Here, a novel eco-friendly energy storage system (ESS) using seawater and an ionic liquid is proposed for the first time; this represents an intermediate system between a battery and a fuel cell, and is accordingly referred to as a hybrid rechargeable cell. Compared to conventional organic electrolytes, the ionic liquid electrolyte significantly enhances the cycle performance of the seawater hybrid rechargeable system, acting as a very stable interface layer between the Sn-C (Na storage) anode and the NASICON (Na3 Zr2 Si2 PO12) ceramic solid electrolyte, making this system extremely promising for cost-efficient and environmentally friendly large-scale energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid oxide fuel cell having monolithic cross flow core and manifolding

DOEpatents

Poeppel, Roger B.; Dusek, Joseph T.

1984-01-01

This invention discloses a monolithic core construction having the flow passageways for the fuel and for the oxidant gases extended transverse to one another, whereby full face core manifolding can be achieved for these gases and their reaction products. The core construction provides that only anode material surround each fuel passageway and only cathode material surround each oxidant passageway, each anode and each cathode further sandwiching at spaced opposing sides electrolyte and interconnect materials to define electrolyte and interconnect walls. Webs of the cathode and anode material hold the electrolyte and interconnect walls spaced apart to define the flow passages. The composite anode and cathode wall structures are further alternately stacked on one another (with the separating electrolyte or interconnect material typically being a single common layer) whereby the fuel passageway and the oxidant passageways are disposed transverse to one another.

Solid oxide fuel cell having monolithic cross flow core and manifolding

DOEpatents

Poeppel, R.B.; Dusek, J.T.

1983-10-12

This invention discloses a monolithic core construction having the flow passageways for the fuel and for the oxidant gases extended transverse to one another, whereby full face core manifolding can be achieved for these gases and their reaction products. The core construction provides that only anode material surround each fuel passageway and only cathode material surround each oxidant passageway, each anode and each cathode further sandwiching at spaced opposing sides electrolyte and interconnect materials to define electrolyte and interconnect walls. Webs of the cathode and anode material hold the electrolyte and interconnect walls spaced apart to define the flow passages. The composite anode and cathode wall structures are further alternately stacked on one another (with the separating electrolyte or interconnect material typically being a single common layer) whereby the fuel passageways and the oxidant passageways are disposed transverse to one another.

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.

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

Solid-State Water Electrolysis with an Alkaline Membrane

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

Leng, YJ; Chen, G; Mendoza, AJ

2012-06-06

We report high-performance, durable alkaline membrane water electrolysis in a solid-state cell. An anion exchange membrane (AEM) and catalyst layer ionomer for hydroxide ion conduction were used without the addition of liquid electrolyte. At 50 degrees C, an AEM electrolysis cell using iridium oxide as the anode catalyst and Pt black as the cathode catalyst exhibited a current density of 399 mA/cm(2) at 1.80 V. We found that the durability of the AEM-based electrolysis cell could be improved by incorporating a highly durable ionomer in the catalyst layer and optimizing the water feed configuration. We demonstrated an AEM-based electrolysis cellmore » with a lifetime of > 535 h. These first-time results of water electrolysis in a solid-state membrane cell are promising for low-cost, scalable hydrogen production.« less

Li 2OHCl crystalline electrolyte for stable metallic lithium anodes

DOE PAGES

Hood, Zachary D.; Wang, Hui; Samuthira Pandian, Amaresh; ...

2016-01-22

In a classic example of stability from instability, we show that Li 2OHCl solid electrolyte forms a stable solid electrolyte interface (SEI) with metallic lithium anode. The Li 2OHCl solid electrolyte can be readily achieved through simple mixing of air-stable LiOH and LiCl precursors with a mild processing temperature under 400 °C. Additionally, we show that continuous, dense Li 2OHCl membranes can be fabricated at temperatures less than 400 °C, standing in great contrast to current processing temperatures of over 1600 °C for most oxide-based solid electrolytes. The ionic conductivity and Arrhenius activation energy were explored for the LiOH-LiCl systemmore » of crystalline solid electrolytes where Li 2OHCl with increased crystal defects was found to have the highest ionic conductivity and reasonable Arrhenius activation energy. The Li 2OHCl solid electrolyte displays stability against metallic lithium, even in extreme conditions past the melting point of lithium metal. Furthermore, to understand this excellent stability, we show that SEI formation is critical in stabilizing the interface between metallic lithium and the Li 2OHCl solid electrolyte.« less

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.

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.

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.

Interfacial reactions in lithium batteries

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

Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng

The lithium-ion battery was first commercially introduced by Sony Corporation on 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage devices for modern portable electronics, as well as for the emerging application for electric vehicles and smart grids. It has been a common sense that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses the parasitic reactions between the lithiated 2 graphitic anodes and the carbonate-based non-aqueous electrolytes.more » Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for rational design of high-energy-density lithiumion batteries with extended cycle/calendar life. In this article, the physical model of the solid electrolyte interphase, as well as the recent research effort to under the nature and role SEI are summarized, and future perspectives on this important research field will also be presented.« less

Interfacial reactions in lithium batteries

DOE PAGES

Chen, Zonghai; Amine, Rachid; Ma, Zi-Feng; ...

2017-06-29

The lithium-ion battery was first commercially introduced by Sony Corporation on 1991 using LiCoO 2 as the cathode material and mesocarbon microbeads as the anode material. After continuous research and development for 25 years, lithium-ion batteries have been the dominant energy storage devices for modern portable electronics, as well as for the emerging application for electric vehicles and smart grids. It has been a common sense that the success of lithium-ion technologies is rooted to the existence of a solid electrolyte interphase (SEI) that kinetically suppresses the parasitic reactions between the lithiated 2 graphitic anodes and the carbonate-based non-aqueous electrolytes.more » Recently, major attention has been paid to the importance of a similar passivation/protection layer on the surface of cathode materials, aiming for rational design of high-energy-density lithiumion batteries with extended cycle/calendar life. In this article, the physical model of the solid electrolyte interphase, as well as the recent research effort to under the nature and role SEI are summarized, and future perspectives on this important research field will also be presented.« less

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.

Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.

PubMed

Kobayashi, Takeshi; Kobayashi, Yo; Tabuchi, Masato; Shono, Kumi; Ohno, Yasutaka; Mita, Yuichi; Miyashiro, Hajime

2013-12-11

The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.

Polymorphous Supercapacitors Constructed from Flexible Three-Dimensional Carbon Network/Polyaniline/MnO2 Composite Textiles.

PubMed

Wang, Jinjie; Dong, Liubing; Xu, Chengjun; Ren, Danyang; Ma, Xinpei; Kang, Feiyu

2018-04-04

Polymorphous supercapacitors were constructed from flexible three-dimensional carbon network/polyaniline (PANI)/MnO 2 composite textile electrodes. The flexible textile electrodes were fabricated through a layer-by-layer construction strategy: PANI, carbon nanotubes (CNTs), and MnO 2 were deposited on activated carbon fiber cloth (ACFC) in turn through an electropolymerization process, "dipping and drying" method, and in situ chemical reaction, respectively. In the fabricated ACFC/PANI/CNTs/MnO 2 textile electrodes, the ACFC/CNT hybrid framework serves as a porous and electrically conductive 3D network for the rapid transmission of electrons and electrolyte ions, where ACFC, PANI, and MnO 2 are high-performance supercapacitor electrode materials. In the electrolyte of H 2 SO 4 solution, the textile electrode-based symmetric supercapacitor delivers superior areal capacitance, energy density, and power density of 4615 mF cm -2 (for single electrode), 157 μW h cm -2 , and 10372 μW cm -2 , respectively, whereas asymmetric supercapacitor assembled with the prepared composite textile as the positive electrode and ACFC as the negative electrode exhibits an improved energy density of 413 μW h cm -2 and a power density of 16120 μW cm -2 . On the basis of the ACFC/PANI/CNTs/MnO 2 textile electrodes, symmetric and asymmetric solid-state textile supercapacitors with a PVA/H 2 SO 4 gel electrolyte were also produced. These solid-state textile supercapacitors exhibit good electrochemical performance and high flexibility. Furthermore, flexible solid-state fiber-like supercapacitors were prepared with fiber bundle electrodes dismantled from the above composite textiles. Overall, this work makes a meaningful exploration of the versatile applications of textile electrodes to produce polymorphous supercapacitors.

Characterization of thin films of the solid electrolyte Li(x)Mg(1-2x)Al(2+x)O4 (x = 0, 0.05, 0.15, 0.25).

PubMed

Put, Brecht; Vereecken, Philippe M; Mees, Maarten J; Rosciano, Fabio; Radu, Iuliana P; Stesmans, Andre

2015-11-21

RF-sputtered thin films of spinel Li(x)Mg(1-2x)Al(2+x)O4 were investigated for use as solid electrolyte. The usage of this material can enable the fabrication of a lattice matched battery stack, which is predicted to lead to superior battery performance. Spinel Li(x)Mg(1-2x)Al(2+x)O4 thin films, with stoichiometry (x) ranging between 0 and 0.25, were formed after a crystallization anneal as shown by X-ray diffraction and transmission electron microscopy. The stoichiometry of the films was evaluated by elastic recoil detection and Rutherford backscattering and found to be slightly aluminum rich. The excellent electronic insulation properties were confirmed by both current-voltage measurements as well as by copper plating tests. The electrochemical stability window of the material was probed using cyclic voltammetry. Lithium plating and stripping was observed together with the formation of a Li-Pt alloy, indicating that Li-ions passed through the film. This observation contradicted with impedance measurements at open circuit potential, which showed no apparent Li-ion conductivity of the film. Impedance spectroscopy as a function of potential showed the occurrence of Li-ion intercalation into the Li(x)Mg(1-2x)Al(2+x)O4 layers. When incorporating Li-ions in the material the ionic conductivity can be increased by 3 orders of magnitude. Therefore it is anticipated that the response of Li(x)Mg(1-2x)Al(2+x)O4 is more adequate for a buffer layer than as the solid electrolyte.

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

Oxygen partial pressure sensor

DOEpatents

Dees, D.W.

1994-09-06

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

Oxygen partial pressure sensor

DOEpatents

Dees, Dennis W.

1994-01-01

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

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.

3D Fiber-Network-Reinforced Bicontinuous Composite Solid Electrolyte for Dendrite-free Lithium Metal Batteries.

PubMed

Li, Dan; Chen, Long; Wang, Tianshi; Fan, Li-Zhen

2018-02-28

Replacement of flammable organic liquid electrolytes with solid Li + conductors is a promising approach to realize excellent performance of Li metal batteries. However, ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites through their grain boundaries, and polymer electrolytes are also faced with instability on the electrode/electrolyte interface and weak mechanical property. Here, we report a three-dimensional fiber-network-reinforced bicontinuous solid composite electrolyte with flexible Li + -conductive network (lithium aluminum titanium phosphate (LATP)/polyacrylonitrile), which helps to enhance electrochemical stability on the electrode/electrolyte interface by isolating Li and LATP and suppress Li dendrites growth by mechanical reinforcement of fiber network for the composite solid electrolyte. The composite electrolyte shows an excellent electrochemical stability after 15 days of contact with Li metal and has an enlarged tensile strength (10.72 MPa) compared to the pure poly(ethylene oxide)-bistrifluoromethanesulfonimide lithium salt electrolyte, leading to a long-term stability and safety of the Li symmetric battery with a current density of 0.3 mA cm -2 for 400 h. In addition, the composite electrolyte also shows good electrochemical and thermal stability. These results provide such fiber-reinforced membranes that present stable electrode/electrolyte interface and suppress lithium dendrite growth for high-safety all-solid-state Li metal batteries.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

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

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Electrochemical properties of composite cathodes using Sm doped layered perovskite for intermediate temperature-operating solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Baek, Seung-Wook; Azad, Abul K.; Irvine, John T. S.; Choi, Won Seok; Kang, Hyunil; Kim, Jung Hyun

2018-02-01

SmBaCo2O5+d (SBCO) showed the lowest observed Area Specific Resistance (ASR) value in the LnBaCo2O5+d (Ln: Pr, Nd, Sm, and Gd) oxide system for the overall temperature ranges tested. The ASR of a composite cathode (mixture of SBCO and Ce0.9Gd0.1O2-d) on a Ce0.9Gd0.1O2-d (CGO91) electrolyte decreased with respect to the CGO91 content; the percolation limit was also achieved for a 50 wt% SBCO and 50 wt% CGO91 (SBCO50) composite cathode. The ASRs of SBCO50 on the dense CGO91 electrolyte in the overall temperature range of 500-750 °C were relatively lower than those of SBCO50 on the CGO91 coated dense 8 mol% yttria-stabilized zirconia (8YSZ) electrolyte for the same temperature range. From 750 °C and for all higher temperatures tested, however, the ASRs of SBCO50 on the CGO91 coated dense 8YSZ electrolyte were lower than those of the CGO91 electrolyte. The maximum power densities of SBCO50 on the Ni-8YSZ/8YSZ/CGO91 buffer layer were 1.034 W cm-2 and 0.611 W cm-2 at 800 °C and 700 °C.

Green fabrication of composite cathode with attractive performance for solid oxide fuel cells through facile inkjet printing

NASA Astrophysics Data System (ADS)

Li, Chao; Chen, Huili; Shi, Huangang; Tade, Moses O.; Shao, Zongping

2015-01-01

The inkjet printing technique has numerous advantages and is attractive in solid oxide fuel cell (SOFC) fabrication, especially for the dense thin electrolyte layer because of its ultrafine powder size. In this study, we exploited the technique for the fabrication of a porous SDC/SSC composite cathode layer using environmentally friendly water-based ink. An optimized powder synthesis method was applied to the preparation of the well-dispersed suspension. In view of the easy sintering of the thin film layer prepared by inkjet printing, 10 wt.% pore former was introduced to the ink. The results indicate that the cell with the inkjet printing cathode layer exhibits a fantastic electrochemical performance, with a PPD as high as 940 mW cm-2 at 750 °C, which is comparable to that of a cell prepared using the conventional wet powder spraying method, suggesting a promising application of inkjet printing on electrode layer fabrication.

Ultrashort pulsed laser ablation for decollation of solid state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Hördemann, C.; Anand, H.; Gillner, A.

2017-08-01

Rechargeable lithium-ion batteries with liquid electrolytes are the main energy source for many electronic devices that we use in our everyday lives. However, one of the main drawbacks of this energy storage technology is the use of liquid electrolyte, which can be hazardous to the user as well as the environment. Moreover, lithium-ion batteries are limited in voltage, energy density and operating temperature range. One of the most novel and promising battery technologies available to overcome the above-mentioned drawbacks is the Solid-State Lithium-Ion Battery (SSLB). This battery type can be produced without limitations to the geometry and is also bendable, which is not possible with conventional batteries1 . Additionally, SSLBs are characterized by high volumetric and gravimetric energy density and are intrinsically safe since no liquid electrolyte is used2-4. Nevertheless, the manufacturing costs of these batteries are still high. The existing production-technologies are comparable to the processes used in the semiconductor industry and single cells are produced in batches with masked-deposition at low deposition rates. In order to decrease manufacturing costs and to move towards continuous production, Roll2Roll production methods are being proposed5, 6. These methods offer the possibility of producing large quantities of substrates with deposited SSLB-layers. From this coated substrate, single cells can be cut out. For the flexible decollation of SSLB-cells from the substrate, new manufacturing technologies have to be developed since blade-cutting, punching or conventional laser-cutting processes lead to short circuiting between the layers. Here, ultra-short pulsed laser ablation and cutting allows the flexible decollation of SSLBs. Through selective ablation of individual layers, an area for the cutting kerf is prepared to ensure a shortcut-free decollation.

Solid-State Electrolyte Anchored with a Carboxylated Azo Compound for All-Solid-State Lithium Batteries.

PubMed

Luo, Chao; Ji, Xiao; Chen, Ji; Gaskell, Karen J; He, Xinzi; Liang, Yujia; Jiang, Jianjun; Wang, Chunsheng

2018-05-23

Organic electrode materials are promising for green and sustainable lithium-ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all-solid-state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li 3 PS 4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4-(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of atmospheric-pressure plasma jet processed carbon nanotubes to liquid and quasi-solid-state gel electrolyte supercapacitors

NASA Astrophysics Data System (ADS)

Kuok, Fei-Hong; Kan, Ken-Yuan; Yu, Ing-Song; Chen, Chieh-Wen; Hsu, Cheng-Che; Cheng, I.-Chun; Chen, Jian-Zhang

2017-12-01

We use a dc-pulse nitrogen atmospheric-pressure plasma jet (APPJ) to calcine carbon nanotubes (CNTs) pastes that are screen-printed on carbon cloth. 30-s APPJ treatment can efficiently oxidize and vaporize the organic binders, thereby forming porous structures. As indicated by X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA), the oxygen content decreases after APPJ treatment owing to the oxidation and vaporization of ethyl cellulose, terpineol, and ethanol. Nitrogen doping was introduced to the materials by the nitrogen APPJ. APPJ-calcination improves the wettability of the CNTs printed on carbon cloth, as evidenced by water contact angle measurement. Raman spectroscopy indicates that reactive species of nitrogen APPJ react violently with CNTs in only 30-s APPJ processing time and introduce defects and/or surface functional groups on CNTs. Carbon cloths with calcined CNT layers are used as electrodes for liquid and quasi-solid-state electrolyte supercapacitors. Under a cyclic voltammetry test with a 2 mV/s potential scan rate, the specific capacitance is 73.84 F/g (areal capacitance = 5.89 mF/cm2) with a 2 M KCl electrolyte and 66.47 F/g (areal capacitance = 6.10 mF/cm2) with a H2SO4/polyvinyl alcohol (PVA) gel electrolyte.

Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

PubMed

Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

2018-05-09

The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

Bragg stack-functionalized counter electrode for solid-state dye-sensitized solar cells.

PubMed

Park, Jung Tae; Prosser, Jacob H; Kim, Dong Jun; Kim, Jong Hak; Lee, Daeyeon

2013-05-01

A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO(2) (om-TiO(2)) and colloidal SiO(2) (col-SiO(2)) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO(2) layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol-gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO(2) layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

1994-07-01

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

Cycling behavior of NCM523/graphite lithium-ion cells in the 3–4.4 V range: Diagnostic studies of full cells and harvested electrodes

DOE PAGES

Gilbert, James A.; Bareño, Javier; Spila, Timothy; ...

2016-09-22

Energy density of full cells containing layered-oxide positive electrodes can be increased by raising the upper cutoff voltage above the current 4.2 V limit. In this article we examine aging behavior of cells, containing LiNi 0.5Co 0.2Mn 0.3O 2 (NCM523)-based positive and graphite-based negative electrodes, which underwent up to ~400 cycles in the 3-4.4 V range. Electrochemistry results from electrodes harvested from the cycled cells were obtained to identify causes of cell performance loss; these results were complemented with data from X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) measurements. Our experiments indicate that the full cell capacitymore » fade increases linearly with cycle number and results from irreversible lithium loss in the negative electrode solid electrolyte interphase (SEI) layer. The accompanying electrode potential shift reduces utilization of active material in both electrodes and causes the positive electrode to cycle at higher states-of-charge. Here, full cell impedance rise on aging arises primarily at the positive electrode and results mainly from changes at the electrode-electrolyte interface; the small growth in negative electrode impedance reflects changes in the SEI layer. Our results indicate that cell performance loss could be mitigated by modifying the electrode-electrolyte interfaces through use of appropriate electrode coatings and/or electrolyte additives.« less

Performance of a hydrogen uranyl phosphate-carbon double-layer solid capacitor

NASA Astrophysics Data System (ADS)

Pham-Thi, M.; Adet, Ph.; Velasco, G.; Colomban, Ph.

1986-05-01

A mixture of commercially available carbon black (C) powders and hydrogen uranyl phosphate (HUP) precipitate can be used as the electrode material for miniaturized double-layer capacitors. A solid cell of C-HUP/HUP/C-HUP has a capacitance of 1 F which, given the device area and thickness of 0.8 sq cm and 0.2 cm respectively, corresponds to an energy density of more than 5 J/cu cm. The charge x voltage factor is higher than 5 x 10 to the -6th s and the working voltage is over 1.6 V. The leakage current is lower than 3 microamps at room temperature. The electrolyte can be operated up to about 120 C if the device is hermetically sealed.

Compositional control of continuously graded anode functional layer

NASA Astrophysics Data System (ADS)

McCoppin, J.; Barney, I.; Mukhopadhyay, S.; Miller, R.; Reitz, T.; Young, D.

2012-10-01

In this work, solid oxide fuel cells (SOFC's) are fabricated with linear-compositionally graded anode functional layers (CGAFL) using a computer-controlled compound aerosol deposition (CCAD) system. Cells with different CGAFL thicknesses (30 um and 50 um) are prepared with a continuous compositionally graded interface deposited between the electrolyte and anode support current collecting regions. The compositional profile was characterized using energy dispersive X-ray spectroscopic mapping. An analytical model of the compound aerosol deposition was developed. The model predicted compositional profiles for both samples that closely matched the measured profiles, suggesting that aerosol-based deposition methods are capable of creating functional gradation on length scales suitable for solid oxide fuel cell structures. The electrochemical performances of the two cells are analyzed using electrochemical impedance spectroscopy (EIS).

Fuel cells with solid polymer electrolyte and their application on vehicles

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

Fateev, V.

1996-04-01

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

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

Solid oxide fuel cells with apatite-type lanthanum silicate-based electrolyte films deposited by radio frequency magnetron sputtering

NASA Astrophysics Data System (ADS)

Liu, Yi-Xin; Wang, Sea-Fue; Hsu, Yung-Fu; Wang, Chi-Hua

2018-03-01

In this study, solid oxide fuel cells (SOFCs) containing high-quality apatite-type magnesium doped lanthanum silicate-based electrolyte films (LSMO) deposited by RF magnetron sputtering are successfully fabricated. The LSMO film deposited at an Ar:O2 ratio of 6:4 on an anode supported NiO/Sm0.2Ce0·8O2-δ (SDC) substrate followed by post-annealing at 1000 °C reveals a uniform and dense c-axis oriented polycrystalline structure, which is well adhered to the anode substrate. A composite SDC/La0·6Sr0·4Co0·2Fe0·8O3-δ cathode layer is subsequently screen-printed on the LSMO deposited anode substrate and fired. The SOFC fabricated with the LSMO film exhibits good mechanical integrity. The single cell with the LSMO layer of ≈2.8 μm thickness reports a total cell resistance of 1.156 and 0.163 Ωcm2, open circuit voltage of 1.051 and 0.982 V, and maximum power densities of 0.212 and 1.490 Wcm-2 at measurement temperatures of 700 and 850 °C, respectively, which are comparable or superior to those of previously reported SOFCs with yttria stabilized zirconia electrolyte films. The results of the present study demonstrate the feasibility of deposition of high-quality LSMO films by RF magnetron sputtering on NiO-SDC anode substrates for the fabrication of SOFCs with good cell performance.

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

NASA Astrophysics Data System (ADS)

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

2007-04-01

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

Lithium Azide as an Electrolyte Additive for All-Solid-State Lithium-Sulfur Batteries.

PubMed

Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide M; Zhang, Heng; Armand, Michel

2017-11-27

Of the various beyond-lithium-ion battery technologies, lithium-sulfur (Li-S) batteries have an appealing theoretical energy density and are being intensely investigated as next-generation rechargeable lithium-metal batteries. However, the stability of the lithium-metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long-term stability of Li-S batteries. Herein, we report lithium azide (LiN 3 ) as a novel electrolyte additive for all-solid-state Li-S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state-of-the-art additive lithium nitrate (LiNO 3 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operation of Thin-Film Electrolyte Metal-Supported Solid Oxide Fuel Cells in Lightweight and Stationary Stacks: Material and Microstructural Aspects

PubMed Central

Roehrens, Daniel; Packbier, Ute; Fang, Qingping; Blum, Ludger; Sebold, Doris; Bram, Martin; Menzler, Norbert

2016-01-01

In this study we report on the development and operational data of a metal-supported solid oxide fuel cell with a thin film electrolyte under varying conditions. The metal-ceramic structure was developed for a mobile auxiliary power unit and offers power densities of 1 W/cm2 at 800 °C, as well as robustness under mechanical, thermal and chemical stresses. A dense and thin yttria-doped zirconia layer was applied to a nanoporous nickel/zirconia anode using a scalable adapted gas-flow sputter process, which allowed the homogeneous coating of areas up to 100 cm2. The cell performance is presented for single cells and for stack operation, both in lightweight and stationary stack designs. The results from short-term operation indicate that this cell technology may be a very suitable alternative for mobile applications. PMID:28773883

An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes

PubMed Central

Fattah, N. F. A.; Ng, H. M.; Mahipal, Y. K.; Numan, Arshid; Ramesh, S.; Ramesh, K.

2016-01-01

Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge–discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g−1, which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application. PMID:28773573

An Approach to Solid-State Electrical Double Layer Capacitors Fabricated with Graphene Oxide-Doped, Ionic Liquid-Based Solid Copolymer Electrolytes.

PubMed

Fattah, N F A; Ng, H M; Mahipal, Y K; Numan, Arshid; Ramesh, S; Ramesh, K

2016-06-06

Solid polymer electrolyte (SPE) composed of semi-crystalline poly (vinylidene fluoride-hexafluoropropylene) [P(VdF-HFP)] copolymer, 1-ethyl-3-methylimidazolium bis (trifluoromethyl sulphonyl) imide [EMI-BTI] and graphene oxide (GO) was prepared and its performance evaluated. The effects of GO nano-filler were investigated in terms of enhancement in ionic conductivity along with the electrochemical properties of its electrical double layer capacitors (EDLC). The GO-doped SPE shows improvement in ionic conductivity compared to the P(VdF-HFP)-[EMI-BTI] SPE system due to the existence of the abundant oxygen-containing functional group in GO that assists in the improvement of the ion mobility in the polymer matrix. The complexation of the materials in the SPE is confirmed in X-ray diffraction (XRD) and thermogravimetric analysis (TGA) studies. The electrochemical performance of EDLC fabricated with GO-doped SPE is examined using cyclic voltammetry and charge-discharge techniques. The maximum specific capacitance obtained is 29.6 F∙g -1 , which is observed at a scan rate of 3 mV/s in 6 wt % GO-doped, SPE-based EDLC. It also has excellent cyclic retention as it is able keep the performance of the EDLC at 94% even after 3000 cycles. These results suggest GO doped SPE plays a significant role in energy storage application.

Selective laser melting porous metallic implants with immobilized silver nanoparticles kill and prevent biofilm formation by methicillin-resistant Staphylococcus aureus.

PubMed

van Hengel, Ingmar A J; Riool, Martijn; Fratila-Apachitei, Lidy E; Witte-Bouma, Janneke; Farrell, Eric; Zadpoor, Amir A; Zaat, Sebastian A J; Apachitei, Iulian

2017-09-01

Implant-associated infection and limited longevity are two major challenges that orthopedic devices need to simultaneously address. Additively manufactured porous implants have recently shown tremendous promise in improving bone regeneration and osseointegration, but, as any conventional implant, are threatened by infection. In this study, we therefore used rational design and additive manufacturing in the form of selective laser melting (SLM) to fabricate porous titanium implants with interconnected pores, resulting in a 3.75 times larger surface area than corresponding solid implants. The SLM implants were biofunctionalized by embedding silver nanoparticles in an oxide surface layer grown using plasma electrolytic oxidation (PEO) in Ca/P-based electrolytes. The PEO layer of the SLM implants released silver ions for at least 28 days. X-ray diffraction analysis detected hydroxyapatite on the SLM PEO implants but not on the corresponding solid implants. In vitro and ex vivo assays showed strong antimicrobial activity of these novel SLM PEO silver-releasing implants, without any signs of cytotoxicity. The rationally designed SLM porous implants outperformed solid implants with similar dimensions undergoing the same biofunctionalization treatment. This included four times larger amount of released silver ions, two times larger zone of inhibition, and one additional order of magnitude of reduction in numbers of CFU in an ex vivo mouse infection model. Copyright © 2017 Elsevier Ltd. All rights reserved.

Review on solid electrolytes for all-solid-state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

2018-06-01

All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

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

PubMed

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

2017-12-13

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

Prediction of battery storage ageing and solid electrolyte interphase property estimation using an electrochemical model

NASA Astrophysics Data System (ADS)

Ashwin, T. R.; Barai, A.; Uddin, K.; Somerville, L.; McGordon, A.; Marco, J.

2018-05-01

Ageing prediction is often complicated due to the interdependency of ageing mechanisms. Research has highlighted that storage ageing is not linear with time. Capacity loss due to storing the battery at constant temperature can shed more light on parametrising the properties of the Solid Electrolyte Interphase (SEI); the identification of which, using an electrochemical model, is systematically addressed in this work. A new methodology is proposed where any one of the available storage ageing datasets can be used to find the property of the SEI layer. A sensitivity study is performed with different molecular mass and densities which are key parameters in modelling the thickness of the SEI deposit. The conductivity is adjusted to fine tune the rate of capacity fade to match experimental results. A correlation is fitted for the side reaction variation to capture the storage ageing in the 0%-100% SoC range. The methodology presented in this paper can be used to predict the unknown properties of the SEI layer which is difficult to measure experimentally. The simulation and experimental results show that the storage ageing model shows good accuracy for the cases at 50% and 90% and an acceptable agreement at 20% SoC.

Preparation of a self-humidifying membrane electrode assembly for fuel cell and its performance analysis

NASA Astrophysics Data System (ADS)

Wang, Cheng; Mao, Zongqiang; Xu, Jingming; Xie, Xiaofeng; Yang, Lizhai

2003-10-01

A novel nano-porous material SiO2-gel was prepared. After being purified by H2O2, then protonized by H2SO4 and desiccated in vacuum, the SiO2-gel, mixed with Nafion solution, was coated between an electrode and a solid electrolyte, which made a new type of self-humidifying membrane electrode assembly. The SiO2 powder was characterized by FTIR, BET and XRD. The surface of the electrodes was characterized by SEM and EDS. The performances of the self-humidifying membrane electrodes were analyzed by polarization discharge and AC impedance under the operation modes of external humidification and self-humidification respectively. Experimental-results indicated that the SiO2 powder held super-hydrophilicity, and the layer of SiO2 and Nafion polymer between electrode and solid electrolyte expanded three-dimension electrochemistry reac-tion area, maintained stability of catalyst layer and enhanced back-diffusion of water from cathode to anode, so the PEM Fuel cell can generate electricity at self-humidification mode. The power density of single PEM fuel cell reached 1.5 W/cm2 under 0.2 Mpa, 70°C and dry hydrogen and oxygen.

Bubble-Sheet-Like Interface Design with an Ultrastable Solid Electrolyte Layer for High-Performance Dual-Ion Batteries.

PubMed

Qin, Panpan; Wang, Meng; Li, Na; Zhu, Haili; Ding, Xuan; Tang, Yongbing

2017-05-01

In this work, a bubble-sheet-like hollow interface design on Al foil anode to improve the cycling stability and rate performance of aluminum anode based dual-ion battery is reported, in which, a carbon-coated hollow aluminum anode is used as both anode materials and current collector. This anode structure can guide the alloying position inside the hollow nanospheres, and also confine the alloy sizes within the hollow nanospheres, resulting in significantly restricted volumetric expansion and ultrastable solid electrolyte interface (SEI). As a result, the battery demonstrates an excellent long-term cycling stability within 1500 cycles with ≈99% capacity retention at 2 C. Moreover, this cell displays an energy density of 169 Wh kg -1 even at high power density of 2113 W kg -1 (10 C, charge and discharge within 6 min), which is much higher than most of conventional lithium ion batteries. The interfacial engineering strategy shown in this work to stabilize SEI layer and control the alloy forming position could be generalized to promote the research development of metal anodes based battery systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

PubMed

Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

2017-03-09

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y 2 O 3 -ZrO 2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO 3-δ (LC) and Sm 0.95 CoO 3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm -2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm 0.95 Co 0.95 Pd 0.05 O 3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm -2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modified cermet fuel electrodes for solid oxide electrochemical cells

DOEpatents

Ruka, Roswell J.; Spengler, Charles J.

1991-01-01

An exterior porous electrode (10), bonded to a solid oxygen ion conducting electrolyte (13) which is in contact with an interior electrode (14), contains coarse metal particles (12) of nickel and/or cobalt, having diameters from 3 micrometers to 35 micrometers, where the coarse particles are coated with a separate, porous, multiphase layer (17) containing fine metal particles of nickel and/or cobalt (18), having diameters from 0.05 micrometers to 1.75 micrometers and conductive oxide (19) selected from cerium oxide, doped cerium oxide, strontium titanate, doped strontium titanate and mixtures thereof.

Method of forming a leak proof plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Kuo, Lewis J. H.; Vora, Shailesh D.

1995-01-01

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an electrode structure of an electrochemical cell by: (A) providing an electrode structure; (B) forming on a selected portion of the electrode surface, an interconnection layer having the general formula La.sub.1-x M.sub.x Cr.sub.1-y N.sub.y O.sub.3, where M is a dopant selected from the group of Ca, Sr, Ba, and mixtures thereof, and where N is a dopant selected from the group of Mg, Co, Ni, Al, and mixtures thereof, and where x and y are each independently about 0.075-0.25, by thermally spraying, preferably plasma arc spraying, a flux added interconnection spray powder, preferably agglomerated, the flux added powder comprising flux particles, preferably including dopant, preferably (CaO).sub.12. (Al.sub.2 O.sub.3).sub.7 flux particles including Ca and Al dopant, and LaCrO.sub.3 interconnection particles, preferably undoped LaCrO.sub.3, to form a dense and substantially gas-tight interconnection material bonded to the electrode structure by a single plasma spraying step; and, (C) heat treating the interconnection layer at from about 1200.degree. to 1350.degree. C. to further densify and heal the micro-cracks and macro-cracks of the thermally sprayed interconnection layer. The result is a substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode structure. The electrode structure can be an air electrode, and a solid electrolyte layer can be applied to the unselected portion of the air electrode, and further a fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell for generation of electrical power.

Method of forming a leak proof plasma sprayed interconnection layer on an electrode of an electrochemical cell

DOEpatents

Kuo, L.J.H.; Vora, S.D.

1995-02-21

A dense, substantially gas-tight, electrically conductive interconnection layer is formed on an electrode structure of an electrochemical cell by: (A) providing an electrode structure; (B) forming on a selected portion of the electrode surface, an interconnection layer having the general formula La{sub 1{minus}x}M{sub x}Cr{sub 1{minus}y}N{sub y}O{sub 3}, where M is a dopant selected from the group of Ca, Sr, Ba, and mixtures thereof, and where N is a dopant selected from the group of Mg, Co, Ni, Al, and mixtures thereof, and where x and y are each independently about 0.075--0.25, by thermally spraying, preferably plasma arc spraying, a flux added interconnection spray powder, preferably agglomerated, the flux added powder comprising flux particles, preferably including dopant, preferably (CaO){sub 12}(Al{sub 2}O{sub 3}){sub 7} flux particles including Ca and Al dopant, and LaCrO{sub 3} interconnection particles, preferably undoped LaCrO{sub 3}, to form a dense and substantially gas-tight interconnection material bonded to the electrode structure by a single plasma spraying step; and (C) heat treating the interconnection layer at from about 1,200 to 1,350 C to further densify and heal the micro-cracks and macro-cracks of the thermally sprayed interconnection layer. The result is a substantially gas-tight, highly doped, electrically conductive interconnection material bonded to the electrode structure. The electrode structure can be an air electrode, and a solid electrolyte layer can be applied to the unselected portion of the air electrode, and further a fuel electrode can be applied to the solid electrolyte, to form an electrochemical cell for generation of electrical power. 4 figs.

Gate-Induced Metal–Insulator Transition in MoS 2 by Solid Superionic Conductor LaF 3

DOE PAGES

Wu, Chun-Lan; Yuan, Hongtao; Li, Yanbin; ...

2018-03-23

Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 10 14 cm –2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, wemore » demonstrate an all solid-state EDL device based on a solid superionic conductor LaF 3, which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF 3 EDL transistors (EDLTs), we observe the metal–insulator transition in MoS 2. Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS 2 transistors. Finally, this result shows the powerful gating capability of LaF 3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.« less

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

NASA Astrophysics Data System (ADS)

Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

2018-04-01

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

Electric double-layer capacitor based on an ionic clathrate hydrate.

PubMed

Lee, Wonhee; Kwon, Minchul; Park, Seongmin; Lim, Dongwook; Cha, Jong-Ho; Lee, Huen

2013-07-01

Herein, we suggest a new approach to an electric double-layer capacitor (EDLC) that is based on a proton-conducting ionic clathrate hydrate (ICH). The ice-like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me4NOH⋅5 H2O show a high specific capacitance, reversible charge-discharge behavior, and a long cycle life. The ionic-hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre-treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more-favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High temperature solid state storage cell

DOEpatents

Rea, Jesse R.; Kallianidis, Milton; Kelsey, G. Stephen

1983-01-01

A completely solid state high temperature storage cell comprised of a solid rechargeable cathode such as TiS.sub.2, a solid electrolyte which remains solid at the high temperature operating conditions of the cell and which exhibits high ionic conductivity at such elevated temperatures such as an electrolyte comprised of lithium iodide, and a solid lithium or other alkali metal alloy anode (such as a lithium-silicon alloy) with 5-50% by weight of said anode being comprised of said solid electrolyte.

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.

Surface protected lithium-metal-oxide electrodes

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho

2016-04-05

A lithium-metal-oxide positive electrode having a layered or spinel structure for a non-aqueous lithium electrochemical cell and battery is disclosed comprising electrode particles that are protected at the surface from undesirable effects, such as electrolyte oxidation, oxygen loss or dissolution by one or more lithium-metal-polyanionic compounds, such as a lithium-metal-phosphate or a lithium-metal-silicate material that can act as a solid electrolyte at or above the operating potential of the lithium-metal-oxide electrode. The surface protection significantly enhances the surface stability, rate capability and cycling stability of the lithium-metal-oxide electrodes, particularly when charged to high potentials.

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.

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

PubMed

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

2018-06-13

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

Extensive ionic partitioning in interfaces that membranous and biomimetic surfaces form with electrolytes: Antitheses of the gold-electrolyte interface

NASA Astrophysics Data System (ADS)

Chilcott, Terry; Guo, Chuan; Coster, Hans

2013-04-01

Maxwell-Wagner modeling of electrical impedance measurements of tetradecane-electrolyte systems yielded three interfacial layers between the tetradecane layer and the bulk electrolytes of concentration ranging from 1-300 mM KCl whereas the gold-electrolyte system yielded only one layer. The conductivity and thickness for the surface layer were orders of magnitude different from that expected for the Gouy-Chapman layer and did not reflect dependencies of the Debye length on concentration. Conductivity values for the three layers were less than those of the bulk electrolyte but exhibited a dependency on concentration similar to that expected for the bulk. Thickness values for the layers indicate an interface extending ~106 Å into the bulk electrolyte, which contrasts with the gold-electrolyte interface that extended only 20-30 Å into the bulk. Maxwell-Wagner characterizations of both interfaces were consistent with spatial distributions of ionic partitioning arising from the Born energy as determined by the dielectric properties of the substrates and electrolyte. The distributions for the membranous and silicon interfaces were similar but the antitheses of that for the gold interface.

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

DOE PAGES

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.

Solid polymer electrolyte composite membrane comprising laser micromachined porous support

DOEpatents

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

2011-01-11

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

Solid polymer electrolyte composite membrane comprising plasma etched porous support

DOEpatents

Liu, Han; LaConti, Anthony B.

2010-10-05

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

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 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-Li 3PS 4 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 decreasedmore » 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-Li 3PS 4 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

Development of planar solid oxide fuel cells for power generation applications

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

Minh, N.Q.

1996-04-01

Planar solid oxide fuel cells (SOFCs) are presently being developed for a variety of electric power generation application. The planar design offers simple cell geometry, high power density, and multiple fabrication and gas manifolding options. Planar SOFC technology has received much attention recently, and significant progress has been made in this area. Recent effort at AlliedSignal has focused on the development of high-performance, lightweight planar SOFCs, having thin-electrolyte films, that can be operated efficiently at reduced temperatures (< 1000{degrees}C). The advantages of reduced-temperature operation include wider material choice (including use of metallic interconnects), expected longer cell life, reduced thermal stress,more » improved reliability, and reduced fuel cell cost. The key aspect in the development of thin-film SIFCs is to incorporate the thin electrolyte layer into the desired structure of cells in a manner that yields the required characteristics. AlliedSignal has developed a simple and cost-effective method based on tape calendering for the fabrication of thin-electrolyte SOFCs. Thin-electrolyte cells made by tape calendering have shown extraordinary performance, e.g., producing more than 500mW/cm{sup 2} at 700{degrees}C and 800mW/cm{sup 2} at 800{degrees}C with hydrogen as fuel and air is oxidant. thin-electrolyte single cells have been incorporated into a compliant metallic stack structure and operated at reduced and operated at reduced-temperature conditions.« less

Developing Cost-Effective Dense Continuous SDC Barrier Layers for SOFCs

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

Nguyen, Hoang Viet P.; Hardy, John S.; Coyle, Christopher A.

Significantly improved performance during electrochemical testing of a cell with a dense continuous pulsed laser deposited (PLD) samarium doped ceria (SDC) layer spurred investigations into the fabrication of dense continuous SDC barrier layers by means of cost-effective deposition using screen printing which is amenable to industrial production of SOFCs. Many approaches to improve the SDC density have been explored including the use of powder with reduced particle sizes, inks with increased solids loading, and doping with sintering aids (1). In terms of sintering aids, dopants like Mo or binary systems of Mo+Cu or Fe+Co greatly enhance SDC sinterability. In fact,more » adding dopants to a screen printed, prefired, porous SDC layer made it possible to achieve a dense continuous barrier layer atop the YSZ electrolyte without sintering above 1200°C. Although the objective of fabricating a dense continuous layer was achieved, additional studies have been initiated to improve the cell performance. Underlying issues with constrained sintering and dopant-enhanced ceria-zirconia solid solubility are also addressed in this paper.« less

Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

PubMed

Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

2018-04-25

Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

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.

Electrochromic device containing metal oxide nanoparticles and ultraviolet blocking material

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

Garcia, Guillermo; Koo, Bonil; Gregoratto, Ivano

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant. The electrochromic device also includes nanoparticles containing one or more transparent conducting oxide (TCO), a solid state electrolyte, a counter electrode, and at least one protective layer to prevent degradation of the one or more nanostructured transition metal oxide bronze. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) and visible radiation as a function of an applied voltage to the device.

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, M.; Abraham, K.M.

1993-10-12

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

Solid polymer electrolyte lithium batteries

DOEpatents

Alamgir, Mohamed; Abraham, Kuzhikalail M.

1993-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

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

Mehdi, Beata L.; Qian, Jiangfeng; Nasybulin, Eduard

Lithium (Li)-ion batteries are currently used for a wide variety of portable electronic devices, electric vehicles and renewable energy applications. In addition, extensive worldwide research efforts are now being devoted to more advanced “beyond Li-ion” battery chemistries - such as lithium-sulfur (Li-S) and lithium-air (Li-O2) - in which the carbon anode is replaced with Li metal. However, the practical application of Li metal anode systems has been highly problematic. The main challenges involve controlling the formation of a solid-electrolyte interphase (SEI) layer and the suppression of Li dendrite growth during the charge/discharge process (achieving “dendrite-free” cycling). The SEI layer formationmore » continuously consumes the electrolyte components creating highly resistive layer, which leads to the rapid decrease of cycling performance and degradation of the Li anode. The growth of Li metal dendrites at the anode contributes to rapid capacity fading (the presence of “dead Li” created during the discharge leads to an increased overpotential) and, in the case of continuous growth, leads to internal short circuits and extreme safety issues. Here we demonstrate the application of an operando electrochemical scanning transmission electron microscopy (ec-(S)TEM) cell to study the SEI layer formation and the initial stages of Li dendrite growth - the goal is to develop a mechanism for mitigating the degradation processes and increasing safety. Bright field (BF) STEM images in Figure 1 A-C show Li metal deposition and dissolution processes at the interface between the Pt working electrode and the lithium hexafluorophosphate (LiPF6) in propylene carbonate (PC) electrolyte during three charge/discharge cycles. A contrast reversal caused by Li metal being lighter/less dense than surrounding electrolyte (Li appears brighter than the background in BF STEM images) allows Li to be uniquely identified from the other components in the system - the only solid material that is less dense than the electrolyte is Li metal. Using these images, we can precisely quantify the total volume of Li deposition, the thickness of the SEI layer (observed as a ring of positive contrast around the electrode) and alloy formation due to Li+ ion insertion during each cycle. Furthermore, at the end of each discharge cycle we can quantify the presence of “dead Li” detached from the Pt electrode, thereby demonstrating the degree of irreversibility (and degradation of Pt electrode) associated with insertion/removal of Li+during this process with direct correlation to electrochemical performance. Such analyses provide significant insights into Li metal dendrite growth, which is critical to understand the complex interfacial reactions needed to be controlled for future Li-based and next generation energy storage systems.« less

Fuel cell with electrolyte feed system

DOEpatents

Feigenbaum, Haim

1984-01-01

A fuel cell having a pair of electrodes at the sites of electrochemical reactions of hydrogen and oxygen and a phosphoric acid electrolyte provided with an electrolyte supporting structure in the form of a laminated matrix assembly disposed between the electrodes. The matrix assembly is formed of a central layer disposed between two outer layers, each being permeable to the flow of the electrolyte. The central layer is provided with relatively large pores while the outer layers are provided with relatively small pores. An external reservoir supplies electrolyte via a feed means to the central layer to compensate for changes in electrolyte volume in the matrix assembly during the operation of fuel cell.

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

PubMed

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

2018-05-07

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

The mechanics of pressed-pellet separators in molten salt batteries

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

Long, Kevin Nicholas; Roberts, Christine Cardinal; Roberts, Scott Alan

2014-06-01

We present a phenomenological constitutive model that describes the macroscopic behavior of pressed-pellet materials used in molten salt batteries. Such materials include separators, cathodes, and anodes. The purpose of this model is to describe the inelastic deformation associated with the melting of a key constituent, the electrolyte. At room temperature, all constituents of these materials are solid and do not transport cations so that the battery is inert. As the battery is heated, the electrolyte, a constituent typically present in the separator and cathode, melts and conducts charge by flowing through the solid skeletons of the anode, cathode, and separator.more » The electrochemical circuit is closed in this hot state of the battery. The focus of this report is on the thermal-mechanical behavior of the separator, which typically exhibits the most deformation of the three pellets during the process of activating a molten salt battery. Separator materials are composed of a compressed mixture of a powdered electrolyte, an inert binder phase, and void space. When the electrolyte melts, macroscopically one observes both a change in volume and shape of the separator that depends on the applied boundary conditions during the melt transition. Although porous flow plays a critical role in the battery mechanics and electrochemistry, the focus of this report is on separator behavior under flow-free conditions in which the total mass of electrolyte is static within the pellet. Specific poromechanics effects such as capillary pressure, pressure-saturation, and electrolyte transport between layers are not considered. Instead, a phenomenological model is presented to describe all such behaviors including the melting transition of the electrolyte, loss of void space, and isochoric plasticity associated with the binder phase rearrangement. The model is appropriate for use finite element analysis under finite deformation and finite temperature change conditions. The model reasonably describes the stress dependent volume and shape change associated with dead load compression and spring-type boundary conditions; the latter is relevant in molten salt batteries. Future work will transition the model towards describing the solid skeleton of the separator in the traditional poromechanics context.« less

Top-down Approach for the Direct Synthesis, Patterning, and Operation of Artificial Micromuscles on Flexible Substrates.

PubMed

Maziz, Ali; Plesse, Cédric; Soyer, Caroline; Cattan, Eric; Vidal, Frédéric

2016-01-27

Recent progress in the field of microsystems on flexible substrates raises the need for alternatives to the stiffness of classical actuation technologies. This paper reports a top-down process to microfabricate soft conducting polymer actuators on substrates on which they ultimately operate. The bending microactuators were fabricated by sequentially stacking layers using a layer polymerization by layer polymerization of conducting polymer electrodes and a solid polymer electrolyte. Standalone microbeams thinner than 10 μm were fabricated on SU-8 substrates associated with a bottom gold electrical contact. The operation of microactuators was demonstrated in air and at low voltage (±4 V).

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.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystallization behavior of the Li2S-P2S5 glass electrolyte in the LiNi1/3Mn1/3Co1/3O2 positive electrode layer.

PubMed

Tsukasaki, Hirofumi; Mori, Yota; Otoyama, Misae; Yubuchi, So; Asano, Takamasa; Tanaka, Yoshinori; Ohno, Takahisa; Mori, Shigeo; Hayashi, Akitoshi; Tatsumisago, Masahiro

2018-04-18

Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) and 75Li 2 S·25P 2 S 5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the β-Li 3 PS 4 precipitated at approximately 200 °C, and then Li 4 P 2 S 6 and Li 2 S precipitated at approximately 400 °C. Because the Li 4 P 2 S 6 and Li 2 S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.

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

Wu, Chun-Lan; Yuan, Hongtao; Li, Yanbin

Electric-double-layer (EDL) gating with liquid electrolyte has been a powerful tool widely used to explore emerging interfacial electronic phenomena. Due to the large EDL capacitance, a high carrier density up to 10 14 cm –2 can be induced, directly leading to the realization of field-induced insulator to metal (or superconductor) transition. However, the liquid nature of the electrolyte has created technical issues including possible side electrochemical reactions or intercalation, and the potential for huge strain at the interface during cooling. In addition, the liquid coverage of active devices also makes many surface characterizations and in situ measurements challenging. Here, wemore » demonstrate an all solid-state EDL device based on a solid superionic conductor LaF 3, which can be used as both a substrate and a fluorine ionic gate dielectric to achieve a wide tunability of carrier density without the issues of strain or electrochemical reactions and can expose the active device surface for external access. Based on LaF 3 EDL transistors (EDLTs), we observe the metal–insulator transition in MoS 2. Interestingly, the well-defined crystal lattice provides a more uniform potential distribution in the substrate, resulting in less interface electron scattering and therefore a higher mobility in MoS 2 transistors. Finally, this result shows the powerful gating capability of LaF 3 solid electrolyte for new possibilities of novel interfacial electronic phenomena.« less

A complete carbon counter electrode for high performance quasi solid state dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Arbab, Alvira Ayoub; Peerzada, Mazhar Hussain; Sahito, Iftikhar Ali; Jeong, Sung Hoon

2017-03-01

The proposed research describes the design and fabrication of a quasi-solid state dye sensitized solar cells (Q-DSSCs) with a complete carbon based counter electrode (CC-CE) and gel infused membrane electrolyte. For CE, the platinized fluorinated tin oxide glass (Pt/FTO) was replaced by the soft cationic functioned multiwall carbon nanotubes (SCF-MWCNT) catalytic layer coated on woven carbon fiber fabric (CFF) prepared on handloom by interlacing of carbon filament tapes. SCF-MWCNT were synthesized by functionalization of cationised lipase from Candida Ragusa. Cationised enzyme solution was prepared at pH ∼3 by using acetic acid. The cationic enzyme functionalization of MWCNT causes the minimum damage to the tubular morphology and assist in fast anchoring of negative iodide ions present in membrane electrolyte. The high electrocatalytic activity and low charge transfer resistance (RCT = 2.12 Ω) of our proposed system of CC-CE shows that the woven CFF coated with cationised lipase treated carbon nanotubes enriched with positive surface ions. The Q-DSSCs fabricated with CC-CE and 5 wt% PEO gel infused PVDF-HFP membrane electrolyte exhibit power conversion efficiency of 8.90% under masking. Our suggested low cost and highly efficient system of CC-CE helps the proposed quasi-solid state DSSCs structure to stand out as sustainable next generation solar cells.

Effects of Propylene Carbonate Content in CsPF 6 -Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-15

The effects Of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite parallel to LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly-affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs+ additive. The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation ofmore » a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li+ ions and allows fast Li+ ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite parallel to NCA full cells under a wide temperature range. The fundamental findings also shed light On the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.« less

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Method of making a layered composite electrode/electrolyte

DOEpatents

Visco, Steven J.; Jacobson, Craig P.; DeJonghe, Lutgard C.

2005-01-25

An electrode/electrolyte structure is prepared by a plurality of methods. An unsintered (possibly bisque fired) moderately catalytic electronically-conductive or homogeneous mixed ionic electronic conductive electrode material is deposited on a layer composed of a sintered or unsintered ionically-conductive electrolyte material prior to being sintered. A layer of particulate electrode material is deposited on an unsintered ("green") layer of electrolyte material and the electrode and electrolyte layers are sintered simultaneously, sometimes referred to as "co-firing," under conditions suitable to fully densify the electrolyte while the electrode retains porosity. Or, the layer of particulate electrode material is deposited on a previously sintered layer of electrolyte, and then sintered. Subsequently, a catalytic material is added to the electrode structure by infiltration of an electrolcatalyst precursor (e.g., a metal salt such as a transition metal nitrate). This may be followed by low temperature firing to convert the precursor to catalyst. The invention allows for an electrode with high electronic conductivity and sufficient catalytic activity to achieve high power density in an ionic (electrochemical) device such as fuel cells and electrolytic gas separation systems.

The role of ultra-thin SiO2 layers in metal-insulator-semiconductor (MIS) photoelectrochemical devices (Presentation Recording)

NASA Astrophysics Data System (ADS)

Esposito, Daniel V.

2015-08-01

Solid-state junctions based on a metal-insulator-semiconductor (MIS) architecture are of great interest for a number of optoelectronic applications such as photovoltaics, photoelectrochemical cells, and photodetection. One major advantage of the MIS junction compared to the closely related metal-semiconductor junction, or Schottky junction, is that the thin insulating layer (1-3 nm thick) that separates the metal and semiconductor can significantly reduce the density of undesirable interfacial mid-gap states. The reduction in mid-gap states helps "un-pin" the junction, allowing for significantly higher built-in-voltages to be achieved. A second major advantage of the MIS junction is that the thin insulating layer can also protect the underlying semiconductor from corrosion in an electrochemical environment, making the MIS architecture well-suited for application in (photo)electrochemical applications. In this presentation, discontinuous Si-based MIS junctions immersed in electrolyte are explored for use as i.) photoelectrodes for solar-water splitting in photoelectrochemical cells (PECs) and ii.) position-sensitive photodetectors. The development and optimization of MIS photoelectrodes for both of these applications relies heavily on understanding how processing of the thin SiO2 layer impacts the properties of nano- and micro-scale MIS junctions, as well as the interactions of the insulating layer with the electrolyte. In this work, we systematically explore the effects of insulator thickness, synthesis method, and chemical treatment on the photoelectrochemical and electrochemical properties of these MIS devices. It is shown that electrolyte-induced inversion plays a critical role in determining the charge carrier dynamics within the MIS photoelectrodes for both applications.

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.

Interfacial Effects in Solid-Liquid Electrolytes for Improved Stability and Performance of Dye-Sensitized Solar Cells.

PubMed

Bella, Federico; Popovic, Jelena; Lamberti, Andrea; Tresso, Elena; Gerbaldi, Claudio; Maier, Joachim

2017-11-01

With the purpose of achieving stable dye-sensitized solar cells (DSSCs) with high efficiency, a new type of soft matter electrolyte is tested in which specific amounts of nanosized silica particles are finely dispersed in short-chained polyethylene glycol dimethylether encompassing an iodide/triiodide redox mediator. This results in a solid-liquid composite having synergistic electrical and favorable mechanical properties. The combination of interfacial effects and particle network formation promotes enhanced ion transport, which directly impacts the short-circuit photocurrent density. Thorough analysis reveals that this newly elaborated class of electrolytes is able to improve, at the same time, the thermal and long-term stability of DSSCs, as well as power conversion efficiency under standard and lower irradiation intensities. Lab-scale devices with champion efficiency exceeding 11% under attenuated sunlight (20 mW cm -2 , with a compact TiO 2 blocking layer) are obtained, along with impressively stable performance under both thermal stress and light soaking in an indoor environment (>96% performance retention after 2500 h of accelerated aging under full sun alternated with thermal ramps), matching the durability criteria applied to silicon solar cells for outdoor applications. The new findings might foster widespread practical application of DSSCs.

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, A.O.

1987-03-10

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection. 1 fig.

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, Arnold O.

1987-01-01

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection.

A high-conduction Ge substituted Li3AsS4 solid electrolyte with exceptional low activation energy

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

Sahu, Gayatri; Rangasamy, Ezhiylmurugan; Li, Juchuan

2014-04-16

In lithium-ion conducting solid electrolytes the potential to enable high-energy-density secondary batteries and offer distinctive safety features as an advantage over traditional liquid electrolytes is shown. Achieving the combination of high ionic conductivity, low activation energy, and outstanding electrochemical stability in crystalline solid electrolytes is a challenge for the synthesis of novel solid electrolytes. We report an exceptionally low activation energy (Ea) and high room temperature superionic conductivity via facile aliovalent substitution of Li 3AsS 4 by Ge, which increased the conductivity by two orders of magnitude as compared to the parent compound. The composition Li 3.334Ge 0.334As 0.666S 4more » has a high ionic conductivity of 1.12 mScm -1 at 27°C. Local Li + hopping in this material is accompanied by distinctive low activation energy Ea of 0.17 eV being the lowest of Li + solid conductors. Finally, our study demonstrates the efficacy of surface passivation of solid electrolyte to achieve compatibility with metallic lithium electrodes.« less

Curvature in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Li, Wenxia; Hasinska, Kathy; Seabaugh, Matt; Swartz, Scott; Lannutti, John

At this point in history, curvature is inherent to the laminated components that comprise solid oxide fuel cells (SOFCs). Surprisingly, however, this fact has never been previously quantified in the literature. In addition, potential curvature changes associated with NiO reduction and re-oxidation during operation have not been investigated. In this report, an optical profilometer was employed to non-destructively quantify the surface curvature or cracking behavior observed on a large scale in industrially manufactured cells. This provides insights into the challenges that the component materials face as well as additional appreciation for why, in spite of a concerted effort to commercialize SOFC power generation, all currently manufactured SOFC stacks fail. Our results demonstrate that cracked electrolyte areas (caused by differential sintering) are flatter than uncracked regions. The height of the electrolyte surface ranged from 86 to 289 μm above the baseline following sintering. Reduction typically results in increases in curvature of up to 214 μm. Initial crack density appears to affect curvature evolution during reduction; the higher the crack density, the smaller the curvature increase following reduction at 600 °C. In general, however, we observed that the electrolyte layer is remarkably resistant to further cracking during these typographic changes. Following oxidation at 750 °C, large changes in curvature (up to 280 μm) are noted that appear to be related to the strength of the bond between the electrolyte and the underlying anode.

Recent Developments of All-Solid-State Lithium Secondary Batteries with Sulfide Inorganic Electrolytes.

PubMed

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

2018-04-20

Due to the increasing demand of security and energy density, all-solid-state lithium ion batteries have become the promising next-generation energy storage devices to replace the traditional liquid batteries with flammable organic electrolytes. In this Minireview, we focus on the recent developments of sulfide inorganic electrolytes for all-solid-state batteries. The challenges of assembling bulk-type all-solid-state batteries for industrialization are discussed, including low ionic conductivity of the present sulfide electrolytes, high interfacial resistance and poor compatibility between electrolytes and electrodes. Many efforts have been focused on the solutions for these issues. Although some progresses have been achieved, it is still far away from practical application. The perspectives for future research on all-solid-state lithium ion batteries are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Tubular solid oxide fuel cells with porous metal supports and ceramic interconnections

DOEpatents

Huang, Kevin [Export, PA; Ruka, Roswell J [Pittsburgh, PA

2012-05-08

An intermediate temperature solid oxide fuel cell structure capable of operating at from 600.degree. C. to 800.degree. C. having a very thin porous hollow elongated metallic support tube having a thickness from 0.10 mm to 1.0 mm, preferably 0.10 mm to 0.35 mm, a porosity of from 25 vol. % to 50 vol. % and a tensile strength from 700 GPa to 900 GPa, which metallic tube supports a reduced thickness air electrode having a thickness from 0.010 mm to 0.2 mm, a solid oxide electrolyte, a cermet fuel electrode, a ceramic interconnection and an electrically conductive cell to cell contact layer.

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

AlF 3 Surface-Coated Li[Li 0.2 Ni 0.17 Co 0.07 Mn 0.56 ]O 2 Nanoparticles with Superior Electrochemical Performance for Lithium-Ion Batteries

DOE PAGES

Sun, Shuwei; Yin, Yanfeng; Wan, Ning; ...

2015-06-24

For Li-rich layered cathode materials considerable attention has been paid owing to their high capacity performance for Li-ion batteries (LIBs). In our work, layered Li-rich Li[Li 0.2Ni 0.17Co 0.07Mn 0.56]O 2 nanoparticles are surface-modified with AlF 3 through a facile chemical deposition method. The AlF 3 surface layers have little impact on the structure of the material and act as buffers to prevent the direct contact of the electrode with the electrolyte; thus, they enhance the electrochemical performance significantly. The 3 wt% AlF 3-coated Li-rich electrode exhibits the best cycling capability and has a considerably enhanced capacity retention of 83.1%more » after 50 cycles. Moreover, the rate performance and thermal stability of the 3 wt% AlF3-coated electrode are also clearly improved. Finally, surface analysis indicates that the AlF 3 coating layer can largely suppress the undesirable growth of solid electrolyte interphase (SEI) film and, therefore, stabilizes the structure upon cycling.« less

Epitaxial thin films

DOEpatents

Hunt, Andrew Tye; Deshpande, Girish; Lin, Wen-Yi; Jan, Tzyy-Jiuan

2006-04-25

Epitatial thin films for use as buffer layers for high temperature superconductors, electrolytes in solid oxide fuel cells (SOFC), gas separation membranes or dielectric material in electronic devices, are disclosed. By using CCVD, CACVD or any other suitable deposition process, epitaxial films having pore-free, ideal grain boundaries, and dense structure can be formed. Several different types of materials are disclosed for use as buffer layers in high temperature superconductors. In addition, the use of epitaxial thin films for electrolytes and electrode formation in SOFCs results in densification for pore-free and ideal gain boundary/interface microstructure. Gas separation membranes for the production of oxygen and hydrogen are also disclosed. These semipermeable membranes are formed by high-quality, dense, gas-tight, pinhole free sub-micro scale layers of mixed-conducting oxides on porous ceramic substrates. Epitaxial thin films as dielectric material in capacitors are also taught herein. Capacitors are utilized according to their capacitance values which are dependent on their physical structure and dielectric permittivity. The epitaxial thin films of the current invention form low-loss dielectric layers with extremely high permittivity. This high permittivity allows for the formation of capacitors that can have their capacitance adjusted by applying a DC bias between their electrodes.

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

NASA Astrophysics Data System (ADS)

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

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

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.; Burrows, B.

1972-01-01

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Baroelectric Effects in Systems with Solid Electrolytes

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

Malov, Y.I.; Sherstnov, S.A.; Ukshe, E.A.

1985-07-01

This paper presents results obtained when measuring the baro-emf of the system Ag/1.1Na/sub 2/O.11A1/sub 2/O/sub 3//Ag at room temperature. The characteristic time dependence of the baro-emf is shown. In all cases the electrode experiencing the higher pressure was at the more negative potential. The signal decays slowly when the pressure is taken off; sometimes the emf will even change sign before the steady-state potential difference is established, which is close to zero. The effects of double-layer relaxation and elastic deformation of the electrolyte's rigid lattice evidently should determine the gradual decay of the emf after load removal.

Anion-Dependent Potential Precycling Effects on Lithium Deposition/Dissolution Reaction Studied by an Electrochemical Quartz Crystal Microbalance.

PubMed

Smaran, Kumar Sai; Shibata, Sae; Omachi, Asami; Ohama, Ayano; Tomizawa, Eika; Kondo, Toshihiro

2017-10-19

The electrochemical quartz crystal microbalance technique was employed to study the initial stage of the electrodeposition and dissolution of lithium utilizing three kinds of electrolyte solutions such as LiPF 6 , LiTFSI, or LiFSI in tetraglyme. The native-SEI (solid-electrolyte interphase) formed by a potential prescan before lithium deposition/dissolution in all three solutions. Simultaneous additional SEI (add-SEI) deposition and its dissolution with lithium deposition and dissolution, respectively, were observed in LiPF 6 and LiTFSI. Conversely, the add-SEI dissolution with lithium deposition and its deposition with lithium dissolution were observed in LiFSI. Additional potential precycling resulted in the accumulation of a "pre-SEI" layer over the native-SEI layer in all of the solutions. With the pre-SEI, only lithium deposition/dissolution were significantly observed in LiTFSI and LiFSI. On the basis of the potential dependences of the mass and resistance changes, the anion-dependent effects of such a pre-SEI layer presence/absence on the lithium deposition/dissolution processes were discussed.

Polymer stability and function for electrolyte and mixed conductor applications

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

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.

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

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

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

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 40more » 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.« less

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

PubMed

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

2017-10-26

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

In Situ Study of Silicon Electrode Lithiation with X-ray Reflectivity

DOE PAGES

Cao, Chuntian; Steinrück, Hans-Georg; Shyam, Badri; ...

2016-10-26

Surface sensitive X-ray reflectivity (XRR) measurements were performed to investigate the electrochemical lithiation of a native oxide terminated single crystalline silicon (100) electrode in real time during the first galvanostatic discharge cycle. This allows us to gain nanoscale, mechanistic insight into the lithiation of Si and the formation of the solid electrolyte interphase (SEI). We describe an electrochemistry cell specifically designed for in situ XRR studies and have determined the evolution of the electron density profile of the lithiated Si layer (Li xSi) and the SEI layer with subnanometer resolution. We propose a three-stage lithiation mechanism with a reaction limited,more » layer-by-layer lithiation of the Si at the Li xSi/Si interface.« less

Stability of the electroosmotic flow of a two-layer electrolyte-dielectric system with external pressure gradient⋆.

PubMed

Gorbacheva, E V; Ganchenko, G S; Demekhin, E A

2018-03-27

The stability of the electroosmotic flow of electrolyte-dielectric viscous liquids under the influence of the DC and AC electric fields along with the external pressure gradient is studied theoretically. Liquids are bounded by two infinite parallel plates. The lower wall bordering the electrolyte is assumed to be a charged surface, and the upper wall is electrically isolated. The charge at the lower boundary is assumed to be immobile, while the surface charge at the free surface is assumed to be mobile. In this paper, we study the micro- and nanosized liquid layers. The mathematical model is described by a nonlinear system of the Nernst-Planck-Poisson-Stokes partial differential equations with the appropriate boundary conditions on the solid surface, the electrolyte/dielectric interface, and on the upper wall. The pressure gradient is highly important for the stability of the flow. For the DC case, the external pressure could either stabilize and destabilize the flow depending on the relative directions of the electroosmotic flow and the pressure-driven flow. For the AC case, the dependence on the value of the external pressure is not monotonous for different wave numbers of perturbations, but, as a rule, the external pressure destabilizes the flow. As the frequency of the electric field increases, the one-dimensional solution of the problem becomes stable.

Carbon Nanotube-CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability.

PubMed

Wang, Xinran; Gu, Wentian; Lee, Jung Tae; Nitta, Naoki; Benson, Jim; Magasinski, Alexandre; Schauer, Mark W; Yushin, Gleb

2015-10-01

Transition metal fluorides (MFx ) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion-type cathode materials for lithium ion batteries. Here, a scalable and low-cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near-theoretical, 550mAhgCoF2-1) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MFx -based materials in batteries with load-bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g(-1) and over 50% after 10 000 cycles at the current density of 1000 mA g(-1) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of electrical double-layer interaction on coal flotation.

PubMed

Harvey, Paul A; Nguyen, Anh V; Evans, Geoffrey M

2002-06-15

In the early 1930s it was first reported that inorganic electrolytes enhance the floatability of coal and naturally hydrophobic minerals. To date, explanations of coal flotation in electrolytes have not been entirely clear. This research investigated the floatability of coal in NaCl and MgCl2 solutions using a modified Hallimond tube to examine the role of the electrical double-layer interaction between bubbles and particles. Flotation of coal was highly dependent on changes in solution pH, type of electrolyte, and electrolyte concentration. Floatability of coal in electrolyte solutions was seen not to be entirely controlled by the electrical double-layer interaction. Coal flotation in low electrolyte concentration solutions decreases with increase in concentration, not expected from the theory since the electrical double layer is compressed, resulting in diminishing the (electrical double layer) repulsion between the bubble and the coal particles. Unlike in low electrolyte concentration solutions, coal flotation in high electrolyte concentration solutions increases with increase in electrolyte concentration. Again, this behavior of coal flotation in high electrolyte concentration solutions cannot be quantitatively explained using the electrical double-layer interaction. Possible mechanisms are discussed in terms of the bubston (i.e., bubble stabilized by ions) phenomenon, which explains the existence of the submicron gas bubbles on the hydrophobic coal surface.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

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

2015-03-28

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

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

Wang, Hui; Chen, Yan; Hood, Zachary D.

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

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

PubMed

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

2017-11-01

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

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.

Dual-Layered Film Protected Lithium Metal Anode to Enable Dendrite-Free Lithium Deposition.

PubMed

Yan, Chong; Cheng, Xin-Bing; Tian, Yang; Chen, Xiang; Zhang, Xue-Qiang; Li, Wen-Jun; Huang, Jia-Qi; Zhang, Qiang

2018-06-01

Lithium metal batteries (such as lithium-sulfur, lithium-air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next-generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short-circuit and thermal runaway of the rechargeable batteries. Herein, a dual-layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual-layered feature with organic components (ROCO 2 Li and ROLi) on the top and abundant inorganic components (Li 2 CO 3 and LiF) in the bottom. The dual-layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite-free Li metal anode. This work demonstrates the concept of rational construction of dual-layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-10

Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content ofmore » 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.« less

Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2018-01-01

Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a rechargeable lithium-ion battery system.

Fuel cell having electrolyte

DOEpatents

Wright, Maynard K.

1989-01-01

A fuel cell having an electrolyte control volume includes a pair of porous opposed electrodes. A maxtrix is positioned between the pair of electrodes for containing an electrolyte. A first layer of backing paper is positioned adjacent to one of the electrodes. A portion of the paper is substantially previous to the acceptance of the electrolyte so as to absorb electrolyte when there is an excess in the matrix and to desorb electrolyte when there is a shortage in the matrix. A second layer of backing paper is positioned adjacent to the first layer of paper and is substantially impervious to the acceptance of electrolyte.

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 Li 2CO 3, LiF and Li 3PO 4, 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 tensionmore » 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.« less

Method for Making a Fuel Cell from a Solid Oxide Monolithic Framework

NASA Technical Reports Server (NTRS)

Sofie, Stephen W. (Inventor); Cable, Thomas L. (Inventor)

2014-01-01

The invention is a novel solid oxide fuel cell (SOFC) stack comprising individual bi-electrode supported fuel cells in which a thin electrolyte is supported between electrodes of essentially equal thickness. Individual cell units are made from graded pore ceramic tape that has been created by the freeze cast method followed by freeze drying. Each piece of graded pore tape later becomes a graded pore electrode scaffold that subsequent to sintering, is made into either an anode or a cathode by means of appropriate solution and thermal treatment means. Each cell unit is assembled by depositing of a thin coating of ion conducting ceramic material upon the side of each of two pieces of tape surface having the smallest pore openings, and then mating the coated surfaces to create an unsintered electrode scaffold pair sandwiching an electrolyte layer. The opposing major outer exposed surfaces of each cell unit is given a thin coating of electrically conductive ceramic, and multiple cell units are stacked, or built up by stacking of individual cell layers, to create an unsintered fuel cell stack. Ceramic or glass edge seals are installed to create flow channels for fuel and air. The cell stack with edge sealants is then sintered into a ceramic monolithic framework. Said solution and thermal treatments means convert the electrode scaffolds into anodes and cathodes. The thin layers of electrically conductive ceramic become the interconnects in the assembled stack.

A review of lithium and non-lithium based solid state batteries

NASA Astrophysics Data System (ADS)

Kim, Joo Gon; Son, Byungrak; Mukherjee, Santanu; Schuppert, Nicholas; Bates, Alex; Kwon, Osung; Choi, Moon Jong; Chung, Hyun Yeol; Park, Sam

2015-05-01

Conventional lithium-ion liquid-electrolyte batteries are widely used in portable electronic equipment such as laptop computers, cell phones, and electric vehicles; however, they have several drawbacks, including expensive sealing agents and inherent hazards of fire and leakages. All solid state batteries utilize solid state electrolytes to overcome the safety issues of liquid electrolytes. Drawbacks for all-solid state lithium-ion batteries include high resistance at ambient temperatures and design intricacies. This paper is a comprehensive review of all aspects of solid state batteries: their design, the materials used, and a detailed literature review of various important advances made in research. The paper exhaustively studies lithium based solid state batteries, as they are the most prevalent, but also considers non-lithium based systems. Non-lithium based solid state batteries are attaining widespread commercial applications, as are also lithium based polymeric solid state electrolytes. Tabular representations and schematic diagrams are provided to underscore the unique characteristics of solid state batteries and their capacity to occupy a niche in the alternative energy sector.

A solid state actuator based on polypyrrole (PPy) and a solid electrolyte NBR working in air

NASA Astrophysics Data System (ADS)

Cho, Misuk; Nam, Jaedo; Choi, Hyouk Ryeol; Koo, Jachoon; Lee, Youngkwan

2005-05-01

The solid polymer electrolyte based conducting polymer actuator was presented. In the preparation of acutuator module, an ionic liquid impregnated a synthetic rubber (NBR) and PPy were used as a solid polymer electrolyte and conducting polymer, respectively. An ionic liquid, 1-butyl-3-methylimidazolium bis (trifluoromethyl sulfonyl)imide (BMITFSI) is gradually dispersed into the NBR film and the conducting polymer, PPy was synthesized on the surface of NBR. The ionic conductivity of new type solid polymer electrolyte as a function of the immersion time was investigated. The cyclic voltammetry responsed and the redox switching dynamics of PEDOT in NBR matrix were studied. The displacement of the actuator was measured by laser beam.

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

Oxygen concentration sensor for an internal combustion engine

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

Nakajima, T.; Okada, Y.; Mieno, T.

1988-09-29

This patent describes an oxygen concentration sensor, comprising: an oxygen ion conductive solid electrolyte member forming a gas diffusion restricted region into which a measuring gas is introduced; a pair of electrodes sandwiching the solid electrolyte member; pump current supply means applying a pump voltage to the pair of electrodes through a current detection element to generate a pump current; and a heater element connected to the solid electrolyte member for heating the solid electrolyte member for heating the solid electrolyte member when a heater current is supplied from a heater current source; wherein the oxygen concentration sensor detects anmore » oxygen concentration in the measuring gas in terms of a current value of the pump current supplied through the current detection element and controls oxygen concentration in the gas diffusion restricted region by conducting oxygen ions through the solid electrolyte member in accordance to the flow of the pump current; and wherein the current detection element is connected to the electrode of the pair of electrodes facing the gas diffusion restricted region for insuring that the current value is representative of the pump current and possible leakage current from the heater current.« less

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, economically and ecologically. Based on the knowledge of the screen printing sensor production a complete solid state electrolyte oxygen sensor could be produced using Inkjet technology. First measurements in oxygen environment already show promising results. A defined oxygen concentration could be seen during exposition of the Inkjet sensors in an oxygen environment. The obtained results demonstrate the potential to use the technology development in other applications such as in situ respiratory gas analysis systems for human spaceflight. Further approaches at the Institute of Space Systems include the implementation of Inkjet printed solid state electrolyte sensors for the use as redundant safety sensors for the Institute's hybrid life support test beds including fuel cells and algal photo bioreactor elements.

Iodine/iodide-free dye-sensitized solar cells.

PubMed

Yanagida, Shozo; Yu, Youhai; Manseki, Kazuhiro

2009-11-17

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

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

NASA Astrophysics Data System (ADS)

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

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

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

PubMed

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

2018-06-01

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

Solid-Liquid Lithium Electrolyte Nanocomposites Derived from Porous Molecular Cages.

PubMed

Petronico, Aaron; Moneypenny, Timothy P; Nicolau, Bruno G; Moore, Jeffrey S; Nuzzo, Ralph G; Gewirth, Andrew A

2018-06-20

We demonstrate that solid-liquid nanocomposites derived from porous organic cages are effective lithium ion electrolytes at room temperature. A solid-liquid electrolyte nanocomposite (SLEN) fabricated from a LiTFSI/DME electrolyte system and a porous organic cage exhibits ionic conductivity on the order of 1 × 10 -3 S cm -1 . With an experimentally measured activation barrier of 0.16 eV, this composite is characterized as a superionic conductor. Furthermore, the SLEN displays excellent oxidative stability up to 4.7 V vs Li/Li + . This simple three-component system enables the rational design of electrolytes from tunable discrete molecular architectures.

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries.

PubMed

Liu, Boyang; Fu, Kun; Gong, Yunhui; Yang, Chunpeng; Yao, Yonggang; Wang, Yanbin; Wang, Chengwei; Kuang, Yudi; Pastel, Glenn; Xie, Hua; Wachsman, Eric D; Hu, Liangbing

2017-08-09

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V 2 O 5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V 2 O 5 cathode was significantly decreased from 2.5 × 10 4 to 71 Ω·cm 2 at room temperature and from 170 to 31 Ω·cm 2 at 100 °C. Additionally, the diffusion resistance in the V 2 O 5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm 2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V 2 O 5 cathode and garnet solid electrolyte without compromising battery safety or performance.

Micro solid oxide fuel cell fabricated on porous stainless steel: a new strategy for enhanced thermal cycling ability

PubMed Central

Kim, Kun Joong; Park, Byung Hyun; Kim, Sun Jae; Lee, Younki; Bae, Hongyeul; Choi, Gyeong Man

2016-01-01

Miniaturized solid oxide fuel cells (micro-SOFCs) are being extensively studied as a promising alternative to Li batteries for next generation portable power. A new micro-SOFC is designed and fabricated which shows enhanced thermal robustness by employing oxide-based thin-film electrode and porous stainless steel (STS) substrate. To deposit gas-tight thin-film electrolyte on STS, nano-porous composite oxide is proposed and applied as a new contact layer on STS. The micro-SOFC fabricated on composite oxide- STS dual layer substrate shows the peak power density of 560 mW cm−2 at 550 °C and maintains this power density during rapid thermal cycles. This cell may be suitable for portable electronic device that requires high power-density and fast thermal cycling. PMID:26928921

Micro solid oxide fuel cell fabricated on porous stainless steel: a new strategy for enhanced thermal cycling ability.

PubMed

Kim, Kun Joong; Park, Byung Hyun; Kim, Sun Jae; Lee, Younki; Bae, Hongyeul; Choi, Gyeong Man

2016-03-01

Miniaturized solid oxide fuel cells (micro-SOFCs) are being extensively studied as a promising alternative to Li batteries for next generation portable power. A new micro-SOFC is designed and fabricated which shows enhanced thermal robustness by employing oxide-based thin-film electrode and porous stainless steel (STS) substrate. To deposit gas-tight thin-film electrolyte on STS, nano-porous composite oxide is proposed and applied as a new contact layer on STS. The micro-SOFC fabricated on composite oxide- STS dual layer substrate shows the peak power density of 560 mW cm(-2) at 550 °C and maintains this power density during rapid thermal cycles. This cell may be suitable for portable electronic device that requires high power-density and fast thermal cycling.

The Electrochemical Performance of Silicon Nanoparticles in Concentrated Electrolyte.

PubMed

Chang, Zeng-Hua; Wang, Jian-Tao; Wu, Zhao-Hui; Gao, Min; Wu, Shuai-Jin; Lu, Shi-Gang

2018-06-11

Silicon is a promising material for anodes in energy-storage devices. However, excessive growth of a solid-electrolyte interphase (SEI) caused by the severe volume change during the (de)lithiation processes leads to dramatic capacity fading. Here, we report a super-concentrated electrolyte composed of lithium bis(fluorosulfonyl)imide (LiFSI) and propylene carbonate (PC) with a molar ratio of 1:2 to improve the cycling performance of silicon nanoparticles (SiNPs). The SiNP electrode shows a remarkably improved cycling performance with an initial delithiation capacity of approximately 3000 mAh g -1 and a capacity of approximately 2000 mAh g -1 after 100 cycles, exhibiting about 6.8 times higher capacity than the cells with dilute electrolyte LiFSI-(PC) 8 . Raman spectra reveal that most of the PC solvent and FSI anions are complexed by Li + to form a specific solution structure like a fluid polymeric network. The reduction of FSI anions starts to play an important role owing to the increased concentration of contact ion pairs (CIPs) or aggregates (AGGs), which contribute to the formation of a more mechanically robust and chemically stable complex SEI layer. The complex SEI layer can effectively suppress the morphology evolution of silicon particles and self-limit the excessive growth, which mitigates the crack propagation of the silicon electrode and the deterioration of the kinetics. This study will provide a new direction for screening cycling-stable electrolytes for silicon-based electrodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, John P.

1992-01-01

A process for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

Electro-mechanical characterization of structural supercapacitors

NASA Astrophysics Data System (ADS)

Gallagher, T.; LaMaster, D.; Ciocanel, C.; Browder, C.

2012-04-01

The paper presents electrical and mechanical properties of structural supercapacitors and discusses limitations associated with the approach taken for the electrical properties evaluation. The structural supercapacitors characterized in this work had the electrodes made of carbon fiber weave, separator made of several cellulose based products, and the solid electrolyte made as PEGDGE based polymer blend. The reported electrical properties include capacitance and leakage resistance; the former was measured using cyclic voltammetry. Mechanical properties have been evaluated thorough tensile and three point bending tests performed on structural supercapacitor coupons. The results indicate that the separator material plays an important role on the electrical as well as mechanical properties of the structural capacitor, and that Celgard 3501 used as separator leads to most benefits for both mechanical and electrical properties. Specific capacitance and leakage resistance as high as 1.4kF/m3 and 380kΩ, respectively, were achieved. Two types of solid polymer electrolytes were used in fabrication, with one leading to higher and more consistent leakage resistance values at the expense of a slight decrease in specific capacitance when compared to the other SPE formulation. The ultimate tensile strength and modulus of elasticity of the developed power storage composite were evaluated at 466MPa and 18.9MPa, respectively. These values are 58% and 69% of the tensile strength and modulus of elasticity values measured for a single layer composite material made with the same type of carbon fiber and with a West System 105 epoxy instead of solid polymer electrolyte.

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

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.

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

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

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

DOE PAGES

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.; ...

2017-02-03

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

RF Magnetron Sputtering Deposited W/Ti Thin Film For Smart Window Applications

NASA Astrophysics Data System (ADS)

Oksuz, Lutfi; Kiristi, Melek; Bozduman, Ferhat; Uygun Oksuz, Aysegul

2014-10-01

Electrochromic (EC) devices can change reversible and persistent their optical properties in the visible region (400-800 nm) upon charge insertion/extraction according to the applied voltage. A complementary type EC is a device containing two electrochromic layers, one of which is anodically colored such as vanadium oxide (V2 O5) while the other cathodically colored such as tungsten oxide (WO3) which is separated by an ionic conduction layer (electrolyte). The use of a solid electrolyte such as Nafion eliminates the need for containment of the liquid electrolyte, which simplifies the cell design, as well as improves safety and durability. In this work, the EC device was fabricated on a ITO/glass slide. The WO3-TiO2 thin film was deposited by reactive RF magnetron sputtering using a 2-in W/Ti (9:1%wt) target with purity of 99.9% in a mixture gas of argon and oxygen. As a counter electrode layer, V2O5 film was deposited on an ITO/glass substrate using V2O3 target with the same conditions of reactive RF magnetron sputtering. Modified Nafion was used as an electrolyte to complete EC device. The transmittance spectra of the complementary EC device was measured by optical spectrophotometry when a voltage of +/-3 V was applied to the EC device by computer controlled system. The surface morphology of the films was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM) (Fig. 2). The cyclic voltammetry (CV) for EC device was performed by sweeping the potential between +/-3 V at a scan rate of 50 mV/s.

An air-stable Na 3SbS 4 superionic conductor prepared by a rapid and economic synthetic procedure

DOE PAGES

Wang, Hui; Chen, Yan; Hood, Zachary D.; ...

2016-01-01

All-solid-state sodium batteries, using abundant sodium resources and solid electrolyte, hold much promise for safe, low cost, large-scale energy storage. To realize the practical applications of all solid Na-ion batteries at ambient temperature, the solid electrolytes are required to have high ionic conductivity, chemical stability, and ideally, easy preparation. Ceramic electrolytes show higher ionic conductivity than polymers, but they often require extremely stringent synthesis conditions, either high sintering temperature above 1000 C or long-time, low-energy ball milling. Herein, we report a new synthesis route for Na 3SbS 4, a novel Na superionic conductor that needs much lower processing temperature belowmore » 200 C and easy operation. This new solid electrolyte exhibits a remarkable ionic conductivity of 1.05 mS cm -1 at 25 °C and is chemically stable under ambient atmosphere. In conclusion, this synthesis process provides unique insight into the current state-of-the-art solid electrolyte preparation and opens new possibilities for the design of similar materials.« less

Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na3PS4 and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries.

PubMed

Wenzel, Sebastian; Leichtweiss, Thomas; Weber, Dominik A; Sann, Joachim; Zeier, Wolfgang G; Janek, Jürgen

2016-10-05

The interfacial stability of solid electrolytes at the electrodes is crucial for an application of all-solid-state batteries and protected electrodes. For instance, undesired reactions between sodium metal electrodes and the solid electrolyte form charge transfer hindering interphases. Due to the resulting large interfacial resistance, the charge transfer kinetics are altered and the overvoltage increases, making the interfacial stability of electrolytes the limiting factor in these systems. Driven by the promising ionic conductivities of Na 3 PS 4 , here we explore the stability and viability of Na 3 PS 4 as a solid electrolyte against metallic Na and compare it to that of Na-β″-Al 2 O 3 (sodium β-alumina). As expected, Na-β″-Al 2 O 3 is stable against sodium, whereas Na 3 PS 4 decomposes with an increasing overall resistance, making Na-β″-Al 2 O 3 the electrolyte of choice for protected sodium anodes and all-solid-state batteries.

Salvinia-Effect-Inspired "Sticky" Superhydrophobic Surfaces by Meniscus-Confined Electrodeposition.

PubMed

Zheng, Deyin; Jiang, Youhua; Yu, Wentao; Jiang, Xiufen; Zhao, Xin; Choi, Chang-Hwan; Sun, Guangyi

2017-11-28

Inspired by the Salvinia effect, we report the fabrication and characterization of a novel "sticky" superhydrophobic surface sustaining a Cassie-Baxter wetting state for water droplets with high contact angles but strong solid-liquid retention. Unlike superhydrophobic surfaces mimicking the lotus or petal effect, whose hydrophobicity and droplet retention are typically regulated by hierarchical micro- and nanostructures made of a homogeneous material with the same surface energy, our superhydrophobic surface merely requires singular microstructures covered with a hydrophobic coating but creatively coupled with hydrophilic tips with different surface energy. Hydrophilic tips are selectively formed by meniscus-confined electrodeposition of a metal (e.g., nickel) layer on top of hydrophobic microstructures. During the electrodeposition process, the superhydrophobic surface retains its plastron so that the electrolyte cannot penetrate into the cavity of hydrophobic microstructures, consequently making the electrochemical reaction between solid and electrolyte occur only on the tip. In contrast to typical superhydrophobic surfaces where droplets are highly mobile, the "sticky" superhydrophobic surface allows a water droplet to have strong local pinning and solid-liquid retention on the hydrophilic tips, which is of great significance in many droplet behaviors such as evaporation.

Silicon algae with carbon topping as thin-film anodes for lithium-ion microbatteries by a two-step facile method

NASA Astrophysics Data System (ADS)

Biserni, E.; Xie, M.; Brescia, R.; Scarpellini, A.; Hashempour, M.; Movahed, P.; George, S. M.; Bestetti, M.; Li Bassi, A.; Bruno, P.

2015-01-01

Silicon-based electrodes for Li-ion batteries (LIB) attract much attention because of their high theoretical capacity. However, their large volume change during lithiation results in poor cycling due to mechanical cracking. Moreover, silicon can hardly form a stable solid electrolyte interphase (SEI) layer with common electrolytes. We present a safe, innovative strategy to prepare nanostructured silicon-carbon anodes in a two-step process. The nanoporosity of Si films accommodates the volume expansion while a disordered graphitic C layer on top promotes the formation of a stable SEI. This approach shows its promises: carbon-coated porous silicon anodes perform in a very stable way, reaching the areal capacity of ∼175 μAh cm-2, and showing no decay for at least 1000 cycles. With requiring only a two-step deposition process at moderate temperatures, this novel very simple cell concept introduces a promising way to possibly viable up-scaled production of next-generation nanostructured Si anodes for lithium-ion microbatteries.

A novel layered perovskite cathode for proton conducting solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xue, Xingjian; Liu, Xingqin; Meng, Guangyao

BaZr 0.1Ce 0.7Y 0.2O 3- δ (BZCY7) exhibits adequate proton conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered SmBa 0.5Sr 0.5Co 2O 5+ δ (SBSC) perovskite demonstrates advanced electrochemical properties based on doped ceria electrolyte. This research fully takes advantage of these advanced properties and develops novel protonic ceramic membrane fuel cells (PCMFCs) of Ni-BZCY7|BZCY7|SBSC. The results show that the open-circuit potential of 1.015 V and maximum power density of 533 mW cm -2 are achieved at 700 °C. With temperature increase, the total cell resistance decreases, among which electrolyte resistance becomes increasingly dominant over polarization resistance. The results also indicate that SBSC perovskite cathode is a good candidate for intermediate temperature PCMFC development, while the developed Ni-BZCY7|BZCY7|SBSC cell is a promising functional material system for next generation SOFCs.

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

Electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.

Fabrication, testing and simulation of all solid state three dimensional Li-ion batteries

DOE PAGES

Talin, Albert Alec; Ruzmetov, Dmitry; Kolmakov, Andrei; ...

2016-11-10

Realization of safe, long cycle life and simple to package solid-state rechargeable batteries with high energy and power density has been a long-standing goal of the energy storage community. [1,2] Much of the research activity has been focused on developing new solid electrolytes with high Li ionic conductivity. In addition, LiPON, the only solid electrolyte currently used in commercial thin film solid state Li-ion batteris (SSLIBs), has a conductivity of ~10 -6 S/cm, compared to ~0.01 S/cm typically observed for liquid organic electrolytes [3].

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries.

PubMed

Hayashi, Akitoshi; Noi, Kousuke; Sakuda, Atsushi; Tatsumisago, Masahiro

2012-05-22

Innovative rechargeable batteries that can effectively store renewable energy, such as solar and wind power, urgently need to be developed to reduce greenhouse gas emissions. All-solid-state batteries with inorganic solid electrolytes and electrodes are promising power sources for a wide range of applications because of their safety, long-cycle lives and versatile geometries. Rechargeable sodium batteries are more suitable than lithium-ion batteries, because they use abundant and ubiquitous sodium sources. Solid electrolytes are critical for realizing all-solid-state sodium batteries. Here we show that stabilization of a high-temperature phase by crystallization from the glassy state dramatically enhances the Na(+) ion conductivity. An ambient temperature conductivity of over 10(-4) S cm(-1) was obtained in a glass-ceramic electrolyte, in which a cubic Na(3)PS(4) crystal with superionic conductivity was first realized. All-solid-state sodium batteries, with a powder-compressed Na(3)PS(4) electrolyte, functioned as a rechargeable battery at room temperature.

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

PubMed Central

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

2017-01-01

Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612

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

PubMed

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

2018-04-07

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

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

All-in-One Gel-Based Electrochromic Devices: Strengths and Recent Developments

PubMed Central

Viñuales, Ana; Rodriguez, Javier; Tena-Zaera, Ramón

2018-01-01

Electrochromic devices (ECDs) have aroused great interest because of their potential applicability in displays and smart systems, including windows, rearview mirrors, and helmet visors. In the last decades, different device structures and materials have been proposed to meet the requirements of commercial applications to boost market entry. To this end, employing simple device architectures and achieving a competitive electrolyte are crucial to accomplish easily implementable, high-performance ECDs. The present review outlines devices comprising gel electrolytes as a single electroactive layer (“all-in-one”) ECD architecture, highlighting some advantages and opportunities they offer over other electrochromic systems. In this context, gel electrolytes not only overcome the drawbacks of liquid and solid electrolytes, such as liquid’s low chemical stability and risk of leaking and soil’s slow switching and lack of transparency, but also exhibit further strengths. These include easier processability, suitability for flexible substrates, and improved stabilization of the chemical species involved in redox processes, leading to better cyclability and opening wide possibilities to extend the electrochromic color palette, as discussed herein. Finally, conclusions and outlook are provided. PMID:29534466

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

PubMed

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

2015-06-24

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

Enhancing cycling durability of Li-ion batteries with hierarchical structured silicon-graphene hybrid anodes.

PubMed

Loveridge, Melanie J; Lain, Michael J; Huang, Qianye; Wan, Chaoying; Roberts, Alexander J; Pappas, George S; Bhagat, Rohit

2016-11-09

Hybrid anode materials consisting of micro-sized silicon (Si) particles interconnected with few-layer graphene (FLG) nanoplatelets and sodium-neutralized poly(acrylic acid) as a binder were evaluated for Li-ion batteries. The hybrid film has demonstrated a reversible discharge capacity of ∼1800 mA h g -1 with a capacity retention of 97% after 200 cycles. The superior electrochemical properties of the hybrid anodes are attributed to a durable, hierarchical conductive network formed between Si particles and the multi-scale carbon additives, with enhanced cohesion by the functional polymer binder. Furthermore, improved solid electrolyte interphase (SEI) stability is achieved from the electrolyte additives, due to the formation of a kinetically stable film on the surface of the Si.

Method for making an electrochemical cell

DOEpatents

Tuller, Harry L.; Kramer, Steve A.; Spears, Marlene A.; Pal, Uday B.

1996-01-01

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 provided.

Apparatus and method for the electrolytic production of metals

DOEpatents

Sadoway, Donald R.

1991-01-01

Improved electrolytic cells and methods for producing metals by electrolytic reduction of a compound dissolved in a molten electrolyte are disclosed. In the improved cells and methods, a protective surface layer is formed upon at least one electrode in the electrolytic reduction cell and, optionally, upon the lining of the cell. This protective surface layer comprises a material that, at the operating conditions of the cell: (a) is not substantially reduced by the metal product; (b) is not substantially reactive with the cell electrolyte to form materials that are reactive with the metal product; and, (c) has an electrochemical potential that is more electronegative than that of the compound undergoing electrolysis to produce the metal product of the cell. The protective surface layer can be formed upon an electrode metal layer comprising a material, the oxide of which also satisfies the protective layer selection criteria. The protective layer material can also be used on the surface of a cell lining.

Garnet Electrolyte with an Ultralow Interfacial Resistance for Li-Metal Batteries.

PubMed

Li, Yutao; Chen, Xi; Dolocan, Andrei; Cui, Zhiming; Xin, Sen; Xue, Leigang; Xu, Henghui; Park, Kyusung; Goodenough, John B

2018-05-23

Garnet-structured Li 7 La 3 Zr 2 O 12 is a promising solid Li-ion electrolyte for all-solid-state Li-metal batteries and Li-redox-flow batteries owing to its high Li-ion conductivity at room temperature and good electrochemical stability with Li metal. However, there are still three major challenges unsolved: (1) the controversial electrochemical window of garnet, (2) the impractically large resistance at a garnet/electrode interface and the fast lithium-dendrite growth along the grain boundaries of the garnet pellet, and (3) the fast degradation during storage. We have found that these challenges are closely related to a thick Li 2 CO 3 layer and the Li-Al-O glass phase on the surface of garnet materials. Here we introduce a simple method to remove Li 2 CO 3 and the protons in the garnet framework by reacting garnet with carbon at 700 °C; moreover, the amount of the Li-Al-O glass phase with a low Li-ion conductivity in the grain boundary on the garnet surface was also reduced. The surface of the carbon-treated garnet pellets is free of Li 2 CO 3 and is wet by a metallic lithium anode, an organic electrolyte, and a solid composite cathode. The carbon post-treatment has reduced significantly the interfacial resistances to 28, 92 (at 65 °C), and 45 Ω cm 2 at Li/garnet, garnet/LiFePO 4 , and garnet/organic-liquid interfaces, respectively. A symmetric Li/garnet/Li, an all-solid-state Li/garnet/LiFePO 4 , and a hybrid Li-S cell show small overpotentials, high Coulombic efficiencies, and stable cycling performance.

Electrolyte materials containing highly dissociated metal ion salts

DOEpatents

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

1996-07-23

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

Wearable supercapacitors on polyethylene terephthalate fabrics with good wash fastness and high flexibility

NASA Astrophysics Data System (ADS)

Wang, Guixia; Babaahmadi, Vahid; He, Nanfei; Liu, Yixin; Pan, Qin; Montazer, Majid; Gao, Wei

2017-11-01

All solid-state micro-supercapacitors (MSC) have emerged as attractive energy-storage units for portable and wearable electronics. Here, we describe a textile-based solid-state MSC via laser scribing of graphene oxide (GO) coatings on a flexible polyethylene terephthalate (PET) fabric. The laser-scribed graphene oxide layers (LGO) possess three-dimensionally porous structure suitable for electrochemical-double-layer formation. To improve the wash fastness and the flexibility of the as-prepared MSCs, glutaraldehyde (GA) was employed to crosslink the GO layers and PVA-gel electrolyte onto the PET fabric. The resultant all solid-state MSCs exhibited excellent flexibility, high areal specific capacitance (756 μF·cm-2 at 20 mV·s-1), and good rate capability when subject to bending and laundering. Furthermore, the MSC device showed a high power density of about 1.4 W·cm-3 and an energy density of 5.3 × 10-5 Wh·cm-3, and retained 98.3% of its initial capacitance after 1000 cycles at a current density of 0.5 mA·cm-2. This work is the first demonstration of in-plane MSCs on PET fabric surfaces with enhanced durability and flexibility.

Simultaneous Stabilization of LiNi0.76Mn0.14Co0.10O2 Cathode and Lithium Metal Anode by LiBOB Additive.

PubMed

Zhao, Wengao; Zou, Lianfeng; Zheng, Jianming; Jia, Haiping; Song, Junhua; Engelhard, Mark H; Wang, Chongmin; Xu, Wu; Yang, Yong; Zhang, Ji-Guang

2018-05-01

The long-term cycling performance, rate capability, and voltage stability of lithium (Li) metal batteries with LiNi0.76Mn0.14Co0.10O2 (NMC76) cathodes is greatly enhanced by lithium bis(oxalato)borate (LiBOB) additive in the LiPF6-based electrolyte. With 2% LiBOB in the electrolyte, a Li||NMC76 cell is able to achieve a high capacity retention of 96.8% after 200 cycles at C/3 rate (1C = 200 mA g-1), which is the best result reported for a Ni-rich NMC cathode coupled with Li metal anode. The significantly enhanced electrochemical performance can be ascribed to the stabilization of both the NMC76-cathode/electrolyte and Li-metal-anode/electrolyte interfaces. LiBOB-containing electrolyte not only facilitates the formation of a more compact solid electrolyte interphase on the Li metal surface, it also forms a enhanced cathode electrolyte interface layer, which efficiently prevents the corrosion of the cathode interface and mitigates the formation of disordered rock-salt phase after cycling. The fundamental findings of this work highlight the importance of recognizing the dual effects of electrolyte additives in simultaneously stabilizing both cathode and anode interfaces, so as to enhance the long-term cycle life of high-energy-density battery systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nano-carbon coating layer prepared by the thermal evaporation of fullerene C60 for lithium metal anodes in rechargeable lithium batteries.

PubMed

Arie, Arenst Andreas; Lee, Joong Kee

2011-07-01

A nano carbon coating layer was prepared by the thermal evaporation of fullerene C60 on the surface of lithium metal anodes for rechargeable lithium batteries. The morphology and structure of the carbon layer was firstly investigated by Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effects of the nano-carbon coating layer on the electrochemical performance of the lithium electrode were then examined by charge-discharge tests and impedance spectroscopy. Raman spectra of carbon coating layer showed two main peaks (D and G peaks), indicating the amorphous structure of the film. A honey comb-like structure of carbon film was observed by TEM photographs, providing a transport path for the transport of lithium ions at the electrode/electrolyte interface. The carbon coated lithium electrodes exhibited a higher initial coulombic efficiency (91%) and higher specific capacity retention (88%) after the 30th cycle at 0.2 C-rate between 3.4 and 4.5 V. Impedance measurements showed that the charge transfer resistance was significantly reduced after cycle tests for the carbon coated electrodes, revealing that the more stable solid electrolyte (SEI) layer was established on their surface. Based on the experimental results, it suggested that the presence of the nano-carbon coating layer might suppress the dendritic growth on the surface of lithium metal electrodes, as confirmed by the observation of SEM images after cycle tests.

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

Thermal power transfer system using applied potential difference to sustain operating pressure difference

NASA Technical Reports Server (NTRS)

Bhandari, Pradeep (Inventor); Fujita, Toshio (Inventor)

1991-01-01

A thermal power transfer system using a phase change liquid gas fluid in a closed loop configuration has a heat exchanger member connected to a gas conduit for inputting thermal energy into the fluid. The pressure in the gas conduit is higher than a liquid conduit that is connected to a heat exchanger member for outputting thermal energy. A solid electrolyte member acts as a barrier between the gas conduit and the liquid conduit adjacent to a solid electrolyte member. The solid electrolyte member has the capacity of transmitting ions of a fluid through the electrolyte member. The ions can be recombined with electrons with the assistance of a porous electrode. An electrical field is applied across the solid electrolyte member to force the ions of the fluid from a lower pressure liquid conduit to the higher pressure gas conduit.

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

PubMed Central

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

NASA Astrophysics Data System (ADS)

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm-1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

Experimental Evaluation of the Synthetic Solid Electrolyte Interface (SSEI) Concept for the Primary Ca-SOCl2 Battery System

DTIC Science & Technology

1988-12-01

coatings based on the Ca(Sr,Y)- Ge-S system can serve as an effective SSEI for Ca anodes in Ca-SOC12 primary cells using 1 M Ca(AlCl4 )2 as the electrolyte...I iy - LFI. CDY 4 EXPERIMENTAL EVALUATION OF THE SYNTHETIC SOLID ELECTROLYTE INTERFACE ( SSEI ) CONCEPT FOR THE PRIMARY Ca-SOC1 2 BA LERY SYSTEM...apply the concept of a synthetic solid electrolyte interface ( SSEI ) to overcome the problem of Ca corro- sion in Ca-SOC 2 primary cells. / To this end

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Nanoporous adsorption effect on altering Li+ diffusion pathway by a highly ordered porous electrolyte additive for high rate all-solid-state lithium metal batteries.

PubMed

Li, Wenwen; Zhang, Sanpei; Wang, Bangrun; Gu, Sui; Xu, Dong; Wang, Jianing; Chen, Chunhua; Wen, Zhaoyin

2018-06-19

Solid polymer electrolytes (SPEs) have shown extraordinary promise for all-solid-state lithium metal batteries with high energy density and flexibility but are mainly limited by the low ionic conductivity and their poor stability with lithium metal anode. In this work, we propose a highly ordered porous electrolyte additive derived from SSZ-13 for high-rate all-solid-state lithium metal batteries. The nanoporous adsorption effect provided by the highly ordered porous nanoparticles in the poly (ethylene oxide) (PEO) electrolyte are found to significantly improve the Li + conductivity (1.91×10 -3 S cm -1 at 60°C, 4.43×10 -5 S cm -1 at 20°C) and widen the electrochemical stability window to 4.7 V vs Li + /Li. Meanwhile, the designed PEO-based electrolyte demonstrates enhanced stability with the lithium metal anode. Through systematically increasing Li + diffusion, widening the electrochemical stability window and enhancing the stability of the SSZ-CPE electrolyte, the LiFePO4/SSZ-CPE/Li cell is optimized to deliver high-rate capability and stable cycling performance, which demonstrates great potential for all-solid-state energy storage application.

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.

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

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

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

1999-01-01

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

Emerging applications of spark plasma sintering in all solid-state lithium-ion batteries and beyond

NASA Astrophysics Data System (ADS)

Zhu, Hongzheng; Liu, Jian

2018-07-01

Solid-state batteries have received increasing attention due to their high safety aspect and high energy and power densities. However, the development of solid-state batteries is hindered by inferior solid-solid interfaces between the solid-state electrolyte and electrode, which cause high interfacial resistance, reduced Li-ion and electron transfer rate, and limited battery performance. Recently, spark plasma sintering (SPS) is emerging as a promising technique for fabricating solid-state electrolyte and electrode pellets with clean and intimate solid-solid interfaces. During the SPS process, the unique reaction mechanism through the combination of current, pressure and high heating rate allow the formation of desirable solid-solid interfaces between active material particles. Herein, this work focuses on the overview of the application of SPS for fabricating solid-state electrolyte and electrode in all solid-state Li-ion batteries, and beyond, such as solid-state Li-S and Na-ion batteries. The correlations among SPS parameters, interfacial resistance, and electrochemical properties of solid-state electrolytes and electrodes are discussed for different material systems. In the end, we point out future opportunities and challenges associated with SPS application in the hot area of solid-state batteries. It is expected that this timely review will stimulate more fundamental and applied research in the development of solid-state batteries by SPS.

Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium-Sulfur Batteries.

PubMed

Li, Guoxing; Huang, Qingquan; He, Xin; Gao, Yue; Wang, Daiwei; Kim, Seong H; Wang, Donghai

2018-02-27

Lithium-sulfur (Li-S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li-S batteries. In this work, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Li salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π-π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li-S batteries with good cycling stability (1000 cycles) and slow capacity decay. This work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.

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

DOE PAGES

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

2017-01-19

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

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

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

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

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

Solid electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Isaacs, H. S.

Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

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

NASA Astrophysics Data System (ADS)

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

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

Increasing Wear Resistance of Titanium Alloys by Anode Plasma Electrolytic Saturation with Interstitial Elements

NASA Astrophysics Data System (ADS)

Belkin, P. N.; Kusmanov, S. A.; Dyakov, I. G.; Silkin, S. A.; Smirnov, A. A.

2017-05-01

In our previous studies, we have shown that anode plasma electrolytic saturation of titanium alloys with nitrogen and carbon can improve their tribological properties. Obtained structure containing oxide layer and solid solution of diffused element in titanium promotes the enhancement of running-in ability and the decrease in the wear rate in some special cases. In this paper, further investigations are reported regarding the tribological properties of alpha- and beta-titanium alloys in wear test against hardened steel (50 HRC) disk using pin-on-disk geometry and balls of Al2O3 (6.25 mm in diameter) or bearing steel (9.6 mm in diameter) with ball-on-plate one and normal load from 5 to 209 N. Reproducible results were obtained under testing samples treated by means of the plasma electrolytic nitriding (PEN) with the mechanical removal of the oxide layer. Friction coefficient of nitrided samples is 0.5-0.9 which is somewhat higher than that for untreated one (0.48-0.75) during dry sliding against Al2O3 ball. An increase in the sliding speed results in the polishing of nitrided samples and reduction of their wear rate by 60 times. This result is obtained for 5 min at 850 °C using PEN in electrolyte containing 5 wt.% ammonia and 10 wt.% ammonium chloride followed by quenching in solution. Optical microscope was employed to assist in the evaluation of the wear behavior. Sizes of wear tracks were measured by profilometer TR200.

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

PubMed

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

2017-07-19

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

Plutonium recovery from spent reactor fuel by uranium displacement

DOEpatents

Ackerman, J.P.

1992-03-17

A process is described for separating uranium values and transuranic values from fission products containing rare earth values when the values are contained together in a molten chloride salt electrolyte. A molten chloride salt electrolyte with a first ratio of plutonium chloride to uranium chloride is contacted with both a solid cathode and an anode having values of uranium and fission products including plutonium. A voltage is applied across the anode and cathode electrolytically to transfer uranium and plutonium from the anode to the electrolyte while uranium values in the electrolyte electrolytically deposit as uranium metal on the solid cathode in an amount equal to the uranium and plutonium transferred from the anode causing the electrolyte to have a second ratio of plutonium chloride to uranium chloride. Then the solid cathode with the uranium metal deposited thereon is removed and molten cadmium having uranium dissolved therein is brought into contact with the electrolyte resulting in chemical transfer of plutonium values from the electrolyte to the molten cadmium and transfer of uranium values from the molten cadmium to the electrolyte until the first ratio of plutonium chloride to uranium chloride is reestablished.

Electrofluidic gating of a chemically reactive surface.

PubMed

Jiang, Zhijun; Stein, Derek

2010-06-01

We consider the influence of an electric field applied normal to the electric double layer at a chemically reactive surface. Our goal is to elucidate how surface chemistry affects the potential for field-effect control over micro- and nanofluidic systems, which we call electrofluidic gating. The charging of a metal-oxide-electrolyte (MOE) capacitor is first modeled analytically. We apply the Poisson-Boltzmann description of the double layer and impose chemical equilibrium between the ionizable surface groups and the solution at the solid-liquid interface. The chemically reactive surface is predicted to behave as a buffer, regulating the charge in the double layer by either protonating or deprotonating in response to the applied field. We present the dependence of the charge density and the electrochemical potential of the double layer on the applied field, the density, and the dissociation constants of ionizable surface groups and the ionic strength and the pH of the electrolyte. We simulate the responses of SiO(2) and Al(2)O(3), two widely used oxide insulators with different surface chemistries. We also consider the limits to electrofluidic gating imposed by the nonlinear behavior of the double layer and the dielectric strength of oxide materials, which were measured for SiO(2) and Al(2)O(3) films in MOE configurations. Our results clarify the response of chemically reactive surfaces to applied fields, which is crucial to understanding electrofluidic effects in real devices.

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Brian, Riley; Szreders, Bernard E.

1989-01-01

In a high temperature solid oxide fuel cell (SOFC), the deposition of an impervious high density thin layer of electrically conductive interconnector material, such as magnesium doped lanthanum chromite, and of an electrolyte material, such as yttria stabilized zirconia, onto a porous support/air electrode substrate surface is carried out at high temperatures (approximately 1100.degree.-1300.degree. C.) by a process of electrochemical vapor deposition. In this process, the mixed chlorides of the specific metals involved react in the gaseous state with water vapor resulting in the deposit of an impervious thin oxide layer on the support tube/air electrode substrate of between 20-50 microns in thickness. An internal heater, such as a heat pipe, is placed within the support tube/air electrode substrate and induces a uniform temperature profile therein so as to afford precise and uniform oxide deposition kinetics in an arrangement which is particularly adapted for large scale, commercial fabrication of SOFCs.

Cassettes for solid-oxide fuel cell stacks and methods of making the same

DOEpatents

Weil, K. Scott; Meinhardt, Kerry D; Sprenkle, Vincent L

2012-10-23

Solid-oxide fuel cell (SOFC) stack assembly designs are consistently investigated to develop an assembly that provides optimal performance, and durability, within desired cost parameters. A new design includes a repeat unit having a SOFC cassette and being characterized by a three-component construct. The three components include an oxidation-resistant, metal window frame hermetically joined to an electrolyte layer of a multi-layer, anode-supported ceramic cell and a pre-cassette including a separator plate having a plurality of vias that provide electrical contact between an anode-side collector within the pre-cassette and a cathode-side current collector of an adjacent cell. The third component is a cathode-side seal, which includes a standoff that supports a cathode channel spacing between each of the cassettes in a stack. Cassettes are formed by joining the pre-cassette and the window frame.

A Facile Methodology for the Development of a Printable and Flexible All-Solid-State Rechargeable Battery.

PubMed

De, Bibekananda; Yadav, Amit; Khan, Salman; Kar, Kamal K

2017-06-14

Development of printable and flexible energy storage devices is one of the most promising technologies for wearable electronics in textile industry. The present work involves the design of a printable and flexible all-solid-state rechargeable battery for wearable electronics in textile applications. Copper-coated carbon fiber is used to make a poly(ethylene oxide) (PEO)-based polymer nanocomposite for a flexible and conductive current collector layer. Lithium iron phosphate (LiFePO 4 ) and titanium dioxide (TiO 2 ) are utilized to prepare the cathode and anode layers, respectively, with PEO and carbon black composites. The PEO- and Li salt-based solid composite separator layer is utilized for the solid-state and safe electrolyte. Fabrication of all these layers and assembly of them through coating on fabrics are performed in the open atmosphere without using any complex processing, as PEO prevents the degradation of the materials in the open atmosphere. The performance of the battery is evaluated through charge-discharge and open-circuit voltage analyses. The battery shows an open-circuit voltage of ∼2.67 V and discharge time ∼2000 s. It shows similar performance at different repeated bending angles (0° to 180°) and continuous bending along with long cycle life. The application of the battery is also investigated for printable and wearable textile applications. Therefore, this printable, flexible, easily processable, and nontoxic battery with this performance has great potential to be used in portable and wearable textile electronics.

Safety shutdown separators

DOEpatents

Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

2015-06-30

The present invention pertains to electrochemical cells which comprise (a) an anode; (b) a cathode; (c) a solid porous separator, such as a polyolefin, xerogel, or inorganic oxide separator; and (d) a nonaqueous electrolyte, wherein the separator comprises a porous membrane having a microporous coating comprising polymer particles which have not coalesced to form a continuous film. This microporous coating on the separator acts as a safety shutdown layer that rapidly increases the internal resistivity and shuts the cell down upon heating to an elevated temperature, such as 110.degree. C. Also provided are methods for increasing the safety of an electrochemical cell by utilizing such separators with a safety shutdown layer.

Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

PubMed

Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

2018-05-04

Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

PubMed

Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

2017-09-01

High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 Li 7La 3Zr 2O 12, 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 smore » 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.« less

Hydrodynamic boundary condition of water on hydrophobic surfaces.

PubMed

Schaeffel, David; Yordanov, Stoyan; Schmelzeisen, Marcus; Yamamoto, Tetsuya; Kappl, Michael; Schmitz, Roman; Dünweg, Burkhard; Butt, Hans-Jürgen; Koynov, Kaloian

2013-05-01

By combining total internal reflection fluorescence cross-correlation spectroscopy with Brownian dynamics simulations, we were able to measure the hydrodynamic boundary condition of water flowing over a smooth solid surface with exceptional accuracy. We analyzed the flow of aqueous electrolytes over glass coated with a layer of poly(dimethylsiloxane) (advancing contact angle Θ = 108°) or perfluorosilane (Θ = 113°). Within an error of better than 10 nm the slip length was indistinguishable from zero on all surfaces.

The sol-gel route: A versatile process for up-scaling the fabrication of gas-tight thin electrolyte layers

NASA Astrophysics Data System (ADS)

Viazzi, Céline; Rouessac, Vincent; Lenormand, Pascal; Julbe, Anne; Ansart, Florence; Guizard, Christian

2011-03-01

Sol-gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol-gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y2O3) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C.

Insight into self-discharge of layered lithium-rich oxide cathode in carbonate-based electrolytes with and without additive

NASA Astrophysics Data System (ADS)

Li, Jianhui; Xing, Lidan; Zhang, Liping; Yu, Le; Fan, Weizhen; Xu, Mengqing; Li, Weishan

2016-08-01

Self-discharge behavior of layered lithium-rich oxide as cathode of lithium ion battery in a carbonated-based electrolyte is understood, and a simple boron-containing compound, trimethyl borate (TMB), is used as an electrolyte additive to suppress this self-discharge. It is found that layered lithium-rich oxide charged under 4.8 V in additive-free electrolyte suffers severe self-discharge and TMB is an effective electrolyte additive for self-discharge suppression. Physical characterizations from XRD, SEM, TEM, XPS and ICP-MS demonstrate that the crystal structure of the layered lithium-rich oxide collapses due to the chemical interaction between the charged oxide and electrolyte. When TMB is applied, the structural integrity of the oxide is maintained due to the protective cathode film generated from the preferential oxidation of TMB.

Synthesis of POSS-based ionic conductors with low glass transition temperatures for efficient solid-state dye-sensitized solar cells.

PubMed

Zhang, Wei; Wang, Zhong-Sheng

2014-07-09

Replacing liquid-state electrolytes with solid-state electrolytes has been proven to be an effective way to improve the durability of dye-sensitized solar cells (DSSCs). We report herein the synthesis of amorphous ionic conductors based on polyhedral oligomeric silsesquioxane (POSS) with low glass transition temperatures for solid-state DSSCs. As the ionic conductor is amorphous and in the elastomeric state at the operating temperature of DSSCs, good pore filling in the TiO2 film and good interfacial contact between the solid-state electrolyte and the TiO2 film can be guaranteed. When the POSS-based ionic conductor containing an allyl group is doped with only iodine as the solid-state electrolyte without any other additives, power conversion efficiency of 6.29% has been achieved with good long-term stability under one-sun soaking for 1000 h.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

PubMed Central

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

2018-01-01

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br− in PIL-M-(Br) and TFSI− in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br− and TFSI−, respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g−1, 40 and 48 kW·kg−1, and 107 and 59.9 Wh·kg−1 were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively. PMID:29642456

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.

Ceramic Electrolyte Membrane Technology: Enabling Revolutionary Electrochemical Energy Storage

DTIC Science & Technology

2015-10-05

ion batteries . Solid-state Li- ion batteries could significantly improve safety and eliminate the need for complex...advancing ceramic electrolyte technology for use in solid-state Li- ion batteries . Solid-state Li- ion batteries could significantly improve safety and...technology for use in solid-state Li- ion batteries and high specific energy Li-S and Li- air batteries . Solid-state Li- ion batteries could

Polyphosphazene Solid Electrolytes.

DTIC Science & Technology

1984-10-01

soL..I’IIN ’ . LAV A - .:.u.s 009 ’-" 4. T .. T. edSutoe .TVCO EO T EI O Polyphosphazene Solid Electrolytes Interim Technical Repor 6. PEAFORMING RG ...Y. T.; Whitmore , D. H. Solid State Ionics 1982, 7, 129. (10) Bauerle, J. E. J. Phys. Chem. Solids 1969, 30, 2657. (11) MacDonald, J. R. J. Chem. Phys

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Solid 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).

High-Performance Sodium Metal Anodes Enabled by a Bifunctional Potassium Salt.

PubMed

Shi, Qiuwei; Zhong, Yiren; Wu, Min; Wang, Hongzhi; Wang, Hailiang

2018-04-12

Developing Na metal anodes that can be deeply cycled with high efficiency for a long time is a prerequisite for rechargeable Na metal batteries to be practically useful despite their notable advantages in theoretical energy density and potential low cost. Their high chemical reactivity with the electrolyte and tendency for dendrite formation are two major issues limiting the reversibility of Na metal electrodes. In this work, we introduce for the first time potassium bis(trifluoromethylsulfonyl)imide (KTFSI) as a bifunctional electrolyte additive to stabilize Na metal electrodes, in which the TFSI - anions decompose into lithium nitride and oxynitrides to render a desirable solid electrolyte interphase layer while the K + cations preferentially adsorb onto Na protrusions and provide electrostatic shielding to suppress dendritic deposition. Through the cooperation of the cations and anions, we have realized Na metal electrodes that can be deeply cycled at a capacity of 10 mAh cm -2 for hundreds of hours. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.