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

Free Energies of Formation Measurements on Solid-State Electrochemical Cells

ERIC Educational Resources Information Center

Rollino, J. A.; Aronson, S.

1972-01-01

A simple experiment is proposed that can provide the student with some insight into the chemical properties of solids. It also demonstrates the relationship between the Gibbs free energy of formation of an ionic solid and the emf of an electrochemical cell. (DF)

POWER AND THERMAL TECHNOLOGIES FOR AIR AND SPACE-SCIENTIFIC RESEARCH PROGRAM Delivery Order 0018: Single Ion Conducting Solid-State Lithium Electrochemical Technologies (Task 4)

DTIC Science & Technology

2010-08-01

a mathematical equation relates the cathode reaction reversible electric potential to the lithium content of the cathode electrode. Based on the...Transport of Lithium in the Cell Cathode Active Material The Nernst -Einstein relation linking the lithium-ion mass diffusivity and its ionic...transient, isothermal and isobaric conditions. The differential model equation describing the lithium diffusion and accumulation in a spherical, active

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.

Electron-rich driven electrochemical solid-state amorphization in Li-Si alloys.

PubMed

Wang, Zhiguo; Gu, Meng; Zhou, Yungang; Zu, Xiaotao; Connell, Justin G; Xiao, Jie; Perea, Daniel; Lauhon, Lincoln J; Bang, Junhyeok; Zhang, Shengbai; Wang, Chongmin; Gao, Fei

2013-09-11

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governs the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability, and phase equilibrium.

Electron-Rich Driven Electrochemical Solid-State Amorphization in Li-Si Alloys

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

Wang, Zhiguo; Gu, Meng; Zhou, Yungang

2013-08-14

The physical and chemical behaviors of materials used in energy storage devices, such as lithium-ion batteries (LIBs), are mainly controlled by an electrochemical process, which normally involves insertion/extraction of ions into/from a host lattice with a concurrent flow of electrons to compensate charge balance. The fundamental physics and chemistry governing the behavior of materials in response to the ions insertion/extraction is not known. Herein, a combination of in situ lithiation experiments and large-scale ab initio molecular dynamics simulations are performed to explore the mechanisms of the electrochemically driven solid-state amorphization in Li-Si systems. We find that local electron-rich condition governsmore » the electrochemically driven solid-state amorphization of Li-Si alloys. This discovery provides the fundamental explanation of why lithium insertion in semiconductor and insulators leads to amorphization, whereas in metals, it leads to a crystalline alloy. The present work correlates electrochemically driven reactions with ion insertion, electron transfer, lattice stability and phase equilibrium.« less

Electrochemical properties of all solid state Li/S battery

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

Yu, Ji-Hyun; Park, Jin-Woo; Wang, Qing

All-solid-state lithium/sulfur (Li/S) battery is prepared using siloxane cross-linked network solid electrolyte at room temperature. The solid electrolytes show high ionic conductivity and good electrochemical stability with lithium and sulfur. In the first discharge curve, all-solid-state Li/S battery shows three plateau potential regions of 2.4 V, 2.12 V and 2.00 V, respectively. The battery shows the first discharge capacity of 1044 mAh g{sup −1}-sulfur at room temperature. This first discharge capacity rapidly decreases in 4th cycle and remains at 512 mAh g{sup −1}-sulfur after 10 cycles.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2003-11-04

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electromechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2004-09-28

An electrochemical energy storage device includes a number of solid-state thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Small Business Innovation Research Award Success Story: FuelCell Energy Inc.

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

None

2011-08-31

This success story describes FuelCell Energy Inc., a small business that manufactures stationary fuel cells. In collaboration with Sustainable Innovations LLC, and with support from a Small Business Innovation Research (SBIR) Award from the U.S. Department of Energy's Fuel Cell Technologies Program, FuelCell Energy Inc. has developed a highly efficient solid state electrochemical hydrogen compressor.

Overview of NASA Ultracapacitor Technology

NASA Technical Reports Server (NTRS)

Hill, Curtis W.

2017-01-01

NASA needed a lower mass, reliable, and safe medium for energy storage for ground-based and space applications. Existing industry electrochemical systems are limited in weight, charge rate, energy density, reliability, and safety. We chose a ceramic perovskite material for development, due to its high inherent dielectric properties, long history of use in the capacitor industry, and the safety of a solid state material.

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.

Titanium dioxide@polypyrrole core-shell nanowires for all solid-state flexible supercapacitors

NASA Astrophysics Data System (ADS)

Yu, Minghao; Zeng, Yinxiang; Zhang, Chong; Lu, Xihong; Zeng, Chenghui; Yao, Chenzhong; Yang, Yangyi; Tong, Yexiang

2013-10-01

Herein, we developed a facile two-step process to synthesize TiO2@PPy core-shell nanowires (NWs) on carbon cloth and reported their improved electrochemical performance for flexible supercapacitors (SCs). The fabricated solid-state SC device based on TiO2@PPy core-shell NWs not only has excellent flexibility, but also exhibits remarkable electrochemical performance.Herein, we developed a facile two-step process to synthesize TiO2@PPy core-shell nanowires (NWs) on carbon cloth and reported their improved electrochemical performance for flexible supercapacitors (SCs). The fabricated solid-state SC device based on TiO2@PPy core-shell NWs not only has excellent flexibility, but also exhibits remarkable electrochemical performance. Electronic supplementary information (ESI) available: Experimental details, XRD pattern, FT-IR absorption spectrum and CV curves of TiO2@PPy NWs, and SEM images of the PPy. See DOI: 10.1039/c3nr03578f

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

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

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

2007-12-07

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

Electrochemical disinfection of repeatedly recycled blackwater in a free‐standing, additive‐free toilet

PubMed Central

Sellgren, Katelyn L.; Klem, Ethan J. D.; Piascik, Jeffrey R.; Stoner, Brian R.

2017-01-01

Abstract Decentralized, energy‐efficient waste water treatment technologies enabling water reuse are needed to sustainably address sanitation needs in water‐ and energy‐scarce environments. Here, we describe the effects of repeated recycling of disinfected blackwater (as flush liquid) on the energy required to achieve full disinfection with an electrochemical process in a prototype toilet system. The recycled liquid rapidly reached a steady state with total solids reliably ranging between 0.50 and 0.65% and conductivity between 20 and 23 mS/cm through many flush cycles over 15 weeks. The increase in accumulated solids was associated with increased energy demand and wide variation in the free chlorine contact time required to achieve complete disinfection. Further studies on the system at steady state revealed that running at higher voltage modestly improves energy efficiency, and established running parameters that reliably achieve disinfection at fixed run times. These results will guide prototype testing in the field. PMID:29242713

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

Titanium dioxide@polypyrrole core-shell nanowires for all solid-state flexible supercapacitors.

PubMed

Yu, Minghao; Zeng, Yinxiang; Zhang, Chong; Lu, Xihong; Zeng, Chenghui; Yao, Chenzhong; Yang, Yangyi; Tong, Yexiang

2013-11-21

Herein, we developed a facile two-step process to synthesize TiO2@PPy core-shell nanowires (NWs) on carbon cloth and reported their improved electrochemical performance for flexible supercapacitors (SCs). The fabricated solid-state SC device based on TiO2@PPy core-shell NWs not only has excellent flexibility, but also exhibits remarkable electrochemical performance.

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.

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.

High-performance solid state supercapacitors assembling graphene interconnected networks in porous silicon electrode by electrochemical methods using 2,6-dihydroxynaphthalen.

PubMed

Romanitan, Cosmin; Varasteanu, Pericle; Mihalache, Iuliana; Culita, Daniela; Somacescu, Simona; Pascu, Razvan; Tanasa, Eugenia; Eremia, Sandra A V; Boldeiu, Adina; Simion, Monica; Radoi, Antonio; Kusko, Mihaela

2018-06-25

The challenge for conformal modification of the ultra-high internal surface of nanoporous silicon was tackled by electrochemical polymerisation of 2,6-dihydroxynaphthalene using cyclic voltammetry or potentiometry and, notably, after the thermal treatment (800 °C, N 2 , 4 h) an assembly of interconnected networks of graphene strongly adhering to nanoporous silicon matrix resulted. Herein we demonstrate the achievement of an easy scalable technology for solid state supercapacitors on silicon, with excellent electrochemical properties. Accordingly, our symmetric supercapacitors (SSC) showed remarkable performance characteristics, comparable to many of the best high-power and/or high-energy carbon-based supercapacitors, their figures of merit matching under battery-like supercapacitor behaviour. Furthermore, the devices displayed high specific capacity values along with enhanced capacity retention even at ultra-high rates for voltage sweep, 5 V/s, or discharge current density, 100 A/g, respectively. The cycling stability tests performed at relatively high discharge current density of 10 A/g indicated good capacity retention, with a superior performance demonstrated for the electrodes obtained under cyclic voltammetry approach, which may be ascribed on the one hand to a better coverage of the porous silicon substrate and, on the other hand, to an improved resilience of the hybrid electrode to pore clogging.

In operando spectroscopic studies of high temperature electrocatalysts used for energy conversion

NASA Astrophysics Data System (ADS)

McIntyre, Melissa Dawn

Solid-state electrochemical cells are efficient energy conversion devices that can be used for clean energy production or for removing air pollutants from exhaust gas emitted by combustion processes. For example, solid oxide fuel cells generate electricity with low emissions from a variety of fuel sources; solid oxide electrolysis cells produce zero-emission H2 fuel; and solid-state DeNOx cells remove NOx gases from diesel exhaust. In order to maintain high conversion efficiencies, these systems typically operate at temperatures ≥ 500°C. The high operating temperatures, however, accelerate chemical and mechanical cell degradation. To improve device durability, a mechanistic understanding of the surface chemistry occurring at the cell electrodes (anode and cathode) is critical in terms of refining cell design, material selection and operation protocols. The studies presented herein utilized in operando Raman spectroscopy coupled with electrochemical measurements to directly correlate molecular/material changes with device performance in solid oxide cells under various operating conditions. Because excessive carbon accumulation with carbon-based fuels destroys anodes, the first three studies investigated strategies for mitigating carbon accumulation on Ni cermet anodes. Results from the first two studies showed that low amounts of solid carbon stabilized the electrical output and improved performance of solid oxide fuel cells operating with syn-gas (H 2/CO fuel mixture). The third study revealed that infiltrating anodes with Sn or BaO suppressed carbon accumulation with CH4 fuel and that H2O was the most effective reforming agent facilitating carbon removal. The last two studies explored how secondary phases formed in traditional solid oxide cell materials doped with metal oxides improve electrochemical performance. Results from the fourth study suggest that the mixed ion-electron conducting Zr5Ti7O24 secondary phase can expand the electrochemically active region and increase electrochemical activity in cermet electrodes. The final study of lanthanum strontium manganite cathodes infiltrated with BaO revealed the reversible decomposition/formation of a Ba3Mn2O8 secondary phase under applied potentials and proposed mechanisms for the enhanced electrocatalytic oxygen reduction associated with this compound under polarizing conditions. Collectively, these studies demonstrate that mechanistic information obtained from molecular/material specific techniques coupled with electrochemical measurements can be used to help optimize materials and operating conditions in solid-state electrochemical cells.

Membrane-entrapped microperoxidase as a 'solid-state' promoter in the electrochemistry of soluble metalloproteins.

PubMed Central

Brunori, M; Santucci, R; Campanella, L; Tranchida, G

1989-01-01

Immobilization of biological systems in solid matrices is presently of great interest, in view of the many potential advantages associated with both the higher stability of the immobilized macromolecules and the potential utilization for biotechnology. In the present paper the electrochemical behaviour of the undecapeptide from cytochrome c (called microperoxidase) tightly entrapped in cellulose triacetate membrane is reported; its utilization as 'solid-state' promoter in the electrochemistry of soluble metalloproteins is presented. The results obtained indicate that: (i) membrane-entrapped microperoxidase undergoes rapid reversible electron transfer at a glassy carbon electrode; (ii) the electrochemical process is diffusion-controlled; (iii) entrapped microperoxidase acts as 'solid-state' promoter in the electrochemistry of soluble cytochrome c and of azurin. PMID:2557833

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.

Challenge for lowering concentration polarization in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shimada, Hiroyuki; Suzuki, Toshio; Yamaguchi, Toshiaki; Sumi, Hirofumi; Hamamoto, Koichi; Fujishiro, Yoshinobu

2016-01-01

In the scope of electrochemical phenomena, concentration polarization at electrodes is theoretically inevitable, and lowering the concentration overpotential to improve the performance of electrochemical cells has been a continuing challenge. Electrodes with highly controlled microstructure, i.e., high porosity and uniform large pores are therefore essential to achieve high performance electrochemical cells. In this study, state-of-the-art technology for controlling the microstructure of electrodes has been developed for realizing high performance support electrodes of solid oxide fuel cells (SOFCs). The key is controlling the porosity and pore size distribution to improve gas diffusion, while maintaining the integrity of the electrolyte and the structural strength of actual sized electrode supports needed for the target application. Planar anode-supported SOFCs developed in this study realize 5 μm thick dense electrolyte (yttria-stabilized zirconia: YSZ) and the anode substrate (Ni-YSZ) of 53.6 vol.% porosity with a large median pore diameter of 0.911 μm. Electrochemical measurements reveal that the performance of the anode-supported SOFCs improves with increasing anode porosity. This Ni-YSZ anode minimizes the concentration polarization, resulting in a maximum power density of 3.09 W cm-2 at 800 °C using humidified hydrogen fuel without any electrode functional layers.

Bench-Scale and Pilot-Scale Treatment Technologies for the ...

EPA Pesticide Factsheets

Coal mine water (CMW) is typically treated to remove suspended solids, acidity, and soluble metals, but high concentrations of total dissolved solids (TDS) have been reported to impact the environment at several CMW discharge points. Consequently, various states have established TDS wastewater regulations and the US EPA has proposed a benchmark conductivity limit to reduce TDS impacts in streams near mining sites. Traditional CMW treatment effectively removes some TDS components, but is not effective in removing major salt ions due to their higher solubility. This paper describes the basic principles, effectiveness, advantages and disadvantages of various TDS removal technologies (adsorption, bioremediation, capacitive deionization, desalination, electro-chemical ion exchange, electrocoagulation, electrodialysis, ion exchange, membrane filtration, precipitation, and reverse osmosis) that have at least been tested in bench- and pilot-scale experiments. Recent discussions about new regulations to include total dissolved solids TDS) limits would propel interest in the TDS removal technologies focused on coal mine water. TDS removal is not a new concept and has been developed using different technologies for a number of applications, but coal mine water has unique characteristics (depending on the site, mining process, and solid-water-oxygen interactions), which make it unlikely to have a single technology predominating over others. What are some novel technolog

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-01-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium’s highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion–conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10−4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium–sulfur batteries. PMID:27307440

Nitrogen doped carbon derived from polyimide/multiwall carbon nanotube composites for high performance flexible all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Kim, Dae Kyom; Kim, Nam Dong; Park, Seung-Keun; Seong, Kwang-dong; Hwang, Minsik; You, Nam-Ho; Piao, Yuanzhe

2018-03-01

Flexible all-solid-state supercapacitors are desirable as potential energy storage systems for wearable technologies. Herein, we synthesize aminophenyl multiwall carbon nanotube (AP-MWCNT) grafted polyimide precursor by in situ polymerization method as a nitrogen-doped carbon precursor. Flexible supercapacitor electrodes are fabricated via a coating of carbon precursor on carbon cloth surface and carbonization at high temperature directly. The as-obtained electrodes, which can be directly used without any binders or additives, can deliver a high specific capacitance of 333.4 F g-1 at 1 A g-1 (based on active material mass) and excellent cycle stability with 103% capacitance retention after 10,000 cycles in a three-electrode system. The flexible all-solid-state supercapacitor device exhibits a high volumetric capacitance of 3.88 F cm-3 at a current density of 0.02 mA cm-3. And also the device can deliver a maximum volumetric energy density of 0.50 mWh cm-3 and presents good cycling stability with 85.3% capacitance retention after 10,000 cycles. This device cell can not only show extraordinary mechanical flexibilities allowing folding, twisting, and rolling but also demonstrate remarkable stable electrochemical performances under their forms. This work provides a novel approach to obtain carbon textile-based flexible supercapacitors with high electrochemical performance and mechanical flexibility.

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

NASA Astrophysics Data System (ADS)

Kun, Kelvin; Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-06-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium's highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (˜3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion-conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10-4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium-sulfur 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

A lithium superionic conductor.

PubMed

Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio

2011-07-31

Batteries are a key technology in modern society. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10(-2) S cm(-1)) only at 50-80 °C, which is one order of magnitude lower than those of organic liquid electrolytes. Here, we report a lithium superionic conductor, Li(10)GeP(2)S(12) that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm(-1) at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window).

Solid-state energy storage module employing integrated interconnect board

DOEpatents

Rouillard, Jean; Comte, Christophe; Daigle, Dominik; Hagen, Ronald A.; Knudson, Orlin B.; Morin, Andre; Ranger, Michel; Ross, Guy; Rouillard, Roger; St-Germain, Philippe; Sudano, Anthony; Turgeon, Thomas A.

2000-01-01

The present invention is directed to an improved electrochemical energy storage device. The electrochemical energy storage device includes a number of solid-state, thin-film electrochemical cells which are selectively interconnected in series or parallel through use of an integrated interconnect board. The interconnect board is typically disposed within a sealed housing which also houses the electrochemical cells, and includes a first contact and a second contact respectively coupled to first and second power terminals of the energy storage device. The interconnect board advantageously provides for selective series or parallel connectivity with the electrochemical cells, irrespective of electrochemical cell position within the housing. In one embodiment, a sheet of conductive material is processed by employing a known milling, stamping, or chemical etching technique to include a connection pattern which provides for flexible and selective interconnecting of individual electrochemical cells within the housing, which may be a hermetically sealed housing. Fuses and various electrical and electro-mechanical devices, such as bypass, equalization, and communication devices for example, may also be mounted to the interconnect board and selectively connected to the electrochemical cells.

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

NASA Technical Reports Server (NTRS)

Chu, Chung-tse; Zheng, Haixing

1996-01-01

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

New Polymer Electrolyte Cell Systems

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

High Power Electrochemical Capacitors

DTIC Science & Technology

2012-03-23

electrochemical properties of vanadium oxide aerogels prepared by a freeze-drying process. Journal of the Electrochemical Society, 2004. 151(5): p...Electrochemical Society, 2002. 149(1): p. A26-A30. 12. Rolison, D.R. and B. Dunn, Electrically conductive oxide aerogels : new materials in...surface area vanadium oxide aerogels . Electrochemical and Solid-State Letters, 2000. 3(10): p. 457-459. 14. Shembel, E., et al., Synthesis, investigation

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.

Ion conduction in crystalline superionic solids and its applications

NASA Astrophysics Data System (ADS)

Chandra, Angesh

2014-06-01

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

Electrochemical Quartz Crystal Microbalance with Dissipation Real-Time Hydrodynamic Spectroscopy of Porous Solids in Contact with Liquids.

PubMed

Sigalov, Sergey; Shpigel, Netanel; Levi, Mikhael D; Feldberg, Moshe; Daikhin, Leonid; Aurbach, Doron

2016-10-18

Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, a new method of characterization of porous solids in contact with liquids has been developed. The dynamic gravimetric information on the growing, dissolving, or stationary stored solid deposits is supplemented by their precise in-operando porous structure characterization on a mesoscopic scale. We present a very powerful method of quartz-crystal admittance modeling of hydrodynamic solid-liquid interactions in order to extract the porous structure parameters of solids during their formation in real time, using different deposition modes. The unique hydrodynamic spectroscopic characterization of electrolytic and rf-sputtered solid Cu coatings that we use for our "proof of concept" provides a new strategy for probing various electrochemically active thin and thick solid deposits, thereby offering inexpensive, noninvasive, and highly efficient quantitative control over their properties. A broad spectrum of applications of our method is proposed, from various metal electroplating and finishing technologies to deeper insight into dynamic build-up and subsequent development of solid-electrolyte interfaces in the operation of Li-battery electrodes, as well as monitoring hydrodynamic consequences of metal corrosion, and growth of biomass coatings (biofouling) on different solid surfaces in seawater.

Chemically and compositionally modified solid solution disordered multiphase nickel hydroxide positive electrode for alkaline rechargeable electrochemical cells

DOEpatents

Ovshinsky, Stanford R.; Corrigan, Dennis; Venkatesan, Srini; Young, Rosa; Fierro, Christian; Fetcenko, Michael A.

1994-01-01

A high capacity, long cycle life positive electrode for use in an alkaline rechargeable electrochemical cell comprising: a solid solution nickel hydroxide material having a multiphase structure that comprises at least one polycrystalline .gamma.-phase including a polycrystalline .gamma.-phase unit cell comprising spacedly disposed plates with at least one chemical modifier incorporated around the plates, the plates having a range of stable intersheet distances corresponding to a 2.sup.+ oxidation state and a 3.5.sup.+, or greater, oxidation state; and at least one compositional modifier incorporated into the solid solution nickel hydroxide material to promote the multiphase structure.

Special Issue on Powering the Future Force: New Power & Energy Technologies for the Warfighter (AMMTIAC Quarterly, Volume 4, Number 1 / WSTIAC Quarterly, Volume 9, Number 1)

DTIC Science & Technology

2009-04-27

an aromatic acidic polymer such as SPEEK or SPSf. Figure 5 shows four basic polymers in which benzimidazole (BIm), amino- benzimidazole (ABIm...Z., A. Manthiram, and M. D. Guiver, “Blend Membranes Based on Sulfonated Polyetheretherketone and Polysulfone Bearing Benzimidazole Side Groups for...Sulfonated Poly(ether ether ketone) and Polysulfone Bearing Benzimidazole Side Groups for Direct Methanol Fuel Cells,” Electrochemical and Solid State Letters

A flexible Li-ion battery with design towards electrodes electrical insulation

NASA Astrophysics Data System (ADS)

Vieira, E. M. F.; Ribeiro, J. F.; Sousa, R.; Correia, J. H.; Goncalves, L. M.

2016-08-01

The application of micro electromechanical systems (MEMS) technology in several consumer electronics leads to the development of micro/nano power sources with high power and MEMS integration possibility. This work presents the fabrication of a flexible solid-state Li-ion battery (LIB) (~2.1 μm thick) with a design towards electrodes electrical insulation, using conventional, low cost and compatible MEMS fabrication processes. Kapton® substrate provides flexibility to the battery. E-beam deposited 300 nm thick Ge anode was coupled with LiCoO2/LiPON (cathode/solid-state electrolyte) in a battery system. LiCoO2 and LiPON films were deposited by RF-sputtering with a power source of 120 W and 100 W, respectively. LiCoO2 film was annealed at 400 °C after deposition. The new design includes Si3N4 and LiPO thin-films, providing electrode electrical insulation and a battery chemical stability safeguard, respectively. Microstructure and battery performance were investigated by scanning electron microscopy, electric resistivity and electrochemical measurements (open circuit potential, charge/discharge cycles and electrochemical impedance spectroscopy). A rechargeable thin-film and lightweight flexible LIB using MEMS processing compatible materials and techniques is reported.

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

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

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

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

PubMed

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

2017-04-01

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

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.

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

PubMed

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

2015-12-15

The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

Spectroscopic and Electrochemical Properties of Lithium-Rich LiFePO4 Cathode Synthesized by Solid-State Reaction

NASA Astrophysics Data System (ADS)

Rosaiah, P.; Hussain, O. M.; Zhu, Jinghui; Qiu, Yejun

2017-08-01

Lithium iron phosphate (Li x FePO4) is synthesized by a solid-state reaction method. The structural, electrical and electrochemical properties are studied in detail. It is found that the increment of lithium concentration (up to x = 1.05) does not affect the structure of LiFePO4 but improves its electrical conductivity as well as electrochemical performance. Surface morphological studies exhibited the formation of rod-like nanoparticles with small size. Electric and dielectric properties are also investigated over a frequency range of 1 Hz-1 MHz at different temperatures. The conductivity increased with increasing temperature, which follows the Arrhenius relation with the activation energy of about 0.31 eV. And the electrochemical tests found that the Li1.05FePO4 cathode possessed improved discharge capacity with better cycling performance.

In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO2 Cathode in a Working All-Solid-State Battery.

PubMed

Gong, Yue; Zhang, Jienan; Jiang, Liwei; Shi, Jin-An; Zhang, Qinghua; Yang, Zhenzhong; Zou, Dongli; Wang, Jiangyong; Yu, Xiqian; Xiao, Ruijuan; Hu, Yong-Sheng; Gu, Lin; Li, Hong; Chen, Liquan

2017-03-29

We report a method for in situ atomic-scale observation of electrochemical delithiation in a working all-solid-state battery using a state-of-the-art chip based in situ transmission electron microscopy (TEM) holder and focused ion beam milling to prepare an all-solid-state lithium-ion battery sample. A battery consisting of LiCoO 2 cathode, LLZO solid state electrolyte and gold anode was constructed, delithiated and observed in an aberration corrected scanning transmission electron microscope at atomic scale. We found that the pristine single crystal LiCoO 2 became nanosized polycrystal connected by coherent twin boundaries and antiphase domain boundaries after high voltage delithiation. This is different from liquid electrolyte batteries, where a series of phase transitions take place at LiCoO 2 cathode during delithiation. Both grain boundaries become more energy favorable along with extraction of lithium ions through theoretical calculation. We also proposed a lithium migration pathway before and after polycrystallization. This new methodology could stimulate atomic scale in situ scanning/TEM studies of battery materials and provide important mechanistic insight for designing better all-solid-state battery.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

NASA Astrophysics Data System (ADS)

Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

2016-06-01

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Investigating Li 2NiO 2–Li 2CuO 2 Solid Solutions as High-Capacity Cathode Materials for Li-Ion Batteries

DOE PAGES

Xu, Jing; Renfrew, Sara; Marcus, Matthew A.; ...

2017-05-11

Li 2Ni 1–xCu xO 2 solid solutions were prepared by a solid-state method to study the correlation between composition and electrochemical performance. Cu incorporation improved the phase purity of Li 2Ni 1–xCu xO 2 with orthorhombic Immm structure, resulting in enhanced capacity. However, the electrochemical profiles suggested Cu incorporation did not prevent irreversible phase transformation during the electrochemical process, instead, it likely influenced the phase transformation upon lithium removal. By combining ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and differential electrochemical mass spectrometry (DEMS) measurements, this study elucidates the relevant phase transformation (e.g., crystal structure, local environment, andmore » charge compensation) and participation of electrons from lattice oxygen during the first cycle in these complex oxides.« less

Metal/Metal Oxide Differential Electrode pH Sensors

NASA Technical Reports Server (NTRS)

West, William; Buehler, Martin; Keymeulen, Didier

2007-01-01

Solid-state electrochemical sensors for measuring the degrees of acidity or alkalinity (in terms of pH values) of liquid solutions are being developed. These sensors are intended to supplant older electrochemical pH sensors that include glass electrode structures and reference solutions. The older sensors are fragile and subject to drift. The present developmental solid-state sensors are more rugged and are expected to be usable in harsh environments. The present sensors are based on a differential-electrode measurement principle. Each sensor includes two electrodes, made of different materials, in equilibrium with the solution of interest.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

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

1994-11-08

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

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

Synthesis and characterization of nanostructured electrodes for solid state ionic devices

NASA Astrophysics Data System (ADS)

Zhang, Yuelan

Solid-state electrochemical energy conversion and storage technologies such as fuel cells and lithium ion batteries will influence the way we use energy and the environment we live in. The demands for advanced power sources with high energy efficiency, minimum environmental impact, and low cost have been the impetus for the development of a new generation of batteries and fuel cells. Currently, lithium ion battery technology's greatest disadvantages are long-term cycling stability and high charge/discharge rate capabilities. On the other hand, fuel cell technology's greatest disadvantage is cost. It is found that these problems could be attenuated by the incorporation of nano-structured materials. But, we are still far away from possessing a solid scientific understanding of what goes on at the nanoscale inside these solid state ionic devices, and what is the relationship between nano-structures and their electrochemical properties, especially between the microstructure and electrode polarization and degradation. Electrode polarization represents a voltage loss in an electrochemical energy conversion process. Such understanding is critical for further progress in solid state ionic devices. This thesis focused on the design, fabrication, and characterization of nanostructured porous electrodes with desired composition and microstructure to minimize electrode polarization losses in the application of fuel cells and lithium ion batteries. Various chemical methods such as sol-gel, hydrothermal, surfactant, colloidal and polymer template-assisted processes have been applied in this work. And various characterization techniques have been used to explore the understanding of the microscopic features with electrochemical interfacial properties of the electrodes. Solid-state diffusion often limits the utilization and rate capability of electrode materials in a lithium-ion battery, especially at high charge/discharge rates. When the fluxes of Li+ insertion or extraction exceeds the diffusion-limited rate of Li+ transport within the bulk phase of an electrode, concentration polarization occurs. Further, large volume changes associated with Li+ insertion or extraction could induce stresses in bulk electrodes, potentially leading to mechanical failure. Porous electrodes with high surface-to-volume ratio would increase the electrochemical reaction surface and suppress the mechanical stress. But porous electrodes also increase the tortuosity of mass transport within solid electrodes. Interconnected porous materials would decrease the percolation threshold for porous electrodes. In this work, electrodes with unique architecture for lithium ion batteries have been fabricated to improve the cycleability, rate capability and capacity retention. Spinel LiMn2O4 with interconnected macropores was created using a glycine-nitrate combustion process. Both microstructure and phase crystallinity were optimized by adjusting the fuel/oxidant ratio. This macroporous LiMn2O4 positive electrode exhibited better capacity retention and rate capability than those with larger particle size prepared by solid state reaction. Detailed electrode kinetic studies indicated that the macroporous microstructure promoted lithium diffusion and the overall reaction process was not controlled by lithium diffusion. Nanostructured tin oxide thin films with columnar grains less than 20 nm were deposited on Au/Si substrate using a combustion CVD method. The microstructure was highly porous and open, and thus was easily accessible to liquid electrolyte. In addition, the microstructure with vertical and radial connectivity of active materials led to decreased tortuosity for mass transport within solid electrodes. Nanoparticles accommodated the large volume change during cycling. These thin film electrodes exhibited highly reversible specific capacity and good capacity retention. It is about 93% after 80 cycles at a charge/discharge rate of 0.3 mA/cm2. When discharged at 0.9 mA/cm2, the obtained capacity retention was about 64% of the capacity at 0.3 mA/cm2. Cathodic interfacial polarization represents the predominant loss in a low-temperature SOFC. In this thesis, several porous nanocomposite electrodes of mixed ionic and electronic conductors (MIEC) with high surface areas were designed and fabricated to improve to minimize the polarization resistance. For the first time, regular, homogeneous and dual porous MIEC electrodes were successfully fabricated using breath figure templating, which is self-assembly of the water droplets in polymer solution. The homogeneous macropores promoted rapid mass transport by decreasing the tortuosity. Further, mesoporous microstructure provided more surface areas for gas adsorption and more TPBs for the electrochemical reactions. The interfacial polarization resistances were 0.94 and 0.39 Ocm 2 at 700 and 750°C, respectively. Furthermore, electrodes consisting of strontium doped lanthanum manganite (LSM) and gadolinium doped ceria (GDC) were developed with a modified sol-gel process for honeycomb SOFCs based on stabilized zirconia electrolytes. The sol gel derived cathodes with fine grain size and large specific surface area, showed much lower interfacial polarization resistances than those prepared by other processing methods. And this process developed strong bonding between the electrode and electrolyte even at low temperatures. The interfacial polarization resistances were 0.65 and 0.16 Ocm 2 at 650 and 750°C, respectively. The mesoscopic regime of overlapping space charge effects had a positive effect on the electrode kinetics. Ceria is a very important catalytic material for fuel reforming in SOFCs and CO poisoning in PEM fuel cells. Especially, the design of a new generation SOFC requires the in-situ reforming of hydrocarbon fuels. In this work, nanostructured ceria was developed via a controlled hydrothermal process in a mixed water-ethanol medium. The microstructure, formation mechanism, and their surface catalytic properties were investigated.

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.

Micro/Nano Fabricated Solid-State Thermoelectric Generator Devices for Integrated High Voltage Power Sources

NASA Astrophysics Data System (ADS)

Fleurial, J.-P.; Ryan, M. A.; Snyder, G. J.; Huang, C.-K.; Whitacre, J. F.; Patel, J.; Lim, J.; Borshchevsky, A.

2002-01-01

Deep space missions have a strong need for compact, high power density, reliable and long life electrical power generation and storage under extreme temperature conditions. Except for electrochemical batteries and solar cells, there are currently no available miniaturized power sources. Conventional power generators devices become inefficient in extreme environments (such as encountered in Mars, Venus or outer planet missions) and rechargeable energy storage devices can only be operated in a narrow temperature range thereby limiting mission duration. The planned development of much smaller spacecrafts incorporating a variety of micro/nanodevices and miniature vehicles will require novel, reliable power technologies. It is also expected that such micro power sources could have a wide range of terrestrial applications, in particular when the limited lifetime and environmental limitations of batteries are key factors. Advanced solid-state thermoelectric combined with radioisotope or waste heat sources and low profile energy storage devices are ideally suited for these applications. The Jet Propulsion Laboratory has been actively pursuing the development of thermoelectric micro/nanodevices that can be fabricated using a combination of electrochemical deposition and integrated circuit processing techniques. Some of the technical challenges associated with these micro/nanodevice concepts, their expected level of performance and experimental fabrication and testing results to date are presented and discussed.

Optical and electrical interfacing technologies for living cell bio-chips.

PubMed

Shacham-Diamand, Y; Belkin, S; Rishpon, J; Elad, T; Melamed, S; Biran, A; Yagur-Kroll, S; Almog, R; Daniel, R; Ben-Yoav, H; Rabner, A; Vernick, S; Elman, N; Popovtzer, R

2010-06-01

Whole-cell bio-chips for functional sensing integrate living cells on miniaturized platforms made by micro-system-technologies (MST). The cells are integrated, deposited or immersed in a media which is in contact with the chip. The cells behavior is monitored via electrical, electrochemical or optical methods. In this paper we describe such whole-cell biochips where the signal is generated due to the genetic response of the cells. The solid-state platform hosts the biological component, i.e. the living cells, and integrates all the required micro-system technologies, i.e. the micro-electronics, micro-electro optics, micro-electro or magneto mechanics and micro-fluidics. The genetic response of the cells expresses proteins that generate: a. light by photo-luminescence or bioluminescence, b. electrochemical signal by interaction with a substrate, or c. change in the cell impedance. The cell response is detected by a front end unit that converts it to current or voltage amplifies and filters it. The resultant signal is analyzed and stored for further processing. In this paper we describe three examples of whole-cell bio chips, photo-luminescent, bioluminescent and electrochemical, which are based on the genetic response of genetically modified E. coli microbes integrated on a micro-fluidics MEMS platform. We describe the chip outline as well as the basic modeling scheme of such sensors. We discuss the highlights and problems of such system, from the point of view of micro-system-technology.

Graphene Based Ultra-Capacitors for Safer, More Efficient Energy Storage

NASA Technical Reports Server (NTRS)

Roberson, Luke B.; Mackey, Paul J.; Zide, Carson J.

2016-01-01

Current power storage methods must be continuously improved in order to keep up with the increasingly competitive electronics industry. This technological advancement is also essential for the continuation of deep space exploration. Today's energy storage industry relies heavily on the use of dangerous and corrosive chemicals such as lithium and phosphoric acid. These chemicals can prove hazardous to the user if the device is ruptured. Similarly they can damage the environment if they are disposed of improperly. A safer, more efficient alternative is needed across a wide range of NASA missions. One solution would a solid-state carbon based energy storage device. Carbon is a safer, less environmentally hazardous alternative to current energy storage materials. Using the amorphous carbon nanostructure, graphene, this idea of a safer portable energy is possible. Graphene was electrochemically produced in the lab and several coin cell devices were built this summer to create a working prototype of a solid-state graphene battery.

Cobalt terephthalate MOF-templated synthesis of porous nano-crystalline Co3O4 by the new indirect solid state thermolysis as cathode material of asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Bigdeli, Hadise; Moradi, Morteza; Hajati, Shaaker; Kiani, Mohammad Ali; Toth, Jozsef

2017-10-01

In this work, two different types of Co3O4 nano-crystals were synthesized by (i) conventional direct solid state thermolysis of cobalt terephthalate metal-organic framework (MOF-71) and (ii) new indirect solid state thermolysis of Co(OH)2 derived by alkaline aqueous treatment of MOF-71. The products were then characterized by X-ray diffraction technique (XRD), Fourier transforms infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Reflection electron energy loss spectroscopy (REELS), Brunauer, Emmett, and Teller (BET), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) techniques. By REELS analysis the energy band gap of MOF-71 was determined to be 3.7 eV. Further, electrochemical performance of each Co3O4 nanostructure was studied by the cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) in a three-electrode system in KOH electrolyte. An asymmetric supercapacitor was fabricated using indirect Co3O4 nanoparticles as cathode and electrochemically reduced graphene oxide as anode, and the electrochemical properties were studied and showed a high energy density of 13.51 Wh kg-1 along with a power density of 9775 W kg-1 and good cycling stability with capacitance retention rate of 85% after 2000 cycles.

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.

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Effect of NaI/I 2 mediators on properties of PEO/LiAlO 2 based all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Yin, Yijing; Zhou, Juanjuan; Mansour, Azzam N.; Zhou, Xiangyang

NaI/I 2 mediators and activated carbon were added into poly(ethylene oxide) (PEO)/lithium aluminate (LiAlO 2) electrolyte to fabricate composite electrodes. All solid-state supercapacitors were fabricated using the as prepared composite electrodes and a Nafion 117 membrane as a separator. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements were conducted to evaluate the electrochemical properties of the supercapacitors. With the addition of NaI/I 2 mediators, the specific capacitance increased by 27 folds up to 150 F g -1. The specific capacitance increased with increases in the concentration of mediators in the electrodes. The addition of mediators also reduced the electrode resistance and rendered a higher electron transfer rate between mediator and mediator. The stability of the all-solid-state supercapacitor was tested over 2000 charge/discharge cycles.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

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

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp; Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp; Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidatemore » for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.« less

Decontamination of produced water containing petroleum hydrocarbons by electrochemical methods: a minireview.

PubMed

dos Santos, Elisama Vieira; Bezerra Rocha, Jessica Horacina; de Araújo, Danyelle Medeiros; de Moura, Dayanne Chianca; Martínez-Huitle, Carlos Alberto

2014-01-01

Produced water (PW) is the largest waste stream generated in oil and gas industries. The drilling and extraction operations that are aimed to maximize the production of oil may be counterbalanced by the huge production of contaminated water (called PW) with pollutants, such as heavy metals, dissolved/suspended solids, and organic compounds. PW is conventionally treated through different physical, chemical, and biological methods. In offshore platforms, because of space constraints, compact physical and chemical systems are used. However, major research efforts are being developed with innovative technologies for treating PW in order to comply with reuse and discharge limits. Among them, electrochemical technologies have been proposed as a promising alternative for the treatment of this kind of wastewaters. Then, this paper presents a minireview of efficient electrochemical technologies used until now for treating PW generated by petrochemical industry.

Quasi-Solid-State Rechargeable Li-O2 Batteries with High Safety and Long Cycle Life at Room Temperature.

PubMed

Cho, Sung Man; Shim, Jimin; Cho, Sung Ho; Kim, Jiwoong; Son, Byung Dae; Lee, Jong-Chan; Yoon, Woo Young

2018-05-09

As interest in electric vehicles and mass energy storage systems continues to grow, Li-O 2 batteries are attracting much attention as a candidate for next-generation energy storage systems owing to their high energy density. However, safety problems related to the use of lithium metal anodes have hampered the commercialization of Li-O 2 batteries. Herein, we introduced a quasi-solid polymer electrolyte with excellent electrochemical, chemical, and thermal stabilities into Li-O 2 batteries. The ion-conducting QSPE was prepared by gelling a polymer network matrix consisting of poly(ethylene glycol) methyl ether methacrylate, methacrylated tannic acid, lithium trifluoromethanesulfonate, and nanofumed silica with a small amount of liquid electrolyte. The quasi-solid-state Li-O 2 cell consisted of a lithium powder anode, a quasi-solid polymer electrolyte, and a Pd 3 Co/multiwalled carbon nanotube cathode, which enhanced the electrochemical performance of the cell. This cell, which exhibited improved safety owing to the suppression of lithium dendrite growth, achieved a lifetime of 125 cycles at room temperature. These results show that the introduction of a quasi-solid electrolyte is a potentially new alternative for the commercialization of solid-state Li-O 2 batteries.

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

Printable Solid-State Lithium-Ion Batteries: A New Route toward Shape-Conformable Power Sources with Aesthetic Versatility for Flexible Electronics.

PubMed

Kim, Se-Hee; Choi, Keun-Ho; Cho, Sung-Ju; Choi, Sinho; Park, Soojin; Lee, Sang-Young

2015-08-12

Forthcoming flexible/wearable electronic devices with shape diversity and mobile usability garner a great deal of attention as an innovative technology to bring unprecedented changes in our daily lives. From the power source point of view, conventional rechargeable batteries (one representative example is a lithium-ion battery) with fixed shapes and sizes have intrinsic limitations in fulfilling design/performance requirements for the flexible/wearable electronics. Here, as a facile and efficient strategy to address this formidable challenge, we demonstrate a new class of printable solid-state batteries (referred to as "PRISS batteries"). Through simple stencil printing process (followed by ultraviolet (UV) cross-linking), solid-state composite electrolyte (SCE) layer and SCE matrix-embedded electrodes are consecutively printed on arbitrary objects of complex geometries, eventually leading to fully integrated, multilayer-structured PRISS batteries with various form factors far beyond those achievable by conventional battery technologies. Tuning rheological properties of SCE paste and electrode slurry toward thixotropic fluid characteristics, along with well-tailored core elements including UV-cured triacrylate polymer and high boiling point electrolyte, is a key-enabling technology for the realization of PRISS batteries. This process/material uniqueness allows us to remove extra processing steps (related to solvent drying and liquid-electrolyte injection) and also conventional microporous separator membranes, thereupon enabling the seamless integration of shape-conformable PRISS batteries (including letters-shaped ones) into complex-shaped objects. Electrochemical behavior of PRISS batteries is elucidated via an in-depth analysis of cell impedance, which provides a theoretical basis to enable sustainable improvement of cell performance. We envision that PRISS batteries hold great promise as a reliable and scalable platform technology to open a new concept of cell architecture and fabrication route toward flexible power sources with exceptional shape conformability and aesthetic versatility.

Design of high-performance cathode materials with single-phase pathway for sodium ion batteries: A study on P2-Nax(LiyMn1-y)O2 compounds

NASA Astrophysics Data System (ADS)

Yang, Lufeng; Li, Xiang; Ma, Xuetian; Xiong, Shan; Liu, Pan; Tang, Yuanzhi; Cheng, Shuang; Hu, Yan-Yan; Liu, Meilin; Chen, Hailong

2018-03-01

Sodium-ion batteries (SIBs) are an emerging electrochemical energy storage technology that has high promise for electrical grid level energy storage. High capacity, long cycle life, and low cost cathode materials are very much desired for the development of high performance SIB systems. Sodium manganese oxides with different compositions and crystal structures have attracted much attention because of their high capacity and low cost. Here we report our investigations into a group of promising lithium doped sodium manganese oxide cathode materials with exceptionally high initial capacity of ∼223 mAh g-1 and excellent capacity retentions, attributed primarily to the absence of phase transformation in a wide potential range of electrochemical cycling, as confirmed by in-operando X-ray diffraction (XRD), Rietveld refinement, and high-resolution 7Li solid-state NMR characterizations. The systematic study of structural evolution and the correlation with the electrochemical behavior of the doped cathode materials provides new insights into rational design of high-performance intercalation compounds by tailoring the composition and the crystal structure evolution in electrochemical cycling.

3D direct writing fabrication of electrodes for electrochemical storage devices

NASA Astrophysics Data System (ADS)

Wei, Min; Zhang, Feng; Wang, Wei; Alexandridis, Paschalis; Zhou, Chi; Wu, Gang

2017-06-01

Among different printing techniques, direct ink writing is commonly used to fabricate 3D battery and supercapacitor electrodes. The major advantages of using the direct ink writing include effectively building 3D structure for energy storage devices and providing higher power density and higher energy density than traditional techniques due to the increased surface area of electrode. Nevertheless, direct ink writing has high standards for the printing inks, which requires high viscosity, high yield stress under shear and compression, and well-controlled viscoelasticity. Recently, a number of 3D-printed energy storage devices have been reported, and it is very important to understand the printing process and the ink preparation process for further material design and technology development. We discussed current progress of direct ink writing technologies by using various electrode materials including carbon nanotube-based material, graphene-based material, LTO (Li4Ti5O12), LFP (LiFePO4), LiMn1-xFexPO4, and Zn-based metallic oxide. Based on achieve electrochemical performance, these 3D-printed devices deliver performance comparable to the energy storage device fabricated using traditional methods still leaving large room for further improvement. Finally, perspectives are provided on the potential future direction of 3D printing for all solid-state electrochemical energy storage devices.

Sensor apparatus using an electrochemical cell

DOEpatents

Thakur, Mrinal

2002-01-01

A novel technology for sensing mechanical quantities such as force, stress, strain, pressure and acceleration has been invented. This technology is based on a change in the electrochemically generated voltage (electromotive force) with application of force, stress, strain, pressure or acceleration. The change in the voltage is due to a change in the internal resistance of the electrochemical cell with a change in the relative position or orientation of the electrodes (anode and cathode) in the cell. The signal to be detected (e.g. force, stress, strain, pressure or acceleration) is applied to one of the electrodes to cause a change in the relative position or orientation between the electrodes. Various materials, solid, semisolid, gel, paste or liquid can be utilized as the electrolyte. The electrolyte must be an ion conductor. The examples of solid electrolytes include specific polymer conductors, polymer composites, ion conducting glasses and ceramics. The electrodes are made of conductors such as metals with dissimilar electronegativities. Significantly enhanced sensitivities, up to three orders of magnitude higher than that of comparable commercial sensors, are obtained. The materials are substantially less expensive than commercially used materials for mechanical sensors.

20th International Conference on Solid State Ionics (SSI 20)

DTIC Science & Technology

2016-05-20

Candidate as a Solid Electrolyte for Lithium - Ion Batteries Miriam Botros1, Ruzica Djenadic1, 2, 3 and Horst Hahn1, 2, 3; 1Joint Research Laboratory...Earth and Algae Based Aqueous Binders Make Environmentally Friendly High-Performance Anodes for Lithium - Ion Batteries Muhammad Hasanuzzaman and...Alberta, Canada. C2.22 Electrochemical Properties of All-Solid-State Lithium - Ion Batteries Using Li2CO3-Li3BO3 Electrolyte Toyoki Okumura, Tomonari

Skeleton/skin structured (RGO/CNTs)@PANI composite fiber electrodes with excellent mechanical and electrochemical performance for all-solid-state symmetric supercapacitors.

PubMed

Liu, Dong; Du, Pengcheng; Wei, Wenli; Wang, Hongxing; Wang, Qi; Liu, Peng

2018-03-01

Polyaniline coated reduced graphene oxide/carbon nanotube composite fibers ((RGO/CNTs)@PANI, RCP) with skeleton/skin structure are designed as fiber-shaped electrodes for high performance all-solid-state symmetric supercapacitor. The one-dimensional reduced graphene oxide/carbon nanotube composite fibers (RGO/CNTs, RC) are prepared via a simple in-situ reduction of graphene oxide in presence of carbon nanotubes in quartz glass pipes, which exhibit excellent mechanical performance of >193.4 MPa of tensile strength. Then polyaniline is coated onto the RC fibers by electrodepositing technique. The electrochemical properties of the RCP fiber-shaped electrodes are optimized by adjusting the feeding ratio of carbon nanotubes. The optimized one exhibits good electrochemical characteristic such as highest volumetric specific capacitance of 193.1 F cm -3 at 1 A cm -3 , as well as excellent cyclic retention of 92.60% after 2000 cyclic voltammetry cycles. Furthermore, the all-solid-state symmetric supercapacitor, fabricated by using the final composite fiber as both positive and negative electrodes pre-coated with the poly(vinyl alcohol)/H 2 SO 4 gel polyelectrolyte, possesses volumetric capacitance of 36.7 F cm -3 at 0.2 A cm -3 and could light up a red light-emitting diode easily. The excellent mechanical and electrochemical performances make the designed supercapacitor as promising high performance wearable energy storage device. Copyright © 2017 Elsevier Inc. All rights reserved.

Flexible solid-state supercapacitors based on carbon nanoparticles/MnO2 nanorods hybrid structure.

PubMed

Yuan, Longyan; Lu, Xi-Hong; Xiao, Xu; Zhai, Teng; Dai, Junjie; Zhang, Fengchao; Hu, Bin; Wang, Xue; Gong, Li; Chen, Jian; Hu, Chenguo; Tong, Yexiang; Zhou, Jun; Wang, Zhong Lin

2012-01-24

A highly flexible solid-state supercapacitor was fabricated through a simple flame synthesis method and electrochemical deposition process based on a carbon nanoparticles/MnO(2) nanorods hybrid structure using polyvinyl alcohol/H(3)PO(4) electrolyte. Carbon fabric is used as a current collector and electrode (mechanical support), leading to a simplified, highly flexible, and lightweight architecture. The device exhibited good electrochemical performance with an energy density of 4.8 Wh/kg at a power density of 14 kW/kg, and a demonstration of a practical device is also presented, highlighting the path for its enormous potential in energy management. © 2011 American Chemical Society

Well Monitoring System For EGS

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

Normann, Randy; Glowka, Dave; Normann, Charles

This grant is a collection of projects designed to move aircraft high temperature electronics technology into the geothermal industry. Randy Normann is the lead. He licensed the HT83SNL00 chip from Sandia National Labs. This chip enables aircraft developed electronics for work within a geothermal well logging tool. However, additional elements are needed to achieve commercially successful logging tools. These elements are offered by a strong list of industrial partners on this grant as: Electrochemical Systems Inc. for HT Rechargeable Batteries, Frequency Management Systems for 300C digital clock, Sandia National Labs for experts in high temperature solder, Honeywell Solid-State Electronics Centermore » for reprogrammable high temperature memory. During the course of this project MagiQ Technologies for high temperature fiber optics.« less

Vertically-aligned Mn(OH) 2 nanosheet films for flexible all-solid-state electrochemical supercapacitors

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

Yang, Ziyuan; Gong, Jiangfeng; Tang, Chunmei

We report that the arrangement of the electrode materials is a significant contributor for constructing high performance supercapacitor. Here, vertically-aligned Mn(OH) 2 nanosheet thin films were synthesized by cathodic electrodeposition technique on flexible Au coated polyethylene terephthalate substrates. Morphologies, microstructures, chemical compositions and valence state of the nanosheet films were characterized systematically. It shows that the nanosheets arranged vertically to the substrate, forming a porous nanowall structures and creating large open framework, which greatly facilitate the adsorption or diffusion of electrolyte ions for faradaic redox reaction. Electrochemical tests of the films show the specific capacitance as high as 240.2 Fmore » g -1 at 1.0 A g -1. The films were employed to assemble symmetric all-solid-state supercapacitors with LiCl/PVA gel severed as solid electrolyte. Finally, the solid devices exhibit high volumetric capacitance of 39.3 mF cm -3 at the current density 0.3 mA cm -3 with robust cycling stability. The superior performance is attributed to the vertically-aligned configuration.« less

Vertically-aligned Mn(OH) 2 nanosheet films for flexible all-solid-state electrochemical supercapacitors

DOE PAGES

Yang, Ziyuan; Gong, Jiangfeng; Tang, Chunmei; ...

2017-08-28

We report that the arrangement of the electrode materials is a significant contributor for constructing high performance supercapacitor. Here, vertically-aligned Mn(OH) 2 nanosheet thin films were synthesized by cathodic electrodeposition technique on flexible Au coated polyethylene terephthalate substrates. Morphologies, microstructures, chemical compositions and valence state of the nanosheet films were characterized systematically. It shows that the nanosheets arranged vertically to the substrate, forming a porous nanowall structures and creating large open framework, which greatly facilitate the adsorption or diffusion of electrolyte ions for faradaic redox reaction. Electrochemical tests of the films show the specific capacitance as high as 240.2 Fmore » g -1 at 1.0 A g -1. The films were employed to assemble symmetric all-solid-state supercapacitors with LiCl/PVA gel severed as solid electrolyte. Finally, the solid devices exhibit high volumetric capacitance of 39.3 mF cm -3 at the current density 0.3 mA cm -3 with robust cycling stability. The superior performance is attributed to the vertically-aligned configuration.« less

Operando observations of solid-state electrochemical reactions in Li-ion batteries by spatially resolved TEM EELS and electron holography.

PubMed

Yamamoto, Kazuo; Iriyama, Yasutoshi; Hirayama, Tsukasa

2017-02-08

All-solid-state Li-ion batteries having incombustible solid electrolytes are promising energy storage devices because they have significant advantages in terms of safety, lifetime and energy density. Electrochemical reactions, namely, Li-ion insertion/extraction reactions, commonly occur around the nanometer-scale interfaces between the electrodes and solid electrolytes. Thus, transmission electron microscopy (TEM) is an appropriate technique to directly observe such reactions, providing important information for understanding the fundamental solid-state electrochemistry and improving battery performance. In this review, we introduce two types of TEM techniques for operando observations of battery reactions, spatially resolved electron energy-loss spectroscopy in a TEM mode for direct detection of the Li concentration profiles and electron holography for observing the electric potential changes due to Li-ion insertion/extraction reactions. We visually show how Li-ion insertion/extractions affect the crystal structures, electronic structures, and local electric potential during the charge-discharge processes in these batteries. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Thermodynamic properties of ternary oxides in the system Ba-Fe-O using solid-state electrochemical cells with oxide and fluoride ion conducting electrolytes

NASA Astrophysics Data System (ADS)

Rakshit, S. K.; Parida, S. C.; Singh, Ziley; Prasad, R.; Venugopal, V.

2004-04-01

The standard molar Gibbs energy of formations of BaFe 12O 19(s), BaFe 2O 4(s), Ba 2Fe 2O 5(s), Ba 3Fe 2O 6(s) and Ba 5Fe 2O 8(s) have been determined using solid-state electrochemical technique employing CaF 2(s) as an electrolyte. The reversible e.m.f. values have been measured in the temperature range from 970 to 1151 K. The oxygen chemical potential corresponding to three phase equilibria involving technologically important compound BaFe 12O 19(s) has been determined using solid-state electrochemical technique employing CSZ as an electrolyte from 1048 to 1221 K. The values of Δ fGm0( T) for the above ternary oxides are given by ΔfG m0( BaFe12O19, s)/ kJ mol -1(±0.6)=-5431.3+1.5317 (T/ K) (970⩽T/ K⩽1151) ΔfG m0( BaFe2O4, s)/ kJ mol -1(±1.3)=-1461.4+0.3745 (T/ K) (970⩽T/ K⩽1151) ΔfG m0( Ba2Fe2O5, s)/ kJ mol -1(±1.4)=-2038.3+0.4433 (T/ K) (970⩽T/ K⩽1149) ΔfG m0( Ba3Fe2O6, s)/ kJ mol -1(±1.5)=-2700.1+0.6090 (T/ K) (969⩽T/ K⩽1150) and ΔfG m0( Ba5Fe2O8, s)/ kJ mol -1(±1.6)=-3984.1+0.9300 (T/ K) (973⩽T/ K⩽1150) The uncertainty estimates for Δ fGm0 includes the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. An isothermal oxygen potential diagram for the system Ba-Fe-O was constructed at 1100 K based on the thermodynamic data obtained in this study.

Enhancement of waste activated sludge aerobic digestion by electrochemical pre-treatment.

PubMed

Song, Li-Jie; Zhu, Nan-Wen; Yuan, Hai-Ping; Hong, Ying; Ding, Jin

2010-08-01

Electrochemical technology with a pair of RuO(2)/Ti mesh plate electrode is first applied to pre-treat Waste Activated Sludge (WAS) prior to aerobic digestion in this study. The effects of various operating conditions were investigated including electrolysis time, electric power, current density, initial pH of sludge and sludge concentration. The study showed that the sludge reduction increased with the electrolysis time, electric power or current density, while decreased with the sludge concentration. Additionally, higher or lower pH than 7.0 was propitious to remove organic matters. The electrochemical pre-treatment removed volatile solids (VS) and volatile suspended solids (VSS) by 2.75% and 7.87%, respectively, with a WAS concentration of 12.9 g/L, electrolysis time of 30 min, electric power of 5 W and initial sludge pH of 10. In the subsequent aerobic digestion, the sludge reductions for VS and VSS after solids retention time (SRT) of 17.5 days were 34.25% and 39.59%, respectively. However, a SRT of 23.5 days was necessary to achieve equivalent reductions without electrochemical pre-treatment. Sludge analysis by Scanning Electron Microscope (SEM) images and infrared (IR) spectra indicated that electrochemical pre-treatment can rupture sludge cells, remove and solubilize intracellular substances, especially protein and polysaccharide, and consequently enhance the aerobic digestion. (c) 2010 Elsevier Ltd. All rights reserved.

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

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

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

DOE PAGES

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng; ...

2017-05-24

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

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

Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang

2016-03-31

Following the discovery of the redox-active 1,4- bis-BF 3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF 3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1Dmore » and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF 3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.« less

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electrochemical reduction processes of solid compounds in high temperature molten salts.

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

Solid electrode processes fall in the central focus of electrochemistry due to their broad-based applications in electrochemical energy storage/conversion devices, sensors and electrochemical preparation. The electrolytic production of metals, alloys, semiconductors and oxides via the electrochemical reduction of solid compounds (especially solid oxides) in high temperature molten salts has been well demonstrated to be an effective and environmentally friendly process for refractory metal extraction, functional materials preparation as well as spent fuel reprocessing. The (electro)chemical reduction of solid compounds under cathodic polarizations generally accompanies a variety of changes at the cathode/melt electrochemical interface which result in diverse electrolytic products with different compositions, morphologies and microstructures. This report summarizes various (electro)chemical reactions taking place at the compound cathode/melt interface during the electrochemical reduction of solid compounds in molten salts, which mainly include: (1) the direct electro-deoxidation of solid oxides; (2) the deposition of the active metal together with the electrochemical reduction of solid oxides; (3) the electro-inclusion of cations from molten salts; (4) the dissolution-electrodeposition process, and (5) the electron hopping process and carbon deposition with the utilization of carbon-based anodes. The implications of the forenamed cathodic reactions on the energy efficiency, chemical compositions and microstructures of the electrolytic products are also discussed. We hope that a comprehensive understanding of the cathodic processes during the electrochemical reduction of solid compounds in molten salts could form a basis for developing a clean, energy efficient and affordable production process for advanced/engineering materials.

High-Performance All-Solid-State Na-S Battery Enabled by Casting-Annealing Technology.

PubMed

Fan, Xiulin; Yue, Jie; Han, Fudong; Chen, Ji; Deng, Tao; Zhou, Xiuquan; Hou, Singyuk; Wang, Chunsheng

2018-04-24

Room-temperature all-solid-state Na-S batteries (ASNSBs) using sulfide solid electrolytes are a promising next-generation battery technology due to the high energy, enhanced safety, and earth abundant resources of both sodium and sulfur. Currently, the sulfide electrolyte ASNSBs are fabricated by a simple cold-pressing process leaving with high residential stress. Even worse, the large volume change of S/Na 2 S during charge/discharge cycles induces additional stress, seriously weakening the less-contacted interfaces among the solid electrolyte, active materials, and the electron conductive agent that are formed in the cold-pressing process. The high and continuous increase of the interface resistance hindered its practical application. Herein, we significantly reduce the interface resistance and eliminate the residential stress in Na 2 S cathodes by fabricating Na 2 S-Na 3 PS 4 -CMK-3 nanocomposites using melting-casting followed by stress-release annealing-precipitation process. The casting-annealing process guarantees the close contact between the Na 3 PS 4 solid electrolyte and the CMK-3 mesoporous carbon in mixed ionic/electronic conductive matrix, while the in situ precipitated Na 2 S active species from the solid electrolyte during the annealing process guarantees the interfacial contact among these three subcomponents without residential stress, which greatly reduces the interfacial resistance and enhances the electrochemical performance. The in situ synthesized Na 2 S-Na 3 PS 4 -CMK-3 composite cathode delivers a stable and highly reversible capacity of 810 mAh/g at 50 mA/g for 50 cycles at 60 °C. The present casting-annealing strategy should provide opportunities for the advancement of mechanically robust and high-performance next-generation ASNSBs.

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

DOE PAGES

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

2016-06-30

A fluorine-doped antiperovskite Li-ion conducto Li 2(OH)X (X=Cl, Br) is shown to be a promising candidat for a solid electrolyte in an all-solid-state Li-ion rechargeabl battery. Substitution of F¯ for OH¯ transforms orthorhombi Li 2OHCl to a room-temperature cubic phase, which show electrochemical stability to 9 V versus Li +/Li and two orders o magnitude higher Li-ion conductivity than that of orthorhombi Li 2OHCl. As a result, an all-solid-state Li/LiFePO 4 with F-dope Li 2OHCl as the solid electrolyte showed good cyclability an a high coulombic efficiency over 40 charge/discharge cycles

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.

Quasi-solid state electrolytes for low-grade thermal energy harvesting using a cobalt redox couple.

PubMed

Taheri, Abuzar; MacFarlane, Douglas; Pozo-Gonzalo, Cristina; Pringle, Jennifer M

2018-06-06

Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low-grade waste heat from a variety of different natural and man-made sources. The development of solid or quasi-solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent-based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3-methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Gogotsi, Yury; Presser, Volker; Kumbur, Emin Caglan

The present invention generally relates to devices for energy storage technologies, and more particularly to electrochemical flow capacitor systems and applications. In some aspects, these flow capacitors have at least one electrode comprising a non-stationary solid or semi-solid composition comprising supercapacitive particles and an electrolytic solvent in electrical communication with at least one current collector, and energy is stored and/or released by charging and/or discharging the electrode(s).

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.

Modeling the hydrodynamic and electrochemical efficiency of semi-solid flow batteries

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

Brunini, VE; Chiang, YM; Carter, WC

2012-05-01

A mathematical model of flow cell operation incorporating hydrodynamic and electrochemical effects in three dimensions is developed. The model and resulting simulations apply to recently demonstrated high energy-density semi-solid flow cells. In particular, state of charge gradients that develop during low flow rate operation and their effects on the spatial non-uniformity of current density within flow cells are quantified. A one-dimensional scaling model is also developed and compared to the full three-dimensional simulation. The models are used to demonstrate the impact of the choice of electrochemical couple on flow cell performance. For semi-solid flow electrodes, which can use solid activemore » materials with a wide variety of voltage-capacity responses, we find that cell efficiency is maximized for electrochemical couples that have a relatively flat voltage vs. capacity curve, operated under slow flow conditions. For example, in flow electrodes limited by macroscopic charge transport, an LiFePO4-based system requires one-third the polarization to reach the same cycling rate as an LiCoO2-based system, all else being equal. Our conclusions are generally applicable to high energy density flow battery systems, in which flow rates can be comparatively low for a given required power. (C) 2012 Elsevier Ltd. All rights reserved.« less

Chip-based generation of carbon nanodots via electrochemical oxidation of screen printed carbon electrodes and the applications for efficient cell imaging and electrochemiluminescence enhancement

NASA Astrophysics Data System (ADS)

Xu, Yuanhong; Liu, Jingquan; Zhang, Jizhen; Zong, Xidan; Jia, Xiaofang; Li, Dan; Wang, Erkang

2015-05-01

A portable lab-on-a-chip methodology to generate ionic liquid-functionalized carbon nanodots (CNDs) was developed via electrochemical oxidation of screen printed carbon electrodes. The CNDs can be successfully applied for efficient cell imaging and solid-state electrochemiluminescence sensor fabrication on the paper-based chips.A portable lab-on-a-chip methodology to generate ionic liquid-functionalized carbon nanodots (CNDs) was developed via electrochemical oxidation of screen printed carbon electrodes. The CNDs can be successfully applied for efficient cell imaging and solid-state electrochemiluminescence sensor fabrication on the paper-based chips. Electronic supplementary information (ESI) available: Experimental section; Fig. S1. XPS spectra of the as-prepared CNDs after being dialyzed for 72 hours; Fig. S2. LSCM images showing time-dependent fluorescence signals of HeLa cells treated by the as-prepared CNDs; Tripropylamine analysis using the Nafion/CNDs modified ECL sensor. See DOI: 10.1039/c5nr01765c

Electron transfer from a solid-state electrode assisted by methyl viologen sustains efficient microbial reductive dechlorination of TCE.

PubMed

Aulenta, Federico; Catervi, Alessandro; Majone, Mauro; Panero, Stefania; Reale, Priscilla; Rossetti, Simona

2007-04-01

The ability to transfer electrons, via an extracellular path, to solid surfaces is typically exploited by microorganisms which use insoluble electron acceptors, such as iron-or manganese-oxides or inert electrodes in microbial fuel cells. The reverse process, i.e., the use of solid surfaces or electrodes as electron donors in microbial respirations, although largely unexplored, could potentially have important environmental applications, particularly for the removal of oxidized pollutants from contaminated groundwater or waste streams. Here we show, for the first time, that an electrochemical cell with a solid-state electrode polarized at -500 mV (vs standard hydrogen electrode), in combination with a low-potential redox mediator (methyl viologen), can efficiently transfer electrochemical reducing equivalents to microorganisms which respire using chlorinated solvents. By this approach, the reductive transformation of trichloroethene, a toxic yet common groundwater contaminant, to harmless end-products such as ethene and ethane could be performed. Furthermore, using a methyl-viologen-modified electrode we could even demonstrate that dechlorinating bacteria were able to accept reducing equivalents directly from the modified electrode surface. The innovative concept, based on the stimulation of dechlorination reactions through the use of solid-state electrodes (we propose for this process the acronym BEARD: Bio-Electrochemically Assisted Reductive Dechlorination), holds promise for in situ bioremediation of chlorinated-solvent-contaminated groundwater, and has several potential advantages over traditional approaches based on the subsurface injection of organic compounds. The results of this study raise the possibility that immobilization of selected redox mediators may be a general strategy for stimulating and controlling a range of microbial reactions using insoluble electrodes as electron donors.

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.

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.

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.

Functional Nanopores: A Solid-state Concept for Artificial Reaction Compartments and Molecular Factories.

PubMed

Puebla-Hellmann, Gabriel; Mayor, Marcel; Lörtscher, Emanuel

2016-01-01

On the road towards the long-term goal of the NCCR Molecular Systems Engineering to create artificial molecular factories, we aim at introducing a compartmentalization strategy based on solid-state silicon technology targeting zeptoliter reaction volumes and simultaneous electrical contact to ensembles of well-oriented molecules. This approach allows the probing of molecular building blocks under a controlled environment prior to their use in a complex molecular factory. Furthermore, these ultra-sensitive electrical conductance measurements allow molecular responses to a variety of external triggers to be used as sensing and feedback mechanisms. So far, we demonstrate the proof-of-concept by electrically contacting self-assembled mono-layers of alkane-dithiols as an established test system. Here, the molecular films are laterally constrained by a circular dielectric confinement, forming a so-called 'nanopore'. Device yields above 85% are consistently achieved down to sub-50 nm nanopore diameters. This generic platform will be extended to create distributed, cascaded reactors with individually addressable reaction sites, including interconnecting micro-fluidic channels for electrochemical communication among nanopores and sensing sites for reaction control and feedback. In this scientific outlook, we will sketch how such a solid-state nanopore concept can be used to study various aspects of molecular compounds tailored for operation in a molecular factory.

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

DOEpatents

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

2018-05-01

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

Process for making dense thin films

DOEpatents

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

2005-07-26

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 firing of device substrate 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.

Li Distribution Heterogeneity in Solid Electrolyte Li10GeP2S12 upon Electrochemical Cycling Probed by 7Li MRI.

PubMed

Chien, Po-Hsiu; Feng, Xuyong; Tang, Mingxue; Rosenberg, Jens T; O'Neill, Sean; Zheng, Jin; Grant, Samuel C; Hu, Yan-Yan

2018-04-19

All-solid-state rechargeable batteries embody the promise for high energy density, increased stability, and improved safety. However, their success is impeded by high resistance for mass and charge transfer at electrode-electrolyte interfaces. Li deficiency has been proposed as a major culprit for interfacial resistance, yet experimental evidence is elusive due to the challenges associated with noninvasively probing the Li distribution in solid electrolytes. In this Letter, three-dimensional 7 Li magnetic resonance imaging (MRI) is employed to examine Li distribution homogeneity in solid electrolyte Li 10 GeP 2 S 12 within symmetric Li/Li 10 GeP 2 S 12 /Li batteries. 7 Li MRI and the derived histograms reveal Li depletion from the electrode-electrolyte interfaces and increased heterogeneity of Li distribution upon electrochemical cycling. Significant Li loss at interfaces is mitigated via facile modification with a poly(ethylene oxide)/bis(trifluoromethane)sulfonimide Li salt thin film. This study demonstrates a powerful tool for noninvasively monitoring the Li distribution at the interfaces and in the bulk of all-solid-state batteries as well as a convenient strategy for improving interfacial stability.

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

Wilson, Richard M. (Compiler)

1996-01-01

Individual papers presented at the conference address the following topics: development of a micro-fiber nickel electrode for nickel-hydrogen cell, high performance nickel electrodes for space power application, bending properties of nickel electrodes for nickel-hydrogen batteries, effect of KOH concentration and anions on the performance of a Ni-H2 battery positive plate, advanced dependent pressure vessel nickel hydrogen spacecraft cell and battery design, electrolyte management considerations in modern nickel hydrogen and nickel cadmium cell and battery design, a novel unitized regenerative proton exchange membrane fuel cell, fuel cell systems for first lunar outpost - reactant storage options, the TMI regenerable solid oxide fuel cell, engineering development program of a closed aluminum-oxygen semi-cell system for an unmanned underwater vehicle, SPE OBOGS on-board oxygen generating system, hermetically sealed aluminum electrolytic capacitor, sol-gel technology and advanced electrochemical energy storage materials, development of electrochemical supercapacitors for EMA applications, and high energy density electrolytic capacitor.

Charge and discharge characteristics of lithium-ion graphite electrodes in solid-state cells

NASA Astrophysics Data System (ADS)

Lemont, S.; Billaud, D.

Lithium ions have been electrochemically intercalated into graphite in solid-state cells operating with solid polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with lithium perchlorate (LiClO 4). The working composite electrode is composed of active-divided natural graphite associated with P(EO) 8-LiClO 4 acting as a binder and a Li + ionic conductor. Intercalation and de-intercalation of Li + were performed using galvanostatic or voltammetry techniques. The curves obtained in our solid-state cells were compared with those performed in liquid ethylene carbonate-LiClO 4 electrolyte. It is shown that in solid-state cells, side reactions occur both in the reduction and in the oxidation processes which leads to some uncertainty in the determination of the maximum reversible capacity of the graphite material.

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

A stable room-temperature sodium-sulfur battery.

PubMed

Wei, Shuya; Xu, Shaomao; Agrawral, Akanksha; Choudhury, Snehashis; Lu, Yingying; Tu, Zhengyuan; Ma, Lin; Archer, Lynden A

2016-06-09

High-energy rechargeable batteries based on earth-abundant materials are important for mobile and stationary storage technologies. Rechargeable sodium-sulfur batteries able to operate stably at room temperature are among the most sought-after platforms because such cells take advantage of a two-electron-redox process to achieve high storage capacity from inexpensive electrode materials. Here we report a room-temperature sodium-sulfur battery that uses a microporous carbon-sulfur composite cathode, and a liquid carbonate electrolyte containing the ionic liquid 1-methyl-3-propylimidazolium-chlorate tethered to SiO2 nanoparticles. We show that these cells can cycle stably at a rate of 0.5 C (1 C=1675, mAh g(-1)) with 600 mAh g(-1) reversible capacity and nearly 100% Coulombic efficiency. By means of spectroscopic and electrochemical analysis, we find that the particles form a sodium-ion conductive film on the anode, which stabilizes deposition of sodium. We also find that sulfur remains interred in the carbon pores and undergo solid-state electrochemical reactions with sodium ions.

A Bamboo-Inspired Nanostructure Design for Flexible, Foldable, and Twistable Energy Storage Devices.

PubMed

Sun, Yongming; Sills, Ryan B; Hu, Xianluo; Seh, Zhi Wei; Xiao, Xu; Xu, Henghui; Luo, Wei; Jin, Huanyu; Xin, Ying; Li, Tianqi; Zhang, Zhaoliang; Zhou, Jun; Cai, Wei; Huang, Yunhui; Cui, Yi

2015-06-10

Flexible energy storage devices are critical components for emerging flexible electronics. Electrode design is key in the development of all-solid-state supercapacitors with superior electrochemical performances and mechanical durability. Herein, we propose a bamboo-like graphitic carbon nanofiber with a well-balanced macro-, meso-, and microporosity, enabling excellent mechanical flexibility, foldability, and electrochemical performances. Our design is inspired by the structure of bamboos, where a periodic distribution of interior holes along the length and graded pore structure at the cross section not only enhance their stability under different mechanical deformation conditions but also provide a high surface area accessible to the electrolyte and low ion-transport resistance. The prepared nanofiber network electrode recovers its initial state easily after 3-folded manipulation. The mechanically robust membrane is explored as a free-standing electrode for a flexible all-solid-state supercapacitor. Without the need for extra support, the volumetric energy and power densities based on the whole device are greatly improved compared to the state-of-the-art devices. Even under continuous dynamic operations of forceful bending (90°) and twisting (180°), the as-designed device still exhibits stable electrochemical performances with 100% capacitance retention. Such a unique supercapacitor holds great promise for high-performance flexible electronics.

A bamboo-inspired nanostructure design for flexible foldable and twistable energy storage devices

DOE PAGES

Sun, Yongming; Sills, Ryan B; Hu, Xianluo; ...

2015-05-26

Flexible energy storage devices are critical components for emerging flexible electronics. Electrode design is key in the development of all-solid-state supercapacitors with superior electrochemical performances and mechanical durability. We propose a bamboo-like graphitic carbon nanofiber with a well-balanced macro-, meso-, and microporosity, enabling excellent mechanical flexibility, foldability, and electrochemical performances. Our design is inspired by the structure of bamboos, where a periodic distribution of interior holes along the length and graded pore structure at the cross section not only enhance their stability under different mechanical deformation conditions but also provide a high surface area accessible to the electrolyte and lowmore » ion-transport resistance. The prepared nanofiber network electrode recovers its initial state easily after 3-folded manipulation. The mechanically robust membrane is explored as a free-standing electrode for a flexible all-solid-state supercapacitor. Without the need for extra support, the volumetric energy and power densities based on the whole device are greatly improved compared to the state-of-the-art devices. Furthermore, even under continuous dynamic operations of forceful bending (90°) and twisting (180°), the as-designed device still exhibits stable electrochemical performances with 100% capacitance retention. As a result, such a unique supercapacitor holds great promise for high-performance flexible electronics.« less

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).

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.

Semi-interpenetrating solid polymer electrolyte based on thiol-ene cross-linker for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Suk, Jungdon; Lee, Yu Hwa; Kim, Do Youb; Kim, Dong Wook; Cho, Song Yun; Kim, Ji Man; Kang, Yongku

2016-12-01

We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 × 10-4 S cm-1), improved mechanical stability, and good electrochemical stability for all-solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 °C and 132 mAh/g at 0.5 °C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety.

Investigation on the interface between Li10GeP2S12 electrolyte and carbon conductive agents in all-solid-state lithium battery.

PubMed

Yoon, Kyungho; Kim, Jung-Joon; Seong, Won Mo; Lee, Myeong Hwan; Kang, Kisuk

2018-05-23

All-solid-state batteries are considered as one of the attractive alternatives to conventional lithium-ion batteries, due to their intrinsic safe properties benefiting from the use of non-flammable solid electrolytes in ASSBs. However, one of the issues in employing the solid-state electrolyte is the sluggish ion transport kinetics arising from the chemical and physical instability of the interfaces among solid components including electrode material, electrolyte and additive agents. In this work, we investigate the stability of the interface between carbon conductive agents and Li 10 GeP 2 S 12 in a composite cathode and its effect on the electrochemical performance of ASSBs. It is found that the inclusion of various carbon conductive agents in composite cathode leads to inferior kinetic performance of the cathode despite expectedly enhanced electrical conductivity of the composite. We observe that the poor kinetic performance is attributed to a large interfacial impedance which is gradually developed upon the inclusions of the various carbon conductive agents regardless of their physical differences. The analysis through X-ray Photoelectron Spectroscopy suggests that the carbon additives in the composite cathode stimulate the electrochemical decomposition of LGPS electrolyte degrading its surface during cycling, indicating the large interfacial resistance stems from the undesirable decomposition of the electrolyte at the interface.

Toward practical all-solid-state lithium-ion batteries with high energy density and safety: Comparative study for electrodes fabricated by dry- and slurry-mixing processes

NASA Astrophysics Data System (ADS)

Nam, Young Jin; Oh, Dae Yang; Jung, Sung Hoo; Jung, Yoon Seok

2018-01-01

Owing to their potential for greater safety, higher energy density, and scalable fabrication, bulk-type all-solid-state lithium-ion batteries (ASLBs) employing deformable sulfide superionic conductors are considered highly promising for applications in battery electric vehicles. While fabrication of sheet-type electrodes is imperative from the practical point of view, reports on relevant research are scarce. This might be attributable to issues that complicate the slurry-based fabrication process and/or issues with ionic contacts and percolation. In this work, we systematically investigate the electrochemical performance of conventional dry-mixed electrodes and wet-slurry fabricated electrodes for ASLBs, by varying the different fractions of solid electrolytes and the mass loading. This information calls for a need to develop well-designed electrodes with better ionic contacts and to improve the ionic conductivity of solid electrolytes. As a scalable proof-of-concept to achieve better ionic contacts, a premixing process for active materials and solid electrolytes is demonstrated to significantly improve electrochemical performance. Pouch-type 80 × 60 mm2 all-solid-state LiNi0·6Co0·2Mn0·2O2/graphite full-cells fabricated by the slurry process show high cell-based energy density (184 W h kg-1 and 432 W h L-1). For the first time, their excellent safety is also demonstrated by simple tests (cutting with scissors and heating at 110 °C).

Development of Thick-Film Thermoelectric Microcoolers Using Electrochemical Deposition

NASA Technical Reports Server (NTRS)

Fleurial, J.-P.; Borshchevsky, A.; Ryan, M. A.; Phillips, W. M.; Snyder, J. G.; Caillat, T.; Kolawa, E. A.; Herman, J. A.; Mueller, P.; Nicolet, M.

2000-01-01

Advanced thermoelectric microdevices integrated into thermal management packages and low power, electrical source systems are of interest for a variety of space and terrestrial applications. By shrinking the size of the thermoelements, or legs, of these devices, it becomes possible to handle much higher heat fluxes, as well as operate at much lower currents and higher voltages that are more compatible with electronic components. The miniaturization of state-of-the-art thermoelectric module technology based on Bi2Te3 alloys is limited due to mechanical and manufacturing constraints for both leg dimensions (100-200 gm thick minimum) and the number of legs (100-200 legs maximum). We are investigating the development of novel microdevices combining high thermal conductivity substrate materials such as diamond, thin film metallization and patterning technology, and electrochemical deposition of thick thermoelectric films. It is anticipated that thermoelectric microcoolers with thousands of thermocouples and capable of pumping more than 200 W/sq cm over a 30 to 60 K temperature difference can be fabricated. In this paper, we report on our progress in developing an electrochemical deposition process for obtaining 10-50 microns thick films of Bi2Te3 and its solid solutions. Results presented here indicate that good quality n-type Bi2Te3, n-type Bi2Te(2.95)Se(0.05) and p-type Bi(0.5)Sb(1.5)Te3 thick films can be deposited by this technique. Some details about the fabrication of the miniature thermoelements are also described.

Carbon nanotubes--electronic/electrochemical properties and application for nanoelectronics and photonics.

PubMed

Sgobba, Vito; Guldi, Dirk M

2009-01-01

The fundamental chemical, redox, electrochemical, photoelectrochemical, optical and optoelectronic features of carbon nanotubes are surveyed with particular emphasis on the most relevant applications as electron donor/electron acceptor or as electron conductor/hole conductor materials, in solutions and in the solid state. Methods that aim at p- and n-doping as a means to favor hole or electron injection/transport are covered as well (critical review, 208 references).

LiCoPO4 cathode from a CoHPO4·xH2O nanoplate precursor for high voltage Li-ion batteries

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

Choi, Daiwon; Li, Xiaolin; Henderson, Wesley A.

2016-02-01

Highly crystalline LiCoPO4/C cathode has been synthesized without any impurities via single step solid-state reaction using CoHPO4xH2O nanoplates as a precursor obtained by simple precipitation route. The electrochemical test shows specific capacity as high as 125mAh/g at charge/discharge rate of C/10. Synthesis approach for obtaining CoHPO4xH2O nanoplate precursor and final LiCoPO4/C cathode using single step solid-state reaction have been characterized using X-ray diffraction, thermos gravimetric analyses (TGA) – differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The electrochemical test and cycling stability using different electrolytes, additive and separator have been investigated.

Nanodisperse transition metal electrodes (NTME) for electrochemical cells

DOEpatents

Striebel, Kathryn A.; Wen, Shi-Jie

2000-01-01

Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

Thermal management system and method for a solid-state energy storing device

DOEpatents

Rouillard, Roger; Domroese, Michael K.; Gauthier, Michel; Hoffman, Joseph A.; Lindeman, David D.; Noel, Joseph-Robert-Gaetan; Radewald, Vern E.; Ranger, Michel; Rouillard, Jean; Shiota, Toshimi; St-Germain, Philippe; Sudano, Anthony; Trice, Jennifer L.; Turgeon, Thomas A.

2000-01-01

An improved electrochemical energy storing device includes a number of thin-film electrochemical cells which are maintained in a state of compression through use of an internal or an external pressure apparatus. A thermal conductor, which is connected to at least one of the positive or negative contacts of each electrochemical cell, conducts current into and out of the electrochemical cells and also conducts thermal energy between the electrochemical cells and thermally conductive material disposed on a wall structure adjacent the conductors. The wall structure includes electrically resistive material, such as an anodized coating or a thin film of plastic. The thermal conductors are fabricated to include a spring mechanism which expands and contacts to maintain mechanical contact between the electrochemical cells and the thermally conductive material in the presence of relative movement between the electrochemical cells and the wall structure. An active cooling apparatus may be employed external to a hermetically sealed housing containing the electrochemical cells to enhance the transfer of thermal energy into and out of the electrochemical cells. An integrated interconnect board may be disposed within the housing onto which a number of electrical and electro-mechanical components are mounted. Heat generated by the components is conducted from the interconnect board to the housing using the thermal conductors.

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

Transforming exoelectrogens for biotechnology using synthetic biology.

PubMed

TerAvest, Michaela A; Ajo-Franklin, Caroline M

2016-04-01

Extracellular electron transfer pathways allow certain bacteria to transfer energy between intracellular chemical energy stores and extracellular solids through redox reactions. Microorganisms containing these pathways, exoelectrogens, are a critical part of microbial electrochemical technologies that aim to impact applications in bioenergy, biosensing, and biocomputing. However, there are not yet any examples of economically viable microbial electrochemical technologies due to the limitations of naturally occurring exoelectrogens. Here we first briefly summarize recent discoveries in understanding extracellular electron transfer pathways, then review in-depth the creation of customized and novel exoelectrogens for biotechnological applications. We analyze engineering efforts to increase current production in native exoelectrogens, which reveals that modulating certain processes within extracellular electron transfer are more effective than others. We also review efforts to create new exoelectrogens and highlight common challenges in this work. Lastly, we summarize work utilizing engineered exoelectrogens for biotechnological applications and the key obstacles to their future development. Fueled by the development of genetic tools, these approaches will continue to expand and genetically modified organisms will continue to improve the outlook for microbial electrochemical technologies. © 2015 Wiley Periodicals, Inc.

Micro/nanofabricated solid-state thermoelectric generator devices for integrated high voltage power sources

NASA Technical Reports Server (NTRS)

Fleurial, J. P.; Snyder, G. J.; Patel, J.; Huang, C. K.; Ryan, M. A.; Averback, R.; Chen, G.; Hill, C.

2002-01-01

The Jet Propulsion Laboratory has been actively pursuing the development of thermoelectric micro/nanodevices that can be fabricated using a combination of electrochemical deposition and integrated circuit processing techniques.

Supercapacitors specialities - Technology review

NASA Astrophysics Data System (ADS)

Münchgesang, Wolfram; Meisner, Patrick; Yushin, Gleb

2014-06-01

Commercial electrochemical capacitors (supercapacitors) are not limited to mobile electronics anymore, but have reached the field of large-scale applications, like smart grid, wind turbines, power for large scale ground, water and aerial transportation, energy-efficient industrial equipment and others. This review gives a short overview of the current state-of-the-art of electrochemical capacitors, their commercial applications and the impact of technological development on performance.

Supercapacitors specialities - Technology review

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

Münchgesang, Wolfram; Meisner, Patrick; Yushin, Gleb

2014-06-16

Commercial electrochemical capacitors (supercapacitors) are not limited to mobile electronics anymore, but have reached the field of large-scale applications, like smart grid, wind turbines, power for large scale ground, water and aerial transportation, energy-efficient industrial equipment and others. This review gives a short overview of the current state-of-the-art of electrochemical capacitors, their commercial applications and the impact of technological development on performance.

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.

Electrochemical membrane incinerator

DOEpatents

Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

2001-03-20

Electrochemical incineration of p-benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 .mu.g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called "supporting electrolyte" was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

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

PubMed

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

2013-07-23

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

Flexible Asymmetrical Solid-State Supercapacitors Based on Laboratory Filter Paper.

PubMed

Zhang, Leicong; Zhu, Pengli; Zhou, Fengrui; Zeng, Wenjin; Su, Haibo; Li, Gang; Gao, Jihua; Sun, Rong; Wong, Ching-Ping

2016-01-26

In this study, a flexible asymmetrical all-solid-state supercapacitor with high electrochemical performance was fabricated with Ni/MnO2-filter paper (FP) as the positive electrode and Ni/active carbon (AC)-filter paper as negative electrode, separated with poly(vinyl alcohol) (PVA)-Na2SO4 electrolyte. A simple procedure, such as electroless plating, was introduced to prepare the Ni/MnO2-FP electrode on the conventional laboratory FP, combined with the subsequent step of electrodeposition. Electrochemical results show that the as-prepared electrodes display outstanding areal specific capacitance (1900 mF/cm(2) at 5 mV/s) and excellent cycling performance (85.1% retention after 1000 cycles at 20 mA/cm(2)). Such a flexible supercapacitor assembled asymmetrically in the solid state exhibits a large volume energy density (0.78 mWh/cm(3)) and superior flexibility under different bending conditions. It has been demonstrated that the supercapacitors could be used as a power source to drive a 3 V light-emitting diode indicator. This study may provide an available method for designing and fabricating flexible supercapacitors with high performance in the application of wearable and portable electronics based on easily available materials.

Monolayer Nickel Cobalt Hydroxyl Carbonate for High Performance All-Solid-State Asymmetric Supercapacitors.

PubMed

Zhao, Yufeng; Ma, Hongnan; Huang, Shifei; Zhang, Xuejiao; Xia, Meirong; Tang, Yongfu; Ma, Zi-Feng

2016-09-07

The emergence of atomically thick nanolayer materials, which feature a short ion diffusion channel and provide more exposed atoms in the electrochemical reactions, offers a promising occasion to optimize the performance of supercapacitors on the atomic level. In this work, a novel monolayer Ni-Co hydroxyl carbonate with an average thickness of 1.07 nm is synthesized via an ordinary one-pot hydrothermal route for the first time. This unique monolayer structure can efficiently rise up the exposed electroactive sites and facilitate the surface dependent electrochemical reaction processes, and thus results in outstanding specific capacitance of 2266 F g(-1). Based on this material, an all-solid-state asymmetric supercapacitor is developed adopting alkaline PVA (poly(vinyl alcohol)) gel (PVA/KOH) as electrolyte, which performs remarkable cycling stability (no capacitance fade after 19 000 cycles) together with promising energy density of 50 Wh kg(-1) (202 μWh cm(-2)) and high power density of 8.69 kW kg(-1) (35.1 mW cm(-2)). This as-assembled all-solid-state asymmetric supercapacitor (AASC) holds great potential in the field of portable energy storage devices.

Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

PubMed

Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

2013-06-21

A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results.

Conjugated amplifying polymers for optical sensing applications.

PubMed

Rochat, Sébastien; Swager, Timothy M

2013-06-12

Thanks to their unique optical and electrochemical properties, conjugated polymers have attracted considerable attention over the last two decades and resulted in numerous technological innovations. In particular, their implementation in sensing schemes and devices was widely investigated and produced a multitude of sensory systems and transduction mechanisms. Conjugated polymers possess numerous attractive features that make them particularly suitable for a broad variety of sensing tasks. They display sensory signal amplification (compared to their small-molecule counterparts) and their structures can easily be tailored to adjust solubility, absorption/emission wavelengths, energy offsets for excited state electron transfer, and/or for use in solution or in the solid state. This versatility has made conjugated polymers a fluorescence sensory platform of choice in the recent years. In this review, we highlight a variety of conjugated polymer-based sensory mechanisms together with selected examples from the recent literature.

A review of high temperature co-electrolysis of H2O and CO2 to produce sustainable fuels using solid oxide electrolysis cells (SOECs): advanced materials and technology.

PubMed

Zheng, Yun; Wang, Jianchen; Yu, Bo; Zhang, Wenqiang; Chen, Jing; Qiao, Jinli; Zhang, Jiujun

2017-03-06

High-temperature solid oxide electrolysis cells (SOECs) are advanced electrochemical energy storage and conversion devices with high conversion/energy efficiencies. They offer attractive high-temperature co-electrolysis routes that reduce extra CO 2 emissions, enable large-scale energy storage/conversion and facilitate the integration of renewable energies into the electric grid. Exciting new research has focused on CO 2 electrochemical activation/conversion through a co-electrolysis process based on the assumption that difficult C[double bond, length as m-dash]O double bonds can be activated effectively through this electrochemical method. Based on existing investigations, this paper puts forth a comprehensive overview of recent and past developments in co-electrolysis with SOECs for CO 2 conversion and utilization. Here, we discuss in detail the approaches of CO 2 conversion, the developmental history, the basic principles, the economic feasibility of CO 2 /H 2 O co-electrolysis, and the diverse range of fuel electrodes as well as oxygen electrode materials. SOEC performance measurements, characterization and simulations are classified and presented in this paper. SOEC cell and stack designs, fabrications and scale-ups are also summarized and described. In particular, insights into CO 2 electrochemical conversions, solid oxide cell material behaviors and degradation mechanisms are highlighted to obtain a better understanding of the high temperature electrolysis process in SOECs. Proposed research directions are also outlined to provide guidelines for future research.

Toward ambient temperature operation with all-solid-state lithium metal batteries with a sp3 boron-based solid single ion conducting polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yunfeng; Cai, Weiwei; Rohan, Rupesh; Pan, Meize; Liu, Yuan; Liu, Xupo; Li, Cuicui; Sun, Yubao; Cheng, Hansong

2016-02-01

The ionic conductivity decay problem of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) when increase the lithium salt of the SPEs up to high concentration is here functionally overcome by the incorporation of a charge delocalized sp3 boron based single ion conducting polymer electrolyte (SIPE) with poly(ethylene oxide) to fabricate solid-state sp3 boron based SIPE membranes (S-BSMs). By characterizations, particularly differential scanning calorimeter (DSC) and ionic conductivity studies, the fabricated S-BSMs showed decreased melting points and increased ionic conductivity as steadily increase the content of sp3 boron based SIPE, which significantly improved the low temperature performance of the all-solid-state lithium batteries. The fabricated Li | S-BSMs | LiFePO4 cells exhibit highly electrochemical stability and excellent cycling at temperature below melting point of PEO, which has never been reported so far for SIPEs based all-solid-state lithium batteries.

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.

Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

2015-03-01

Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

On-chip supercapacitors with ultrahigh volumetric performance based on electrochemically co-deposited CuO/polypyrrole nanosheet arrays

NASA Astrophysics Data System (ADS)

Qian, Tao; Zhou, Jinqiu; Xu, Na; Yang, Tingzhou; Shen, Xiaowei; Liu, Xuejun; Wu, Shishan; Yan, Chenglin

2015-10-01

We introduce a new method for fabricating unique on-chip supercapacitors based on CuO/polypyrrole core/shell nanosheet arrays by means of direct electrochemical co-deposition on interdigital-like electrodes. The prepared all-solid-state device demonstrates exceptionally high specific capacitance of 1275.5 F cm-3 (˜40 times larger than that of CuO-only supercapacitors) and high-energy-density of 28.35 mWh cm-3, which are both significantly greater than other solid-state supercapacitors. More importantly, the device maintains approximately 100% capacity retention at 2.5 A cm-3 after 3000 cycles. The in situ co-deposition of CuO/polypyrrole nanosheets on interdigital substrate enables effective charge transport, electrode fabrication integrity, and device integration. Because of their high energy, power density, and stable cycling stability, these newly developed on-chip supercapacitors permit fast, reliable applications in portable and miniaturized electronic devices.

Solid-state synthesis of uniform Li2MnSiO4/C/graphene composites and their performance in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gong, Huaxu; Zhu, Yongchun; Wang, Linlin; Wei, Denghu; Liang, Jianwen; Qian, Yitai

2014-01-01

Uniform nanospherical Li2MnSiO4/C/graphene composites have been obtained by polyethylene glycol-600 (PEG-600) assisted solid-state reaction using spherical SiO2 as precursor, and heat treatment with the mixed carbon sources (glucose, cellulose acetate and graphene oxide). The transmission electron microscope (TEM) images show that Li2MnSiO4 nanospheres with size of 50 nm are embedded in the three-dimensional (3D) nest-like carbon network. Electrochemical measurements reveal that the composites exhibit first discharge capacity of 215.3 mAh g-1 under 0.05 C, together with a stable discharge capacity of 175 mAh g-1 after 40 cycles. The 3D carbon network and the carbon layer (amorphous carbon and graphene) are favorable for improving the electrochemical performance.

On-chip supercapacitors with ultrahigh volumetric performance based on electrochemically co-deposited CuO/polypyrrole nanosheet arrays.

PubMed

Qian, Tao; Zhou, Jinqiu; Xu, Na; Yang, Tingzhou; Shen, Xiaowei; Liu, Xuejun; Wu, Shishan; Yan, Chenglin

2015-10-23

We introduce a new method for fabricating unique on-chip supercapacitors based on CuO/polypyrrole core/shell nanosheet arrays by means of direct electrochemical co-deposition on interdigital-like electrodes. The prepared all-solid-state device demonstrates exceptionally high specific capacitance of 1275.5 F cm(-3) (∼40 times larger than that of CuO-only supercapacitors) and high-energy-density of 28.35 mWh cm(-3), which are both significantly greater than other solid-state supercapacitors. More importantly, the device maintains approximately 100% capacity retention at 2.5 A cm(-3) after 3000 cycles. The in situ co-deposition of CuO/polypyrrole nanosheets on interdigital substrate enables effective charge transport, electrode fabrication integrity, and device integration. Because of their high energy, power density, and stable cycling stability, these newly developed on-chip supercapacitors permit fast, reliable applications in portable and miniaturized electronic devices.

Core Perylene Diimide Designs via Direct Bay- and ortho-(Poly)trifluoromethylation: Synthesis, Isolation, X-Ray Structures, Optical and Electronic Properties

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

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue-Bin

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay- and ortho-substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Moreover, analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects from substituting electron-withdrawing groups at all three positions.« less

Core Perylene Diimide Designs via Direct Bay and Ortho (Poly)trifluoromethylation: Synthesis, Isolation, X-ray Structures, Optical and Electronic Properties

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

Clikeman, Tyler T.; Bukovsky, Eric V.; Wang, Xue B.

2015-09-22

We developed an efficient solvent- and catalyst-free direct polytrifluoromethylation of solid perylene-3,4,9,10-tetracarboxylic dianhydride that produced a new family of (poly)perfluoroalkyl bay and ortho substituted PDIs with two different imide substituents. Direct hydrogen substitution with CN group led to the synthesis of a cyanated perfluoroalkyl PDI derivative for the first time. Absorption, steady-state and time-resolved emission, X-ray diffraction, electrochemical, and gas-phase electron affinity data allowed for systematic studies of substitution effects at bay, ortho, and imide positions in the new PDIs. Solid-state packing showed remarkable variations in the intermolecular interactions that are important for charge transport and photophysical properties. Analysis ofmore » the electrochemical data for 143 electron poor PDIs, including newly reported compounds, revealed some general trends and peculiar effects of electron withdrawing group substitution at all three positions.« less

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

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

Highly Efficient Plastic Crystal Ionic Conductors for Solid-state Dye-sensitized Solar Cells

PubMed Central

Hwang, Daesub; Kim, Dong Young; Jo, Seong Mu; Armel, Vanessa; MacFarlane, Douglas R.; Kim, Dongho; Jang, Sung-Yeon

2013-01-01

We have developed highly efficient, ambient temperature, solid-state ionic conductors (SSICs) for dye-sensitized solar cells (DSSCs) by doping a molecular plastic crystal, succinonitrile (SN), with trialkyl-substituted imidazolium iodide salts. High performance SSICs with enhanced ionic conductivity (2–4 mScm−1) were obtained. High performance solid-state DSSCs with power conversion efficiency of 7.8% were fabricated using our SSICs combined with unique hierarchically nanostructured TiO2 sphere (TiO2-SP) photoelectrodes; these electrodes have significant macroporosity, which assists penetration of the solid electrolyte into the electrode. The performance of our solid-state DSSCs is, to the best of our knowledge, the highest reported thus far for cells using plastic crystal-based SSICs, and is comparable to that of the state-of-the-art DSSCs which use ionic liquid type electrolytes. This report provides a logical strategy for the development of efficient plastic crystal-based SSICs for DSSCs and other electrochemical devices. PMID:24343425

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

Graetz J.; Meng, Y.S.; McGilvray, T.

Oxides and their tailored structures are at the heart of electrochemical energy storage technologies and advances in understanding and controlling the dynamic behaviors in the complex oxides, particularly at the interfaces, during electrochemical processes will catalyze creative design concepts for new materials with enhanced and better-understood properties. Such knowledge is not accessible without new analytical tools. New innovative experimental techniques are needed for understanding the chemistry and structure of the bulk and interfaces, more importantly how they change with electrochemical processes in situ. Analytical Transmission Electron Microscopy (TEM) is used extensively to study electrode materials ex situ and is onemore » of the most powerful tools to obtain structural, morphological, and compositional information at nanometer scale by combining imaging, diffraction and spectroscopy, e.g., EDS (energy dispersive X-ray spectrometry) and Electron Energy Loss Spectrometry (EELS). Determining the composition/structure evolution upon electrochemical cycling at the bulk and interfaces can be addressed by new electron microscopy technique with which one can observe, at the nanometer scale and in situ, the dynamic phenomena in the electrode materials. In electrochemical systems, for instance in a lithium ion battery (LIB), materials operate under conditions that are far from equilibrium, so that the materials studied ex situ may not capture the processes that occur in situ in a working battery. In situ electrochemical operation in the ultra-high vacuum column of a TEM has been pursued by two major strategies. In one strategy, a 'nano-battery' can be fabricated from an all-solid-state thin film battery using a focused ion beam (FIB). The electrolyte is either polymer based or ceramic based without any liquid component. As shown in Fig. 1a, the interfaces between the active electrode material/electrolyte can be clearly observed with TEM imaging, in contrast to the composite electrodes/electrolyte interfaces in conventional lithium ion batteries, depicted in Fig.1b, where quantitative interface characterization is extremely difficult if not impossible. A second strategy involves organic electrolyte, though this approach more closely resembles the actual operation conditions of a LIB, the extreme volatility In Situ Analytical Electron Microscopy for Probing Nanoscale Electrochemistry by Ying Shirley Meng, Thomas McGilvray, Ming-Che Yang, Danijel Gostovic, Feng Wang, Dongli Zeng, Yimei Zhu, and Jason Graetz of the organic electrolytes present significant challenges for designing an in situ cell that is suitable for the vacuum environment of the TEM. Significant progress has been made in the past few years on the development of in situ electron microscopy for probing nanoscale electrochemistry. In 2008, Brazier et al. reported the first cross-section observation of an all solid-state lithium ion nano-battery by TEM. In this study the FIB was used to make a 'nano-battery,' from an all solid-state battery prepared by pulsed laser deposition (PLD). In situ TEM observations were not possible at that time due to several key challenges such as the lack of a suitable biasing sample holder and vacuum transfer of sample. In 2010, Yamamoto et al. successfully observed changes of electric potential in an all-solid-state lithium ion battery in situ with electron holography (EH). The 2D potential distribution resulting from movement of lithium ions near the positive-electrode/electrolyte interface was quantified. More recently Huang et al. and Wang et al. reported the in situ observations of the electrochemical lithiation of a single SnO{sub 2} nanowire electrode in two different in situ setups. In their approach, a vacuum compatible ionic liquid is used as the electrolyte, eliminating the need for complicated membrane sealing to prevent the evaporation of carbonate based organic electrolyte into the TEM column. One main limitation of this approach is that EELS spectral imaging is not possible due to the high plasmon signal of the ionic liquid. To this end, we have developed a novel in situ instrumental system combining analytical electron microscopy with advanced spectroscopy to probe the dynamic phenomena in an all solid-state nano-battery. In situ electron microscopy is a versatile technique that yields insights into challenging questions that could not be obtained using other techniques. However, in order to fully exploit the capabilities, a very carefully thought-out plan of action is essential. It is important to recognize that this is not just a simple characterization tool, but a collection of tools that make up a complete experimental set-up: the choice of FIB operation conditions, specimen holder for biasing, grid materials and design as well as microscope environment must be thoroughly considered before performing an experiment.« less

Carbon-Based Solid-State Calcium Ion-Selective Microelectrode and Scanning Electrochemical Microscopy: A Quantitative Study of pH-Dependent Release of Calcium Ions from Bioactive Glass.

PubMed

Ummadi, Jyothir Ganesh; Downs, Corey J; Joshi, Vrushali S; Ferracane, Jack L; Koley, Dipankar

2016-03-15

Solid-state ion-selective electrodes are used as scanning electrochemical microscope (SECM) probes because of their inherent fast response time and ease of miniaturization. In this study, we report the development of a solid-state, low-poly(vinyl chloride), carbon-based calcium ion-selective microelectrode (Ca(2+)-ISME), 25 μm in diameter, capable of performing an amperometric approach curve and serving as a potentiometric sensor. The Ca(2+)-ISME has a broad linear response range of 5 μM to 200 mM with a near Nernstian slope of 28 mV/log[a(Ca(2+))]. The calculated detection limit for Ca(2+)-ISME is 1 μM. The selectivity coefficients of this Ca(2+)-ISME are log K(Ca(2+),A) = -5.88, -5.54, and -6.31 for Mg(2+), Na(+), and K(+), respectively. We used this new type of Ca(2+)-ISME as an SECM probe to quantitatively map the chemical microenvironment produced by a model substrate, bioactive glass (BAG). In acidic conditions (pH 4.5), BAG was found to increase the calcium ion concentration from 0.7 mM ([Ca(2+)] in artificial saliva) to 1.4 mM at 20 μm above the surface. In addition, a solid-state dual SECM pH probe was used to correlate the release of calcium ions with the change in local pH. Three-dimensional pH and calcium ion distribution mapping were also obtained by using these solid-state probes. The quantitative mapping of pH and Ca(2+) above the BAG elucidates the effectiveness of BAG in neutralizing and releasing calcium ions in acidic conditions.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-03-02

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

DOEpatents

Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

2010-11-23

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

Electrochemical investigations of advanced materials for microelectronic and energy storage devices

NASA Astrophysics Data System (ADS)

Goonetilleke, Pubudu Chaminda

A broad range of electrochemical techniques are employed in this work to study a selected set of advanced materials for applications in microelectronics and energy storage devices. The primary motivation of this study has been to explore the capabilities of certain modern electrochemical techniques in a number of emerging areas of material processing and characterization. The work includes both aqueous and non-aqueous systems, with applications in two rather general areas of technology, namely microelectronics and energy storage. The sub-systems selected for investigation are: (i) Electrochemical mechanical and chemical mechanical planarization (ECMP and CMP, respectively), (ii) Carbon nanotubes in combination with room temperature ionic liquids (ILs), and (iii) Cathode materials for high-performance Li ion batteries. The first group of systems represents an important building block in the fabrication of microelectronic devices. The second and third groups of systems are relevant for new energy storage technologies, and have generated immense interests in recent years. A common feature of these different systems is that they all are associated with complex surface reactions that dictate the performance of the devices based on them. Fundamental understanding of these reactions is crucial to further development and expansion of their associated technologies. It is the complex mechanistic details of these surface reactions that we address using a judicious combination of a number of state of the art electrochemical techniques. The main electrochemical techniques used in this work include: (i) Cyclic voltammetry (CV) and slow scan cyclic voltammetry (SSCV, a special case of CV); (ii) Galvanostatic (or current-controlled) measurements; (iii) Electrochemical impedance spectroscopy (EIS), based on two different methodologies, namely, Fourier transform EIS (FT-EIS, capable of studying fast reaction kinetics in a time-resolved mode), and EIS using frequency response analysis (employed to study slow reactions such as solid state diffusion of Li). The designs of both the experimental equipment and the control variables change for studying the different aqueous and non-aqueous systems. The protocols for data analysis also change depending on the systems. In addition, it often becomes necessary to combine different aspects of the different experimental methods to obtain the necessary information about the system(s) under study. The experimental strategies and the associated theoretical considerations for developing these strategies are discussed in appropriate contexts of this work. CNT electrodes in combination with IL electrolytes are potentially important for electrochemical super-capacitors. We have carried out electrochemical investigation of such a system involving a paper-electrode of multiwall CNT in the IL of 1-Ethyl-3-methyl imidazolium ethylsulfate (EMIM-EtSO4). Our study concentrated on the analytical aspects of cyclic voltammetry (CV) to probe the double layer capacitance of these relatively unconventional systems. (that involve rather large charge-discharge time constants). Both theoretical and experimental aspects of CV for such systems have been discussed, focusing in particular, on the effects of faradaic side-reactions, electrolyte resistance and voltage scan speeds. The results have been analyzed using an electrode equivalent circuit model, demonstrating a method to account for the typical artifacts expected in CV of CNT-IL interfaces. Chemical-mechanical planarization (CMP) of copper has now become an integral part of modern semiconductor fabrication technology. Recently, electrochemical-mechanical planarization (ECMP) has emerged as a possible extension of CMP, where through voltage-activated removal of Cu surface layers, one can substantially minimize the down-force necessary for mechanical polishing However, the detailed electrochemical factors that are central to designing efficient abrasive-free electrolytes for ECMP are not clearly understood at the present time. The present work has addressed this issue by studying the relative electrochemical effects of selected different chemical additives. Controlling the surface reactions (that is controlling the voltage-induced material removal) in ECMP requires a carefully designed combination of a number of electrochemical input variables (voltage activation program and electrolyte composition). We have studied the main experimental factors for designing these parameters, using triangular and rectangular-voltage-pulse modulated dissolution of Cu in electrolytes of different chemical compositions. Applications of rechargeable Li ion batteries have considerably expanded in recent years. As a result, research activities involving material-fabrication and characterization for these batteries also have expanded during this period. The importance of studying these specific materials lies in the fact that the cathode plays a major role in its contribution to the battery performance LiMn2O4 cathodes are being considered for next generation of Li ion batteries. The current work focuses on a specific problem commonly associated with Li cathode systems, namely surface film formation on the cathodes. LiMn2O4 cathodes tend to develop native surface films in carbonate electrolytes. By combining D.C. SSCV with A.C. EIS, we have studied how these films would react with an electrolyte of LiBF4 in ethylene and diethyl carbonates. We have demonstrated that such reactions could affect the measurement of the characteristic electrochemical parameters of the cathode, namely the intercalation capacitance, initial capacity-loss, coulometric titration profiles, and the solid state diffusion coefficient of Li+. A generalized framework for data analysis, based on the considerations of electrode equivalent circuits, has been used to combine the results of the D.C. and A.C. measurements.

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.

Space Electrochemical Research and Technology Conference, 2nd, Cleveland, OH, Apr. 11-13, 1989, Proceedings

NASA Technical Reports Server (NTRS)

O'Donnell, Patricia M. (Editor)

1990-01-01

Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.

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.

Nonstoichiometric fluorides—Solid electrolytes for electrochemical devices: A review

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Sobolev, B. P.

2007-09-01

The solid electrolytes with fluorine-ion conductivity that were revealed during the analysis of the phase diagrams of the MF m - RF n systems within the program of search for new multicomponent fluoride crystalline materials carried out at the Shubnikov Institute of Crystallography, Russian Academy of Sciences, are described. The most widespread and promising materials are the nonstoichiometric phases with fluorite (CaF2) and tysonite (LaF3) structures, which are formed in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, or Pb; R = Sc, Y, or La-Lu). These phases have superionic fluorine conductivity due to the anion sublattice disorder. The ionic conductivity of crystals of both structure types has been studied and the limits of its change with composition and temperature are determined. Nonstoichiometric fluorides are used as solid electrolytes in chemical sensors, fluorine sources, and batteries. The prospects of the use of fluorine-ion conductors in solid-state electrochemical devices, principles of their operation, and the problems of optimization of their composition are discussed.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

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

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Lowering the operational temperature of all-solid-state lithium polymer cell with highly conductive and interfacially robust solid polymer electrolytes

NASA Astrophysics Data System (ADS)

Aldalur, Itziar; Martinez-Ibañez, Maria; Piszcz, Michal; Rodriguez-Martinez, Lide M.; Zhang, Heng; Armand, Michel

2018-04-01

Novel solid polymer electrolytes (SPEs), comprising of comb polymer matrix grafted with soft and disordered polyether moieties (Jeffamine®) and lithium bis(fluorosulfonyl)imide (LiFSI) are investigated in all-solid-state lithium metal (Li°) polymer cells. The LiFSI/Jeffamine-based SPEs are fully amorphous at room temperature with glass transitions as low as ca. -55 °C. They show higher ionic conductivities than conventional poly(ethylene oxide) (PEO)-based SPEs at ambient temperature region, and good electrochemical compatibility with Li° electrode. These exceptional properties enable the operational temperature of Li° | LiFePO4 cells to be decreased from an elevated temperature (70 °C) to room temperature. Those results suggest that LiFSI/Jeffamine-based SPEs can be promising electrolyte candidates for developing safe and high performance all-solid-state Li° batteries.

Vertically-aligned Co(OH)2 Nanosheet Films for Flexible All-solid-state Electrochemical Supercapacitor

NASA Astrophysics Data System (ADS)

Tian, Yazhou; Gong, Jiangfeng; Zhu, Weihua

2017-11-01

Vertically-aligned Co(OH)2 nanosheets were cathodically electrodeposited on a piece of gold coated polyethylene terephthalate (Au-PET) as an electrode material for supercapacitor. The Co(OH)2 electrode showed a high capacitance of 2695 F g-1 at 8 A g-1 in 1 M KOH aqueous electrolyte. Besides, the films were employed to assemble symmetric all-solid-state supercapacitors with PVA/LiCl gel served as solid electrolyte. The device exhibits an areal capacitance of 50.5 μF cm-2 at the current density of 2 μA cm-2 accompanied by excellent cycle stability.

Mechanically delaminated few layered MoS2 nanosheets based high performance wire type solid-state symmetric supercapacitors

NASA Astrophysics Data System (ADS)

Krishnamoorthy, Karthikeyan; Pazhamalai, Parthiban; Veerasubramani, Ganesh Kumar; Kim, Sang Jae

2016-07-01

Two dimensional nanostructures are increasingly used as electrode materials in flexible supercapacitors for portable electronic applications. Herein, we demonstrated a ball milling approach for achieving few layered molybdenum disulfide (MoS2) via exfoliation from their bulk. Physico-chemical characterizations such as X-ray diffraction, field emission scanning electron microscope, and laser Raman analyses confirmed the occurrence of exfoliated MoS2 sheets with few layers from their bulk via ball milling process. MoS2 based wire type solid state supercapacitors (WSCs) are fabricated and examined using cyclic voltammetry (CV), electrochemical impedance spectroscopy, and galvanostatic charge discharge (CD) measurements. The presence of rectangular shaped CV curves and symmetric triangular shaped CD profiles suggested the mechanism of charge storage in MoS2 WSC is due to the formation of electrochemical double layer capacitance. The MoS2 WSC device delivered a specific capacitance of 119 μF cm-1, and energy density of 8.1 nW h cm-1 with better capacitance retention of about 89.36% over 2500 cycles, which ensures the use of the ball milled MoS2 for electrochemical energy storage devices.

ECLSS evolution: Advanced instrumentation interface requirements. Volume 3: Appendix C

NASA Technical Reports Server (NTRS)

1991-01-01

An Advanced ECLSS (Environmental Control and Life Support System) Technology Interfaces Database was developed primarily to provide ECLSS analysts with a centralized and portable source of ECLSS technologies interface requirements data. The database contains 20 technologies which were previously identified in the MDSSC ECLSS Technologies database. The primary interfaces of interest in this database are fluid, electrical, data/control interfaces, and resupply requirements. Each record contains fields describing the function and operation of the technology. Fields include: an interface diagram, description applicable design points and operating ranges, and an explaination of data, as required. A complete set of data was entered for six of the twenty components including Solid Amine Water Desorbed (SAWD), Thermoelectric Integrated Membrane Evaporation System (TIMES), Electrochemical Carbon Dioxide Concentrator (EDC), Solid Polymer Electrolysis (SPE), Static Feed Electrolysis (SFE), and BOSCH. Additional data was collected for Reverse Osmosis Water Reclaimation-Potable (ROWRP), Reverse Osmosis Water Reclaimation-Hygiene (ROWRH), Static Feed Solid Polymer Electrolyte (SFSPE), Trace Contaminant Control System (TCCS), and Multifiltration Water Reclamation - Hygiene (MFWRH). A summary of the database contents is presented in this report.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

DOEpatents

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Pushing the Theoretical Limit of Li-CFx Batteries: A Tale of Bi-functional Electrolyte

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

Rangasamy, Ezhiylmurugan; Li, Juchuan; Sahu, Gayatri

2014-01-01

In a typical battery, electrodes deliver capacities less or equal the theoretical maxima of the electrode materials.1 The inert electrolyte functions solely as the ionic conductor without contribution to the cell capacity because of its distinct mono-function in the concept of conventional batteries. Here we demonstrate that the most energy-dense Li-CFx battery2 delivers a capacity exceeding the theoretical maximum of CFx with a solid electrolyte of Li3PS4 (LPS) that has dual functions: as the inert electrolyte at the anode and the active component at the cathode. Such a bi-functional electrolyte reconciles both inert and active characteristics through a synergistic dischargemore » mechanism of CFx and LPS. Li3PS4 is known as an inactive solid electrolyte with a broad electrochemical window over 5 V.3 The synergy at the cathode is through LiF, the discharge product of CFx, which activates the electrochemical discharge of LPS at a close electrochemical potential of CFx. Therefore, the solid-state Li-CFx batteries output 126.6% energy beyond their theoretic limits without compromising the stability of the cell voltage. The extra energy comes from the electrochemical discharge of LPS, the inert electrolyte. This bi-functional electrolyte revolutionizes the concept of conventional batteries and opens a new avenue for the design of batteries with an unprecedentedly high energy density.« less

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Solid state laser technology - A NASA perspective

NASA Technical Reports Server (NTRS)

Allario, F.

1985-01-01

NASA's program for developing solid-state laser technology and applying it to the Space Shuttle and Space Platform is discussed. Solid-state lasers are required to fulfill the Earth Observation System's requirements. The role of the Office of Aeronautics and Space Technology in developing a NASA tunable solid-state laser program is described. The major goals of the program involve developing a solid-state pump laser in the green, using AlGaAs array technology, pumping a Nd:YAG/SLAB crystal or glass, and fabricating a lidar system, with either a CO2 laser at 10.6 microns or a Nd:YAG laser at 1.06 microns, to measure tropospheric winds to an accuracy of + or - 1 m/s and a vertical resolution of 1 km. The procedures to be followed in order to visualize this technology plan include: (1) material development and characterization, (2) laser development, and (3) implementation of the lasers.

Flexible all solid-state supercapacitors based on chemical vapor deposition derived graphene fibers.

PubMed

Li, Xinming; Zhao, Tianshuo; Chen, Qiao; Li, Peixu; Wang, Kunlin; Zhong, Minlin; Wei, Jinquan; Wu, Dehai; Wei, Bingqing; Zhu, Hongwei

2013-11-07

Flexible all-solid-state supercapacitors based on graphene fibers are demonstrated in this study. Surface-deposited oxide nanoparticles are used as pseudo-capacitor electrodes to achieve high capacitance. This supercapacitor electrode has an areal capacitance of 42 mF cm(-2), which is comparable to the capacitance for fiber-based supercapacitors reported to date. During the bending and cycling of the fiber-based supercapacitor, the stability could be maintained without sacrificing the electrochemical performance, which provides a novel and simple way to develop flexible, lightweight and efficient graphene-based devices.

A Quasi-Solid-State Li-Ion Capacitor Based on Porous TiO2 Hollow Microspheres Wrapped with Graphene Nanosheets.

PubMed

Wang, Faxing; Wang, Chun; Zhao, Yujuan; Liu, Zaichun; Chang, Zheng; Fu, Lijun; Zhu, Yusong; Wu, Yuping; Zhao, Dongyuan

2016-12-01

The quasi-solid-state Li-ion capacitor is demonstrated with graphene nanosheets prepared by an electrochemical exfoliation as the positive electrode and the porous TiO 2 hollow microspheres wrapped with the same graphene nanosheets as the negative electrode, using a Li-ion conducting gel polymer electrolyte. This device may be the key to bridging the gap between conventional lithium-ion batteries and supercapacitors, meanwhile meeting the safety demands of electronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous nitrogen-doped carbon-glass ceramic cathodes for solid-state lithium-oxygen batteries.

PubMed

Kichambare, Padmakar; Rodrigues, Stanley; Kumar, Jitendra

2012-01-01

The composite of nitrogen-doped carbon (N-C) blend with lithium aluminum germanium phosphate (LAGP) was studied as cathode material in a solid-state lithium-oxygen cell. Composite electrodes exhibit high electrochemical activity toward oxygen reduction. Compared to the cell capacity of N-C blend cathode, N-C/LAGP composite cathode exhibits six times higher discharge cell capacity. A significant enhancement in cell capacity is attributed to higher electrocatalytic activity and fast lithium ion conduction ability of LAGP in the cathode. © 2011 American Chemical Society

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.

Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method making the same

DOEpatents

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

2011-03-08

The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. A preferred embodiment of the invented electrochemical cell generally comprises a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. A preferred novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

Aluminum oxyhydroxide based separator/electrolyte and battery system, and a method of making the same

DOEpatents

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

2011-02-15

The instant invention relates a solid-state electrochemical cell and a novel separator/electrolyte incorporated therein. The invented electrochemical cell generally comprising: a unique metal oxyhydroxide based (i.e. AlOOH) separator/electrolyte membrane sandwiched between a first electrode and a second electrode. The novel separator/electrolyte comprises a nanoparticulate metal oxyhydroxide, preferably AlOOH and a salt which are mixed and then pressed together to form a monolithic metal oxyhydroxide-salt membrane.

Electrochemical Protection of Thin Film Electrodes in Solid State Nanopores

PubMed Central

Harrer, Stefan; Waggoner, Philip S.; Luan, Binquan; Afzali-Ardakani, Ali; Goldfarb, Dario L.; Peng, Hongbo; Martyna, Glenn; Rossnagel, Stephen M.; Stolovitzky, Gustavo A.

2011-01-01

We have eliminated electrochemical surface oxidation and reduction as well as water decomposition inside sub-5-nm wide nanopores in conducting TiN membranes using a surface passivation technique. Nanopore ionic conductances, and therefore pore diameters, were unchanged in passivated pores after applying potentials of ±4.5 V for as long as 24 h. Water decomposition was eliminated by using aqueous 90% glycerol solvent. The use of a protective self-assembled monolayer of hexadecylphosphonic acid was also investigated. PMID:21597142

Systematic investigation on Cadmium-incorporation in Li₂FeSiO₄/C cathode material for lithium-ion batteries.

PubMed

Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

2014-05-27

Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li(+)-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material.

Systematic investigation on Cadmium-incorporation in Li2FeSiO4/C cathode material for lithium-ion batteries

PubMed Central

Zhang, Lu-Lu; Duan, Song; Yang, Xue-Lin; Liang, Gan; Huang, Yun-Hui; Cao, Xing-Zhong; Yang, Jing; Ni, Shi-Bing; Li, Ming

2014-01-01

Cadmium-incorporated Li2FeSiO4/C composites have been successfully synthesized by a solid-state reaction assisted with refluxing. The effect and mechanism of Cd-modification on the electrochemical performance of Li2FeSiO4/C were investigated in detail by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectra, transmission electron microscopy, positron annihilation lifetime spectroscopy and Doppler broadening spectrum, and electrochemical measurements. The results show that Cd not only exists in an amorphous state of CdO on the surface of LFS particles, but also enters into the crystal lattice of LFS. Positron annihilation lifetime spectroscopy and Doppler broadening spectrum analyses verify that Cd-incorporation increases the defect concentration and the electronic conductivity of LFS, thus improve the Li+-ion diffusion process. Furthermore, our electrochemical measurements verify that an appropriate amount of Cd-incorporation can achieve a satisfied electrochemical performance for LFS/C cathode material. PMID:24860942

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

A high-capacitance flexible solid-state supercapacitor based on polyaniline and Metal-Organic Framework (UiO-66) composites

NASA Astrophysics Data System (ADS)

Shao, Liang; Wang, Qian; Ma, Zhonglei; Ji, Zhanyou; Wang, Xiaoying; Song, Doudou; Liu, Yuguo; Wang, Ni

2018-03-01

Metal-Organic Frameworks (MOFs) attract increasing attention in the field of energy storage, however, poor conductivity in most MOFs largely hinders their electrical properties. In this work, an effective strategy is developed to make the polyaniline (PANI) molecular chains grow in the pores of UiO-66 as one of the MOFs (labeled as PANI/UiO-66) to form a fixed interpenetrating network structure by using the highly stable porous MOFs, through a variety of synergistic effects to enhance the conductivity and electrochemical properties. Moreover, the design and analysis about PANI/UiO-66 is reported for the first time to our knowledge. In addition, PANI/UiO-66 exhibits an extraordinary capacitance of 1015 F g-1 at 1 A g-1 by electrochemical test. At the same time, the symmetric flexible solid-state supercapacitors is also assembled and tested. The resultant supercapacitor shows a favorable specific capacitance of 647 F g-1 at 1 A g-1 and a high cycling stability (91% capacitance retention after 5000 cycles). The bending test indicates that the obtained supercapacitor is flexible and its performance is only decreased 10% after 800 bending cycles with a bending angle of 180. This flexible solid-state supercapacitor shows great potential in energy storage device.

A physics-based fractional order model and state of energy estimation for lithium ion batteries. Part I: Model development and observability analysis

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Fan, Guodong; Pan, Ke; Wei, Guo; Zhu, Chunbo; Rizzoni, Giorgio; Canova, Marcello

2017-11-01

The design of a lumped parameter battery model preserving physical meaning is especially desired by the automotive researchers and engineers due to the strong demand for battery system control, estimation, diagnosis and prognostics. In light of this, a novel simplified fractional order electrochemical model is developed for electric vehicle (EV) applications in this paper. In the model, a general fractional order transfer function is designed for the solid phase lithium ion diffusion approximation. The dynamic characteristics of the electrolyte concentration overpotential are approximated by a first-order resistance-capacitor transfer function in the electrolyte phase. The Ohmic resistances and electrochemical reaction kinetics resistance are simplified to a lumped Ohmic resistance parameter. Overall, the number of model parameters is reduced from 30 to 9, yet the accuracy of the model is still guaranteed. In order to address the dynamics of phase-change phenomenon in the active particle during charging and discharging, variable solid-state diffusivity is taken into consideration in the model. Also, the observability of the model is analyzed on two types of lithium ion batteries subsequently. Results show the fractional order model with variable solid-state diffusivity agrees very well with experimental data at various current input conditions and is suitable for electric vehicle applications.

Monitoring the Electrochemical Processes in the Lithium–Air Battery by Solid State NMR Spectroscopy

PubMed Central

2013-01-01

A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

New fluorescent azo-Schiff base Cu(II) and Zn(II) metal chelates; spectral, structural, electrochemical, photoluminescence and computational studies

NASA Astrophysics Data System (ADS)

Purtas, Fatih; Sayin, Koray; Ceyhan, Gokhan; Kose, Muhammet; Kurtoglu, Mukerrem

2017-06-01

A new Schiff base containing azo chromophore group obtained by condensation of 2-hydroxy-4-[(E)-phenyldiazenyl]benzaldehyde with 3,4-dimethylaniline (HL) are used for the syntheses of new copper(II) and zinc(II) chelates, [Cu(L)2], and [Zn(L)2], and characterized by physico-chemical and spectroscopic methods such as 1H and 13C NMR, IR, UV.-Vis. and elemental analyses. The solid state structure of the ligand was characterized by single crystal X-ray diffraction study. X-ray diffraction data was then used to calculate the harmonic oscillator model of aromaticity (HOMA) indexes for the rings so as to investigate of enol-imine and keto-amine tautomeric forms in the solid state. The phenol ring C10-C15 shows a considerable deviation from the aromaticity with HOMA value of 0.837 suggesting the shift towards the keto-amine tautomeric form in the solid state. The analytical data show that the metal to ligand ratio in the chelates was found to be 1:2. Theoretical calculations of the possible isomers of the ligand and two metal complexes are performed by using B3LYP method. Electrochemical and photoluminescence properties of the synthesized azo-Schiff bases were also investigated.

Polycarbonate-based polyurethane as a polymer electrolyte matrix for all-solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Bao, Junjie; Shi, Gaojian; Tao, Can; Wang, Chao; Zhu, Chen; Cheng, Liang; Qian, Gang; Chen, Chunhua

2018-06-01

Four kinds of polycarbonate-based polyurethane with 8-14 wt% hard segments content are synthesized via reactions of polycarbonatediol, hexamethylene diisocyanate and diethylene glycol. The mechanical strength of the polyurethanes increase with the increase of hard segments content. Solid polymer electrolytes composed of the polycarbonate-based polyurethanes and LiTFSI exhibits fascinating characteristics for all-solid-state lithium batteries with a high ionic conductivity of 1.12 × 10-4 S cm-1 at 80 °C, an electrochemical stability window up to 4.5 V (vs. Li+/Li), excellent mechanical strength and superior interfacial stability against lithium metal. The all-solid-state batteries using LiFePO4 cathode can deliver high discharge capacities (161, 158, 134 and 93 mAh g-1 at varied rates of 0.2, 0.5, 1 and 2 C) at 80 °C and excellent cycling performance (with 91% capacity retention after 600 cycles at 1 C). All the results indicate that such a polyurethane-based solid polymer electrolyte can be a promising candidate for all-solid-state lithium batteries.

Materials and Molecular Research Division annual report 1983

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

Searcy, A.W.; Muller, R.H.; Peterson, C.V.

1984-07-01

Progress is reported in the following fields: materials sciences (metallurgy and ceramics, solid-state physics, materials chemistry), chemical sciences (fundamental interactions, processes and techniques), actinide chemistry, fossil energy, electrochemical energy storage systems, superconducting magnets, semiconductor materials and devices, and work for others. (DLC)

Advanced Oxygen Systems for Aircraft (Systemes d’Oxygene Avances)

DTIC Science & Technology

1996-04-01

This purge gas sweeps out the nitrogen and at the same time fills the micro- pore structure of the molecular sieve with the product gas. When the...electrochemical (amperometry, voltametry , polarography, coulometry), (c) spectrometry (mass spectrometry, ultraviolet spectrometry), (d) solid-state

Achieving High-Energy-High-Power Density in a Flexible Quasi-Solid-State Sodium Ion Capacitor.

PubMed

Li, Hongsen; Peng, Lele; Zhu, Yue; Zhang, Xiaogang; Yu, Guihua

2016-09-14

Simultaneous integration of high-energy output with high-power delivery is a major challenge for electrochemical energy storage systems, limiting dual fine attributes on a device. We introduce a quasi-solid-state sodium ion capacitor (NIC) based on a battery type urchin-like Na2Ti3O7 anode and a capacitor type peanut shell derived carbon cathode, using a sodium ion conducting gel polymer as electrolyte, achieving high-energy-high-power characteristics in solid state. Energy densities can reach 111.2 Wh kg(-1) at power density of 800 W kg(-1), and 33.2 Wh kg(-1) at power density of 11200 W kg(-1), which are among the best reported state-of-the-art NICs. The designed device also exhibits long-term cycling stability over 3000 cycles with capacity retention ∼86%. Furthermore, we demonstrate the assembly of a highly flexible quasi-solid-state NIC and it shows no obvious capacity loss under different bending conditions.

Preliminary Electrochemical Characterization of Anode Supported Solid Oxide Cell (AS-SOC) Produced in the Institute of Power Engineering Operated in Electrolysis Mode (SOEC)

NASA Astrophysics Data System (ADS)

Kupecki, Jakub; Motyliński, Konrad; Skrzypkiewicz, Marek; Wierzbicki, Michał; Naumovich, Yevgeniy

2017-12-01

The article discusses the operation of solid oxide electrochemical cells (SOC) developed in the Institute of Power Engineering as prospective key components of power-to-gas systems. The fundamentals of the solid oxide cells operated as fuel cells (SOFC - solid oxide fuel cells) and electrolysers (SOEC - solid oxide fuel cells) are given. The experimental technique used for electrochemical characterization of cells is presented. The results obtained for planar cell with anodic support are given and discussed. Based on the results, the applicability of the cells in power-to-gas systems (P2G) is evaluated.

Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery.

PubMed

Zhang, Wenbo; Richter, Felix H; Culver, Sean P; Leichtweiss, Thomas; Lozano, Juan G; Dietrich, Christian; Bruce, Peter G; Zeier, Wolfgang G; Janek, Jürgen

2018-06-20

All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degradation mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy density, the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO 2 cathode and the Li 10 GeP 2 S 12 solid electrolyte interface. Indium and Li 4 Ti 5 O 12 are used as anode materials to avoid the instability problems associated with Li-metal anodes. Capacity fading and increased impedances are observed during long-term cycling. Postmortem analysis with scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy show that electrochemically driven mechanical failure and degradation at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochemically more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.

3D printing technologies for electrochemical energy storage

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

Zhang, Feng; Wei, Min; Viswanathan, Vilayanur V.

Fabrication of electrodes and electrolytes play an important role in promoting the performance of electrochemical energy storage (EES) devices such as batteries and supercapacitors. Traditional fabrication techniques have limited capability in controlling the geometry and architecture of the electrode and solid-state electrolytes, which would otherwise compromise the performance. 3D printing, a disruptive manufacturing technology, has emerged as an innovative approach to fabricating EES devices from nanoscale to macroscale and from nanowatt to megawatt, providing great opportunities to accurately control device geometry (e.g., dimension, porosity, morphology) and structure with enhanced specific energy and power densities. Moreover, the additive manufacturing nature ofmore » 3D printing provides excellent controllability of the electrode thickness with much simplified process in a cost effective manner. With the unique spatial and temporal material manipulation capability, 3D printing can integrate multiple nanomaterials in the same print, and multi-functional EES devices (including functional gradient devices) can be fabricated. Herein, we review recent advances in 3D printing of EES devices. We focused on two major 3D printing technologies including direct writing and inkjet printing. The direct material deposition characteristics of these two processes enable them to print on a variety of flat substrates, even a conformal one, well suiting them to applications such as wearable devices and on-chip integrations. Other potential 3D printing techniques such as freeze nano-printing, stereolithography, fused deposition modeling, binder jetting, laminated object manufacturing, and metal 3D printing are also introduced. The advantages and limitations of each 3D printing technology are extensively discussed. More importantly, we provide a perspective on how to integrate the emerging 3D printing with existing technologies to create structures over multiple length scale from macro to nano for EES applications.« less

3D printing technologies for electrochemical energy storage

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

Zhang, Feng; Wei, Min; Viswanathan, Vilayanur V.

We present that fabrication and assembly of electrodes and electrolytes play an important role in promoting the performance of electrochemical energy storage (EES) devices such as batteries and supercapacitors. Traditional fabrication techniques have limitations in controlling the geometry and architecture of the electrode and solid-state electrolytes, which would otherwise compromise the performance. 3D printing, a disruptive manufacturing technology, has emerged as an innovative approach to fabricating EES devices from nanoscale to macroscale, providing great opportunities to accurately control device geometry (e.g., dimension, porosity, and morphology) and structure with enhanced specific energy and power densities. Moreover, the “additive” manufacturing nature ofmore » 3D printing provides excellent controllability of the electrode thickness with much simplified process in a cost effective manner. Additionally, with the unique spatial and temporal material manipulation capability, 3D printing can integrate multiple nano-materials in the same print, and multi-functional EES devices (including functional gradient devices) can be fabricated. Herein, we review recent advances in 3D printing of EES devices. We focus on two major 3D printing technologies including direct writing and inkjet printing. The direct material deposition characteristics of these two processes enable them to print on a variety of flat substrates, even a conformal one, well suiting them to applications such as wearable devices and on-chip integrations. Other potential 3D printing techniques such as freeze nano-printing, stereolithography, fused deposition modeling, binder jetting, laminated object manufacturing, and metal 3D printing are also introduced. The advantages and limitations of each 3D printing technology are extensively discussed. More importantly, we provide a perspective on how to integrate the emerging 3D printing with existing technologies to create structures over multiple length scale from nano to macro for EES applications.« less

3D printing technologies for electrochemical energy storage

DOE PAGES

Zhang, Feng; Wei, Min; Viswanathan, Vilayanur V.; ...

2017-08-24

We present that fabrication and assembly of electrodes and electrolytes play an important role in promoting the performance of electrochemical energy storage (EES) devices such as batteries and supercapacitors. Traditional fabrication techniques have limitations in controlling the geometry and architecture of the electrode and solid-state electrolytes, which would otherwise compromise the performance. 3D printing, a disruptive manufacturing technology, has emerged as an innovative approach to fabricating EES devices from nanoscale to macroscale, providing great opportunities to accurately control device geometry (e.g., dimension, porosity, and morphology) and structure with enhanced specific energy and power densities. Moreover, the “additive” manufacturing nature ofmore » 3D printing provides excellent controllability of the electrode thickness with much simplified process in a cost effective manner. Additionally, with the unique spatial and temporal material manipulation capability, 3D printing can integrate multiple nano-materials in the same print, and multi-functional EES devices (including functional gradient devices) can be fabricated. Herein, we review recent advances in 3D printing of EES devices. We focus on two major 3D printing technologies including direct writing and inkjet printing. The direct material deposition characteristics of these two processes enable them to print on a variety of flat substrates, even a conformal one, well suiting them to applications such as wearable devices and on-chip integrations. Other potential 3D printing techniques such as freeze nano-printing, stereolithography, fused deposition modeling, binder jetting, laminated object manufacturing, and metal 3D printing are also introduced. The advantages and limitations of each 3D printing technology are extensively discussed. More importantly, we provide a perspective on how to integrate the emerging 3D printing with existing technologies to create structures over multiple length scale from nano to macro for EES applications.« less

Electrochemical performance of all-solid-state Li batteries based LiMn 0.5Ni 0.5O 2 cathode and NASICON-type electrolyte

NASA Astrophysics Data System (ADS)

Xie, J.; Imanishi, N.; Zhang, T.; Hirano, A.; Takeda, Y.; Yamamoto, O.; Zhao, X. B.; Cao, G. S.

LiNi 0.5Mn 0.5O 2 thin films have been deposited on the NASICON-type glass ceramics, Li 1+ x+ yAl xTi 2- xSi yP 3- yO 12 (LATSP), by radio frequency (RF) magnetron sputtering followed by annealing. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. All-solid-state Li/PEO 18-Li(CF 3SO 2) 2N/LATSP/LiNi 0.5Mn 0.5O 2/Au cells are fabricated using the LiNi 0.5Mn 0.5O 2 thin films and the LATSP electrolyte. The electrochemical performance of the cells is investigated by galvanostatic cycling, cyclic voltammetry (CV), potentiostatic intermittent titration technique (PITT) and electrochemical impedance spectroscopy (EIS). Interfacial reactions between LiNi 0.5Mn 0.5O 2 and LATSP occur at a temperature as low as 300 °C with the formation of Mn 3O 4, resulting in an increased obstacle for Li-ion diffusion across the LiNi 0.5Mn 0.5O 2/LATSP interface. The electrochemical performance of the cells is limited by the interfacial resistance between LATSP and LiNi 0.5Mn 0.5O 2 as well as the Li-ion diffusion kinetics in LiNi 0.5Mn 0.5O 2 bulk.

Cobalt-Doped Nickel Phosphite for High Performance of Electrochemical Energy Storage.

PubMed

Li, Bing; Shi, Yuxin; Huang, Kesheng; Zhao, Mingming; Qiu, Jiaqing; Xue, Huaiguo; Pang, Huan

2018-03-01

Compared to single metallic Ni or Co phosphides, bimetallic Ni-Co phosphides own ameliorative properties, such as high electrical conductivity, remarkable rate capability, upper specific capacity, and excellent cycle performance. Here, a simple one-step solvothermal process is proposed for the synthesis of bouquet-like cobalt-doped nickel phosphite (Ni 11 (HPO 3 ) 8 (OH) 6 ), and the effect of the structure on the pseudocapacitive performance is investigated via a series of electrochemical measurements. It is found that when the cobalt content is low, the glycol/deionized water ratio is 1, and the reaction is under 200 °C for 20 h, the morphology of the sample is uniform and has the highest specific surface area. The cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 electrode presents a maximum specific capacitance of 714.8 F g -1 . More significantly, aqueous and solid-state flexible electrochemical energy storage devices are successfully assembled. The aqueous device shows a high energy density of 15.48 mWh cm -2 at the power density of 0.6 KW cm -2 . The solid-state device shows a high energy density of 14.72 mWh cm -2 at the power density of 0.6 KW cm -2 . These excellent performances confirm that the cobalt-doped Ni 11 (HPO 3 ) 8 (OH) 6 are promising materials for applications in electrochemical energy storage devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Local Atomic Structure and Chemical Bonding in Sodium Tin Phases

DOE PAGES

Baggetto, Loic; Bridges, Craig A.; Jumas, Dr. Jean-Claude; ...

2014-09-25

To understand these electrochemically-derived materials we have reinvestigated the formation of Na-Sn alloys to identify all the phases which form when x ≥ 1 (NaxSn) and characterized the local bonding around the Sn atoms with X-ray diffraction, 119Sn M ssbauer spectroscopy, and X-ray absorption spectroscopies. The results from the well-defined crystallographic materials were compared to the spectroscopic measurements of the local Sn structures in the electrochemically prepared materials. The reinvestigation of the Na-Sn compounds yields a number of new results: (i) Na 7Sn 3 is a new thermodynamically-stable phase with a rhombohedral structure and R-3m space group; (ii) orthorhombic Namore » 9Sn 4 (Cmcm) has relatively slow formation kinetics suggesting why it does not form at room temperature during the electrochemical reaction; (iii) orthorhombic Na 14.78Sn 4 (Pnma), better described as Na 16-xSn 4, is Na-richer than cubic Na 15Sn 4 (I-43d). Characterization of electrochemically prepared Na-Sn alloys indicate that, at the exception of Na 7Sn 3 and Na 15Sn 4, different crystal structures than similar Na-Sn compositions prepared via classic solid state reactions are formed. These phases are composed of disordered structures characteristic of kinetic-driven solid-state amorphization reactions. In these structures, Sn coordinates in asymmetric environments, which differ significantly from the environments present in Na-Sn model compounds.« less

Tunable solid-state laser technology for applications to scientific and technological experiments from space

NASA Technical Reports Server (NTRS)

Allario, F.; Taylor, L. V.

1986-01-01

Current plans for the Earth Observing System (EOS) include development of a lidar facility to conduct scientific experiments from a polar orbiting platforms. A recommended set of experiments were scoped, which includes techniques of atmospheric backscatter (Lidar), Differential Absorption Lidar (DIAL), altimetry, and retroranging. Preliminary assessments of the resources (power, weight, volume) required by the Eos Lidar Facility were conducted. A research program in tunable solid state laser technology was developed, which includes laser materials development, modeling and experiments on the physics of solid state laser materials, and development of solid state laser transmitters with a strong focus on Eos scientific investigations. Some of the system studies that were conducted which highlight the payoff of solid state laser technology for the Eos scientific investigations will be discussed. Additionally, a summary of some promising research results which have recently emerged from the research program will be presented.

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).

Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors.

PubMed

Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming

2016-08-01

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g(-1) ). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm(-2) and 153 F g(-1) ) and a high energy density of 13.6 Wh kg(-1) , superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An All-Solid-State Fiber-Shaped Aluminum-Air Battery with Flexibility, Stretchability, and High Electrochemical Performance.

PubMed

Xu, Yifan; Zhao, Yang; Ren, Jing; Zhang, Ye; Peng, Huisheng

2016-07-04

Owing to the high theoretical energy density of metal-air batteries, the aluminum-air battery has been proposed as a promising long-term power supply for electronics. However, the available energy density from the aluminum-air battery is far from that anticipated and is limited by current electrode materials. Herein we described the creation of a new family of all-solid-state fiber-shaped aluminum-air batteries with a specific capacity of 935 mAh g(-1) and an energy density of 1168 Wh kg(-1) . The synthesis of an electrode composed of cross-stacked aligned carbon-nanotube/silver-nanoparticle sheets contributes to the remarkable electrochemical performance. The fiber shape also provides the aluminum-air batteries with unique advantages; for example, they are flexible and stretchable and can be woven into a variety of textiles for large-scale applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flexible Supercapacitors Based on Polyaniline Arrays Coated Graphene Aerogel Electrodes

NASA Astrophysics Data System (ADS)

Yang, Yu; Xi, Yunlong; Li, Junzhi; Wei, Guodong; Klyui, N. I.; Han, Wei

2017-06-01

Flexible supercapacitors(SCs) made by reduced graphene oxide (rGO)-based aerogel usually suffer from the low energy density, short cycle life and bad flexibility. In this study, a new, synthetic strategy was developed for enhancing the electrochemical performances of rGO aerogel-based supercapacitor via electrodeposition polyaniline arrays on the prepared ultralight rGO aerogel. The novel hybrid composites with coated polyaniline (PANI) arrays growing on the rGO surface can take full advantage of the rich open-pore and excellent conductivity of the crosslinking framework structure of 3D rGO aerogel and high capacitance contribution from the PANI. The obtained hybrid composites exhibit excellent electrochemical performance with a specific capacitance of 432 F g-1 at the current density of 1 A g-1, robust cycling stability to maintain 85% after 10,000 charge/discharge cycles and high energy density of 25 W h kg-1. Furthermore, the flexible all-solid-state supercapacitor have superior flexibility and outstanding stability under different bending states from the straight state to the 90° status. The high-performance flexible all-solid-state SCs together with the lighting tests demonstrate it possible for applications in portable electronics.

Flexible Supercapacitors Based on Polyaniline Arrays Coated Graphene Aerogel Electrodes.

PubMed

Yang, Yu; Xi, Yunlong; Li, Junzhi; Wei, Guodong; Klyui, N I; Han, Wei

2017-12-01

Flexible supercapacitors(SCs) made by reduced graphene oxide (rGO)-based aerogel usually suffer from the low energy density, short cycle life and bad flexibility. In this study, a new, synthetic strategy was developed for enhancing the electrochemical performances of rGO aerogel-based supercapacitor via electrodeposition polyaniline arrays on the prepared ultralight rGO aerogel. The novel hybrid composites with coated polyaniline (PANI) arrays growing on the rGO surface can take full advantage of the rich open-pore and excellent conductivity of the crosslinking framework structure of 3D rGO aerogel and high capacitance contribution from the PANI. The obtained hybrid composites exhibit excellent electrochemical performance with a specific capacitance of 432 F g -1 at the current density of 1 A g -1 , robust cycling stability to maintain 85% after 10,000 charge/discharge cycles and high energy density of 25 W h kg -1 . Furthermore, the flexible all-solid-state supercapacitor have superior flexibility and outstanding stability under different bending states from the straight state to the 90° status. The high-performance flexible all-solid-state SCs together with the lighting tests demonstrate it possible for applications in portable electronics.

Electrochemical impedance spectroscopy for quantitative interface state characterization of planar and nanostructured semiconductor-dielectric interfaces

NASA Astrophysics Data System (ADS)

Meng, Andrew C.; Tang, Kechao; Braun, Michael R.; Zhang, Liangliang; McIntyre, Paul C.

2017-10-01

The performance of nanostructured semiconductors is frequently limited by interface defects that trap electronic carriers. In particular, high aspect ratio geometries dramatically increase the difficulty of using typical solid-state electrical measurements (multifrequency capacitance- and conductance-voltage testing) to quantify interface trap densities (D it). We report on electrochemical impedance spectroscopy (EIS) to characterize the energy distribution of interface traps at metal oxide/semiconductor interfaces. This method takes advantage of liquid electrolytes, which provide conformal electrical contacts. Planar Al2O3/p-Si and Al2O3/p-Si0.55Ge0.45 interfaces are used to benchmark the EIS data against results obtained from standard electrical testing methods. We find that the solid state and EIS data agree very well, leading to the extraction of consistent D it energy distributions. Measurements carried out on pyramid-nanostructured p-Si obtained by KOH etching followed by deposition of a 10 nm ALD-Al2O3 demonstrate the application of EIS to trap characterization of a nanostructured dielectric/semiconductor interface. These results show the promise of this methodology to measure interface state densities for a broad range of semiconductor nanostructures such as nanowires, nanofins, and porous structures.

Electrochemical Catalyst-Support Effects and Their Stabilizing Role for IrOx Nanoparticle Catalysts during the Oxygen Evolution Reaction.

PubMed

Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias; Bergmann, Arno; Gliech, Manuel; Ferreira de Araújo, Jorge; Willinger, Elena; Schlögl, Robert; Teschner, Detre; Strasser, Peter

2016-09-28

Redox-active support materials can help reduce the noble-metal loading of a solid chemical catalyst while offering electronic catalyst-support interactions beneficial for catalyst durability. This is well known in heterogeneous gas-phase catalysis but much less discussed for electrocatalysis at electrified liquid-solid interfaces. Here, we demonstrate experimental evidence for electronic catalyst-support interactions in electrochemical environments and study their role and contribution to the corrosion stability of catalyst/support couples. Electrochemically oxidized Ir oxide nanoparticles, supported on high surface area carbons and oxides, were selected as model catalyst/support systems for the electrocatalytic oxygen evolution reaction (OER). First, the electronic, chemical, and structural state of the catalyst/support couple was compared using XANES, EXAFS, TEM, and depth-resolved XPS. While carbon-supported oxidized Ir particle showed exclusively the redox state (+4), the Ir/IrOx/ATO system exhibited evidence of metal/metal-oxide support interactions (MMOSI) that stabilized the metal particles on antimony-doped tin oxide (ATO) in sustained lower Ir oxidation states (Ir(3.2+)). At the same time, the growth of higher valent Ir oxide layers that compromise catalyst stability was suppressed. Then the electrochemical stability and the charge-transfer kinetics of the electrocatalysts were evaluated under constant current and constant potential conditions, where the analysis of the metal dissolution confirmed that the ATO support mitigates Ir(z+) dissolution thanks to a stronger MMOSI effect. Our findings raise the possibility that MMOSI effects in electrochemistry-largely neglected in the past-may be more important for a detailed understanding of the durability of oxide-supported nanoparticle OER catalysts than previously thought.

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.

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.

High-performance all-solid-state flexible supercapacitors based on two-step activated carbon cloth

NASA Astrophysics Data System (ADS)

Jiang, Shulan; Shi, Tielin; Zhan, Xiaobin; Long, Hu; Xi, Shuang; Hu, Hao; Tang, Zirong

2014-12-01

A simple and effective strategy is proposed to activate carbon cloth for the fabrication of flexible and high-performance supercapacitors. Firstly, the carbon cloth surface is exfoliated as nanotextures through wet chemical treatment, then an annealing process is applied at H2/N2 atmosphere to reduce the surface oxygen functional groups which are mainly introduced from the first step. The activated carbon cloth electrode shows excellent wettablity, large surface area and delivers remarkable electrochemical performance. A maximum areal capacitance of 485.64 mF cm-2 at the current density of 2 mA cm-2 is achieved for the activated carbon cloth electrode, which is considerably larger than the resported results for carbon cloth. Furthermore, the flexible all-solid-state supercapacitor, which is fabricated based on the activated carbon cloth electrodes, shows high areal capacitance, superior cycling stability as well as stable electrochemical performance even under constant bending or twisting conditions. An areal capacitance of 161.28 mF cm-2 is achieved at the current density of 12.5 mA cm-2, and 104% of its initial capacitance is retained after 30,000 charging/discharging cycles. This study would also provide an effective way to boost devices' electrochemical performance by accommodating other active materials on the activated carbon cloth.

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.

Fiber-based all-solid-state flexible supercapacitors for self-powered systems.

PubMed

Xiao, Xu; Li, Tianqi; Yang, Peihua; Gao, Yuan; Jin, Huanyu; Ni, Weijian; Zhan, Wenhui; Zhang, Xianghui; Cao, Yuanzhi; Zhong, Junwen; Gong, Li; Yen, Wen-Chun; Mai, Wenjie; Chen, Jian; Huo, Kaifu; Chueh, Yu-Lun; Wang, Zhong Lin; Zhou, Jun

2012-10-23

All-solid-state flexible supercapacitors based on a carbon/MnO(2) (C/M) core-shell fiber structure were fabricated with high electrochemical performance such as high rate capability with a scan rate up to 20 V s(-1), high volume capacitance of 2.5 F cm(-3), and an energy density of 2.2 × 10(-4) Wh cm(-3). By integrating with a triboelectric generator, supercapacitors could be charged and power commercial electronic devices, such as a liquid crystal display or a light-emitting-diode, demonstrating feasibility as an efficient storage component and self-powered micro/nanosystems.

A Photoelectrochemical Solar Cell: An Undergraduate Experiment.

ERIC Educational Resources Information Center

Boudreau, Sharon M.; And Others

1983-01-01

Preparation and testing of a cadmium selenide photoelectrical solar cell was introduced into an environmental chemistry course to illustrate solid state semiconductor and electrochemical principles. Background information, procedures, and results are provided for the experiment which can be accomplished in a three- to four-hour laboratory session…

Printable organic and inorganic materials for flexible electrochemical devices

NASA Astrophysics Data System (ADS)

Wojcik, Pawel Jerzy

The growing demand of consumer printed electronics such as smart cards, smart packaging, automotive displays, electronic paper and others led to the increased interest in fully printed electrochemical devices. These components are expected to be developed based on printed thin films derived from cheap and widely accessible compounds. This dissertation presents the long stretch of technical research that was performed to realize printed energy efficient concepts such as electrochromic displays and smart-windows. Within this broad theme, the presented study had a number of specific objectives, however, the overall aim was to develop low-cost material systems (i.e. printable mixtures) at a lab-scale, which would be compatible with large-scale roll-to-roll processing. Presented results concern three main topics: (i) dual-phase inorganic electrochromic material processed at low temperature, (ii) enhancement in electrochromic performance via metaloxide nanoparticles engineering, and (iii) highly conductive and mechanically stable solid-state electrolyte. First two topics are related to crystallographic structure of metal-oxide films derived from sol-gel precursor, which is shown to be critical for electrochemical performance. The proposed method of microstructure control enables development of electrochromic films which outperform their amorphous or nanocrystalline analogues presented in the state-of-the-art due to their superior chemical and physical properties. Developed materials and processes resulted in electrochemical devices exhibiting optical density on the level of 0.82 and switching time shorter than 3 seconds, reaching performance at practical level. Third topic concerns a new concept of solid state electrolyte based on plastic crystal doped with lithium salt, dispersed in a thermosetting polymer resin network. This soft matter printable electrolyte meets requirements for electrochromic applications, exhibiting ionic conductivities of 10. -6 - 10. -4 S cm-1 at ambient temperature, Young'sModulus in the range of 0.1 - 1.4 MPa and operational temperature up to 115°C. In order to extract information from massive computational data, model developed material systems and optimize composition, an efficient mathematical methodology based on statistical techniques was applied. This approach significantly reduces the number of experiments to be realized, while maintaining a high accuracy of the analysis. Using this approach the number of experiments has been reduced from 162 down to 30 in case of dual-phase electrochromic films, and from 729 down to 28 in study on solid-state electrolyte (when comparing to classical three-level full factorial approach). Coupling of statistical methods with formulation of electrochemically active materials shows the potential to maximize the capabilities of these systems.

Ferrocene bound poly(vinyl chloride) as ion to electron transducer in electrochemical ion sensors.

PubMed

Pawlak, Marcin; Grygolowicz-Pawlak, Ewa; Bakker, Eric

2010-08-15

We report here on the synthesis of poly(vinyl chloride) (PVC) covalently modified with ferrocene groups (FcPVC) and the electrochemical behavior of the resulting polymeric membranes in view of designing all solid state voltammetric ion sensors. The Huisgen cycloaddition ("click chemistry") was found to be a simple and efficient method for ferrocene attachment. A degree of PVC modification with ferrocene groups between 1.9 and 6.1 mol % was achieved. The chemical modification of the PVC backbone does not significantly affect the ion-selective properties (selectivity, mobility, and solvent casting ability) of potentiometric sensing membranes applying this polymer. Importantly, the presence of such ferrocene groups may eliminate the need for an additional redox-active layer between the membrane and the inner electric contact in all solid state sensor designs. Electrochemical doping of this system was studied in a symmetrical sandwich configuration: glassy carbon electrode |FcPVC| glassy carbon electrode. Prior electrochemical doping from aqueous solution, resulting in a partial oxidation of the ferrocene groups, was confirmed to be necessary for the sandwich configuration to pass current effectively. The results suggest that only approximately 2.3 mol % of the ferrocene groups are electrochemically accessible, likely due to surface confined electrochemical behavior in the polymer. Indeed, cyclic voltammetry of aqueous hexacyanoferrate (III) remains featureless at cathodic potentials (down to -0.5 V). This indicates that the modified membrane is not responsive to redox-active species in the sample solution, making it possible to apply this polymer as a traditional, single membrane. Yet, the redox capacity of the electrode modified with this type of membrane was more than 520 microC considering a 20 mm(2) active electrode area, which appears to be sufficient for numerous practical ion voltammetric applications. The electrode was observed to operate reproducibly, with 1% standard deviation, when applying pulsed amperometric techniques.

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

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.

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

PubMed

Boehme, Simon C; Azpiroz, Jon Mikel; Aulin, Yaroslav V; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Infante, Ivan; Houtepen, Arjan J

2015-05-13

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Porous electronic current collector bodies for electrochemical cell configurations

DOEpatents

Pollack, William; Reichner, Philip

1989-01-01

A high-temperature, solid electrolyte electrochemical cell configuration is made comprising a plurality of elongated electrochemical cells 1, having inner electrodes 3, outer electrodes 6 and solid electrolyte 4 therebetween, the cells being electronically connected in series and parallel by flexible, porous, fibrous strips 7, where the strips contain flexible, electronically conductive fibers bonded together and coated with a refractory oxide, and where the oxide coating is effective to prevent additional bonding of fibers during electrochemical cell operation at high temperatures.

Synthesis and characterizaton of inorganic materials for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Shanmugam, Rengarajan

Development of low-cost energy storage devices is critical for wide-scale implementation of intermittent renewable energy technologies and improving the electricity grid. Commercial devices remain prohibitively expensive or lack the performance specifications for a wider market reach. Na-ion batteries would perfectly suited for these large-scale applications as the raw materials (such as soda ash, salt, etc.) are plentiful, inexpensive and geographically unconstrained. However, extensive materials research on insertion electrodes is required for better understanding of the electrochemical and structural properties and engineering high performance Na-ion batteries. This thesis research involves exploratory study on new insertion materials with various crystallographic structure-types and extensive characterization of promising new inorganic compositions. Tunnel-type materials, sodium nickel phosphate-Na4Ni7(PO4)6, and sodium cobalt titanate- Na0.8Co0.4Ti1.6O4, were investigated to capitalize on the intrinsic structural stability offered by framework materials. Sol-gel and solid-state reaction synthetic techniques were employed for inorganic powder synthesis. Galvanostatic and potentiostatic testing confirm reversible sodium insertion/de-insertion reactions albeit with inadequate electrochemical characteristics (high voltage hysteresis> 1V). Subsequent efforts involved investigating layer-structured materials supporting fast ionic transport for better electrochemical performance. P2-sodium nickel titanate, Na2/3[Ni1/3Ti2/3]O2 (P2NT), with prismatic sodium co-ordination, was synthesized by solid-state technique. The 'bifunctional' oxide contains Ni2+/4+ and Ti4+/3+ redox couples with redox potentials of 3.6 V, 0.7 V vs. Na/Na+, respectively. This bifunctional approach would simplify electrode processing and provide cost reduction opportunities in battery manufacturing. The structural changes monitored using ex-situ XRD demonstrate a favorably broad solid-solution domain. Manganese substitution, to form P2-Na2/3[Ni1/3Mn1/3Ti1/3]O2 (P2NMT), provides an enhanced high-current performance due to faster interfacial kinetics and accelerated charge carrier transport as shown by impedance spectroscopy and DC testing. Structural properties of P2NT material were studied using neutron diffraction and atomisitic simulations. Rietveld refinement shows that Naf sites have lower site occupancy than Nae sites due to unfavorable repulsive interactions from inline transition metal atoms. Buckingham and Morse-type models accurately predicted the experimental lattice parameters. The energy landscape was explored using energy minimization runs on disordered supercells. The simulated density maps are in agreement with the experiment densities with evidence of stacking fault formation. O3-sodium nickel titanate, Na0.9[Ni0.45Ti0.55]O2 (O3NT) with octahedral sodium co-ordination was synthesized by solid-state reaction technique. The influence of titanium on the poor cycleability of the O3-type electrodes was investigated. Ex-situ XRD shows two phase regions, comprised of O3+P3 phases, and a solid solution region, comprised of P3 phase. O3NT provides an excellent capacity retention of 99% for 115 cycles at C/2 rate. The good cycleability is attributed to the relative invariance of net impedance during electrode cycling using impedance spectroscopy.

Fundamentally Addressing Bromine Storage through Reversible Solid-State Confinement in Porous Carbon Electrodes: Design of a High-Performance Dual-Redox Electrochemical Capacitor.

PubMed

Yoo, Seung Joon; Evanko, Brian; Wang, Xingfeng; Romelczyk, Monica; Taylor, Aidan; Ji, Xiulei; Boettcher, Shannon W; Stucky, Galen D

2017-07-26

Research in electric double-layer capacitors (EDLCs) and rechargeable batteries is converging to target systems that have battery-level energy density and capacitor-level cycling stability and power density. This research direction has been facilitated by the use of redox-active electrolytes that add faradaic charge storage to increase energy density of the EDLCs. Aqueous redox-enhanced electrochemical capacitors (redox ECs) have, however, performed poorly due to cross-diffusion of soluble redox couples, reduced cycle life, and low operating voltages. In this manuscript, we propose that these challenges can be simultaneously met by mechanistically designing a liquid-to-solid phase transition of oxidized catholyte (or reduced anolyte) with confinement in the pores of electrodes. Here we demonstrate the realization of this approach with the use of bromide catholyte and tetrabutylammonium cation that induces reversible solid-state complexation of Br 2 /Br 3 - . This mechanism solves the inherent cross-diffusion issue of redox ECs and has the added benefit of greatly stabilizing the reactive bromine generated during charging. Based on this new mechanistic insight on the utilization of solid-state bromine storage in redox ECs, we developed a dual-redox EC consisting of a bromide catholyte and an ethyl viologen anolyte with the addition of tetrabutylammonium bromide. In comparison to aqueous and organic electric double-layer capacitors, this system enhances energy by factors of ca. 11 and 3.5, respectively, with a specific energy of ∼64 W·h/kg at 1 A/g, a maximum power density >3 kW/kg, and cycling stability over 7000 cycles.

Solid State Ultracapacitor

NASA Technical Reports Server (NTRS)

Rolin, Terry D.

2015-01-01

NASA analyzes, tests, packages, and fabricates electrical, electronic, and electromechanical (EEE) parts used in space vehicles. One area that NASA wishes to advance is energy storage and delivery. Currently, space vehicles use rechargeable batteries that utilize silver zinc or lithium ion electrochemical processes. These current state-of-the-art rechargeable batteries cannot be rapidly charged, contain harmful chemicals, and suffer from early wear-out mechanisms. A solid state ultracapacitor is an EEE part that offers significant advantages over current electrochemical and electrolytic devices. The objective of this research is to develop an internal barrier layer ultracapacitor (IBLC) using novel dielectric materials as a battery replacement with a focus on these advantages: longer life, lower mass-toweight ratio, rapid charging, on-demand pulse power, improved on-pad standby time without maintenance, and environmental friendliness. The approach is unique in two areas. A deposition technique is used that has been shown to produce a more uniformly coated nanoparticle than sol-gel, which has resulted in colossal permittivities. These particles are then distributed in an ink formulation developed at NASA Marshall Space Flight Center (MSFC) and deposited utilizing a 3D aerosol jet technique. This additive manufacturing technique controls layer thickness, resulting in extremely large capacitance and energy density.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-07-05

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2015-11-10

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

A high-performance flexible fibre-shaped electrochemical capacitor based on electrochemically reduced graphene oxide.

PubMed

Li, Yingru; Sheng, Kaixuan; Yuan, Wenjing; Shi, Gaoquan

2013-01-11

A fibre-shaped solid electrochemical capacitor based on electrochemically reduced graphene oxide has been fabricated, exhibiting high specific capacitance and rate capability, long cycling life and attractive flexibility.

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

Borotungstic Acid (BWA)-Polyacrylamide (PAM) Solid Polymer Electrolytes for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Foong, Yee Wei

Solid polymer electrolytes (SPEs) are key enablers for thin and flexible electrochemical capacitors in wearable technologies. Polyacrylamide (PAM) is one such promising hygroscopic polymer host, but its performance had not been optimized. This thesis enhanced PAM with borotungstic acid (BWA) as the heteropolyacid conductors. The BWA-PAM electrolyte achieved a high initial conductivity of ca. 27 mS cm-1, but suffered from a short service life (< 40% conductivity retention after 28 days) due to dehydration. BWA-PAM modified with acidic (H3PO4) and neutral (glycerol) plasticizers showed improved conductivity of ca. 30 mS cm-1 and service life (≥ 70% conductivity retention after 28 days). The high BWA and H3PO4 content accelerated the hydrolysis of PAM to polyacrylic acid, resulting in the undesirable precipitation of NH4+-substituted BWA; whereas, glycerol was found to suppress this reaction. The solid CNT-graphite cells with the optimized electrolytes demonstrated a capacitance of ca. 19.5 mF cm -2; a high rate capability (≥ 75% capacitance retention) at 1Vs -1; excellent cycle life (≥ 90% retention of its initial capacitance); and maintained ca. -85° phase angle over 10,000 charging-discharging cycles.

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; DelCastillo, Linda

2009-01-01

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography.

PubMed

Yu, Young-Sang; Farmand, Maryam; Kim, Chunjoong; Liu, Yijin; Grey, Clare P; Strobridge, Fiona C; Tyliszczak, Tolek; Celestre, Rich; Denes, Peter; Joseph, John; Krishnan, Harinarayan; Maia, Filipe R N C; Kilcoyne, A L David; Marchesini, Stefano; Leite, Talita Perciano Costa; Warwick, Tony; Padmore, Howard; Cabana, Jordi; Shapiro, David A

2018-03-02

Battery function is determined by the efficiency and reversibility of the electrochemical phase transformations at solid electrodes. The microscopic tools available to study the chemical states of matter with the required spatial resolution and chemical specificity are intrinsically limited when studying complex architectures by their reliance on two-dimensional projections of thick material. Here, we report the development of soft X-ray ptychographic tomography, which resolves chemical states in three dimensions at 11 nm spatial resolution. We study an ensemble of nano-plates of lithium iron phosphate extracted from a battery electrode at 50% state of charge. Using a set of nanoscale tomograms, we quantify the electrochemical state and resolve phase boundaries throughout the volume of individual nanoparticles. These observations reveal multiple reaction points, intra-particle heterogeneity, and size effects that highlight the importance of multi-dimensional analytical tools in providing novel insight to the design of the next generation of high-performance devices.

Method of preparing an electrochemical cell in uncharged state

DOEpatents

Shimotake, Hiroshi; Bartholme, Louis G.; Arntzen, John D.

1977-02-01

A secondary electrochemical cell is assembled in an uncharged state for the preparation of a lithium alloy-transition metal sulfide cell. The negative electrode includes a material such as aluminum or silicon for alloying with lithium as the cell is charged. The positive electrode is prepared by blending particulate lithium sulfide, transition metal powder and electrolytic salt in solid phase. The mixture is simultaneously heated to a temperature in excess of the melting point of the electrolyte and pressed onto an electrically conductive substrate to form a plaque. The plaque is assembled as a positive electrode within the cell. During the first charge cycle lithium alloy is formed within the negative electrode and transition metal sulfide such as iron sulfide is produced within the positive electrode.

An all-solid-state yarn supercapacitor using cotton yarn electrodes coated with polypyrrole nanotubes.

PubMed

Wei, Chengzhuo; Xu, Qi; Chen, Zeqi; Rao, Weida; Fan, Lingling; Yuan, Ye; Bai, Zikui; Xu, Jie

2017-08-01

A novel all-solid-state yarn supercapacitor (YSC) has been fabricated by using the cotton yarns coated with polypyrrole (PPy) nanotubes. The interconnected network structure of PPy can increase the surface area as well as the electrode/electrolyte interface area, thus resulting in improved electrochemical performance. For the proposed YSC, a high areal-specific capacitance of 74.0mFcm -2 and a desirable energy density of 7.5μWhcm -2 are achieved. The flexibility of the YSC demonstrates that it is suitable for the integration as flexible power sources in wearable electronic textiles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spectroscopic optimization of all-solid-state electrochromic devices using PANI

NASA Astrophysics Data System (ADS)

Hugot-Le Goff, Anne; Bernard, Marie-Claude; Bich, Vu T.; Binh, Nguyen T.; Zeng, Wen

1997-12-01

The interesting optical properties of polyaniline (PANI) allowed its utilization in all solid-state electrochromic devices. Using a sulfonic acid polymer as solid electrolyte gave to PANI an unusual optical behavior leading to electrochromic properties very superior to the properties that it has in any liquid inorganic electrolyte. The improved conductivity of PANI doped with AMP-sulfonate is displayed by the presence of a free-carriers tail even at pH as high as 4.5. The free-carriers tail is studied using UV/vis/near IR spectroscopy, and the kinetics of coloration/bleaching are studied using Optical Multichannel Analysis in the 1.5 - 3 eV range. The modifications of the PANI optical features by solid-state doping are examined. The possibility to still improve the performances of these devices--in particular their rate of color change--by using `secondarily doped' PANI is investigated, which requires a preliminary spectrochemical analysis of PANI films doped with camphorsulfonic acid and treated in m-cresol during their electrochemical polarization.

A survey of current solid state star tracker technology

NASA Astrophysics Data System (ADS)

Armstrong, R. W.; Staley, D. A.

1985-12-01

This paper is a survey of the current state of the art in design of star trackers for spacecraft attitude determination systems. Specific areas discussed are sensor technology, including the current state-of-the-art solid state sensors and techniques of mounting and cooling the sensor, analog image preprocessing electronics performance, and digital processing hardware and software. Three examples of area array solid state star tracker development are presented - ASTROS, developed by the Jet Propulsion Laboratory, the Retroreflector Field Tracker (RFT) by Ball Aerospace, and TRW's MADAN. Finally, a discussion of solid state line arrays explores the possibilities for one-dimensional imagers which offer simplified scan control electronics.

Chemically durable polymer electrolytes for solid-state alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Park, Eun Joo; Capuano, Christopher B.; Ayers, Katherine E.; Bae, Chulsung

2018-01-01

Generation of high purity hydrogen using electrochemical splitting of water is one of the most promising methods for sustainable fuel production. The materials to be used as solid-state electrolytes for alkaline water electrolyzer require high thermochemical stability against hydroxide ion attack in alkaline environment during the operation of electrolysis. In this study, two quaternary ammonium-tethered aromatic polymers were synthesized and investigated for anion exchange membrane (AEM)-based alkaline water electrolyzer. The membranes properties including ion exchange capacity (IEC), water uptake, swelling degree, and anion conductivity were studied. The membranes composed of all C-C bond polymer backbones and flexible side chain terminated by cation head groups exhibited remarkably good chemical stability by maintaining structural integrity in 1 M NaOH solution at 95 °C for 60 days. Initial electrochemical performance and steady-state operation performance were evaluated, and both membranes showed a good stabilization of the cell voltage during the steady-state operation at the constant current density at 200 mA/cm2. Although both membranes in current form require improvement in mechanical stability to afford better durability in electrolysis operation, the next generation AEMs based on this report could lead to potentially viable AEM candidates which can provide high electrolysis performance under alkaline operating condition.

Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study

NASA Astrophysics Data System (ADS)

Sharma, Neeraj; Peterson, Vanessa K.; Elcombe, Margaret M.; Avdeev, Maxim; Studer, Andrew J.; Blagojevic, Ned; Yusoff, Rozila; Kamarulzaman, Norlida

The structural response to electrochemical cycling of the components within a commercial Li-ion battery (LiCoO 2 cathode, graphite anode) is shown through in situ neutron diffraction. Lithuim insertion and extraction is observed in both the cathode and anode. In particular, reversible Li incorporation into both layered and spinel-type LiCoO 2 phases that comprise the cathode is shown and each of these components features several phase transitions attributed to Li content and correlated with the state-of-charge of the battery. At the anode, a constant cell voltage correlates with a stable lithiated graphite phase. Transformation to de-lithiated graphite at the discharged state is characterised by a sharp decrease in both structural cell parameters and cell voltage. In the charged state, a two-phase region exists and is composed of the lithiated graphite phase and about 64% LiC 6. It is postulated that trapping Li in the solid|electrolyte interface layer results in minimal structural changes to the lithiated graphite anode across the constant cell voltage regions of the electrochemical cycle.

Microwave synthesis and electrochemical properties of lithium manganese borate as cathode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Ma, Ting; Muslim, Arzugul; Su, Zhi

2015-05-01

Nano structured LiMnBO3/C cathode materials are synthesized by a fast microwave solid-state reaction method using MnCO3, Li2CO3, H3BO3 and glucose as starting materials for the first time. The crystal structure, morphology and electrochemical properties of LiMnBO3/C composites are characterized by X-ray diffraction (XRD), raman spectroscopy (Ramon), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge-discharge tests. The result shows that not only monoclinic LiMnBO3/C but also hexagonal LiMnBO3/C cathode materials can be successfully synthesized by microwave solid-state method with power of 240 W in different time. Compared with h-LiMnBO3/C and mixed phase LiMnBO3/C, m-LiMnBO3/C displays lower charge-transfer resistance and the Warburg impedance, so it reveals a higher first discharge capacity of 156.3 mAh g-1 at 0.05 C within 1.8V-4.6 V, The value increases up to 173.2 mAh g-1 caused by the activation process. Even after 50 cycles, the discharge capacity of m-LiMnBO3/C still remains at 148.2 mAh g-1.

All-solid state symmetric supercapacitors based on compressible and flexible free-standing 3D carbon nanotubes (CNTs)/poly(3,4-ethylenedioxythiophene) (PEDOT) sponge electrodes

NASA Astrophysics Data System (ADS)

He, Xin; Yang, Wenyao; Mao, Xiling; Xu, Lu; Zhou, Yujiu; Chen, Yan; Zhao, Yuetao; Yang, Yajie; Xu, Jianhua

2018-02-01

Flexible supercapacitors that maintain electrochemical performance under deformation have attracted much attention for the potential application in the flexible electronics market. A compressible and flexible free-standing electrodes sponge and all-solid-state symmetric supercapacitors based on as-prepared electrodes are presented. The carbon nanotubes (CNTs) framework is synthesized by chemical vapor deposition (CVD) method, and then composited with poly (3,4-ethylenedioxythiophene) PEDOT by the electrodeposition. This CNTs/PEDOT sponge electrode shows highest mass-specific capacitance of 147 Fg-1 at 0.5 A g-1, tuned by the PEDOT mass loading, and exhibits good cyclic stability with the evidence that more than 95% of capacitance is remained after 3000 cycles. Furthermore, the symmetric supercapacitor shows the highest energy density of 12.6 Wh kg-1 under the power density of 1 kW kg-1 and highest power density of 10.2 kW kg-1 with energy density of 8 Wh kg-1, which exhibits both high energy density and power density. The electrochemical performance of composite electrode also indicates that the operate voltage of device could be extend to 1.4 V by the n-doping and p-doping process in different potential of PEDOT component. This flexible supercapacitor maintains stable electrochemical performance working on different bending condition, which shows promising prospect for wearable energy storage applications.

When Al-Doped Cobalt Sulfide Nanosheets Meet Nickel Nanotube Arrays: A Highly Efficient and Stable Cathode for Asymmetric Supercapacitors.

PubMed

Huang, Jun; Wei, Junchao; Xiao, Yingbo; Xu, Yazhou; Xiao, Yujuan; Wang, Ying; Tan, Licheng; Yuan, Kai; Chen, Yiwang

2018-03-27

Although cobalt sulfide is a promising electrode material for supercapacitors, its wide application is limited by relative poor electrochemical performance, low electrical conductivity, and inefficient nanostructure. Here, we demonstrated that the electrochemical activity of cobalt sulfide could be significantly improved by Al doping. We designed and fabricated hierarchical core-branch Al-doped cobalt sulfide nanosheets anchored on Ni nanotube arrays combined with carbon cloth (denoted as CC/H-Ni@Al-Co-S) as an excellent self-standing cathode for asymmetric supercapacitors (ASCs). The combination of structural and compositional advantages endows the CC/H-Ni@Al-Co-S electrode with superior electrochemical performance with high specific capacitance (1830 F g -1 /2434 F g -1 at 5 mV s -1 /1 A g -1 ) and excellent rate capability (57.2%/72.3% retention at 1000 mV s -1 /100 A g -1 ). The corresponding all-solid-state ASCs with CC/H-Ni@Al-Co-S and multilayer graphene/CNT film as cathode and anode, respectively, achieve a high energy density up to 65.7 W h kg -1 as well as superb cycling stability (90.6% retention after 10 000 cycles). Moreover, the ASCs also exhibit good flexibility and stability under different bending conditions. This work provides a general, effective route to prepare high-performance electrode materials for flexible all-solid-state energy storage devices.

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

Dehoff, Ryan R.; List, III, Frederick Alyious; Carver, Keith

ORNL Manufacturing Demonstration Facility worked with ECM Technologies LLC to investigate the use of precision electro-chemical machining technology to polish the surface of parts created by Arcam electron beam melting. The goals for phase one of this project have been met. The project goal was to determine whether electro-chemical machining is a viable method to improve the surface finish of Inconel 718 parts fabricated using the Arcam EBM method. The project partner (ECM) demonstrated viability for parts of both simple and complex geometry. During the course of the project, detailed process knowledge was generated. This project has resulted in themore » expansion of United States operations for ECM Technologies.« less

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

PubMed Central

Bakierska, Monika; Świętosławski, Michał; Dziembaj, Roman; Molenda, Marcin

2016-01-01

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material. PMID:28773819

Miniaturized radioisotope solid state power sources

NASA Astrophysics Data System (ADS)

Fleurial, J.-P.; Snyder, G. J.; Patel, J.; Herman, J. A.; Caillat, T.; Nesmith, B.; Kolawa, E. A.

2000-01-01

Electrical power requirements for the next generation of deep space missions cover a wide range from the kilowatt to the milliwatt. Several of these missions call for the development of compact, low weight, long life, rugged power sources capable of delivering a few milliwatts up to a couple of watts while operating in harsh environments. Advanced solid state thermoelectric microdevices combined with radioisotope heat sources and energy storage devices such as capacitors are ideally suited for these applications. By making use of macroscopic film technology, microgenrators operating across relatively small temperature differences can be conceptualized for a variety of high heat flux or low heat flux heat source configurations. Moreover, by shrinking the size of the thermoelements and increasing their number to several thousands in a single structure, these devices can generate high voltages even at low power outputs that are more compatible with electronic components. Because the miniaturization of state-of-the-art thermoelectric module technology based on Bi2Te3 alloys is limited due to mechanical and manufacturing constraints, we are developing novel microdevices using integrated-circuit type fabrication processes, electrochemical deposition techniques and high thermal conductivity substrate materials. One power source concept is based on several thermoelectric microgenerator modules that are tightly integrated with a 1.1W Radioisotope Heater Unit. Such a system could deliver up to 50mW of electrical power in a small lightweight package of approximately 50 to 60g and 30cm3. An even higher degree of miniaturization and high specific power values (mW/mm3) can be obtained when considering the potential use of radioisotope materials for an alpha-voltaic or a hybrid thermoelectric/alpha-voltaic power source. Some of the technical challenges associated with these concepts are discussed in this paper. .

Mixed Valence in Conjugated Anion Radicals. Solution and Solid State Studies

DTIC Science & Technology

1991-05-24

voltammetry was performed using a BAS-100 electrochemical analyzer. Bulk electrolyses were performed with a Princeton Applied Research (PAR) model 173...extracted with several small portions of CH 2 CI 2. The combined organic layers are then washed once again with water . After drying over Na2 SO4 the

An Extraordinary Sulfonated-Graphenal-Polymer-Based Electrolyte Separator for All-Solid-State Supercapacitors.

PubMed

Liu, Xubo; Men, Chuanling; Zhang, Xiaohua; Li, Qingwen

2016-09-01

Sulfonated graphenal polymers can be assembled up by poly(vinyl alcohol) adhesion. The porous assembly structure results in a remarkably improved ionic conductivity and thus enhances electrochemical performances such as specific capacitance, capacitance retention, and cycling stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wearable Solid-State Supercapacitors Operating at High Working Voltage with a Flexible Nanocomposite Electrode.

PubMed

Li, Xiaoyan; Wang, Jun; Zhao, Yaping; Ge, Fengyan; Komarneni, Sridhar; Cai, Zaisheng

2016-10-05

The proposed approach for fabricating ultralight self-sustained electrodes facilitates the structural integration of highly flexible carbon nanofibers, amino-modified multiwalled carbon nanotubes (AM-MWNT), and MnO 2 nanoflakes for potential use in wearable supercapacitors. Because of the higher orientation of AM-MWNT and the sublimation of terephthalic acid (PTA) in the carbonization process, freestanding electrodes could be realized with high porosity and flexibility and could possess remarkable electrochemical properties without using polymer substrates. Wearable symmetric solid-state supercapacitors were further assembled using a LiCl/PVA gel electrolyte, which exhibit a maximum energy density of 44.57 Wh/kg (at a power density of 337.1 W/kg) and a power density of 13330 W/kg (at an energy density of 19.64 Wh/kg) with a working voltage as high as 1.8 V. Due to the combination of several favorable traits such as flexibility, high energy density, and excellent electrochemical cyclability, the presently developed wearable supercapacitors with wide potential windows are expected to be useful for new kinds of portable electric devices.

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).

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

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-06-07

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solid cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.

Co9 S8 /Co as a High-Performance Anode for Sodium-Ion Batteries with an Ether-Based Electrolyte.

PubMed

Zhao, Yingying; Pang, Qiang; Wei, Yingjin; Wei, Luyao; Ju, Yanming; Zou, Bo; Gao, Yu; Chen, Gang

2017-12-08

Co 9 S 8 has been regarded as a desirable anode material for sodium-ion batteries because of its high theoretical capacity. In this study, a Co 9 S 8 anode material containing 5.5 wt % Co (Co 9 S 8 /Co) was prepared by a solid-state reaction. The electrochemical properties of the material were studied in carbonate and ether-based electrolytes (EBE). The results showed that the material had a longer cycle life and better rate capability in EBE. This excellent electrochemical performance was attributed to a low apparent activation energy and a low overpotential for Na deposition in EBE, which improved the electrode kinetic properties. Furthermore, EBE suppressed side reactions of the electrode and electrolyte, which avoided the formation of a solid electrolyte interphase film. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Electrochemical heat engine

DOEpatents

Elliott, Guy R. B.; Holley, Charles E.; Houseman, Barton L.; Sibbitt, Jr., Wilmer L.

1978-01-01

Electrochemical heat engines produce electrochemical work, and mechanical motion is limited to valve and switching actions as the heat-to-work cycles are performed. The electrochemical cells of said heat engines use molten or solid electrolytes at high temperatures. One or more reactions in the cycle will generate a gas at high temperature which can be condensed at a lower temperature with later return of the condensate to electrochemical cells. Sodium, potassium, and cesium are used as the working gases for high temperature cells (above 600 K) with halogen gases or volatile halides being used at lower temperature. Carbonates and halides are used as molten electrolytes and the solid electrolyte in these melts can also be used as a cell separator.

Topotactic Reactions, Structural Studies, and Lithium Intercalation in Cation-Deficient Spinels with Formula Close to Li 2Mn 4O 9

NASA Astrophysics Data System (ADS)

Palos, A. Ibarra; Anne, M.; Strobel, P.

2001-08-01

The composition Li2Mn4O9, reported as a spinel oxide containing vacancies on both tetrahedral and octahedral sites [A. de Kock et al., Mater. Res. Bull. 25, 657 (1990)], was approached using three different preparation routes: low-temperature solid state reaction (A), chemical delithiation (B), and electrochemical delithiation (C). Rietveld refinements from neutron diffraction data confirmed the double-vacancy scheme proposed previously for product A, but with more tetrahedral and fewer octahedral vacancies than in the ideal Li2Mn4O9 formula. Low-temperature solid state reactions systematically result in broad reflections. Sample B, which was obtained topotactically, exhibits much narrower reflections. But chemical analyses, thermogravimetry, and neutron diffraction show that the acid treatment introduces significant amounts of protons, resulting in a formula close to Li0.92HMn4O9. Samples A and B were cycled electrochemically in lithium cells at 3 V with better stability than LiMn2O4, probably due to their higher initial manganese oxidation state. No separate electrochemical step linked to the filling of vacancies is observed in A, whereas B gives an additional redox step ca. 200 mV above the main plateau. This feature is not observed on compounds A or C; it is reversible, and seems to be a specific property of this spinel with a low initial cell parameter (8.09 Å). Sample A2 with double cation vacancies is especially stable on cycling at 3 V, and shows a very small volume variation on lithium intercalation.

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.

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

PubMed

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

2018-05-09

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

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

Development of 3D Urchin-Shaped Coaxial Manganese Dioxide@Polyaniline (MnO2@PANI) Composite and Self-Assembled 3D Pillared Graphene Foam for Asymmetric All-Solid-State Flexible Supercapacitor Application.

PubMed

Ghosh, Kalyan; Yue, Chee Yoon; Sk, Md Moniruzzaman; Jena, Rajeeb Kumar

2017-05-10

We have fabricated high-energy-density all-solid-state flexible asymmetric supercapacitor by using a facile novel 3D hollow urchin-shaped coaxial manganese dioxide@polyaniline (MnO 2 @PANI) composite as positive electrode and 3D graphene foam (GF) as negative electrode materials with polyvinyl alcohol (PVA)/KOH gel electrolyte. The coaxial MnO 2 @PANI composite was fabricated by hydrothermal route followed by oxidation without use of an external oxidant. The formation mechanism of the 3D hollow MnO 2 @PANI composite occurs first by nucleation and growth of the MnO 2 crystal species via dissolution-recrystallization and oriented attachment mechanisms followed by the oxidation of aniline monomers on the MnO 2 crystalline template. The self-assembled 3D graphene block was synthesized by hydrothermal route using vitamin C as a reducing agent. The microstructures of the composites are analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The morphology is characterized by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), which clearly showed the formation of urchin-shaped coaxial MnO 2 @PANI composite. The electrochemical studies are explored by cyclic voltammetry, electrochemical impedance spectrometry, and cyclic charge-discharge tests. The symmetric all-solid-state flexible MnO 2 @PANI//MnO 2 @PANI and GF//GF supercapacitors exhibit the specific capacitance of 129.2 and 82.1 F g -1 at 0.5 A/g current density, respectively. The solid-state asymmetric supercapacitor shows higher energy density (37 Wh kg -1 ) with respect to the solid-state symmetric supercapacitors MnO 2 @PANI//MnO 2 @PANI and GF//GF, where the obtained energy density are found to be 17.9 and 11.4 Wh kg -1 , respectively, at 0.5 A/g current density. Surprisingly, the asymmetric supercapacitor shows a high energy density of 22.3 Wh kg -1 at a high current density of 5 A g -1 . The solid-state asymmetric supercapacitor shows a good cyclic stability in which ∼11% capacitance loss was observed after 5000 cycles.

Electrochemical detection of Piscirickettsia salmonis genomic DNA from salmon samples using solid-phase recombinase polymerase amplification.

PubMed

Del Río, Jonathan Sabaté; Svobodova, Marketa; Bustos, Paulina; Conejeros, Pablo; O'Sullivan, Ciara K

2016-12-01

Electrochemical detection of solid-phase isothermal recombinase polymerase amplification (RPA) of Piscirickettsia salmonis in salmon genomic DNA is reported. The electrochemical biosensor was constructed by surface functionalization of gold electrodes with a thiolated forward primer specific to the genomic region of interest. Solid-phase RPA and primer elongation were achieved in the presence of the specific target sequence and biotinylated reverse primers. The formation of the subsequent surface-tethered duplex amplicons was electrochemically monitored via addition of streptavidin-linked HRP upon completion of solid-phase RPA. Successful quantitative amplification and detection were achieved in less than 1 h at 37 °C, calibrating with PCR-amplified genomic DNA standards and achieving a limit of detection of 5 · 10 -8  μg ml -1 (3 · 10 3 copies in 10 μl). The presented system was applied to the analysis of eight real salmon samples, and the method was also compared to qPCR analysis, observing an excellent degree of correlation. Graphical abstract Schematic of use of electrochemical RPA for detection of Psiricketessia salmonis in salmon liver.

Advances in solid state laser technology for space and medical applications

NASA Technical Reports Server (NTRS)

Byvik, C. E.; Buoncristiani, A. M.

1988-01-01

Recent developments in laser technology and their potential for medical applications are discussed. Gas discharge lasers, dye lasers, excimer lasers, Nd:YAG lasers, HF and DF lasers, and other commonly used lasers are briefly addressed. Emerging laser technology is examined, including diode-pumped lasers and other solid state lasers.

Improving low-temperature performance of spinel LiNi0.5Mn1.5O4 electrode and LiNi0.5Mn1.5O4/Li4Ti5O12 full-cell by coating solid-state electrolyte Li-Al-Ti-P-O

NASA Astrophysics Data System (ADS)

Bi, Kun; Zhao, Shi-Xi; Huang, Chao; Nan, Ce-Wen

2018-06-01

Octahedral cathode materials LiNi0.5Mn1.5O4 (LNMO), with primary particles size of 300-600 nm are prepared through one-step co-precipitation. Then solid-state electrolyte Li2O-Al2O3-TiO2-P2O5 (LATP) was coated on LNMO to form continuous surface-modification layer. There is no obviously difference of structure, morphology between coated LATP LiNi0.5Mn1.5O4 (LATP-LNMO) and pristine LiNi0.5Mn1.5O4 (P-LNMO). Low-temperature electrochemical performance of P-LNMO and LATP-LNMO electrodes, including charge-discharge capacity, cycle performance, middle discharge voltage and electrochemical impedance spectra (EIS), were measured systematically with three electrode. The results reveal that LATP-LNMO electrode presents superior electrochemical performance at low temperature, compared to P-LNMO electrode. At -20 °C, the capacity retention of LATP-LNMO (61%) is much higher than that of P-LNMO (39%). According to EIS, the enhancement of performance of LATP-LNMO cathode at low temperature can be attribute to LATP coating, which not only promotes lithium-ion diffusion at electrode/electrolyte interface but also decreases the charge transfer resistance. Finally, the electrochemical performances of full cell of LATP-LNMO or P-LNMO cathode vs Li4Ti5O12 anode are investigated. The energy density can be achieved to 270 Wh·Kg-1 at -20 °C if using LATP-LNMO, which is much better than that of P-LNMO.

Cr{sub 2}O{sub 5} as new cathode for rechargeable sodium ion batteries

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

Feng, Xu-Yong; Chien, Po-Hsiu; Rose, Alyssa M.

2016-10-15

Chromium oxide, Cr{sub 2}O{sub 5}, was synthesized by pyrolyzing CrO{sub 3} at 350 °C and employed as a new cathode in rechargeable sodium ion batteries. Cr{sub 2}O{sub 5}/Na rechargeable batteries delivered high specific capacities up to 310 mAh/g at a current density of C/16 (or 20 mA/g). High-resolution solid-state {sup 23}Na NMR both qualitatively and quantitatively revealed the reversible intercalation of Na ions into the bulk electrode and participation of Na ions in the formation of the solid-electrolyte interphase largely at low potentials. Amorphization of the electrode structure occurred during the first discharge revealed by both NMR and X-ray diffractionmore » data. CrO{sub 3}-catalyzed electrolyte degradation and loss in electronic conductivity led to gradual capacity fading. The specific capacity stabilized at >120 mAh/g after 50 charge-discharge cycles. Further improvement in electrochemical performance is possible via electrode surface modification, polymer binder incorporation, or designs of new morphologies. - Graphical abstract: Electrochemical profile of a Cr{sub 2}O{sub 5}/Na battery cell and high-resolution solid-state {sup 23}Na MAS NMR spectrum of a Cr{sub 2}O{sub 5} electrode discharged to 2 V. - Highlights: • Cr{sub 2}O{sub 5} was synthesized and used as a new cathode in rechargeable Na ion batteries. • A high capacity of 310 mAh/g and an energy density of 564 Wh/kg were achieved. • High-resolution solid-state {sup 23}Na NMR was employed to follow the reaction mechanisms.« less

Towards greener and more sustainable batteries for electrical energy storage

NASA Astrophysics Data System (ADS)

Larcher, D.; Tarascon, J.-M.

2015-01-01

Ever-growing energy needs and depleting fossil-fuel resources demand the pursuit of sustainable energy alternatives, including both renewable energy sources and sustainable storage technologies. It is therefore essential to incorporate material abundance, eco-efficient synthetic processes and life-cycle analysis into the design of new electrochemical storage systems. At present, a few existing technologies address these issues, but in each case, fundamental and technological hurdles remain to be overcome. Here we provide an overview of the current state of energy storage from a sustainability perspective. We introduce the notion of sustainability through discussion of the energy and environmental costs of state-of-the-art lithium-ion batteries, considering elemental abundance, toxicity, synthetic methods and scalability. With the same themes in mind, we also highlight current and future electrochemical storage systems beyond lithium-ion batteries. The complexity and importance of recycling battery materials is also discussed.

Electrochemical and thermal studies of lithium ion batteries

NASA Astrophysics Data System (ADS)

Lu, Wenquan

The structural, electrochemical, and thermal characteristics of carbonaceous anodes and LiNi0.8Co0.2O2 cathode in Li-ion cells were investigated using various electrochemical and calorimetric techniques. The electrode-electrolyte interface was investigated for various carbonaceous materials such as graphite with different shapes, surface modified graphite with copper, and novel carbon material derived from sepiolite template. The structural and morphological properties were determined using XRD, TGA, SEM, BET techniques. The electrochemical characteristics were studied using conventional electrochemical techniques such as galvanostatic charge/discharge cycling, cyclic voltammetry, and impedance (AC and DC) methods. It was observed that the electrochemical active surface area instead of the BET area plays a critical role in the irreversible capacity loss associated with the carbonaceous anodes. It was also found that the exfoliation of carbon anodes especially in PC based electrolyte could be significantly reduced by protective copper coating of the natural graphite. LiNi0.8Co0.2O2 cathode material was found to possess high energy density and excellent cycling characteristics. The structural and electrochemical properties of LiNi0.8Co 0.2O2 synthesized by sol-gel and solid-state methods were studied. Results of the AC impedance spectroscopy carried out on LiNi 0.8Co0.2O2 cathodes revealed that the charge transfer resistance is a function of the state of charge. The solid state Li + diffusion was calculated to be around 10-13 cm2/s in the oxide particle by Warburg impedance method. In addition, the cell fabricated with LiNi0.8Co0.2O 2 cathode showed excellent energy and power performance under static and dynamic load conditions that prevail in Electric and Hybrid Vehicles. Thermal properties of the LiNi0.8Co0.2O2 cathode, carbonaceous anodes, and Li-ion cells fabricated with these electrodes were also investigated using isothermal microcalorimetry (IMC), differential scanning calorimetry (DSC) and accelerated rate calorimetry (ARC). Isothermal micro-calorimeter was used to investigate the thermal behavior of the Li-ion cell and its electrodes. The overall heat changes during charge-discharge processes were explained in terms of the irreversible (resistive) and reversible (entropic) heats. It was observed that the reversible heat strongly depends on the structural or phase change occurring in the electrodes during Li-ion insertion and extraction reactions. It was also found that the contribution of the reversible heat to the overall cell heat generation rate was significant only at low cycling rates.

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

NASA Astrophysics Data System (ADS)

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

2018-07-01

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

Electrochemical biosensors for Salmonella: State of the art and challenges in food safety assessment.

PubMed

Silva, Nádia F D; Magalhães, Júlia M C S; Freire, Cristina; Delerue-Matos, Cristina

2018-01-15

According to the recent statistics, Salmonella is still an important public health issue in the whole world. Legislated reference methods, based on counting plate methods, are sensitive enough but are inadequate as an effective emergency response tool, and are far from a rapid device, simple to use out of lab. An overview of the commercially available rapid methods for Salmonella detection is provided along with a critical discussion of their limitations, benefits and potential use in a real context. The distinguished potentialities of electrochemical biosensors for the development of rapid devices are highlighted. The state-of-art and the newest technologic approaches in electrochemical biosensors for Salmonella detection are presented and a critical analysis of the literature is made in an attempt to identify the current challenges towards a complete solution for Salmonella detection in microbial food control based on electrochemical biosensors. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrochemical state and internal variables estimation using a reduced-order physics-based model of a lithium-ion cell and an extended Kalman filter

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

Stetzel, KD; Aldrich, LL; Trimboli, MS

2015-03-15

This paper addresses the problem of estimating the present value of electrochemical internal variables in a lithium-ion cell in real time, using readily available measurements of cell voltage, current, and temperature. The variables that can be estimated include any desired set of reaction flux and solid and electrolyte potentials and concentrations at any set of one-dimensional spatial locations, in addition to more standard quantities such as state of charge. The method uses an extended Kalman filter along with a one-dimensional physics-based reduced-order model of cell dynamics. Simulations show excellent and robust predictions having dependable error bounds for most internal variables.more » (C) 2014 Elsevier B.V. All rights reserved.« less

Obstacles and opportunities in the commercialization of the solid state electronic fluorescent lighting ballast

NASA Astrophysics Data System (ADS)

Johnson, D. R.; Marcus, A. A.; Campbell, R. S.; Sommers, P.; Skumatz, L.; Berk, B.; Petty, P.; Eschbach, C.

1981-10-01

A solid state ballast (SSB), which improves the efficiency of fluorescent lights, is described. The first generation of solid state electronic ballasts was developed and the technology was transferred to the private sector. The opportunities for rapid dissemination of this technology into the marketplace is examined. Product characteristics and their influence on the commercialization of the SSB, a description of the technology delivery system presently used by the ballast industry, an analysis of the market for SSB, and identification of some high leverage opportunities to accelerate the commercialization process are included.

Coupled diffusion and mechanics in battery electrodes

NASA Astrophysics Data System (ADS)

Eshghinejad, Ahmadreza

We are living in a world with continuous production and consumption of energy. The energy production in the past decades has started to move away from petrochemical sources toward sustainable sources such as solar, wind and geothermal. Also, the energy consumption is further adapting to the sustainable sources. For instance, in recent years electric vehicles are growing fast that can consume sustainable electric energy stored in their batteries. In this direction, in order to further move toward sustainable energy, materials are becoming increasingly important for storing electric energy. Although, currently the technologies such as Li-ion batteries and solid-oxide fuel cells are commercially available for energy applications, improvements are crucial for the next generation of many other technologies producing or consuming sustainable energies. A critical aspect of the electrochemical activities involved in energy storage technologies such as Li-ion batteries and solid-oxide fuel cells is the diffusion of ions into the electrode materials. This process ultimately governs various functional properties of the batteries such as capacity and charging/discharging rates. The first goal of this dissertation is to develop mathematical tools to analyze the ionic diffusion and investigate its coupling with mechanics in electrodes. For this purpose, a thermodynamics-based modeling framework is developed and numerically solved using two numerical methods to analyze ionic diffusion in heterogeneous and structured electrodes. The next goal of this dissertation is to develop and analyze characterization techniques to probe the electrochemical processes at the nano-scale. To this end, the mathematical models are first employed to model a previously developed Atomic Force Microscopy based technique to probe local electrochemical activities called Electrochemical Strain Microscopy (ESM). This method probes the activities by inducing AC electric field to perturb ionic activities and measuring the surface vibrations. Different aspects of this technique are analyzed and the limitations are discussed. Such limitations moves the dissertation toward development of a new technique for probing the electrochemical activities, to overcome the previous limitations, called Scanning Thermo-ionic Microscopy (STIM). In this method, the local activities are probed by inducing AC temperature oscillations to perturb ionic activities and measuring the surface vibrations. The principle mathematical analysis of the coupled governing equations and the method of probing electrochemical activities are discussed in detail. Also, the method is implemented into the AFM hardware/software and the STIM response is confirmed using experiments on LiFePO4 and Sm-doped Ceria as well-known battery and fuel cell electrodes. The STIM method provides a clean method for analyzing energy storage materials and designing novel nano-structured materials for improved performance. Finally, conclusion of the presented work is discussed in the last chapter and the future works to continue the development of the modeling and experiments are listed.

The electrochemical fluorination of polymeric materials for high energy density aqueous and non-aqueous battery and fuel cell separators

NASA Technical Reports Server (NTRS)

Liu, C. C.

1983-01-01

A computerized system was established and the electrochemical fluorination of trichloroethylene, polyacrylic acid and polyvinyl alcohol in anhydrous hydrogen fluoride was attempted. Both solid substrates as well as membranes were used. Some difficulties were found in handling and analyzing the solid substrates and membranes. Further studies are needed in this area. A microprocessor aided electrochemical fluorination system capable of obtaining highly reproducible experimental results was established.

All-solid-state flexible supercapacitors based on highly dispersed polypyrrole nanowire and reduced graphene oxide composites.

PubMed

Yu, Chenfei; Ma, Peipei; Zhou, Xi; Wang, Anqi; Qian, Tao; Wu, Shishan; Chen, Qiang

2014-10-22

Highly dispersed polypyrrole nanowires are decorated on reduced graphene oxide sheets using a facile in situ synthesis route. The prepared composites exhibit high dispersibility, large effective surface area, and high electric conductivity. All-solid-state flexible supercapacitors are assembled based on the prepared composites, which show excellent electrochemical performances with a specific capacitance of 434.7 F g(-1) at a current density of 1 A g(-1). The as-fabricated supercapacitor also exhibits excellent cycling stability (88.1% capacitance retention after 5000 cycles) and exceptional mechanical flexibility. In addition, outstanding power and energy densities were obtained, demonstrating the significant potential of prepared material for flexible and portable energy storage devices.

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

NASA Astrophysics Data System (ADS)

Raj, R.; Wolfenstine, J.

2017-03-01

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

Rechargeable thin film battery and method for making the same

DOEpatents

Goldner, Ronald B.; Liu, Te-Yang; Goldner, Mark A.; Gerouki, Alexandra; Haas, Terry E.

2006-01-03

A rechargeable, stackable, thin film, solid-state lithium electrochemical cell, thin film lithium battery and method for making the same is disclosed. The cell and battery provide for a variety configurations, voltage and current capacities. An innovative low temperature ion beam assisted deposition method for fabricating thin film, solid-state anodes, cathodes and electrolytes is disclosed wherein a source of energetic ions and evaporants combine to form thin film cell components having preferred crystallinity, structure and orientation. The disclosed batteries are particularly useful as power sources for portable electronic devices and electric vehicle applications where high energy density, high reversible charge capacity, high discharge current and long battery lifetimes are required.

The solid state detector technology for picosecond laser ranging

NASA Technical Reports Server (NTRS)

Prochazka, Ivan

1993-01-01

We developed an all solid state laser ranging detector technology, which makes the goal of millimeter accuracy achievable. Our design and construction philosophy is to combine the techniques of single photon ranging, ultrashort laser pulses, and fast fixed threshold discrimination while avoiding any analog signal processing within the laser ranging chain. The all solid state laser ranging detector package consists of the START detector and the STOP solid state photon counting module. Both the detectors are working in an optically triggered avalanche switching regime. The optical signal is triggering an avalanche current buildup which results in the generation of a uniform, fast risetime output pulse.

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, Peter C.; Lessing, Paul A.

1995-01-01

A chemical reactor for oxygenating hydrocarbons includes: a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed.

Nanoionic devices: Interface nanoarchitechtonics for physical property tuning and enhancement

NASA Astrophysics Data System (ADS)

Tsuchiya, Takashi; Terabe, Kazuya; Yang, Rui; Aono, Masakazu

2016-11-01

Nanoionic devices have been developed to generate novel functions overcoming limitations of conventional materials synthesis and semiconductor technology. Various physical properties can be tuned and enhanced by local ion transport near the solid/solid interface. Two electronic carrier doping methods can be used to achieve extremely high-density electronic carriers: one is electrostatic carrier doping using an electric double layer (EDL); the other is electrochemical carrier doping using a redox reaction. Atomistic restructuring near the solid/solid interface driven by a DC voltage, namely, interface nanoarchitechtonics, has huge potential. For instance, the use of EDL enables high-density carrier doping in potential superconductors, which can hardly accept chemical doping, in order to achieve room-temperature superconductivity. Optical bandgap and photoluminescence can be controlled for various applications including smart windows and biosensors. In situ tuning of magnetic properties is promising for low-power-consumption spintronics. Synaptic plasticity in the human brain is achieved in neuromorphic devices.

U.S. Army High Energy Laser (HEL) technology program

NASA Astrophysics Data System (ADS)

Lavan, Michael J.; Wachs, John J.

2011-11-01

The US Army is investing in Solid State Laser (SSL) technology to assess counter rocket, artillery, and mortar (C-RAM) and counter unmanned aerial vehicle (C-UAV) capabilities of solid state based HEL systems, as well as other potential applications for HELs of interest to the Army. The Army HEL program thrust areas are systematically moving the technology forward toward weaponization, including solid state laser technologies, advances in beam control technology, and conducting major demonstrations. The High Energy Laser Mobile Demonstrator (HELMD) will be a major step toward demonstrating HEL weapon capability to the soldier. The US Army will continue to pursue technologies that enable more compact systems compatible with, for example, a Stryker tactical vehicle as a crucial part of our strategy to provide a capability to the warfighter that can maneuver with the force.

Patterning of a-C DLC films: exploration of an aqueous electro-oxidative mechanism

NASA Astrophysics Data System (ADS)

Mühl, Thomas; Myhra, Sverre

2007-06-01

Conducting ion-beam assisted CVD deposited a-C type DLC films can be patterned electro-oxidatively by masked and maskless probe-induced STM-based lithography. The former constitutes a parallel rapid processing technology, with the tip acting as a distant stationary electrode. The latter is a higher spatial resolution serial technology, with the tip defining a travelling local electro-chemical cell. The mechanism is based on electro-oxidative conversion of solid carbon to gaseous CO or CO2 in the presence of an aqueous phase, either as a bulk fluid or as a thin adsorbed film. The process is constrained kinetically in the early stages by limitations on charge transport through the surface barrier at the fluid-to-solid interface and subsequently by the availability of oxidants and by their transport to reactive sites. The as-received surface is terminated by chemisorbed oxygen, leading to the formation of an insulating surface barrier. The threshold potential for initiation of conversion depends on the width of the barrier. The results may have implications for new technologies exploiting the properties of carbon-based materials, but may also add to the present understanding of the electrochemistry of carbon solids.

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

PubMed

Funke, Klaus

2013-08-01

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

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

PubMed Central

Funke, Klaus

2013-01-01

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

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

PubMed

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

2015-03-11

The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF6 in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid-solid interfaces and their evolving chemistries.

Effect of distribution, interface property and density of hydrogel-embedded vertically aligned carbon nanotube arrays on the properties of a flexible solid state supercapacitor

NASA Astrophysics Data System (ADS)

Zhu, Qi; Yuan, Xietao; Zhu, Yihao; Ni, Jiangfeng; Zhang, Xiaohua; Yang, Zhaohui

2018-05-01

In this paper we fabricate a robust flexible solid-state supercapacitor (FSC) device by embedding a conductive poly(vinyl alcohol) hydrogel into aligned carbon nanotube (CNT) arrays. We carefully investigate the effect of distribution, interface properties and densification of CNTs in the gel matrix on the electrochemical properties of an FSC. The total electrochemical capacitance of the device is measured to be 227 mF cm‑3 with a maximum energy density of 0.02 mWh cm‑3, which is dramatically enhanced compared with a similar device composed of non-parallel CNTs. Additionally, controllable in situ electrochemical oxidation greatly improved the compatibility between the hydrophobic CNTs and the hydrophilic hydrogel, which decreased the resistance of the device and introduced extra pseudocapacitance. After such oxidation treatment the energy storage ability further doubled to 430 mF cm‑3 with a maximum energy density of 0.04 mWh cm‑3 . The FSCs based on densified CNT arrays exhibited a much higher volumetric capacitance of 1140 mF cm‑3 and a larger energy density of 0.1 mWh cm‑3, with a large power density of 14 mW cm‑3. All devices show excellent stability of capacitance after at least 10 000 charge–discharge cycles with a loss of less than 2%. These easy-to-assemble hybrid arrays thus potentially provide a new method for manufacturing wearable devices and implantable medical devices.

Effect of distribution, interface property and density of hydrogel-embedded vertically aligned carbon nanotube arrays on the properties of a flexible solid state supercapacitor.

PubMed

Zhu, Qi; Yuan, Xietao; Zhu, Yihao; Ni, Jiangfeng; Zhang, Xiaohua; Yang, Zhaohui

2018-05-11

In this paper we fabricate a robust flexible solid-state supercapacitor (FSC) device by embedding a conductive poly(vinyl alcohol) hydrogel into aligned carbon nanotube (CNT) arrays. We carefully investigate the effect of distribution, interface properties and densification of CNTs in the gel matrix on the electrochemical properties of an FSC. The total electrochemical capacitance of the device is measured to be 227 mF cm -3 with a maximum energy density of 0.02 mWh cm -3 , which is dramatically enhanced compared with a similar device composed of non-parallel CNTs. Additionally, controllable in situ electrochemical oxidation greatly improved the compatibility between the hydrophobic CNTs and the hydrophilic hydrogel, which decreased the resistance of the device and introduced extra pseudocapacitance. After such oxidation treatment the energy storage ability further doubled to 430 mF cm -3 with a maximum energy density of 0.04 mWh cm -3 . The FSCs based on densified CNT arrays exhibited a much higher volumetric capacitance of 1140 mF cm -3 and a larger energy density of 0.1 mWh cm -3 , with a large power density of 14 mW cm -3 . All devices show excellent stability of capacitance after at least 10 000 charge-discharge cycles with a loss of less than 2%. These easy-to-assemble hybrid arrays thus potentially provide a new method for manufacturing wearable devices and implantable medical devices.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

In situ study of LaY2Ni9 compound as Ni MH negative-electrode material

NASA Astrophysics Data System (ADS)

Latroche, M.; Isnard, O.

2008-03-01

The behavior of a Ni-MH (metal hydride) negative composite electrode made of LaY2Ni9 active material has been studied dynamically using in situ neutron diffraction during a complete charge-discharge electrochemical cycle. From the analysis of the collected diffraction patterns, the phase identity, phase amount variations and cell volume evolutions have been determined as a function of the electrochemical state of (dis)charge. The active material shows a typical two-phase behavior with equilibrium between a hydrogen-poor α phase and a hydrogen-rich β one. The lower electrochemical reversible capacity as compared to solid-gas properties has been interpreted in terms of hydrogen gas evolving during charge and kinetic limitation due to slow β to α transformation during discharge, which hinders high discharge rates.

Solid State Technology Branch of NASA Lewis Research Center

NASA Technical Reports Server (NTRS)

1992-01-01

A collection of papers written by the members of the Solid State Technology Branch of NASA LeRC from Jun. 1991 - Jun. 1992 is presented. A range of topics relating to superconductivity, Monolithic Microwave Circuits (MMIC's), coplanar waveguides, and material characterization is covered.

Materials for suspension (semi-solid) electrodes for energy and water technologies

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

Hatzell, Kelsey B.; Boota, Muhammad; Gogotsi, Yury

2015-01-01

Suspension or semi-solid electrodes have recently gained increased attention for large-scale applications such as grid energy storage, capacitive water deionization, and wastewater treatment. A suspension electrode is a multiphase material system comprised of an active (charge storing) material suspended in ionic solution (electrolyte). Gravimetrically, the electrolyte is the majority component and aids in physical transport of the active material. For the first time, this principle enables, scalability of electrochemical energy storage devices (supercapacitors and batteries) previously limited to small and medium scale applications. This critical review describes the ongoing material challenges encompassing suspension-based systems. The research described here combines classicalmore » aspects of electrochemistry, colloidal science, material science, fluid mechanics, and rheology to describe ion and charge percolation, adsorption of ions, and redox charge storage processes in suspension electrodes. Our review summarizes the growing inventory of material systems, methods and practices used to characterize suspension electrodes, and describes universal material system properties (rheological, electrical, and electrochemical) that are pivotal in the design of high performing systems. We include a discussion of the primary challenges and future research directions.« less

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

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at leastmore » 5 mAh/cm.sup.2 at a C-rate of C/2.« 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.

Pinpoint and bulk electrochemical reduction of insulating silicon dioxide to silicon.

PubMed

Nohira, Toshiyuki; Yasuda, Kouji; Ito, Yasuhiko

2003-06-01

Silicon dioxide (SiO(2)) is conventionally reduced to silicon by carbothermal reduction, in which the oxygen is removed by a heterogeneous-homogeneous reaction sequence at approximately 1,700 degrees C. Here we report pinpoint and bulk electrochemical methods for removing oxygen from solid SiO(2) in a molten CaCl(2) electrolyte at 850 degrees C. This approach involves a 'contacting electrode', in which a metal wire supplies electrons to a selected region of the insulating SiO(2). Bulk reduction of SiO(2) is possible by increasing the number of contacting points. The same method was also demonstrated with molten LiCl-KCl-CaCl(2) at 500 degrees C. The novelty and relative simplicity of this method might lead to new processes in silicon semiconductor technology, as well as in high-purity silicon production. The methodology may be applicable to electrochemical processing of a wide variety of insulating materials, provided that the electrolyte dissolves the appropriate constituent ion(s) of the material.

New frontiers in materials science opened by ionic liquids.

PubMed

Torimoto, Tsukasa; Tsuda, Tetsuya; Okazaki, Ken-ichi; Kuwabata, Susumu

2010-03-19

Ionic liquids (ILs) including ambient-temperature molten salts, which exist in the liquid state even at room temperature, have a long research history. However, their applications were once limited because ILs were considered as highly moisture-sensitive solvents that should be handled in a glove box. After the first synthesis of moisture-stable ILs in 1992, their unique physicochemical properties became known in all scientific fields. ILs are composed solely of ions and exhibit several specific liquid-like properties, e.g., some ILs enable dissolution of insoluble bio-related materials and the use as tailor-made lubricants in industrial applications under extreme physicochemical conditions. Hybridization of ILs and other materials provides quasi-solid materials, which can be used to fabricate highly functional devices. ILs are also used as reaction media for electrochemical and chemical synthesis of nanomaterials. In addition, the negligible vapor pressure of ILs allows the fabrication of electrochemical devices that are operated under ambient conditions, and many liquid-vacuum technologies, such as X-ray photoelectron spectroscopy (XPS) analysis of liquids, electron microscopy of liquids, and sputtering and physical vapor deposition onto liquids. In this article, we review recent studies on ILs that are employed as functional advanced materials, advanced mediums for materials production, and components for preparing highly functional materials.

Random Walk Analysis of the Effect of Mechanical Degradation on All-Solid-State Battery Power

DOE PAGES

Bucci, Giovanna; Swamy, Tushar; Chiang, Yet-Ming; ...

2017-09-06

Mechanical and electrochemical phenomena are coupled in defining the battery reliability, particularly for solid-state batteries. Micro-cracks act as barriers to Li-ion diffusion in the electrolyte, increasing the average electrode’s tortuosity. In our previous work, we showed that solid electrolytes are likely to suffer from mechanical degradation if their fracture energy is lower than 4 J m -2 [G. Bucci, T. Swamy, Y.-M. Chiang, and W. C. Carter, J. Mater. Chem. A (2017)]. Here we study the effect of electrolyte micro-cracking on the effective conductivity of composite electrodes. Via random analyzes, we predict the average diffusivity of lithium in a solid-statemore » electrode to decrease linearly with the extension of mechanical degradation. Furthermore, the statistical distribution of first passage times indicates that the microstructure becomes more and more heterogeneous as damage progresses. In addition to power and capacity loss, a non-uniform increase of the electrode tortuosity can lead to heterogeneous lithiation and further stress localization. Finally, the understanding of these phenomena at the mesoscale is essential to the implementation of safe high-energy solid-state batteries.« less

Random Walk Analysis of the Effect of Mechanical Degradation on All-Solid-State Battery Power

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

Bucci, Giovanna; Swamy, Tushar; Chiang, Yet-Ming

Mechanical and electrochemical phenomena are coupled in defining the battery reliability, particularly for solid-state batteries. Micro-cracks act as barriers to Li-ion diffusion in the electrolyte, increasing the average electrode’s tortuosity. In our previous work, we showed that solid electrolytes are likely to suffer from mechanical degradation if their fracture energy is lower than 4 J m -2 [G. Bucci, T. Swamy, Y.-M. Chiang, and W. C. Carter, J. Mater. Chem. A (2017)]. Here we study the effect of electrolyte micro-cracking on the effective conductivity of composite electrodes. Via random analyzes, we predict the average diffusivity of lithium in a solid-statemore » electrode to decrease linearly with the extension of mechanical degradation. Furthermore, the statistical distribution of first passage times indicates that the microstructure becomes more and more heterogeneous as damage progresses. In addition to power and capacity loss, a non-uniform increase of the electrode tortuosity can lead to heterogeneous lithiation and further stress localization. Finally, the understanding of these phenomena at the mesoscale is essential to the implementation of safe high-energy solid-state batteries.« less

Studies on Ionic Conductivity and Electrochemical Stability of Plasticized Photopolymerized Polymer Electrolyte Membranes for Solid State Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

He, Ruixuan

In pursuit of safer and more flexible solid-state lithium ion batteries, solid polymer electrolytes have emerged as a promising candidate. The present dissertation entails exploration of solid plasticized, photopolymerized (i.e. ultraviolent-cured) polymer electrolyte membranes (PEM) for fulfilling the critical requirements of electrolytes, such as high ionic conductivity and good thermal and electrochemical stability, among others. Electrochemical performance of PEMs containing lithium ion half-cells was also investigated at different two temperatures. Phase diagram approach was adopted to guide the fabrication of two types of plasticized PEMs. Prepolymer poly (ethylene glycol) diacrylate (PEGDA) was used as a matrix for building an ionic conductive and mechanically sturdy network. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated as a source of lithium ions, while a solid plasticizer succinonitrile (SCN) and a liquid plasticizer tetraethylene glycol dimethyl ether (TEGDME) were incorporated in the respective systems. The important role of plasticizer on the enhancement of ionic conductivity (sigma) to the superionic conductive level (10-3 S/cm) was revealed in both systems. It is worth noting that photopolymerization induced crystallization (PIC) occurred during UV-curing in the SCN-rich region of the ternary PEGDA/LiTFSI/SCN ternary mixtures. The PEM thus formed contained a plastic crystal phase, which showed lower σ relative to their amorphous PEGDA/LiTFSI/TEGDME counterpart. Comparisons on other thermal and electrochemical properties of the two types of PEMs are presented in Chapter IV. For the PEGDA/LiTFSI/SCN PEMs, fundamental study was carried out to clarify the relationship between σ and glass transition temperature (T g). In lithium salt/polymer binary PEMs, increase in Tg and reduction in σ were observed; these may be attributed to ion-dipole complexation between dissociated lithium cations and ether oxygen upon salt addition. Notably, above the threshold salt concentration of 7 mol %, dual loss tangent peaks were observed in dynamic mechanical studies. These might be ascribed to segmental relaxations of ion-dipole complexed networks and that of polymer chains surrounding the undissociated lithium salt acting like "fillers". Upon SCN incorporation, these two peaks merged into one that was further suppressed below the Tg of the pure network, whereas σ improved to the superionic conductor level. The role of SCN on the σ enhancement as both plasticizer for the polymer network and ionizer for the salt is discussed in Chapter V. In order to improve the mechanical toughness of the highly conductive PEGDA/LiTFSI/SCN PEM, effects of prepolymer molecular weight on mechanical and electrochemical properties of PEMs were further investigated. By increasing molecular weight of PEGDA from 700 to 6000 g/mol, toughness and elongation at break were enhanced as expected. Interestingly, improved ionic conductivity was achieved simultaneously. The dual improvement may be attributed to the less chemical crosslinked points and the more flexible chain motion in the looser network of PEGDA6000-PEM relative to its PEGDA700 counterpart. Subsequently, high thermal stability and electrochemical stability of both types of PEMs, as well as the satisfactory room temperature charge/discharge cycling performance of PEM containing lithium ion half-cells were observed. The pertinent information is documented in Chapter VI. Finally, the investigation of the charge/discharge cycling performance of solid-state LiFePO4 half-cells at an elevated temperature of 60°C is discussed in Chapter VII. In the half-cells, particularly, SCN plasticized PEMs with and without electrolyte modifier lithium bis(oxalato)borate (LiBOB) were respectively employed. Rapid decline of capacity and increase of cell resistance were found in the unmodified PEM containing cell; however, these deteriorations were greatly suppressed upon LiBOB modification. Electrochemical and thermal compatibility of PEMs towards different electrodes were examined in several symmetric cells and half-cells. Detailed characterization on LiFePO 4 electrodes and PEMs retrieved from these cells implied that the observed battery failure might be triggered by an amide-forming side reaction that took place at the interface of a SCN plasticized PEM and a lithium electrode at high temperature. Of particular importance is the fact that this detrimental side reaction was effectively suppressed upon LiBOB electrolyte modifier addition. Plausible mechanisms are discussed.

The Evolution of High Temperature Gas Sensors.

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

Garzon, F. H.; Brosha, E. L.; Mukundan, R.

2001-01-01

Gas sensor technology based on high temperature solid electrolytes is maturing rapidly. Recent advances in metal oxide catalysis and thin film materials science has enabled the design of new electrochemical sensors. We have demonstrated prototype amperometric oxygen sensors, nernstian potentiometric oxygen sensors that operate in high sulfur environments, and hydrocarbon and carbon monoxide sensing mixed potentials sensors. Many of these devices exhibit part per million sensitivities, response times on the order of seconds and excellent long-term stability.

Progress in battery technology since the First CSULB Annual Battery Conference and prospects for the future

NASA Astrophysics Data System (ADS)

Pickett, David F., Jr.

1992-04-01

An evaluation is made of noteworthy trends in the development of advanced electrochemical cells since January 1986. The advancements noted encompass LiAr batteries, spacecraft power supply Ni-H and Li-SO2 batteries, battery-powered biomedical devices, rechargeable Li-ion batteries, and the development of ambient temperature rechargeable lithium polymer solid electrolyte batteries. Attention is given to OSHA regulatory guidelines for recently commercially introduced advanced battery systems.

Electrochemical processing of solid waste

NASA Technical Reports Server (NTRS)

Bockris, John OM.

1987-01-01

An investigation of electrochemical waste treatment methods suitable for closed, or partially closed, life support systems for manned space exploration is discussed. The technique being investigated involves the electrolysis of solid waste where the aim is to upgrade waste material (mainly fecal waste) to generate gases that can be recycled in a space station or planetary space environment.

Convection of tin in a Bridgman system. I - Flow characterization by effective diffusivity measurements

NASA Technical Reports Server (NTRS)

Sears, B.; Narayanan, R.; Anderson, T. J.; Fripp, A. L.

1992-01-01

An electrochemical titration method was used to investigate the dynamic states in a cylindrical layer of convecting tin. The liquid tin was contained in a cell, with curved boundaries made of quartz and flat boundaries made of a solid state electrolyte - yttria-stabilized zirconia (YSZ). The electrolyte acted as a window through which a trace amount of oxygen could be pumped in or out by the application of a constant voltage. The concentration at the YSZ interface was monitored by operating the electrochemical cell in the galvanic mode. Experimentally determined effective diffusivities of oxygen were compared with the molecular diffusivity. Dynamic states in the convective flow were thus inferred. Temperature measurements were simultaneously made in order to identify the onset of oscillations from a steady convective regime. The experiments were conducted for two different aspect ratios for various imposed temperature gradients and two different orientations with respect to gravity. Transcritical states were identified and comparison to two-dimensional numerical models were made.

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography

DOE PAGES

Yu, Young-Sang; Farmand, Maryam; Kim, Chunjoong; ...

2018-03-02

Battery function is determined by the efficiency and reversibility of the electrochemical phase transformations at solid electrodes. The microscopic tools available to study the chemical states of matter with the required spatial resolution and chemical specificity are intrinsically limited when studying complex architectures by their reliance on two-dimensional projections of thick material. Here in this paper, we report the development of soft X-ray ptychographic tomography, which resolves chemical states in three dimensions at 11 nm spatial resolution. We study an ensemble of nano-plates of lithium iron phosphate extracted from a battery electrode at 50% state of charge. Using a setmore » of nanoscale tomograms, we quantify the electrochemical state and resolve phase boundaries throughout the volume of individual nanoparticles. These observations reveal multiple reaction points, intra-particle heterogeneity, and size effects that highlight the importance of multi-dimensional analytical tools in providing novel insight to the design of the next generation of high-performance devices.« less

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography

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

Yu, Young-Sang; Farmand, Maryam; Kim, Chunjoong

Battery function is determined by the efficiency and reversibility of the electrochemical phase transformations at solid electrodes. The microscopic tools available to study the chemical states of matter with the required spatial resolution and chemical specificity are intrinsically limited when studying complex architectures by their reliance on two-dimensional projections of thick material. Here in this paper, we report the development of soft X-ray ptychographic tomography, which resolves chemical states in three dimensions at 11 nm spatial resolution. We study an ensemble of nano-plates of lithium iron phosphate extracted from a battery electrode at 50% state of charge. Using a setmore » of nanoscale tomograms, we quantify the electrochemical state and resolve phase boundaries throughout the volume of individual nanoparticles. These observations reveal multiple reaction points, intra-particle heterogeneity, and size effects that highlight the importance of multi-dimensional analytical tools in providing novel insight to the design of the next generation of high-performance devices.« less

Assessment of all-solid-state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Braun, P.; Uhlmann, C.; Weiss, M.; Weber, A.; Ivers-Tiffée, E.

2018-07-01

All-solid-state lithium-ion batteries (ASSBs) are considered as next generation energy storage systems. A model might be very useful, which describes all contributions to the internal cell resistance, enables an optimization of the cell design, and calculates the performance of an open choice of cell architectures. A newly developed one-dimensional model for ASSBs is presented, based on a design concept which employs the use of composite electrodes. The internal cell resistance is calculated by linking two-phase transmission line models representing the composite electrodes with an ohmic resistance representing the solid electrolyte (separator). Thereby, electrical parameters, i.e. ionic and electronic conductivity, electrochemical parameters, i.e. charge-transfer resistance at interfaces and lithium solid-state diffusion, and microstructure parameters, i.e. electrode thickness, particle size, interface area, phase composition and tortuosity, are considered as the most important material and design parameters. Subsequently, discharge curves are simulated, and energy- and power-density characteristics of all-solid-state cell architectures are calculated. These model calculations are discussed and compared with experimental data from literature for a high power LiCoO2-Li10GeP2S12/Li10GeP2S12/Li4Ti5O12-Li10GeP2S12 cell.

Structure Evolution and Reactivity of the Sc(2- x)V xO3+δ (0 ≤ x ≤ 2.0) System.

PubMed

Lussier, Joey A; Simon, Fabian J; Whitfield, Pamela S; Singh, Kalpana; Thangadurai, Venkataraman; Bieringer, Mario

2018-05-07

Solid oxide fuel cells (SOFCs) are solid-state electrochemical devices that directly convert chemical energy of fuels into electricity with high efficiency. Because of their fuel flexibility, low emissions, high conversion efficiency, no moving parts, and quiet operation, they are considered as a promising energy conversion technology for low carbon future needs. Solid-state oxide and proton conducting electrolytes play a crucial role in improving the performance and market acceptability of SOFCs. Defect fluorite phases are some of the most promising fast oxide ion conductors for use as electrolytes in SOFCs. We report the synthesis, structure, phase diagram, and high-temperature reactivity of the Sc (2- x) V x O 3+δ (0 ≤ x ≤ 2.00) oxide defect model system. For all Sc (2- x) V x O 3.0 phases with x ≤ 1.08 phase-pure bixbyite-type structures are found, whereas for x ≥ 1.68 phase-pure corundum structures are reported, with a miscibility gap found for 1.08 < x < 1.68. Structural details obtained from the simultaneous Rietveld refinements using powder neutron and X-ray diffraction data are reported for the bixbyite phases, demonstrating a slight V 3+ preference toward the 8b site. In situ X-ray diffraction experiments were used to explore the oxidation of the Sc (2- x) V x O 3.0 phases. In all cases ScVO 4 was found as a final product, accompanied by Sc 2 O 3 for x < 1.0 and V 2 O 5 when x > 1.0; however, the oxidative pathway varied greatly throughout the series. Comments are made on different synthesis strategies, including the effect on crystallinity, reaction times, rate-limiting steps, and reaction pathways. This work provides insight into the mechanisms of solid-state reactions and strategic guidelines for targeted materials synthesis.

Synthesis and characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole: investigation on backbone/pendant interactions in a conducting redox polymer.

PubMed

Huang, Hao; Karlsson, Christoffer; Strømme, Maria; Gogoll, Adolf; Sjödin, Martin

2017-04-19

We herein report the synthesis and electrochemical characterization of poly-3-((2,5-hydroquinone)vinyl)-1H-pyrrole, consisting of a polypyrrole backbone derivatized at the beta position by a vinyl-hydroquinone pendant group. The structure of the polymer was characterized by solid state NMR spectroscopy. The interactions between the polypyrrole backbone and the oxidized quinone or reduced hydroquinone pendant groups are probed by several in situ methods. In situ attenuated total reflectance-Fourier transform infrared spectroscopy shows a spectroscopic response from both the doping of the polymer backbone and the redox activity of the pendant groups. Using an in situ Electrochemical Quartz Crystal Microbalance we reveal that the polymer doping is unaffected by the pendant group redox chemistry, as opposed to previous reports. Despite the continuous doping the electrochemical conversion from the hydroquinone state to the quinone state results in a significant conductance drop, as observed by in situ conductivity measurements using an Interdigitated Array electrode set-up. Twisting of the conducting polymer backbone as a result of a decreased separation between pendant groups due to π-π stacking in the oxidized state is suggested as the cause of this conductance drop.

Synthesis and processing of materials for direct thermal-to-electric energy conversion and storage

NASA Astrophysics Data System (ADS)

Thompson, Travis

Currently, fossil fuels are the primary source of energy. Mechanical heat engines convert the chemical potential energy in fossil fuels to useful electrical energy through combustion; a relatively low efficiency process that generates carbon dioxide. This practice has led to a significant increase in carbon dioxide emissions and is contributing to climate change. However, not all heat engines are mechanical. Alternative energy generation technologies to mechanical heat engines are known, yet underutilized. Thermoelectric generators are solid-state devices originally developed by NASA to power deep space spacecraft, which can also convert heat into electricity but without any moving parts. Similar to their mechanical counterparts, any heat source, including the burning of fossil fuels, can be used. However, clean heat sources, such as concentrated solar, can alternatively be used. Since the energy sources for many of the alternative energy technologies is intermittent, including concentrated solar for thermoelectric devices, load matching is difficult or impossible and an energy storage technology is needed in addition to the energy conversion technology. This increases the overall cost and complexity of the systems since two devices are required and represents a significant barrier for mass adoption of an alternative energy technology. However, it is possible to convert heat energy to electrical energy and store excess charge for use at a later time when the demand increases, in a single device. One such of a device is a thermogalvanic generator and is the electrochemical analog of electronic thermoelectric devices. Essentially, a thermogalvanic device represents the combination of thermoelectric and galvanic systems. As such, the rich history of strategies developed by both the thermoelectric community to better the performance of thermoelectric devices and by the electrochemical community to better traditional galvanic devices (i.e. batteries) can be applied to thermogalvanic devices. Although thermogalvanic devices are known, there has been little exploration into the use of thermogalvanic devices for power generation and energy storage. First, this work formalizes the energy problem and introduces the operating principles of thermoelectric, galvanic, and thermogalvanic devices. Second, oxide based thermoelectric materials are explored from a synthetic and processing standpoint. Out of necessity, a new synthetic technique was invented and a novel hot-press technique was developed. Third, a solid Li-ion conducting electrolyte, based on the garnet crystal structure, is identified for the use in a thermogalvanic cell. In order to better understand the conductivity behavior, an in-depth exploration into the variables that control the ionic transport is performed on the electrolyte. Third, a thermogalvanic cell is constructed using this garnet based Li-ion conducting solid electrolyte and the first demonstration of such a cell is presented. Finally, strategies to improve the performance of thermogalvanic cells based on garnet type solid electrolytes are outlined for future work. The purpose of this work is to use an interdisciplinary approach to marry together the electrochemistry of galvanic systems with the strategies used to better semiconductor based thermoelectric materials and ceramics processing techniques to fabricate these systems. This dissertation will explore the interplay of these areas.

Solid-state chemistry and particle engineering with supercritical fluids in pharmaceutics.

PubMed

Pasquali, Irene; Bettini, Ruggero; Giordano, Ferdinando

2006-03-01

The present commentary aims to review the modern and innovative strategies in particle engineering by the supercritical fluid technologies and it is principally concerned with the aspects of solid-state chemistry. Supercritical fluids based processes for particle production have been proved suitable for controlling solid-state, morphology and particle size of pharmaceuticals, in some cases on an industrial scale. Supercritical fluids should be considered in a prominent position in the development processes of drug products for the 21st century. In this respect, this innovative technology will help in meeting the more and more stringent requirements of regulatory authorities in terms of solid-state characterisation and purity, and environmental acceptability.

Method and apparatus for producing oxygenates from hydrocarbons

DOEpatents

Kong, P.C.; Lessing, P.A.

1995-06-27

A chemical reactor for oxygenating hydrocarbons includes: (a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; (b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; (c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and (d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed. 4 figs.

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

The role of graphene for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Raccichini, Rinaldo; Varzi, Alberto; Passerini, Stefano; Scrosati, Bruno

2015-03-01

Since its first isolation in 2004, graphene has become one of the hottest topics in the field of materials science, and its highly appealing properties have led to a plethora of scientific papers. Among the many affected areas of materials science, this 'graphene fever' has influenced particularly the world of electrochemical energy-storage devices. Despite widespread enthusiasm, it is not yet clear whether graphene could really lead to progress in the field. Here we discuss the most recent applications of graphene -- both as an active material and as an inactive component -- from lithium-ion batteries and electrochemical capacitors to emerging technologies such as metal-air and magnesium-ion batteries. By critically analysing state-of-the-art technologies, we aim to address the benefits and issues of graphene-based materials, as well as outline the most promising results and applications so far.

Solid State Research, 1980:1.

DTIC Science & Technology

1980-02-15

ESD-TR-79-325 H 1 Solid State Research 1980 Prepared under Electronic Systems Division Contract FI%28-80-C-0002 by Lincoln Laboratory MASSkCHIISETTS...it is no longer needed. MASSACHUSETTS IN*STITUTE OF TECHNOLOGY LINCOLN LABORATORY V SOLID STATE RESEARCH QUARTERLY TECHNICAL SUMMARY REPORT I NOVEMBER...January 1990. The topics covered a-e Solid State Device Research , Quantum Electronics, Materials Rese.rch, Microelec- tronics, and Analog Device

Synthesis cathode material LiNi0.80Co0.15Al0.05O2 with two step solid-state method under air stream

NASA Astrophysics Data System (ADS)

Xia, Shubiao; Zhang, Yingjie; Dong, Peng; Zhang, Yannan

2014-01-01

A facile generic strategy of solid-state reaction under air atmosphere is employed to prepare LiNi0.8Co0.15Al0.05O2 layer structure micro-sphere as cathodes for Li-ion batteries. The impurity phase has been eliminated wholly without changing the R-3m space group of LiNi0.8Co0.15Al0.05O2. The electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathodes depend on the sintering step, temperature, particle size and uniformity. The sample pre-sintered at 540 °C for 12 h and then sintered at 720 °C for 28 h exhibits the best electrochemical performance, which delivers a reversible capacity of 180.4, 165.8, 154.7 and 135.6 mAhg-1 at 0.2 C, 1 C, 2 C and 5 C, respectively. The capacity retention keeps over 87% after 76 cycles at 1 C. This method is simple, cheap and mass-productive, and thus suitable to large scale production of NCA cathodes directly used for lithium ion batteries.

Flexible Asymmetric Solid-State Supercapacitors by Highly Efficient 3D Nanostructured α-MnO2 and h-CuS Electrodes.

PubMed

Patil, Amar M; Lokhande, Abhishek C; Shinde, Pragati A; Lokhande, Chandrakant D

2018-05-16

A simplistic and economical chemical way has been used to prepare highly efficient nanostructured, manganese oxide (α-MnO 2 ) and hexagonal copper sulfide (h-CuS) electrodes directly on cheap and flexible stainless steel sheets. Flexible solid-state α-MnO 2 /flexible stainless steel (FSS)/polyvinyl alcohol (PVA)-LiClO 4 /h-CuS/FSS asymmetric supercapacitor (ASC) devices have been fabricated using PVA-LiClO 4 gel electrolyte. Highly active surface areas of α-MnO 2 (75 m 2 g -1 ) and h-CuS (83 m 2 g -1 ) electrodes contribute to more electrochemical reactions at the electrode and electrolyte interface. The ASC device has a prolonged working potential of +1.8 V and accomplishes a capacitance of 109.12 F g -1 at 5 mV s -1 , energy density of 18.9 Wh kg -1 , and long-term electrochemical cycling with a capacity retention of 93.3% after 5000 cycles. Additionally, ASC devices were successful in glowing seven white-light-emitting diodes for more than 7 min after 30 s of charging. Outstandingly, real practical demonstration suggests "ready-to-sell" products for industries.

Electrochemically addressable trisradical rotaxanes organized within a metal–organic framework

DOE PAGES

McGonigal, Paul R.; Deria, Pravas; Hod, Idan; ...

2015-08-17

The organization of trisradical rotaxanes within the channels of a Zr 6-based metal–organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. Robust ZrIV–carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet–visible–near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and 1H nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components canmore » be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal–organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. In conclusion, the results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.« less

Characterization of the Terminal Iron(IV) Imides {[PhBPtBu2(pz’)]FeIV≡NAd}+

PubMed Central

Thomas, Christine M.; Mankad, Neal P.; Peters, Jonas C.

2008-01-01

New hybrid bis(phosphine)(pyrazole)borate tripodal ligands ([PhBPtBu2(pz’)]−) are reported that support pseudotetrahedral iron in the oxidation states +1, +2, +3, and +4. The higher oxidation states are stabilized by a terminal Fe≡NR linkage. Of particular interest is the generation and thorough characterization of an S = 1 FeIV≡NR+ imide cation using this new ligand system. The latter species can be observed electrochemically and spectroscopically, and its solid-state crystal structure is reported. PMID:16608321

Microbial battery for efficient energy recovery.

PubMed

Xie, Xing; Ye, Meng; Hsu, Po-Chun; Liu, Nian; Criddle, Craig S; Cui, Yi

2013-10-01

By harnessing the oxidative power of microorganisms, energy can be recovered from reservoirs of less-concentrated organic matter, such as marine sediment, wastewater, and waste biomass. Left unmanaged, these reservoirs can become eutrophic dead zones and sites of greenhouse gas generation. Here, we introduce a unique means of energy recovery from these reservoirs-a microbial battery (MB) consisting of an anode colonized by microorganisms and a reoxidizable solid-state cathode. The MB has a single-chamber configuration and does not contain ion-exchange membranes. Bench-scale MB prototypes were constructed from commercially available materials using glucose or domestic wastewater as electron donor and silver oxide as a coupled solid-state oxidant electrode. The MB achieved an efficiency of electrical energy conversion of 49% based on the combustion enthalpy of the organic matter consumed or 44% based on the organic matter added. Electrochemical reoxidation of the solid-state electrode decreased net efficiency to about 30%. This net efficiency of energy recovery (unoptimized) is comparable to methane fermentation with combined heat and power.

Microbial battery for efficient energy recovery

PubMed Central

Xie, Xing; Ye, Meng; Hsu, Po-Chun; Liu, Nian; Criddle, Craig S.; Cui, Yi

2013-01-01

By harnessing the oxidative power of microorganisms, energy can be recovered from reservoirs of less-concentrated organic matter, such as marine sediment, wastewater, and waste biomass. Left unmanaged, these reservoirs can become eutrophic dead zones and sites of greenhouse gas generation. Here, we introduce a unique means of energy recovery from these reservoirs—a microbial battery (MB) consisting of an anode colonized by microorganisms and a reoxidizable solid-state cathode. The MB has a single-chamber configuration and does not contain ion-exchange membranes. Bench-scale MB prototypes were constructed from commercially available materials using glucose or domestic wastewater as electron donor and silver oxide as a coupled solid-state oxidant electrode. The MB achieved an efficiency of electrical energy conversion of 49% based on the combustion enthalpy of the organic matter consumed or 44% based on the organic matter added. Electrochemical reoxidation of the solid-state electrode decreased net efficiency to about 30%. This net efficiency of energy recovery (unoptimized) is comparable to methane fermentation with combined heat and power. PMID:24043800

Electrochemical energy storage devices comprising self-compensating polymers

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

Johnson, Paul; Bautista-Martinez, Jose Antonio; Friesen, Cody

The disclosed technology relates generally to devices comprising conductive polymers and more particularly to electrochemical devices comprising self-compensating conductive polymers. In one aspect, electrochemical energy storage device comprises a negative electrode comprising an active material including a redox-active polymer. The device additionally comprises a positive electrode comprising an active material including a redox-active polymer. The device further comprises an electrolyte material interposed between the negative electrode and positive electrode and configured to conduct mobile counterions therethrough between the negative electrode and positive electrode. At least one of the negative electrode redox-active polymer and the positive electrode redox-active polymer comprises amore » zwitterionic polymer unit configured to reversibly switch between a zwitterionic state in which the zwitterionic polymer unit has first and second charge centers having opposite charge states that compensate each other, and a non-zwitterionic state in which the zwitterionic polymer unit has one of the first and second charge centers whose charge state is compensated by mobile counterions.« less

Solid State Technology Branch of NASA Lewis Research Center: Fifth Annual Digest

NASA Technical Reports Server (NTRS)

1993-01-01

The digest is a collection of papers written by the members of the Solid State Technology Branch of NASA Lewis Research Center from June 1992-June 1993. The papers cover a range of topics relating to superconductivity, monolithic microwave integrated circuits (MMIC's), coplanar waveguide, and material characterization.

Electrically erasable non-volatile memory via electrochemical deposition of multifractal aggregates

NASA Astrophysics Data System (ADS)

West, William Clark

An electrically erasable non-volatile memory system based on the electrochemical deposition of Ag or Cu from a solid electrolyte is presented. This memory system, referred to as Metal Dendrite Memory, is characterized by its simplicity of design and operation, low power consumption, and potentially high cell density. By applying a small DC voltage (2.5-5V) across a Cu or Ag doped As-S amorphous chalcogenide film sandwiched between two metal electrodes, a metal filament can be electrodeposited, shorting the large impedance solid electrolyte ("on" state). Application of smaller amplitude voltage pulses (1-1.5V) across the metal filament ruptures the short, returning the cell to the high impedance state ("off" state). The state of the cell is read by applying very small amplitude voltage pulses (0.25V). These "read" voltage pulses do not disturb the state of the cell even after 10sp7 pulses. Due to difficulties in characterizing this solid electrolyte system via conventional techniques, the MDM cells have been examined using low excitation characterization methods such as Impedance Spectroscopy (IS) and polarization measurements. These studies have yielded a self-consistent equivalent circuit model as well as parameters such as ionic diffusivity and conductivity, double layer and geometric capacitances. In addition to materials characterization, the speed at which the MDM cells operate has been systematically studied using a series of statistically designed experiments, demonstrating the importance of photodoping time and applied voltage on device speed. These results were further examined using IS and Rutherford Backscattering Spectrometry (RBS). The morphology of the growing electrodeposit was studied in several different electrode arrangements and excitation conditions. Under migrationally limited conditions, the electrodeposit grew in multifractal patterns, as measured using lacunarity analysis. If a conducting film was deposited parallel to the growth direction, the electrodeposition could be driven from Diffusion Limited Aggregation (DLA) to Densely Branched Morphology (DBM) modes by changing the voltage applied to the cell. In summary, this study has laid the groundwork for future research and development of MDM memory systems by identifying many important characteristics of the MDM cell. These findings include quantitative measurement of ionic transport values, identification of the electrochemical mechanisms involved in MDM data storage, determination of parameters that are statistically significant in affecting data storage speed, and determination of the effect of cell geometry and bias on electrodeposit morphology.

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

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solidmore » cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.« less

Design principles for solid-state lithium superionic conductors.

PubMed

Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand

2015-10-01

Lithium solid electrolytes can potentially address two key limitations of the organic electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochemical stability. However, achieving a Li(+) conductivity in the solid state comparable to existing liquid electrolytes (>1 mS cm(-1)) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centred cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic conductivity, and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.

Systems Ln-Fe-O ( Ln=Eu, Gd): thermodynamic properties of ternary oxides using solid-state electrochemical cells

NASA Astrophysics Data System (ADS)

Parida, S. C.; Rakshit, S. K.; Dash, S.; Singh, Ziley; Prasad, R.; Venugopal, V.

2003-05-01

The standard molar Gibbs energies of formation of LnFeO 3(s) and Ln3Fe 5O 12(s) where Ln=Eu and Gd have been determined using solid-state electrochemical technique employing different solid electrolytes. The reversible e.m.f.s of the following solid-state electrochemical cells have been measured in the temperature range from 1050 to 1255 K. Cell (I): (-)Pt / { LnFeO 3(s)+ Ln2O 3(s)+Fe(s)} // YDT/CSZ // {Fe(s)+Fe 0.95O(s)} / Pt(+); Cell (II): (-)Pt/{Fe(s)+Fe 0.95O(s)}//CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+); Cell (III): (-)Pt/{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}//YSZ//{Ni(s)+NiO(s)}/Pt(+); and Cell(IV):(-)Pt/{Fe(s)+Fe 0.95O(s)}//YDT/CSZ//{ LnFeO 3(s)+ Ln3Fe 5O 12(s)+Fe 3O 4(s)}/Pt(+). The oxygen chemical potentials corresponding to the three-phase equilibria involving the ternary oxides have been computed from the e.m.f. data. The standard Gibbs energies of formation of solid EuFeO 3, Eu 3Fe 5O 12, GdFeO 3 and Gd 3Fe 5O 12 calculated by the least-squares regression analysis of the data obtained in the present study are given by Δ fG°m(EuFeO 3, s) /kJ mol -1 (± 3.2)=-1265.5+0.2687( T/K) (1050 ⩽ T/K ⩽ 1570), Δ fG°m(Eu 3Fe 5O 12, s)/kJ mol -1 (± 3.5)=-4626.2+1.0474( T/K) (1050 ⩽ T/K ⩽ 1255), Δ fG°m(GdFeO 3, s) /kJ mol -1 (± 3.2)=-1342.5+0.2539( T/K) (1050 ⩽ T/K ⩽ 1570), and Δ fG°m(Gd 3Fe 5O 12, s)/kJ·mol -1 (± 3.5)=-4856.0+1.0021( T/K) (1050 ⩽ T/K ⩽ 1255). The uncertainty estimates for Δ fG°m include the standard deviation in the e.m.f. and uncertainty in the data taken from the literature. Based on the thermodynamic information, oxygen potential diagrams for the systems Eu-Fe-O and Gd-Fe-O and chemical potential diagrams for the system Gd-Fe-O were computed at 1250 K.

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

DOE PAGES

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

2015-02-23

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

Development of a 5 kW Prototype Coal-Based Fuel Cell

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

Chuang, Steven S.C.; Mirzababaei, Jelvehnaz; Rismanchian, Azadeh

2014-01-20

The University of Akron Fuel Cell Laboratory pioneered the development of a laboratory scale coal-based fuel cell, which allows the direct use of high sulfur content coal as fuel. The initial research and coal fuel cell technology development (“Coal-based Fuel Cell,” S. S. C. Chuang, PCT Int. Appl. 2006, i.e., European Patent Application, 35 pp. CODEN: PIXXD2 WO 2006028502 A2 20060316) have demonstrated that it is feasible to electrochemically oxidize carbon to CO2, producing electricity. The key innovative concept of this coal-based fuel cell technology is that carbon in coal can be converted through an electrochemical oxidation reaction into manageablemore » carbon dioxide, efficiently generating electricity without involving coal gasification, reforming, and water-gas shift reaction. This study has demonstrated that electrochemical oxidation of carbon can take place on the Ni anode surface and the CO and CO 2 product produced can further react with carbon to initiate the secondary reaction. A carbon injection system was developed to inject the solid fuel without bringing air into the anode chamber; a fuel cell stack was developed and tested to demonstrate the feasibility of the fuel cell stack. Further improvement of anode catalyst activity and durability is needed to bring this novel coal fuel cell to a highly efficient, super clean, multi-use electric generation technology, which promises to provide low cost electricity by expanding the utilization of U.S. coal supplies and relieving our dependence on foreign oil.« less

Preparation and electrochemical properties of Zr-site substituted Li7La3(Zr2-xMx)O12 (M = Ta, Nb) solid electrolytes

NASA Astrophysics Data System (ADS)

Huang, Mian; Shoji, Mao; Shen, Yang; Nan, Ce-Wen; Munakata, Hirokazu; Kanamura, Kiyoshi

2014-09-01

Li7La3Zr2O12 (LLZ) solid electrolytes with Zr site partially substituted by Ta and Nb elements were prepared via the conventional solid-state reaction. All the compositions could lead to the cubic garnet-type structure after sintering at 1150 °C. The use of γ-Al2O3 as a sintering aid in the preparation of doped LLZ was studied. It was shown that Al could help to improve the micro-structure for Nb doping, but not necessary for Ta doping. The Ta and Nb doping enhanced the ionic conductivity at 25 °C to 4.09 × 10-4 S cm-1 and 4.50 × 10-4 S cm-1, respectively. A conductivity as high as 1.23 × 10-3 S cm-1 was obtained when measured at 50 °C in air for the Nb-doped LLZ. All-solid-state batteries with LLZTa and LLZNb solid electrolytes were assembled and tested. The cyclic voltammetry (CV) measurement indicated the successful working of the batteries.

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

An automatic analyzer of solid state nuclear track detectors using an optic RAM as image sensor

NASA Astrophysics Data System (ADS)

Staderini, Enrico Maria; Castellano, Alfredo

1986-02-01

An optic RAM is a conventional digital random access read/write dynamic memory device featuring a quartz windowed package and memory cells regularly ordered on the chip. Such a device is used as an image sensor because each cell retains data stored in it for a time depending on the intensity of the light incident on the cell itself. The authors have developed a system which uses an optic RAM to acquire and digitize images from electrochemically etched CR39 solid state nuclear track detectors (SSNTD) in the track count rate up to 5000 cm -2. On the digital image so obtained, a microprocessor, with appropriate software, performs image analysis, filtering, tracks counting and evaluation.

Fabrication, characterization and applications of iron selenide

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

Hussain, Raja Azadar, E-mail: hussainazadar@yahoo.com; Badshah, Amin; Lal, Bhajan

This review article presents fabrication of FeSe by solid state reactions, solution chemistry routes, chemical vapor deposition, spray pyrolysis and chemical vapor transport. Different properties and applications such as crystal structure and phase transition, band structure, spectroscopy, superconductivity, photocatalytic activity, electrochemical sensing, and fuel cell activity of FeSe have been discussed. - Graphical abstract: Iron selenide can be synthesized by solid state reactions, chemical vapor deposition, solution chemistry routes, chemical vapor transport and spray pyrolysis. - Highlights: • Different fabrication methods of iron selenide (FeSe) have been reviewed. • Crystal structure, band structure and spectroscopy of FeSe have been discussed.more » • Superconducting, catalytic and fuel cell application of FeSe have been presented.« less

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, W.D.

1999-06-15

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions. 4 figs.

Gradient isolator for flow field of fuel cell assembly

DOEpatents

Ernst, William D.

1999-01-01

Isolator(s) include isolating material and optionally gasketing material strategically positioned within a fuel cell assembly. The isolating material is disposed between a solid electrolyte and a metal flow field plate. Reactant fluid carried by flow field plate channel(s) forms a generally transverse electrochemical gradient. The isolator(s) serve to isolate electrochemically a portion of the flow field plate, for example, transversely outward from the channel(s), from the electrochemical gradient. Further, the isolator(s) serve to protect a portion of the solid electrolyte from metallic ions.

Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

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

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observedmore » by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less

Characterization of Copper Corrosion Products in Drinking Water by Combining Electrochemical and Surface Analyses

EPA Science Inventory

This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

Characterization of Copper Corrosion Products Formed in Drinking Water by Combining Electrochemical and Surface Analyses

EPA Science Inventory

This study focuses on the application of electrochemical approaches to drinking water copper corrosion problems. Applying electrochemical approaches combined with copper solubility measurements, and solid surface analysis approaches were discussed. Tafel extrapolation and Electro...

Fabrication of solid oxide fuel cell by electrochemical vapor deposition

DOEpatents

Riley, B.; Szreders, B.E.

1988-04-26

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/ /minus/ 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.

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.

Recent advances and challenges for diode-pumped solid-state lasers as an inertial fusion energy driver candidate

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

Payne, S.A.; Beach, R.J.; Bibeau, C.

We discuss how solid-state laser technology can serve in the interests of fusion energy beyond the goals of the National Ignition Facility (NIF), which is now being constructed to ignite a deuterium-tritium target to fusion conditions in the laboratory for the first time. We think that advanced solid-state laser technology can offer the repetition-rate and efficiency needed to drive a fusion power plant, in contrast to the single-shot character of NIF. As discuss below, we propose that a gas-cooled, diode-pumped Yb:S-FAP laser can provide a new paradigm for fusion laser technology leading into the next century.

Modeling integrated photovoltaic–electrochemical devices using steady-state equivalent circuits

PubMed Central

Winkler, Mark T.; Cox, Casandra R.; Nocera, Daniel G.; Buonassisi, Tonio

2013-01-01

We describe a framework for efficiently coupling the power output of a series-connected string of single-band-gap solar cells to an electrochemical process that produces storable fuels. We identify the fundamental efficiency limitations that arise from using solar cells with a single band gap, an arrangement that describes the use of currently economic solar cell technologies such as Si or CdTe. Steady-state equivalent circuit analysis permits modeling of practical systems. For the water-splitting reaction, modeling defines parameters that enable a solar-to-fuels efficiency exceeding 18% using laboratory GaAs cells and 16% using all earth-abundant components, including commercial Si solar cells and Co- or Ni-based oxygen evolving catalysts. Circuit analysis also provides a predictive tool: given the performance of the separate photovoltaic and electrochemical systems, the behavior of the coupled photovoltaic–electrochemical system can be anticipated. This predictive utility is demonstrated in the case of water oxidation at the surface of a Si solar cell, using a Co–borate catalyst.

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilized TiN nanowire arrays for high-performance and flexible supercapacitors.

PubMed

Lu, Xihong; Wang, Gongming; Zhai, Teng; Yu, Minghao; Xie, Shilei; Ling, Yichuan; Liang, Chaolun; Tong, Yexiang; Li, Yat

2012-10-10

Metal nitrides have received increasing attention as electrode materials for high-performance supercapacitors (SCs). However, most of them are suffered from poor cycling stability. Here we use TiN as an example to elucidate the mechanism causing the capacitance loss. X-ray photoelectron spectroscopy analyses revealed that the instability is due to the irreversible electrochemical oxidation of TiN during the charging/discharging process. Significantly, we demonstrate for the first time that TiN can be stabilized without sacrificing its electrochemical performance by using poly(vinyl alcohol) (PVA)/KOH gel as the electrolyte. The polymer electrolyte suppresses the oxidation reaction on electrode surface. Electrochemical studies showed that the TiN solid-state SCs exhibit extraordinary stability up to 15,000 cycles and achieved a high volumetric energy density of 0.05 mWh/cm(3). The capability of effectively stabilizing nitride materials could open up new opportunities in developing high-performance and flexible SCs.

Significantly enhanced robustness and electrochemical performance of flexible carbon nanotube-based supercapacitors by electrodepositing polypyrrole

NASA Astrophysics Data System (ADS)

Chen, Yanli; Du, Lianhuan; Yang, Peihua; Sun, Peng; Yu, Xiang; Mai, Wenjie

2015-08-01

Here, we report robust, flexible CNT-based supercapacitor (SC) electrodes fabricated by electrodepositing polypyrrole (PPy) on freestanding vacuum-filtered CNT film. These electrodes demonstrate significantly improved mechanical properties (with the ultimate tensile strength of 16 MPa), and greatly enhanced electrochemical performance (5.6 times larger areal capacitance). The major drawback of conductive polymer electrodes is the fast capacitance decay caused by structural breakdown, which decreases cycling stability but this is not observed in our case. All-solid-state SCs assembled with the robust CNT/PPy electrodes exhibit excellent flexibility, long lifetime (95% capacitance retention after 10,000 cycles) and high electrochemical performance (a total device volumetric capacitance of 4.9 F/cm3). Moreover, a flexible SC pack is demonstrated to light up 53 LEDs or drive a digital watch, indicating the broad potential application of our SCs for portable/wearable electronics.

High-capacity electrode materials for electrochemical energy storage: Role of nanoscale effects

DOE PAGES

Nanda, Jagjit; Martha, Surendra K.; Kalyanaraman, Ramki

2015-06-02

In this review, we summarize the current state-of-the art electrode materials used for high-capacity lithium-ion-based batteries and their significant role towards revolutionizing the electrochemical energy storage landscape in the area of consumer electronics, transportation and grid storage application. We discuss the role of nanoscale effects on the electrochemical performance of high-capacity battery electrode materials. Decrease in the particle size of the primary electrode materials from micron to nanometre size improves the ionic and electronic diffusion rates significantly. Nanometre-thick solid electrolyte (such as lithium phosphorous oxynitride) and oxides (such as Al 2O 3, ZnO, TiO 2 etc.) material coatings also improvemore » the interfacial stability and rate capability of a number of battery chemistries. Finally, we elucidate these effects in terms of different high-capacity battery chemistries based on intercalation and conversion mechanism.« less

Electrochemical Upgrading of Bio-Oil

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

Elangovan, S.; Larsen, Dennis; Bay, Insoo

Bio-oil produced by fast pyrolysis of biomass is a potential source of low carbon, renewable hydrocarbon fuel. However, the properties such as low heating value, incomplete volatility, acidity, instability, and incompatibility with standard fuels restrict its use. The undesirable properties of pyrolysis oil result from its chemical composition that mostly consists of different classes of oxygenated organic compounds. Current process of Hydrodeoxygenation to remove oxygen involves high-temperature, high-pressure processing in the presence of hydrogen and catalyst. An alternative process of deoxygenation of bio-oil using solid-state, oxygen conductor based electrochemical cell is under investigation. The electrolysis process removes oxygen from themore » oxygenated organic molecule as well from steam to produce hydrogen in-situ allowing for a distributed, small scale integrated upgrading unit. Mixtures of model compounds and a slip stream of pyrolysis vapor were tested. The results show the potential for integrating a pyrolyzer and an electrochemical device for stabilizing pyrolysis oil.« less

Separators - Technology review: Ceramic based separators for secondary batteries

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

Nestler, Tina; Schmid, Robert; Münchgesang, Wolfram

Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ('Energiewende') was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membranemore » - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators. Two prominent examples, the lithium-ion and sodium-sulfur battery, are described to show the current stage of development. New routes are presented as promising technologies for safe and long-life electrochemical storage cells.« less

Separators - Technology review: Ceramic based separators for secondary batteries

NASA Astrophysics Data System (ADS)

Nestler, Tina; Schmid, Robert; Münchgesang, Wolfram; Bazhenov, Vasilii; Schilm, Jochen; Leisegang, Tilmann; Meyer, Dirk C.

2014-06-01

Besides a continuous increase of the worldwide use of electricity, the electric energy storage technology market is a growing sector. At the latest since the German energy transition ("Energiewende") was announced, technological solutions for the storage of renewable energy have been intensively studied. Storage technologies in various forms are commercially available. A widespread technology is the electrochemical cell. Here the cost per kWh, e. g. determined by energy density, production process and cycle life, is of main interest. Commonly, an electrochemical cell consists of an anode and a cathode that are separated by an ion permeable or ion conductive membrane - the separator - as one of the main components. Many applications use polymeric separators whose pores are filled with liquid electrolyte, providing high power densities. However, problems arise from different failure mechanisms during cell operation, which can affect the integrity and functionality of these separators. In the case of excessive heating or mechanical damage, the polymeric separators become an incalculable security risk. Furthermore, the growth of metallic dendrites between the electrodes leads to unwanted short circuits. In order to minimize these risks, temperature stable and non-flammable ceramic particles can be added, forming so-called composite separators. Full ceramic separators, in turn, are currently commercially used only for high-temperature operation systems, due to their comparably low ion conductivity at room temperature. However, as security and lifetime demands increase, these materials turn into focus also for future room temperature applications. Hence, growing research effort is being spent on the improvement of the ion conductivity of these ceramic solid electrolyte materials, acting as separator and electrolyte at the same time. Starting with a short overview of available separator technologies and the separator market, this review focuses on ceramic-based separators. Two prominent examples, the lithium-ion and sodium-sulfur battery, are described to show the current stage of development. New routes are presented as promising technologies for safe and long-life electrochemical storage cells.

Ionogel Electrolytes through Sol-Gel Processing

NASA Astrophysics Data System (ADS)

Horowitz, Ariel I.

Electrical energy needs have intensified due to the ubiquity of personal electronics, the decarbonization of energy services through electrification, and the use of intermittent renewable energy sources. Despite developments in mechanical and thermal methods, electrochemical technologies are the most convenient and effective means of storing electrical energy. These technologies include both electrochemical cells, commonly called batteries, and electrochemical double-layer capacitors, or "supercapacitors", which store energy electrostatically. Both device types require an ion-conducting electrolyte. Current devices use solutions of complex salts in organic solvents, leading to both toxicity and flammability concerns. These drawbacks can be avoided by replacing conventional electrolytes with room-temperature molten salts, known as ionic liquids (ILs). ILs are non-volatile, non-flammable, and offer high conductivity and good electrochemical stability. Device mass can be reduced by combining ILs with a solid scaffold material to form an "ionogel," further improving performance metrics. In this work, sol-gel chemistry is explored as a means of forming ionogel electrolytes. Sol-gel chemistry is a solution-based, industrially-relevant, well-studied technique by which solids such as silica can be formed in situ. Previous works used a simple acid-catalyzed sol-gel reaction to create brittle, glassy ionogels. Here, both the range of products that can be accomplished through sol-gel processing and the understanding of interactions between ILs and the sol-gel reaction network are greatly expanded. This work introduces novel ionogel materials, including soft and compliant silica-supported ionogels and PDMS-supported ionogels. The impacts of the reactive formulation, IL identity, and casting time are detailed. It is demonstrated that variations in formulation can lead to rapid gelation and open pore structures in the silica scaffold or slow gelation and more dense silica morphologies. The IL identity is shown to have an impact on the apparent strength of the acid catalyst, leading to significant shifts in gelation time. Delayed casting is proven to be an optimal technique for avoiding pore blockage when combining ionogels with high surface area electrodes for supercapacitor applications. Finally, a simple recycling process is proposed, establishing that ILs can be easily reclaimed from silica-supported ionogels and reused, thereby validating the reputation of ILs as "green" materials.

The Solid State Image Sensor's Contribution To The Development Of Silicon Technology

NASA Astrophysics Data System (ADS)

Weckler, Gene P.

1985-12-01

Until recently, a solid-state image sensor with full television resolution was a dream. However, the dream of a solid state image sensor has been a driving force in the development of silicon technology for more than twenty-five years. There are probably many in the main stream of semiconductor technology who would argue with this; however, the solid state image sensor was conceived years before the invention of the semi conductor RAM or the microprocessor (i.e., even before the invention of the integrated circuit). No other potential application envisioned at that time required such complexity. How could anyone have ever hoped in 1960 to make a semi conductor chip containing half-a-million picture elements, capable of resolving eight to twelve bits of infornation, and each capable of readout rates in the tens of mega-pixels per second? As early as 1960 arrays of p-n junctions were being investigated as the optical targets in vidicon tubes, replacing the photoconductive targets. It took silicon technology several years to catch up with these dreamers.

Cathode for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.; Gruzalski, Greg R.; Luck, Christopher F.

2001-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Method for making an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1996-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Exploratory technology research program for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kinoshita, K.

1992-06-01

The U.S. Department of Energy's Office of Propulsion Systems provides support for an electrochemical energy storage program, that includes research and development (R&D) on advanced rechargeable batteries and fuel cells. A major goal of this program is to develop electrochemical power sources suitable for application in electric vehicles. The program centers on advanced systems that offer the potential for high performance and low life-cycle costs. The DOE Electrochemical Energy Storage Program is divided into two projects: the Electric Vehicle Advanced Battery Systems Development (EVABS) Program and the Exploratory Technology Research (ETR) Program. The EVABS Program management responsibility has been assigned to Sandia National Laboratory, and the Lawrence Berkeley Laboratory is responsible for management of the ETR Program. The EVABS and ETR Programs include an integrated matrix of R&D efforts designed to advance progress on several candidate electrochemical systems. The United States Advanced Battery Consortium (USABC), a tripartite undertaking between DOE, the U.S. automobile manufacturers and the Electric Power Research Institute (EPRI), was formed in 1991 to accelerate the development of advanced batteries for consumer EVs. The role of the ETR Program is to perform supporting research on the advanced battery systems under development by the USABC and EVABS Program, and to evaluate new systems with potentially superior performance, durability and/or cost characteristics. The specific goal of the ETR Program is to identify the most promising electrochemical technologies and transfer them to the USABC, the battery industry and/or the EVABS Program for further development and scaleup. This report summarizes the research, financial and management activities relevant to the ETR Program in FY 1991.

Oxygen production using solid-state zirconia electrolyte technology

NASA Technical Reports Server (NTRS)

Suitor, Jerry W.; Clark, Douglas J.

1991-01-01

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

RAPID COMMUNICATION: Formation of MgB2 at ambient temperature with an electrochemical process: a plausible mechanism

NASA Astrophysics Data System (ADS)

Jadhav, A. B.; Subhedar, K. M.; Hyam, R. S.; Talaptra, A.; Sen, Pintu; Bandyopadhyay, S. K.; Pawar, S. H.

2005-06-01

The binary intermetallic MgB2 superconductor has been synthesized by many research groups. However, the mechanism of its formation is not clearly understood. In this communication, a comprehensive mechanism of the formation of MgB2 from Le Chatelier's principle of equilibrium reaction has been explained both for solid-state reaction and electrodeposition methods.

Materials and Manufacturing Challenges of Direct Methanol Fuel Cells

DTIC Science & Technology

2009-04-27

SPSf. Figure 5 shows four basic polymers in which benzimidazole (BIm), amino- benzimidazole (ABIm), nitrobenzimidazole (NBIm), and perimidine (PImd...Membranes Based on Sulfonated Polyetheretherketone and Polysulfone Bearing Benzimidazole Side Groups for Fuel Cells,” Electrochemistry Communications...Bearing Benzimidazole Side Groups for Direct Methanol Fuel Cells,” Electrochemical and Solid State Letters, Vol. 10, 2007, p. B70-B73. [12] Fu, Y.-Z

Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO 2

DOE PAGES

Xu, Jing; Lin, Feng; Nordlund, Dennis; ...

2016-02-25

Phase pure LiNiO 2 was prepared using a solid-state method and the optimal synthesis conditions led to a remarkably high capacity of 200 mA h g $-$1 with excellent retention. The combination of bulk and surface characterization elucidated an essential role of the excess Li in phase formation during synthesis and the subsequent electrochemical performance.

Analysis of measurements for solid state laser remote lidar system

NASA Technical Reports Server (NTRS)

Amzajerdian, Farzin

1995-01-01

The merits of using lidar systems for remote measurements of various atmospheric processes such as wind, turbulence, moisture, and aerosol concentration are widely recognized. Although the lidar technology has progressed considerably over the past two decades, significant research particularly in the area of solid state lidars remains to be conducted in order to fully exploit this technology. The work performed by the UAH (University of Alabama in Huntsville) personnel under this Delivery Order concentrated on analyses of measurements required in support of solid state laser remote sensing lidar systems which are to be designed, deployed, and used to measure atmospheric processes and constituents. UAH personnel has studied and recommended to NASA/MSFC the requirements of the optical systems needed to characterize the detection devices suitable for solid state wavelengths and to evaluate various heterodyne detection schemes. The 2-micron solid state laser technology was investigated and several preliminary laser designs were developed and their performance for remote sensing of atmospheric winds and clouds from a spaceborne platform were specified. In addition to the laser source and the detector, the other critical technologies necessary for global wind measurements by a spaceborne solid state coherent lidar systems were identified to be developed and demonstrated. As part of this work, an analysis was performed to determine the atmospheric wind velocity estimation accuracy using the line-of-sight measurements of a scanning coherent lidar. Under this delivery order, a computer database of materials related to the theory, development, testing, and operation of lidar systems was developed to serve as a source of information for lidar research and development.

Growth mechanism and magnetic and electrochemical properties of Na{sub 0.44}MnO{sub 2} nanorods as cathode material for Na-ion batteries

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

Demirel, S.; Oz, E.; Altin, E.

Nanorods of Na{sub 0.44}MnO{sub 2} are a promising cathode material for Na-ion batteries due to their large surface area and single crystalline structure. We report the growth mechanism of Na{sub 0.44}MnO{sub 2} nanorods via solid state synthesis and their physical properties. The structure and the morphology of the Na{sub 0.44}MnO{sub 2} nanorods are investigated by X-ray diffraction (XRD), scanning and tunneling electron microscopy (SEM and TEM), and energy-dispersive X-ray (EDX) techniques. The growth mechanism of the rods is investigated and the effects of vapor pressure and partial melting of Na-rich regions are discussed. The magnetic measurements show an antiferromagnetic phasemore » transition at 25 K and the μ{sub eff} is determined as 3.41 and 3.24 μ{sub B} from the χ–T curve and theoretical calculation, respectively. The electronic configuration and spin state of Mn{sup 3+} and Mn{sup 4+} are discussed in detail. The electrochemical properties of the cell fabricated using the nanorods are investigated and the peaks in the voltammogram are attributed to the diffusion of Na ions from different sites. Na intercalation process is explained by one and two Margules and van Laar models. - Highlights: • We synthesized Na{sub 0.44}MnO{sub 2} nanorods via a simple solid state reaction technique. • Our studies show that excess Na plays a crucial role in the nanorod formation. • Magnetization measurements show that Mn{sup 3+} ions are in LS and HS states. • The electrochemical properties of the cell fabricated using the nanorods are investigated. • Na intercalation process is explained by one and two Margules and van Laar models.« less

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

Novel Li[(CF3SO2)(n-C4F9SO2)N]-Based Polymer Electrolytes for Solid-State Lithium Batteries with Superior Electrochemical Performance.

PubMed

Ma, Qiang; Qi, Xingguo; Tong, Bo; Zheng, Yuheng; Feng, Wenfang; Nie, Jin; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan; Zhou, Zhibin

2016-11-02

Solid polymer electrolytes (SPEs) would be promising candidates for application in high-energy rechargeable lithium (Li) batteries to replace the conventional organic liquid electrolytes, in terms of the enhanced safety and excellent design flexibility. Herein, we first report novel perfluorinated sulfonimide salt-based SPEs, composed of lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (Li[(CF 3 SO 2 )(n-C 4 F 9 SO 2 )N], LiTNFSI) and poly(ethylene oxide) (PEO), which exhibit relatively efficient ionic conductivity (e.g., 1.04 × 10 -4 S cm -1 at 60 °C and 3.69 × 10 -4 S cm -1 at 90 °C) and enough thermal stability (>350 °C), for rechargeable Li batteries. More importantly, the LiTNFSI-based SPEs could not only deliver the excellent interfacial compatibility with electrodes (e.g., Li-metal anode, LiFePO 4 and sulfur composite cathodes), but also afford good cycling performances for the Li|LiFePO 4 (>300 cycles at 1C) and Li-S cells (>500 cycles at 0.5C), in comparison with the conventional LiTFSI (Li[(CF 3 SO 2 ) 2 N])-based SPEs. The interfacial impedance and morphology of the cycled Li-metal electrodes are also comparatively analyzed by electrochemical impedance spectra and scanning electron microscopy, respectively. These indicate that the LiTNFSI-based SPEs would be potential alternatives for application in high-energy solid-state Li batteries.

New solid-state chemistry technologies to bring better drugs to market: knowledge-based decision making.

PubMed

Park, Aeri; Chyall, Leonard J; Dunlap, Jeanette; Schertz, Christine; Jonaitis, David; Stahly, Barbara C; Bates, Simon; Shipplett, Rex; Childs, Scott

2007-01-01

Modern drug development demands constant deployment of more effective technologies to mitigate the high cost of bringing new drugs to market. In addition to cost savings, new technologies can improve all aspects of pharmaceutical development. New technologies developed at SSCI, Inc. include solid form development of an active pharmaceutical ingredients. (APIs) are PatternMatch software and capillary-based crystallisation techniques that not only allow for fast and effective solid form screening, but also extract maximum property information from the routine screening data that is generally available. These new technologies offer knowledge-based decision making during solid form development of APIs and result in more developable API solid forms.

Studies of electrochemical interfaces by TOF neutron reflectometry at the IBR-2 reactor

NASA Astrophysics Data System (ADS)

Petrenko, V. I.; Gapon, I. V.; Rulev, A. A.; Ushakova, E. E.; Kataev, E. Yu; Yashina, L. V.; Itkis, D. M.; Avdeev, M. V.

2018-03-01

The operation performance of electrochemical energy conversion and storage systems such as supercapacitors and batteries depends on the processes occurring at the electrochemical interfaces, where charge separation and chemical reactions occur. Here, we report about the tests of the neutron reflectometry cells specially designed for operando studies of structural changes at the electrochemical interfaces between solid electrodes and liquid electrolytes. The cells are compatible with anhydrous electrolytes with organic solvents, which are employed today in all lithium ion batteries and most supercapacitors. The sensitivity of neutron reflectometry applied at the time-of-flight (TOF) reflectometer at the pulsed reactor IBR-2 is discussed regarding the effect of solid electrolyte interphase (SEI) formation on metal electrode surface.

Fabrication of advanced electrochemical energy materials using sol-gel processing techniques

NASA Technical Reports Server (NTRS)

Chu, C. T.; Chu, Jay; Zheng, Haixing

1995-01-01

Advanced materials play an important role in electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. They are being used as both electrodes and electrolytes. Sol-gel processing is a versatile solution technique used in fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. The application of sol-gel processing in the fabrication of advanced electrochemical energy materials will be presented. The potentials of sol-gel derived materials for electrochemical energy applications will be discussed along with some examples of successful applications. Sol-gel derived metal oxide electrode materials such as V2O5 cathodes have been demonstrated in solid-slate thin film batteries; solid electrolytes materials such as beta-alumina for advanced secondary batteries had been prepared by the sol-gel technique long time ago; and high surface area transition metal compounds for capacitive energy storage applications can also be synthesized with this method.

Post-mortem characterization of fs laser-generated micro-pillars in Li(Ni1/3Mn1/3Co1/3)O2 electrodes by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Smyrek, P.; Zheng, Y.; Seifert, H. J.; Pfleging, W.

2016-03-01

NMC thick films were prepared by tape-casting and subsequent ultrafast laser-structuring. The lithium distribution in electrochemically cycled and unstructured or fs laser-structured NMC cathodes was investigated by using Laser-Induced Breakdown Spectroscopy (LIBS). The main goal is to develop an optimized three dimensional cell architecture with improved electrochemical properties based on studies of the homogeneity of the local State-of-Charge. LIBS experiments were carried out using a LIBS workstation equipped with a mode-locked diode pumped solid state Nd:YAG laser operating at a wavelength of 1063 nm. The element distribution was investigated using two different techniques: element mapping and element depth-profiling of the unstructured / fs laser-structured electrode surface. Results achieved from post-mortem studies using LIBS will be presented.

Electrochemical micro sensor

DOEpatents

Setter, Joseph R.; Maclay, G. Jordan

1989-09-12

A micro-amperometric electrochemical sensor for detecting the presence of a pre-determined species in a fluid material is disclosed. The sensor includes a smooth substrate having a thin coating of solid electrolytic material deposited thereon. The working and counter electrodes are deposited on the surface of the solid electrolytic material and adhere thereto. Electrical leads connect the working and counter electrodes to a potential source and an apparatus for measuring the change in an electrical signal caused by the electrochemical oxidation or reduction of the species. Alternatively, the sensor may be fabricated in a sandwich structure and also may be cylindrical, spherical or other shapes.

Development of Self-Powered Wireless-Ready High Temperature Electrochemical Sensors for In-Situ Corrosion Monitoring for Boiler Tubes in Next Generation Coal-based Power Systems

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

Liu, Xingbo

The key innovation of this project is the synergy of the high temperature sensor technology based on the science of electrochemical measurement and state-of-the-art wireless communication technology. A novel self-powered wireless high temperature electrochemical sensor system has been developed for coal-fired boilers used for power generation. An initial prototype of the in-situ sensor demonstrated the capability of the wireless communication system in the laboratory and in a pilot plant (Industrial USC Boiler Setting) environment to acquire electrochemical potential and current signals during the corrosion process. Uniform and localized under-coal ash deposit corrosion behavior of Inconel 740 superalloy has been studiedmore » at different simulated coal ash hot corrosion environments using the developed sensor. Two typical potential noise patterns were found to correlate with the oxidation and sulfidation stages in the hot coal ash corrosion process. Two characteristic current noise patterns indicate the extent of the corrosion. There was a good correlation between the responses of electrochemical test data and the results from corroded surface analysis. Wireless electrochemical potential and current noise signals from a simulated coal ash hot corrosion process were concurrently transmitted and recorded. The results from the performance evaluation of the sensor confirm a high accuracy in the thermodynamic and kinetic response represented by the electrochemical noise and impedance test data.« less

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.

Solid State Ionics Advanced Materials for Emerging Technologies

NASA Astrophysics Data System (ADS)

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

2006-06-01

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

A Na+ Superionic Conductor for Room-Temperature Sodium Batteries

NASA Astrophysics Data System (ADS)

Song, Shufeng; Duong, Hai M.; Korsunsky, Alexander M.; Hu, Ning; Lu, Li

2016-08-01

Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10-3 S cm-1. We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor.

A Na+ Superionic Conductor for Room-Temperature Sodium Batteries

PubMed Central

Song, Shufeng; Duong, Hai M.; Korsunsky, Alexander M.; Hu, Ning; Lu, Li

2016-01-01

Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10−3 S cm−1. We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor. PMID:27572915

A Na(+) Superionic Conductor for Room-Temperature Sodium Batteries.

PubMed

Song, Shufeng; Duong, Hai M; Korsunsky, Alexander M; Hu, Ning; Lu, Li

2016-08-30

Rechargeable lithium ion batteries have ruled the consumer electronics market for the past 20 years and have great significance in the growing number of electric vehicles and stationary energy storage applications. However, in addition to concerns about electrochemical performance, the limited availability of lithium is gradually becoming an important issue for further continued use and development of lithium ion batteries. Therefore, a significant shift in attention has been taking place towards new types of rechargeable batteries such as sodium-based systems that have low cost. Another important aspect of sodium battery is its potential compatibility with the all-solid-state design where solid electrolyte is used to replace liquid one, leading to simple battery design, long life span, and excellent safety. The key to the success of all-solid-state battery design is the challenge of finding solid electrolytes possessing acceptable high ionic conductivities at room temperature. Herein, we report a novel sodium superionic conductor with NASICON structure, Na3.1Zr1.95Mg0.05Si2PO12 that shows high room-temperature ionic conductivity of 3.5 × 10(-3) S cm(-1). We also report successful fabrication of a room-temperature solid-state Na-S cell using this conductor.

Electrochemical treatment of evaporated residue of soak liquor generated from leather industry.

PubMed

Boopathy, R; Sekaran, G

2013-09-15

The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (km) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm(-2) was 0.41 kWh m(-3) for the removal of COD and 2.57 kWh m(-3) for the removal of TKN. Copyright © 2013 Elsevier B.V. All rights reserved.

A Model of Solid State Gas Sensors

NASA Astrophysics Data System (ADS)

Woestman, J. T.; Brailsford, A. D.; Shane, M.; Logothetis, E. M.

1997-03-01

Solid state gas sensors are widely used to measure the concentrations of gases such as CO, CH_4, C_3H_6, H_2, C_3H8 and O2 The applications of these sensors range from air-to-fuel ratio control in combustion processes including those in automotive engines and industrial furnaces to leakage detection of inflammable and toxic gases in domestic and industrial environments. As the need increases to accurately measure smaller and smaller concentrations, problems such as poor selectivity, stability and response time limit the use of these sensors. In an effort to overcome some of these limitations, a theoretical model of the transient behavior of solid state gas sensors has been developed. In this presentation, a model for the transient response of an electrochemical gas sensor to gas mixtures containing O2 and one reducing species, such as CO, is discussed. This model accounts for the transport of the reactive species to the sampling electrode, the catalyzed oxidation/reduction reaction of these species and the generation of the resulting electrical signal. The model will be shown to reproduce the results of published steady state models and to agree with experimental steady state and transient data.

Extended papers selected from ESSDERC 2015

NASA Astrophysics Data System (ADS)

Grasser, Tibor; Schmitz, Jurriaan; Lemme, Max C.

2016-11-01

This special issue of Solid State Electronics includes 28 papers which have been carefully selected from the best presentations given at the 45th European Solid-State Device Research Conference (ESSDERC 2015) held from September 14-18, 2015 in Graz, Austria. These papers cover a wide range of topics related to the research on solid-state devices. These topics are used also to organize the conference submissions and presentations into 7 tracks: CMOS Processes, Devices and Integration; Opto-, Power- and Microwave Devices; Modeling & Simulation; Characterization, Reliability & Yield; Advanced & Emerging Memories; MEMS, Sensors & Display Technologies; Emerging Non-CMOS Devices & Technologies.

A novel adenine-based metal organic framework derived nitrogen-doped nanoporous carbon for flexible solid-state supercapacitor.

PubMed

Li, Haowen; Fu, Dongying; Zhang, Xian-Ming

2018-01-01

In this article, we have synthesized a series of nitrogen-doped nanoporous carbon (NPC) from metal organic framework of UiO-66 with different ratios of adenine and 1,4-benzendicarboxylate (H 2 BDC) coated on carbon nanotube film (CNTF) to obtain a flexible porous electrode (NPC/CNTF). It is worth noting that the introduction of adenine at different ratios did not change the structure of UiO-66. We also investigated the effect of carbonization temperature from 800 to 1000°C on the electrochemical properties of the NPC. The ratio (H 2 BDC:adenine) 9 : 1 and the NPC carbonized at 900°C (denoted as NPC-1-900) exhibits better electrochemical properties. The results show that NPC-1-900/CNTF electrode exhibits an exceptional areal capacitance of 121.5 mF cm -2 compared to that of PC-900/CNTF electrode (22.8 mF cm -2 ) at 5 mV s -1 in a three-electrode system, indicating that the incorporation of nitrogen is beneficial to the electrochemical properties of nanoporous carbon. A symmetric flexible solid-state supercapacitor of NPC-1-900/CNTF has also been assembled and tested. Electrochemical data show that the device exhibited superior areal capacitance (43.2 mF cm -2 ) at the scan rate of 5 mV s -1 ; the volumetric energy density is 57.3 µWh cm -3 and the volumetric power density is 2.4 mW cm -3 at the current density of 0.5 mA cm -2 based on poly(vinyl alcohol)/H 3 PO 4 gel electrolyte. For practical application, we have also studied the bending tests of the device, which show that the device exhibits outstanding mechanical stability under different bending angles. Furthermore, the flexible device shows excellent cyclic stability, which can retain 91.5% of the initial capacitance after 2000 cycles.

A novel adenine-based metal organic framework derived nitrogen-doped nanoporous carbon for flexible solid-state supercapacitor

PubMed Central

Li, Haowen; Zhang, Xian-Ming

2018-01-01

In this article, we have synthesized a series of nitrogen-doped nanoporous carbon (NPC) from metal organic framework of UiO-66 with different ratios of adenine and 1,4-benzendicarboxylate (H2BDC) coated on carbon nanotube film (CNTF) to obtain a flexible porous electrode (NPC/CNTF). It is worth noting that the introduction of adenine at different ratios did not change the structure of UiO-66. We also investigated the effect of carbonization temperature from 800 to 1000°C on the electrochemical properties of the NPC. The ratio (H2BDC:adenine) 9 : 1 and the NPC carbonized at 900°C (denoted as NPC-1-900) exhibits better electrochemical properties. The results show that NPC-1-900/CNTF electrode exhibits an exceptional areal capacitance of 121.5 mF cm−2 compared to that of PC-900/CNTF electrode (22.8 mF cm−2) at 5 mV s−1 in a three-electrode system, indicating that the incorporation of nitrogen is beneficial to the electrochemical properties of nanoporous carbon. A symmetric flexible solid-state supercapacitor of NPC-1-900/CNTF has also been assembled and tested. Electrochemical data show that the device exhibited superior areal capacitance (43.2 mF cm−2) at the scan rate of 5 mV s−1; the volumetric energy density is 57.3 µWh cm−3 and the volumetric power density is 2.4 mW cm−3 at the current density of 0.5 mA cm−2 based on poly(vinyl alcohol)/H3PO4 gel electrolyte. For practical application, we have also studied the bending tests of the device, which show that the device exhibits outstanding mechanical stability under different bending angles. Furthermore, the flexible device shows excellent cyclic stability, which can retain 91.5% of the initial capacitance after 2000 cycles. PMID:29410815

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode

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

Huang, J Y; Zhong, L; Wang, C M

2010-12-09

We report the creation of a nanoscale electrochemical device inside a transmission electron microscope—consisting of a single tin dioxide (SnO{sub 2}) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO{sub 2}) cathode—and the in situ observation of the lithiation of the SnO{sub 2} nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a “Medusa zone” containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfitmore » stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.« less

Electrochemical slurry compositions and methods for preparing the same

DOEpatents

Doherty, Tristan; Limthongkul, Pimpa; Butros, Asli; Duduta, Mihai; Cross, III, James C.

2016-11-01

Embodiments described herein generally relate to semi-solid suspensions, and more particularly to systems and methods for preparing semi-solid suspensions for use as electrodes in electrochemical devices such as, for example batteries. In some embodiments, a method for preparing a semi-solid electrode includes combining a quantity of an active material with a quantity of an electrolyte to form an intermediate material. The intermediate material is then combined with a conductive additive to form an electrode material. The electrode material is mixed to form a suspension having a mixing index of at least about 0.80 and is then formed into a semi-solid electrode.

Sensor apparatus using an electrochemical cell

DOEpatents

Thakur, Mrinal

2003-07-01

A method for sensing mechanical quantities such as force, stress, strain, pressure and acceleration is disclosed. This technology is based on a change in the electrochemically generated voltage (electromotive force) with application of force, stress, strain, pressure or acceleration. The change in the voltage is due to a change in the internal resistance of the electrochemical cell with a change in the relative position or orientation of the electrodes (anode and cathode) in the cell. The signal to be detected (e.g. force, stress, strain, pressure or acceleration) is applied to one of the electrodes to cause a change in the relative position or orientation between the electrodes. Various materials, solid, semisolid, gel, paste or liquid can be utilized as the electrolyte. The electrolyte must be an ion conductor. The examples of solid electrolytes include specific polymer conductors, polymer composites, ion conducting glasses and ceramics. The electrodes are made of conductors such as metals with dissimilar electro negativities. Significantly enhanced sensitivities, up to three orders of magnitude higher than that of comparable commercial sensors, are obtained. The materials are substantially less expensive than commercially used materials for mechanical sensors. An apparatus for sensing such mechanical quantities using materials such as doped 1,4 cis-polyisopropene and nafion. The 1,4 cis-polyisopropene may be doped with lithium perchlorate or iodine. The output voltage signal increases with an increase of the sensing area for a given stress. The device can be used as an intruder alarm, among other applications.

Roles of Cationic and Elemental Calcium in the Electro-Reduction of Solid Metal Oxides in Molten Calcium Chloride

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Jiang, Kai; Ma, Meng; Wang, Dihua; Jin, Xianbo; Chen, George Z.

2007-06-01

Previous work, mainly from this research group, is re-visited on electrochemical reduction of solid metal oxides, in the form of compacted powder, in molten CaCl2, aiming at further understanding of the roles of cationic and elemental calcium. The discussion focuses on six aspects: 1.) debate on two mechanisms proposed in the literature, i. e. electro-metallothermic reduction and electro-reduction (or electro-deoxidation), for the electrolytic removal of oxygen from solid metals or metal oxides in molten CaCl2; 2.) novel metallic cavity working electrodes for electrochemical investigations of compacted metal oxide powders in high temperature molten salts assisted by a quartz sealed Ag/AgCl reference electrode (650 ºC- 950 ºC); 3.) influence of elemental calcium on the background current observed during electrolysis of solid metal oxides in molten CaCl2; 4.) electrochemical insertion/ inclusion of cationic calcium into solid metal oxides; 5.) typical features of cyclic voltammetry and chronoamperometry (potentiostatic electrolysis) of metal oxide powders in molten CaCl2; and 6.) some kinetic considerations on the electrolytic removal of oxygen.

Influence of temperature on the aging behavior of 18650-type lithium ion cells: A comprehensive approach combining electrochemical characterization and post-mortem analysis

NASA Astrophysics Data System (ADS)

Friesen, Alex; Mönnighoff, Xaver; Börner, Markus; Haetge, Jan; Schappacher, Falko M.; Winter, Martin

2017-02-01

The understanding of the aging behavior of lithium ion batteries in automotive and energy storage applications is essential for the acceptance of the technology. Therefore, aging experiments were conducted on commercial 18650-type state-of-the-art cells to determine the influence of the temperature during electrochemical cycling on the aging behavior of the different cell components. The cells, based on Li(Ni0.5Co0.2Mn0.3)O2 (NCM532)/graphite, were aged at 20 °C and 45 °C to different states of health. The electrochemical performance of the investigated cells shows remarkable differences depending on the cycling temperature. At contrast to the expected behavior, the cells cycled at 45 °C show a better electrochemical performance over lifetime than the cells cycled at 20 °C. Comprehensive post-mortem analyses revealed the main aging mechanisms, showing a complex interaction between electrodes and electrolyte. The main aging mechanisms of the cells cycled at 45 °C differ strongly at contrast to cells cycled at 20 °C. A strong correlation between the formed SEI, the electrolyte composition and the electrochemical performance over lifetime was observed.

Flexible all-solid-state supercapacitors based on polyaniline orderly nanotubes array.

PubMed

Li, Huihua; Song, Juan; Wang, Linlin; Feng, Xiaomiao; Liu, Ruiqing; Zeng, Wenjin; Huang, Zhendong; Ma, Yanwen; Wang, Lianhui

2017-01-07

Flexible all-solid-state supercapacitors are crucial to meet the growing needs for portable electronic devices such as foldable phones and wearable electronics. As promising candidates for pseudocapacitor electrode materials, polyaniline (PANI) orderly nanotube arrays are prepared via a simple template electrodeposition method. The structures of the final product were characterized using various characterization techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). The obtained PANI nanotube film could be directly used as a flexible all-solid-state supercapacitor electrode. Electrochemical results show that the areal capacitance of a PANI nanotube-based supercapacitor with the deposition cycle number of 100 can achieve a maximum areal capacitance of 237.5 mF cm -2 at a scan rate of 10 mV s -1 and maximum energy density of 24.31 mW h cm -2 at a power density of 2.74 mW cm -2 . In addition, the prepared supercapacitor exhibits excellent flexibility under different bending conditions. It retains 95.2% of its initial capacitance value after 2000 cycles at a current density of 1.0 mA cm -1 , which displays its superior cycling stability. Moreover, the prepared flexible all-solid-state supercapacitor can power a light-emitting-diode (LED), which meets the practical applications of micropower supplies.

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

Murgia, Fabrizio; Antitomaso, Philippe; Stievano, Lorenzo

The ternary Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} was successfully synthetized using a simple and cost-effective solid-state microwave-assisted reaction. While solid-state routes require days of high-temperature treatment under inert atmosphere, highly pure and crystalline Cu{sub 2}Mo{sub 6}S{sub 8} could be obtained in only 400 s from this precursor, the Chevrel binary phase Mo{sub 6}S{sub 8} was then obtained by copper removal through acidic leaching, and was evaluated as a positive electrode material for Mg-battery. The electrochemical performance in half-cell configuration shows reversible capacity exceeding 80 mAh/g, which is comparable to previous works carried out with materials synthesized by conventional high-temperaturemore » solid-state routes. - Graphical abstract: Ultrafast micro-wave synthesis of Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} towards Mo{sub 6}S{sub 8} as positive electrode of Mg-battery. - Highlights: • Chevrel phase Cu{sub 2}Mo{sub 6}S{sub 8} is synthesized by fast microwave-assisted solid-state reaction. • Highly-pure and well-crystalline Cu{sub 2}Mo{sub 6}S{sub 8} is obtained. • Mo{sub 6}S{sub 8} obtained from leaching is tested as a positive electrode for Mg batteries.« less

Solid state potentiometric gaseous oxide sensor

NASA Technical Reports Server (NTRS)

Wachsman, Eric D. (Inventor); Azad, Abdul Majeed (Inventor)

2003-01-01

A solid state electrochemical cell (10a) for measuring the concentration of a component of a gas mixture (12) includes first semiconductor electrode (14) and second semiconductor electrode (16) formed from first and second semiconductor materials, respectively. The materials are selected so as to undergo a change in resistivity upon contacting a gas component, such as CO or NO. An electrolyte (18) is provided in contact with the first and second semiconductor electrodes. A reference cell can be included in contact with the electrolyte. Preferably, a voltage response of the first semiconductor electrode is opposite in slope direction to that of the second semiconductor electrode to produce a voltage response equal to the sum of the absolute values of the control system uses measured pollutant concentrations to direct adjustment of engine combustion conditions.

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

NASA Astrophysics Data System (ADS)

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

2009-03-01

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

Solid state technology: A compilation. [on semiconductor devices

NASA Technical Reports Server (NTRS)

1973-01-01

A compilation, covering selected solid state devices developed and integrated into systems by NASA to improve performance, is presented. Data are also given on device shielding in hostile radiation environments.

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.

Compliant Nanospring Interfaces

DTIC Science & Technology

2017-01-26

for new generation lithium ion batteries ”, Nano Letters, 2015. [21] Krishnan R, Lu TM and Koratkar N, “Functionally strain-graded nanoscoops for high...for Lithium - Ion Batteries , Electrochem. Solid-State Lett. 2003, 6(9), A198-A201. [48] Teki R, Datta MK, Krishnan R, Parker TC, Lu TM, Kumta PN and...Koratkar N. Nanostructured silicon anodes for lithium ion rechargeable batteries , Small, 2009, 5, 2236-2242. [49] Fleischauer MD, Li J and Brett

High-Performance Flexible All-Solid-State Asymmetric Supercapacitors Based on Vertically Aligned CuSe@Co(OH) 2 Nanosheet Arrays

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

Gong, Jiangfeng; Tian, Yazhou; Yang, Ziyuan

The developments of electrode active materials provide the opportunities for next-generation energy storage devices. The arrangement of electrode materials on the substrate has recently emerged as a promising strategy for preparing high-performance supercapacitors. In this paper, we demonstrate a novel vertically aligned CuSe@Co(OH) 2 nanosheet arrays electrode for supercapacitor application. The materials are thoroughly characterized by structural and spectroscopic techniques. Electrochemical performance of CuSe@Co(OH) 2 nanosheet arrays are investigated in detail, which exhibit a specific capacitance as much as 1180 F g -1 at a current density of 1 A g -1. A flexible asymmetric all-solid-state supercapacitor is fabricated usingmore » CuSe@Co(OH) 2 nanosheet arrays as the positive electrode and activated carbon as the negative electrode. The device delivers a volumetric capacitance of 441.4 mF cm -3 with maximum energy density and maximum power density is 0.17 and 62.1 mW cm -3, as well as robust cycling stability (~80.4% capacitance retention after 10 000 cycles), excellent flexibility, and mechanical stability. Finally, the excellent electrochemical performance can be attributed to its unique vertically aligned configuration.« less

High-Performance Flexible All-Solid-State Asymmetric Supercapacitors Based on Vertically Aligned CuSe@Co(OH) 2 Nanosheet Arrays

DOE PAGES

Gong, Jiangfeng; Tian, Yazhou; Yang, Ziyuan; ...

2018-01-04

The developments of electrode active materials provide the opportunities for next-generation energy storage devices. The arrangement of electrode materials on the substrate has recently emerged as a promising strategy for preparing high-performance supercapacitors. In this paper, we demonstrate a novel vertically aligned CuSe@Co(OH) 2 nanosheet arrays electrode for supercapacitor application. The materials are thoroughly characterized by structural and spectroscopic techniques. Electrochemical performance of CuSe@Co(OH) 2 nanosheet arrays are investigated in detail, which exhibit a specific capacitance as much as 1180 F g -1 at a current density of 1 A g -1. A flexible asymmetric all-solid-state supercapacitor is fabricated usingmore » CuSe@Co(OH) 2 nanosheet arrays as the positive electrode and activated carbon as the negative electrode. The device delivers a volumetric capacitance of 441.4 mF cm -3 with maximum energy density and maximum power density is 0.17 and 62.1 mW cm -3, as well as robust cycling stability (~80.4% capacitance retention after 10 000 cycles), excellent flexibility, and mechanical stability. Finally, the excellent electrochemical performance can be attributed to its unique vertically aligned configuration.« less

Synthesis and electrochemical characterization of LiMn0.6Fe0.4PO4/C cathode material via a modified-solid state reaction method.

PubMed

Kim, Hyun-Ju; Jin, Bong-Soo; Bae, Dong-Sik; Kim, Seong-Bae; Kim, Hyun-Soo

2013-05-01

LiMn0.6Fe0.4PO4/C cathode material is synthesized via a modified-solid state reaction method. The calcination temperature is adjusted in the range of 500-700 degrees C for 10 h. The crystal structure, morphology, and carbon coating layer of the synthesized LiMn0.6Fe0.4PO4/C are analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), respectively. The electrochemical performance of LiMn0.6Fe0.4PO4/C, such as initial capacity, rate capability, cycling performance and EIS is also evaluated. The synthesized cathode material shows around 100-200 nm of primary particle size with no impurities. The highest initial discharge capacity of 162.1 mA h g(-1) and columbic efficiency of 98.5% are obtained at a heat treatment temperature of 600 degrees C. In addition, LiMn0.6Fe0.4PO4/C active material shows the high capacity retention of 85% at 5 C compared to 0.2 C. It also shows the excellent capacity retention of 97.5% after the 50th charge/discharge.

Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite

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

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(VI) on mineral surfaces is often considered a one-step two-electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies Indicates U(VI) can undergo a one-electron reduction to U(V) without further progression to U(VI),. We investigated reduction pathways of uranium by reducing U(VI) electrochemically on a, magnetite electrode at,pH 3.4. Cyclic voltammetry confirms the one-electron reduction of U(VI) . Formation of nanosize uranium precipitates on the magnetite surface at reducing potentials and dissolution of the solids at oxidizing potentials are observed by in situ electrochemical atomic force microscopy. XPS, analysis Of the magnetitemore » electrodes polarized in uranium solutions at voltages - from -0.1 to -0.9 V (E-U(VI)/U(V)(0)= -0.135 V vs Ag/AgCl) show the presence of, only U(V) and U(VI). The sample with the highest U(V)/U(VI) ratio was prepared at -0.7 V, where the longest average U-O-axial distance of 2.05 + 0.01 A was evident in the same sample revealed by extended X-ray absorption fine structure analysis. The results demonstrate that the electrochemical reduction of U(VI) On magnetite only yields,U(V), even at a potential of -0.9 V, which favors the one-electron reduction mechanism, U(V) does not disproportionate but stabilizes on magnetite through precipitation Of mixed-valence state -U(V)/U(VI) solids.« less

On-line Technology Information System (OTIS): Solid Waste Management Technology Information Form (SWM TIF)

NASA Technical Reports Server (NTRS)

Levri, Julie A.; Boulanger, Richard; Hogan, John A.; Rodriguez, Luis

2003-01-01

Contents include the following: What is OTIS? OTIS use. Proposed implementation method. Development history of the Solid Waste Management (SWM) Technology Information Form (TIF) and OTIS. Current development state of the SWM TIF and OTIS. Data collection approach. Information categories. Critiques/questions/feedback.

The Operating Principle of a Fully Solid State Active Magnetic Regenerator

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

Abdelaziz, Omar

As an alternative refrigeration technology, magnetocaloric refrigeration has the potential to be safer, quieter, more efficient, and more environmentally friendly than the conventional vapor compression refrigeration technology. Most of the reported active magnetic regenerator (AMR) systems that operate based on the magnetocaloric effect use heat transfer fluid to exchange heat, which results in complicated mechanical subsystems and components such as rotating valves and hydraulic pumps. This paper presents an operating principle of a fully solid state AMR, in which an alternative mechanism for heat transfer between the AMR and the heat source/sink is proposed. The operating principle of the fullymore » solid state AMR is based on moving rods/sheets (e.g. copper, brass, iron or aluminum), which are employed to replace the heat transfer fluid. Such fully solid state AMR would provide a significantly higher heat transfer rate than a conventional AMR because the conductivity of moving solid rods/plates is high and it enables the increase in the machine operating frequency hence the cooling capacity. The details of operating principle are presented and discussed here. One of the key enabling features for this technology is the contact between the moving rods/sheets and magnetocaloric material, and heat exchange mechanism at the heat source/sink. This paper provides an overview of the design for a fully solid state magnetocaloric refrigeration system along with guidelines for their optimal design.« less

Exploratory Technology Research Program for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kinoshita, Kim

1994-09-01

The U.S. Department of Energy's Office of Propulsion Systems provides support for an Electrochemical Energy Storage Program, that includes research and development (R&D) on advanced rechargeable batteries and fuel cells. A major goal of this program is to develop electrochemical power sources suitable for application in electric vehicles (EV's). The program centers on advanced systems that offer the potential for high performance and low life-cycle costs, both of which are necessary to permit significant penetration into commercial markets. The DOE Electrochemical Energy Storage Program is divided into two projects: the Electric Vehicle Advanced Battery Systems (EVABS) Development Program and the Exploratory Technology Research (ETR) Program. The EVABS Program management responsibility has been assigned to Sandia National Laboratories (SNL); Lawrence Berkeley Laboratory (LBL) is responsible for management of the ETR Program. The EVABS and ETR Programs include an integrated matrix of R&D efforts designed to advance progress on selected candidate electrochemical systems. The United States Advanced Battery Consortium (USABC), a tripartite undertaking between DOE, the U.S. automobile manufacturers and the Electric Power Research Institute (EPRI), was formed in 1991 to accelerate the development of advanced batteries for consumer EV's. The role of the FIR Program is to perform supporting research on the advanced battery systems under development by the USABC and EVABS Program, and to evaluate new systems with potentially superior performance, durability and/or cost characteristics. The specific goal of the ETR Program is to identify the most promising electrochemical technologies and transfer them to the USABC, the battery industry and/or the EVABS Program for further development and scale-up. This report summarizes the research, financial and management activities relevant to the ETR Program in CY 1993.

Exploratory Technology Research Program for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kinoshita, Kim

1994-09-01

The U.S. Department of Energy's Office of Propulsion Systems provides support for an Electrochemical Energy Storage Program, that includes research and development (R&D) on advanced rechargeable batteries and fuel cells. A major goal of this program is to develop electrochemical power sources suitable for application in electric vehicles (EV's). The program centers on advanced systems that offer the potential for high performance and low life-cycle costs, both of which are necessary to permit significant penetration into commercial markets. The DOE Electrochemical Energy Storage Program is divided into two projects: the Electric Vehicle Advanced Battery Systems (EVABS) Development Program and the Exploratory Technology Research (ETR) Program. The EVABS Program management responsibility has been assigned to Sandia National Laboratories (SNL); Lawrence Berkeley Laboratory (LBL) is responsible for management of the FIR Program. The EVABS and ETR Programs include an integrated matrix of R&D efforts designed to advance progress on selected candidate electrochemical systems. The United States Advanced Battery Consortium (USABC), a tripartite undertaking between DOE, the U.S. automobile manufacturers and the Electric Power Research Institute (EPRI), was formed in 1991 to accelerate the development of advanced batteries for consumer EV's. The role of the FIR Program is to perform supporting research on the advanced battery systems under development by the USABC and EVABS Program, and to evaluate new systems with potentially superior performance, durability and/or cost characteristics. The specific goal of the ETR Program is to identify the most promising electrochemical technologies and transfer them to the USABC, the battery industry and/or the EVABS Program for further development and scale-up. This report summarizes the research, financial and management activities relevant to the ETR Program in CY 1993.

Solid State Technology Branch of NASA Lewis Research Center: Fifth Annual Digest

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

Not Available

1993-08-01

The digest is a collection of papers written by the members of the Solid State Technology Branch of NASA Lewis Research Center from June 1992-June 1993. The papers cover a range of topics relating to superconductivity, monolithic microwave integrated circuits (MMIC`s), coplanar waveguide, and material characterization. Individual papers are abstracted separately on the data base.

Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface.

PubMed

Williamson, M J; Tromp, R M; Vereecken, P M; Hull, R; Ross, F M

2003-08-01

Dynamic processes at the solid-liquid interface are of key importance across broad areas of science and technology. Electrochemical deposition of copper, for example, is used for metallization in integrated circuits, and a detailed understanding of nucleation, growth and coalescence is essential in optimizing the final microstructure. Our understanding of processes at the solid-vapour interface has advanced tremendously over the past decade due to the routine availability of real-time, high-resolution imaging techniques yielding data that can be compared quantitatively with theory. However, the difficulty of studying the solid-liquid interface leaves our understanding of processes there less complete. Here we analyse dynamic observations--recorded in situ using a novel transmission electron microscopy technique--of the nucleation and growth of nanoscale copper clusters during electrodeposition. We follow in real time the evolution of individual clusters, and compare their development with simulations incorporating the basic physics of electrodeposition during the early stages of growth. The experimental technique developed here is applicable to a broad range of dynamic phenomena at the solid-liquid interface.

3D Printed Graphene Based Energy Storage Devices

NASA Astrophysics Data System (ADS)

Foster, Christopher W.; Down, Michael P.; Zhang, Yan; Ji, Xiaobo; Rowley-Neale, Samuel J.; Smith, Graham C.; Kelly, Peter J.; Banks, Craig E.

2017-03-01

3D printing technology provides a unique platform for rapid prototyping of numerous applications due to its ability to produce low cost 3D printed platforms. Herein, a graphene-based polylactic acid filament (graphene/PLA) has been 3D printed to fabricate a range of 3D disc electrode (3DE) configurations using a conventional RepRap fused deposition moulding (FDM) 3D printer, which requires no further modification/ex-situ curing step. To provide proof-of-concept, these 3D printed electrode architectures are characterised both electrochemically and physicochemically and are advantageously applied as freestanding anodes within Li-ion batteries and as solid-state supercapacitors. These freestanding anodes neglect the requirement for a current collector, thus offering a simplistic and cheaper alternative to traditional Li-ion based setups. Additionally, the ability of these devices’ to electrochemically produce hydrogen via the hydrogen evolution reaction (HER) as an alternative to currently utilised platinum based electrodes (with in electrolysers) is also performed. The 3DE demonstrates an unexpectedly high catalytic activity towards the HER (-0.46 V vs. SCE) upon the 1000th cycle, such potential is the closest observed to the desired value of platinum at (-0.25 V vs. SCE). We subsequently suggest that 3D printing of graphene-based conductive filaments allows for the simple fabrication of energy storage devices with bespoke and conceptual designs to be realised.

3D Printed Graphene Based Energy Storage Devices

PubMed Central

Foster, Christopher W.; Down, Michael P.; Zhang, Yan; Ji, Xiaobo; Rowley-Neale, Samuel J.; Smith, Graham C.; Kelly, Peter J.; Banks, Craig E.

2017-01-01

3D printing technology provides a unique platform for rapid prototyping of numerous applications due to its ability to produce low cost 3D printed platforms. Herein, a graphene-based polylactic acid filament (graphene/PLA) has been 3D printed to fabricate a range of 3D disc electrode (3DE) configurations using a conventional RepRap fused deposition moulding (FDM) 3D printer, which requires no further modification/ex-situ curing step. To provide proof-of-concept, these 3D printed electrode architectures are characterised both electrochemically and physicochemically and are advantageously applied as freestanding anodes within Li-ion batteries and as solid-state supercapacitors. These freestanding anodes neglect the requirement for a current collector, thus offering a simplistic and cheaper alternative to traditional Li-ion based setups. Additionally, the ability of these devices’ to electrochemically produce hydrogen via the hydrogen evolution reaction (HER) as an alternative to currently utilised platinum based electrodes (with in electrolysers) is also performed. The 3DE demonstrates an unexpectedly high catalytic activity towards the HER (−0.46 V vs. SCE) upon the 1000th cycle, such potential is the closest observed to the desired value of platinum at (−0.25 V vs. SCE). We subsequently suggest that 3D printing of graphene-based conductive filaments allows for the simple fabrication of energy storage devices with bespoke and conceptual designs to be realised. PMID:28256602

In situ analysis of capacity fade in thin-film anodes for high performance Li-ion all-solid-state batteries

NASA Astrophysics Data System (ADS)

Leite, Marina S.; Gong, Chen; Ruzmetov, Dmitry; Talin, A. Alec

There is still a pressing need to understand how the solid-interfaces in Li-ion all-solid-batteries form, including their chemical composition and electrical characteristics. In order to resolve the origin of the degradation mechanism in Al anodes, we combine in situ scanning electron microscopy in ultra-high vacuum with electrochemical cycling, in addition to ex situ characterization of the morphological, chemical, and electrical changes of the Al anodes upon lithiation. An AlLi alloy capped by a stable Al-Li-O is formed on the top surface of the anode, trapping Li, which results in the capacity fade, from 48.0 to 41.5 μ.Ah/cm2 in two cycles. The addition of a Cu capping layer is insufficient to prevent the device degradation because of the fast Li diffusion within Al. Yet, Si present extremely stable cycling: >92% of capacity retention after 100 cycles, with average Coulombic efficiency of 98%. Our in situ measurements represent a new platform for probing the real-time degradation of electrodes in all-solid-state batteries for energy storage devices.

Electrochemical Control of Peptide Self-Organization on Atomically Flat Solid Surfaces: A Case Study with Graphite.

PubMed

Seki, Takakazu; So, Christopher R; Page, Tamon R; Starkebaum, David; Hayamizu, Yuhei; Sarikaya, Mehmet

2018-02-06

The nanoscale self-organization of biomolecules, such as proteins and peptides, on solid surfaces under controlled conditions is an important issue in establishing functional bio/solid soft interfaces for bioassays, biosensors, and biofuel cells. Electrostatic interaction between proteins and surfaces is one of the most essential parameters in the adsorption and self-assembly of proteins on solid surfaces. Although the adsorption of proteins has been studied with respect to the electrochemical surface potential, the self-assembly of proteins or peptides forming well-organized nanostructures templated by lattice structure of the solid surfaces has not been studied in the relation to the surface potential. In this work, we utilize graphite-binding peptides (GrBPs) selected by the phage display method to investigate the relationship between the electrochemical potential of the highly ordered pyrolytic graphite (HOPG) and peptide self-organization forming long-range-ordered structures. Under modulated electrical bias, graphite-binding peptides form various ordered structures, such as well-ordered nanowires, dendritic structures, wavy wires, amorphous (disordered) structures, and islands. A systematic investigation of the correlation between peptide sequence and self-organizational characteristics reveals that the presence of the bias-sensitive amino acid modules in the peptide sequence has a significant effect on not only surface coverage but also on the morphological features of self-assembled structures. Our results show a new method to control peptide self-assembly by means of applied electrochemical bias as well as peptide design-rules for the construction of functional soft bio/solid interfaces that could be integrated in a wide range of practical implementations.

Modeling the Voltage Dependence of Electrochemical Reactions at Solid-Solid and Solid-Liquid Interfaces in Batteries

NASA Astrophysics Data System (ADS)

Leung, Kevin

2015-03-01

Electrochemical reactions at electrode/electrolyte interfaces are critically dependent on the total electrochemical potential or voltage. In this presentation, we briefly review ab initio molecular dynamics (AIMD)-based estimate of voltages on graphite basal and edge planes, and then apply similar concepts to solid-solid interfaces relevant to lithium ion and Li-air batteries. Thin solid films on electrode surfaces, whether naturally occuring during power cycling (e.g., undesirable lithium carbonate on Li-air cathodes) or are artificially introduced, can undergo electrochemical reactions as the applied voltage varies. Here the onset of oxidation of lithium carbonate and other oxide thin films on model gold electrode surfaces is correlated with the electronic structure in the presence/absence of solvent molecules. Our predictions help determine whether oxidation first occurs at the electrode-thin film or electrolyte-thin film interface. Finally, we will critically compare the voltage estimate methodology used in the fuel cell community with the lithium cohesive energy calibration method broadly applied in the battery community, and discuss why they may yield different predictions. This work was supported by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DESC0001160. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

High-Resolution Solid-State NMR Spectroscopy: Characterization of Polymorphism in Cimetidine, a Pharmaceutical Compound

ERIC Educational Resources Information Center

Pacilio, Julia E.; Tokarski, John T.; Quiñones, Rosalynn; Iuliucci, Robbie J.

2014-01-01

High-resolution solid-state NMR (SSNMR) spectroscopy has many advantages as a tool to characterize solid-phase material that finds applications in polymer chemistry, nanotechnology, materials science, biomolecular structure determination, and others, including the pharmaceutical industry. The technology associated with achieving high resolution…

Solid-State Lithium Conductors for Lithium Metal Batteries Based on Electrospun Nanofiber/Plastic Crystal Composites.

PubMed

Zhou, Yundong; Wang, Xiaoen; Zhu, Haijin; Yoshizawa-Fujita, Masahiro; Miyachi, Yukari; Armand, Michel; Forsyth, Maria; Greene, George W; Pringle, Jennifer M; Howlett, Patrick C

2017-08-10

Organic ionic plastic crystals (OIPCs) are a class of solid-state electrolytes with good thermal stability, non-flammability, non-volatility, and good electrochemical stability. When prepared in a composite with electrospun polyvinylidene fluoride (PVdF) nanofibers, a 1:1 mixture of the OIPC N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C 2 mpyr][FSI]) and lithium bis(fluorosulfonyl)imide (LiFSI) produced a free-standing, robust solid-state electrolyte. These high-concentration Li-containing electrolyte membranes had a transference number of 0.37(±0.02) and supported stable lithium symmetric-cell cycling at a current density of 0.13 mA cm -2 . The effect of incorporating PVdF in the Li-containing plastic crystal was investigated for different ratios of PVdF and [Li][FSI]/[C 2 mpyr][FSI]. In addition, Li|LiNi 1/3 Co 1/3 Mn 1/3 O 2 cells were prepared and cycled at ambient temperature and displayed a good rate performance and stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile solid-state synthesis of Ni@C nanosheet-assembled hierarchical network for high-performance lithium storage

NASA Astrophysics Data System (ADS)

Gu, Jinghe; Li, Qiyun; Zeng, Pan; Meng, Yulin; Zhang, Xiukui; Wu, Ping; Zhou, Yiming

2017-08-01

Micro/nano-architectured transition-metal@C hybrids possess unique structural and compositional features toward lithium storage, and are thus expected to manifest ideal anodic performances in advanced lithium-ion batteries (LIBs). Herein, we propose a facile and scalable solid-state coordination and subsequent pyrolysis route for the formation of a novel type of micro/nano-architectured transition-metal@C hybrid (i.e., Ni@C nanosheet-assembled hierarchical network, Ni@C network). Moreover, this coordination-pyrolysis route has also been applied for the construction of bare carbon network using zinc salts instead of nickel salts as precursors. When applied as potential anodic materials in LIBs, the Ni@C network exhibits Ni-content-dependent electrochemical performances, and the partially-etched Ni@C network manifests markedly enhanced Li-storage performances in terms of specific capacities, cycle life, and rate capability than the pristine Ni@C network and carbon network. The proposed solid-state coordination and pyrolysis strategy would open up new opportunities for constructing micro/nano-architectured transition-metal@C hybrids as advanced anode materials for LIBs.

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

NASA Astrophysics Data System (ADS)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

High H⁻ ionic conductivity in barium hydride.

PubMed

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

2015-01-01

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

Superstructure ZrV2O7 nanofibres: thermal expansion, electronic and lithium storage properties.

PubMed

Li, Qidong; Zhao, Yanming; Kuang, Quan; Fan, Qinghua; Dong, Youzhong; Liu, Xudong

2016-11-30

ZrV 2 O 7 has attracted much attention as a negative thermal expansion (NTE) material due to its isotropic negative structure. However, rarely has investigation of the lithium storage behaviors been carried out except our first report on it. Meanwhile, the electrochemical behaviors and energy storage characteristics have not been studied in depth and will be explored in this article. Herein, we report on the synthesis, characterization and lithium intercalation mechanism of superstructure ZrV 2 O 7 nanofibres that were prepared through a facile solution-based method with a subsequent annealing process. The thermal in situ XRD technique combined with the Rietveld refinement method is adopted to analyze the change in the temperature-dependent crystal structure. Benefiting from the nanostructured morphology and relatively high electronic conductivity, it presents acceptable cyclic stability and rate capability. According to the operando evolution of the XRD patterns obtained from electrochemical in situ measurements, the Li intercalation mechanism of the solid solution process with a subsequent conversion reaction can be concluded. Finally, the amorphous state of the electrodes after the initial fully discharged state can effectively enhance the electrochemical performances.

Electrolyte for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1997-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte amorphous lithium phosphorus oxynitride which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Electrolyte for an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1997-01-28

Described is a thin-film battery, especially a thin-film microbattery, and a method for making the same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte amorphous lithium phosphorus oxynitride which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

Method of making an electrolyte for an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1996-04-30

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

Method of making an electrolyte for an electrochemical cell

DOEpatents

Bates, John B.; Dudney, Nancy J.

1996-01-01

Described is a thin-film battery, especially a thin-film microbattery, and a method for making same having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between -15.degree. C. and 150.degree. C.

Method for making an electrochemical cell

DOEpatents

Bates, J.B.; Dudney, N.J.

1996-10-22

Described is a thin-film battery, especially a thin-film microbattery, and a method for making the same, having application as a backup or primary integrated power source for electronic devices. The battery includes a novel electrolyte which is electrochemically stable and does not react with the lithium anode and a novel vanadium oxide cathode. Configured as a microbattery, the battery can be fabricated directly onto a semiconductor chip, onto the semiconductor die or onto any portion of the chip carrier. The battery can be fabricated to any specified size or shape to meet the requirements of a particular application. The battery is fabricated of solid state materials and is capable of operation between {minus}15 C and 150 C. 9 figs.

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-stage Electrolysis Stack

NASA Technical Reports Server (NTRS)

Setlock, John A (Inventor); Green, Robert D (Inventor); Farmer, Serene (Inventor)

2016-01-01

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O.sup.2-) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

Generation of High Pressure Oxygen via Electrochemical Pumping in a Multi-Stage Electrolysis Stack

NASA Technical Reports Server (NTRS)

Setlock, John A (Inventor); Green, Robert D (Inventor); Farmer, Serene (Inventor)

2017-01-01

An oxygen pump can produce high-purity high-pressure oxygen. Oxygen ions (O(2-)) are electrochemically pumped through a multi-stage electrolysis stack of cells. Each cell includes an oxygen-ion conducting solid-state electrolyte between cathode and anode sides. Oxygen dissociates into the ions at the cathode side. The ions migrate across the electrolyte and recombine at the anode side. An insulator is between adjacent cells to electrically isolate each individual cell. Each cell receives a similar volt potential. Recombined oxygen from a previous stage can diffuse through the insulator to reach the cathode side of the next stage. Each successive stage similarly incrementally pressurizes the oxygen to produce a final elevated pressure.

The indirect electrochemical refining of lunar ores

NASA Technical Reports Server (NTRS)

Semkow, Krystyna W.; Sammells, Anthony F.

1987-01-01

Recent work performed on an electrolytic cell is reported which addresses the implicit limitations in various approaches to refining lunar ores. The cell uses an oxygen vacancy conducting stabilized zirconia solid electrolyte to effect separation between a molten salt catholyte compartment where alkali metals are deposited, and an oxygen-evolving anode of composition La(0.89)Sr(0.1)MnO3. The cell configuration is shown and discussed along with a polarization curve and a steady-state current-voltage curve. In a practical cell, cathodically deposited liquid lithium would be continuously removed from the electrolytic cell and used as a valuable reducing agent for ore refining under lunar conditions. Oxygen would be indirectly electrochemically extracted from lunar ores for breathing purposes.

Solid State Physics in the People's Republic of China. A Trip Report of the American Solid State Physics Delegation.

ERIC Educational Resources Information Center

Fitzgerald, Anne; Slichter, Charles P.

This is the fifth chapter of a six chapter report which discusses Chinese research and education in solid state physics, and their relations to technology and the other sciences. This specific chapter concerns the communication of information in the scientific community and the transfer of information to students and practical users…

Corrosion of metals in wood : comparing the results of a rapid test method with long-term exposure tests across six wood treatments

Treesearch

Samuel L. Zelinka; Donald S. Stone

2011-01-01

This paper compares two methods of measuring the corrosion of steel and galvanized steel in wood: a long-term exposure test in solid wood and a rapid test method where fasteners are electrochemically polarized in extracts of wood treated with six different treatments. For traditional wood preservatives, the electrochemical extract method correlates with solid wood...

Electrochemical degradation, kinetics & performance studies of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Das, Debanjan

Linear and Non-linear electrochemical characterization techniques and equivalent circuit modelling were carried out on miniature and sub-commercial Solid Oxide Fuel Cell (SOFC) stacks as an in-situ diagnostic approach to evaluate and analyze their performance under the presence of simulated alternative fuel conditions. The main focus of the study was to track the change in cell behavior and response live, as the cell was generating power. Electrochemical Impedance Spectroscopy (EIS) was the most important linear AC technique used for the study. The distinct effects of inorganic components usually present in hydrocarbon fuel reformates on SOFC behavior have been determined, allowing identification of possible "fingerprint" impedance behavior corresponding to specific fuel conditions and reaction mechanisms. Critical electrochemical processes and degradation mechanisms which might affect cell performance were identified and quantified. Sulfur and siloxane cause the most prominent degradation and the associated electrochemical cell parameters such as Gerisher and Warburg elements are applied respectively for better understanding of the degradation processes. Electrochemical Frequency Modulation (EFM) was applied for kinetic studies in SOFCs for the very first time for estimating the exchange current density and transfer coefficients. EFM is a non-linear in-situ electrochemical technique conceptually different from EIS and is used extensively in corrosion work, but rarely used on fuel cells till now. EFM is based on exploring information obtained from non-linear higher harmonic contributions from potential perturbations of electrochemical systems, otherwise not obtained by EIS. The baseline fuel used was 3 % humidified hydrogen with a 5-cell SOFC sub-commercial planar stack to perform the analysis. Traditional methods such as EIS and Tafel analysis were carried out at similar operating conditions to verify and correlate with the EFM data and ensure the validity of the obtained information. The obtained values closely range from around 11 mA cm-2 - 16 mA cm -2 with reasonable repeatability and excellent accuracy. The potential advantages of EFM compared to traditional methods were realized and our primary aim at demonstrating this technique on a SOFC system are presented which can act as a starting point for future research efforts in this area. Finally, an approach based on in-situ State of Health tests by EIS was formulated and investigated to understand the most efficient fuel conditions for suitable long term operation of a solid oxide fuel cell stack under power generation conditions. The procedure helped to reflect the individual effects of three most important fuel characteristics CO/H2 volumetric ratio, S/C ratio and fuel utilization under the presence of a simulated alternative fuel at 0.4 A cm-2. Variation tests helped to identify corresponding electrochemical/chemical processes, narrow down the most optimum operating regimes considering practical behavior of simulated reformer-SOFC system arrangements. At the end, 8 different combinations of the optimized parameters were tested long term with the stack, and the most efficient blend was determined.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries

DOE PAGES

Kerman, Kian; Luntz, Alan; Viswanathan, Venkatasubramanian; ...

2017-06-09

Solid state electrolyte systems boasting Li+ conductivity of >10 mS cm -1 at room temperature have opened the potential for developing a solid state battery with power and energy densities that are competitive with conventional liquid electrolyte systems. The primary focus of this review is twofold. First, differences in Li penetration resistance in solid state systems are discussed, and kinetic limitations of the solid state interface are highlighted. Second, technological challenges associated with processing such systems in relevant form factors are elucidated, and architectures needed for cell level devices in the context of product development are reviewed. Specific research vectorsmore » that provide high value to advancing solid state batteries are outlined and discussed.« less

Electrochemical properties of copper-based compounds with polyanion frameworks

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

Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota

The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed basedmore » on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.« less

Emerging solid-state laser technology by lidar/DIAL remote sensing

NASA Technical Reports Server (NTRS)

Killinger, Dennis

1992-01-01

Significant progress has been made in recent years in the development of new, solid-state laser sources. This talk will present an overview of some of the new developments in solid-state lasers, and their application toward lidar/DIAL measurements of the atmosphere. Newly emerging lasers such as Ho:YAG, Tm:YAG, OPO, and Ti:Sapphire will be covered, along with the spectroscopic parameters required for differential operational modes of atmospheric remote sensing including Doppler-Windshear lidar, Tunable laser detection of water/CO2, and broad linewidth OPO's for open path detection of pollutant hydrocarbon gases. Additional considerations of emerging laser technology for lidar/DIAL will also be covered.

Solid State Laser

NASA Technical Reports Server (NTRS)

1990-01-01

The Titan-CW Ti:sapphire (titanium-doped sapphire) tunable laser is an innovation in solid-state laser technology jointly developed by the Research and Solid State Laser Divisions of Schwartz Electro-optics, Inc. (SEO). SEO is producing the laser for the commercial market, an outgrowth of a program sponsored by Langley Research Center to develop Ti:sapphire technology for space use. SEO's Titan-CW series of Ti:sapphire tunable lasers have applicability in analytical equipment designed for qualitative analysis of carbohydrates and proteins, structural analysis of water, starch/sugar analyses, and measurements of salt in meat. Further applications are expected in semiconductor manufacture, in medicine for diagnosis and therapy, and in biochemistry.

Elimination of active species crossover in a room temperature, neutral pH, aqueous flow battery using a ceramic NaSICON membrane

NASA Astrophysics Data System (ADS)

Allcorn, Eric; Nagasubramanian, Ganesan; Pratt, Harry D.; Spoerke, Erik; Ingersoll, David

2018-02-01

Flow batteries are an attractive technology for energy storage of grid-scale renewables. However, performance issues related to ion-exchange membrane (IEM) fouling and crossover of species have limited the success of flow batteries. In this work we propose the use of the solid-state sodium-ion conductor NaSICON as an IEM to fully eliminate active species crossover in room temperature, aqueous, neutral pH flow batteries. We measure the room temperature conductivity of NaSICON at 2.83-4.67 mS cm-1 and demonstrate stability of NaSICON in an aqueous electrolyte with conductivity values remaining near 2.5 mS cm-1 after 66 days of exposure. Charge and discharge of a full H-cell battery as well as symmetric cycling in a flow battery configuration using NaSICON as an IEM in both cases demonstrates the capability of the solid-state IEM. Extensive analysis of aged cells through electrochemical impedance spectroscopy (EIS) and UV-vis spectroscopy show no contaminant species having crossed over the NaSICON membrane after 83 days of exposure, yielding an upper limit to the permeability of NaSICON of 4 × 10-10 cm2 min-1. The demonstration of NaSICON as an IEM enables a wide new range of chemistries for application to flow batteries that would previously be impeded by species crossover and associated degradation.

Elimination of active species crossover in a room temperature, neutral pH, aqueous flow battery using a ceramic NaSICON membrane

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

Allcorn, Eric; Nagasubramanian, Ganesan; Pratt, III, Harry D.

Flow batteries are an attractive technology for energy storage of grid-scale renewables. However, performance issues related to ion-exchange membrane (IEM) fouling and crossover of species have limited the success of flow batteries. In this work we propose the use of the solid-state sodium-ion conductor NaSICON as an IEM to fully eliminate active species crossover in room temperature, aqueous, neutral pH flow batteries. We measure the room temperature conductivity of NaSICON at 2.83–4.67 mS cm –1 and demonstrate stability of NaSICON in an aqueous electrolyte with conductivity values remaining near 2.5 mS cm –1 after 66 days of exposure. Charge andmore » discharge of a full H-cell battery as well as symmetric cycling in a flow battery configuration using NaSICON as an IEM in both cases demonstrates the capability of the solid-state IEM. Extensive analysis of aged cells through electrochemical impedance spectroscopy (EIS) and UV–vis spectroscopy show no contaminant species having crossed over the NaSICON membrane after 83 days of exposure, yielding an upper limit to the permeability of NaSICON of 4 × 10 –10 cm 2 min –1. As a result, the demonstration of NaSICON as an IEM enables a wide new range of chemistries for application to flow batteries that would previously be impeded by species crossover and associated degradation.« less

Elimination of active species crossover in a room temperature, neutral pH, aqueous flow battery using a ceramic NaSICON membrane

DOE PAGES

Allcorn, Eric; Nagasubramanian, Ganesan; Pratt, III, Harry D.; ...

2018-01-04

Flow batteries are an attractive technology for energy storage of grid-scale renewables. However, performance issues related to ion-exchange membrane (IEM) fouling and crossover of species have limited the success of flow batteries. In this work we propose the use of the solid-state sodium-ion conductor NaSICON as an IEM to fully eliminate active species crossover in room temperature, aqueous, neutral pH flow batteries. We measure the room temperature conductivity of NaSICON at 2.83–4.67 mS cm –1 and demonstrate stability of NaSICON in an aqueous electrolyte with conductivity values remaining near 2.5 mS cm –1 after 66 days of exposure. Charge andmore » discharge of a full H-cell battery as well as symmetric cycling in a flow battery configuration using NaSICON as an IEM in both cases demonstrates the capability of the solid-state IEM. Extensive analysis of aged cells through electrochemical impedance spectroscopy (EIS) and UV–vis spectroscopy show no contaminant species having crossed over the NaSICON membrane after 83 days of exposure, yielding an upper limit to the permeability of NaSICON of 4 × 10 –10 cm 2 min –1. As a result, the demonstration of NaSICON as an IEM enables a wide new range of chemistries for application to flow batteries that would previously be impeded by species crossover and associated degradation.« less

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, R.R.

1990-11-20

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used. 5 figs.

Method of electrode fabrication for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1990-01-01

A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used.

Non-aqueous electrolytes for electrochemical cells

DOEpatents

Zhang, Zhengcheng; Dong, Jian; Amine, Khalil

2016-06-14

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

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

Water at Interfaces.

PubMed

Björneholm, Olle; Hansen, Martin H; Hodgson, Andrew; Liu, Li-Min; Limmer, David T; Michaelides, Angelos; Pedevilla, Philipp; Rossmeisl, Jan; Shen, Huaze; Tocci, Gabriele; Tyrode, Eric; Walz, Marie-Madeleine; Werner, Josephina; Bluhm, Hendrik

2016-07-13

The interfaces of neat water and aqueous solutions play a prominent role in many technological processes and in the environment. Examples of aqueous interfaces are ultrathin water films that cover most hydrophilic surfaces under ambient relative humidities, the liquid/solid interface which drives many electrochemical reactions, and the liquid/vapor interface, which governs the uptake and release of trace gases by the oceans and cloud droplets. In this article we review some of the recent experimental and theoretical advances in our knowledge of the properties of aqueous interfaces and discuss open questions and gaps in our understanding.

High efficiency and stability of quasi-solid-state dye-sensitized ZnO solar cells using graphene incorporated soluble polystyrene gel electrolytes

NASA Astrophysics Data System (ADS)

Bi, Shi-Qing; Meng, Fan-Li; Zheng, Yan-Zhen; Han, Xue; Tao, Xia; Chen, Jian-Feng

2014-12-01

We report on the preparation of highly effective composite electrolytes by combining the two-dimensional graphene (Gra) and soluble polystyrene (PS) nanobeads on Pt counter electrode for the quasi-solid-state electrolytes of ZnO based dye-sensitized solar cells (DSCs). Under an optimized Gra/electrolyte ratio of 12 mg mL-1, the ionic conductivity (σ) of Gra-PS electrolyte was significantly improved from 32.8 mS cm-1 to 39.8 mS cm-1. And the electrochemical impedance spectroscopy (EIS) analysis proved that the ZnO-DSC with the optimized composite electrolyte possessed the lowest impedance value. As a result, the overall power conversion efficiencies (PCEs) of quasi-solid-state ZnO-DSCs significantly enhanced to 5.08% from initial 4.09%. Moreover, the results of long-term stability assays showed that the gel-state Gra-PS ZnO-DSC could retain over 90% of its initial PCE after radiation of 1000 h under full sunlight outdoors. It is anticipated that this work may provide an effective way to increase the cell efficiency by the introduction of Gra into gel electrolyte as well as a great potential for practical application.

Model anodes and anode models for understanding the mechanism of hydrogen oxidation in solid oxide fuel cells.

PubMed

Bessler, Wolfgang G; Vogler, Marcel; Störmer, Heike; Gerthsen, Dagmar; Utz, Annika; Weber, André; Ivers-Tiffée, Ellen

2010-11-14

This article presents a literature review and new results on experimental and theoretical investigations of the electrochemistry of solid oxide fuel cell (SOFC) model anodes, focusing on the nickel/yttria-stabilized zirconia (Ni/YSZ) materials system with operation under H(2)/H(2)O atmospheres. Micropatterned model anodes were used for electrochemical characterization under well-defined operating conditions. Structural and chemical integrity was confirmed by ex situ pre-test and post-test microstructural and chemical analysis. Elementary kinetic models of reaction and transport processes were used to assess reaction pathways and rate-determining steps. The comparison of experimental and simulated electrochemical behaviors of pattern anodes shows quantitative agreement over a wide range of operating conditions (p(H(2)) = 8×10(2) - 9×10(4) Pa, p(H(2)O) = 2×10(1) - 6×10(4) Pa, T = 400-800 °C). Previously published experimental data on model anodes show a strong scatter in electrochemical performance. Furthermore, model anodes exhibit a pronounced dynamics on multiple time scales which is not reproduced in state-of-the-art models and which is also not observed in technical cermet anodes. Potential origin of these effects as well as consequences for further steps in model anode and anode model studies are discussed.

Smart aircraft fastener evaluation (SAFE) system: a condition-based corrosion detection system for aging aircraft

NASA Astrophysics Data System (ADS)

Schoess, Jeffrey N.; Seifert, Greg; Paul, Clare A.

1996-05-01

The smart aircraft fastener evaluation (SAFE) system is an advanced structural health monitoring effort to detect and characterize corrosion in hidden and inaccessible locations of aircraft structures. Hidden corrosion is the number one logistics problem for the U.S. Air Force, with an estimated maintenance cost of $700M per year in 1990 dollars. The SAFE system incorporates a solid-state electrochemical microsensor and smart sensor electronics in the body of a Hi-Lok aircraft fastener to process and autonomously report corrosion status to aircraft maintenance personnel. The long-term payoff for using SAFE technology will be in predictive maintenance for aging aircraft and rotorcraft systems, fugitive emissions applications such as control valves, chemical pipeline vessels, and industrial boilers. Predictive maintenance capability, service, and repair will replace the current practice of scheduled maintenance to substantially reduce operational costs. A summary of the SAFE concept, laboratory test results, and future field test plans is presented.

Wearable energy-dense and power-dense supercapacitor yarns enabled by scalable graphene-metallic textile composite electrodes.

PubMed

Liu, Libin; Yu, You; Yan, Casey; Li, Kan; Zheng, Zijian

2015-06-11

One-dimensional flexible supercapacitor yarns are of considerable interest for future wearable electronics. The bottleneck in this field is how to develop devices of high energy and power density, by using economically viable materials and scalable fabrication technologies. Here we report a hierarchical graphene-metallic textile composite electrode concept to address this challenge. The hierarchical composite electrodes consist of low-cost graphene sheets immobilized on the surface of Ni-coated cotton yarns, which are fabricated by highly scalable electroless deposition of Ni and electrochemical deposition of graphene on commercial cotton yarns. Remarkably, the volumetric energy density and power density of the all solid-state supercapacitor yarn made of one pair of these composite electrodes are 6.1 mWh cm(-3) and 1,400 mW cm(-3), respectively. In addition, this SC yarn is lightweight, highly flexible, strong, durable in life cycle and bending fatigue tests, and integratable into various wearable electronic devices.

Wearable energy-dense and power-dense supercapacitor yarns enabled by scalable graphene–metallic textile composite electrodes

PubMed Central

Liu, Libin; Yu, You; Yan, Casey; Li, Kan; Zheng, Zijian

2015-01-01

One-dimensional flexible supercapacitor yarns are of considerable interest for future wearable electronics. The bottleneck in this field is how to develop devices of high energy and power density, by using economically viable materials and scalable fabrication technologies. Here we report a hierarchical graphene–metallic textile composite electrode concept to address this challenge. The hierarchical composite electrodes consist of low-cost graphene sheets immobilized on the surface of Ni-coated cotton yarns, which are fabricated by highly scalable electroless deposition of Ni and electrochemical deposition of graphene on commercial cotton yarns. Remarkably, the volumetric energy density and power density of the all solid-state supercapacitor yarn made of one pair of these composite electrodes are 6.1 mWh cm−3 and 1,400 mW cm−3, respectively. In addition, this SC yarn is lightweight, highly flexible, strong, durable in life cycle and bending fatigue tests, and integratable into various wearable electronic devices. PMID:26068809

Emerging electrochemical energy conversion and storage technologies

NASA Astrophysics Data System (ADS)

Badwal, Sukhvinder; Giddey, Sarbjit; Munnings, Christopher; Bhatt, Anand; Hollenkamp, Tony

2014-09-01

Electrochemical cells and systems play a key role in a wide range of industry sectors. These devices are critical enabling technologies for renewable energy; energy management, conservation and storage; pollution control / monitoring; and greenhouse gas reduction. A large number of electrochemical energy technologies have been developed in the past. These systems continue to be optimized in terms of cost, life time and performance, leading to their continued expansion into existing and emerging market sectors. The more established technologies such as deep-cycle batteries and sensors are being joined by emerging technologies such as fuel cells, large format lithium-ion batteries, electrochemical reactors; ion transport membranes and supercapacitors. This growing demand (multi billion dollars) for electrochemical energy systems along with the increasing maturity of a number of technologies is having a significant effect on the global research and development effort which is increasing in both in size and depth. A number of new technologies, which will have substantial impact on the environment and the way we produce and utilize energy, are under development. This paper presents an overview of several emerging electrochemical energy technologies along with a discussion some of the key technical challenges.

Emerging electrochemical energy conversion and storage technologies

PubMed Central

Badwal, Sukhvinder P. S.; Giddey, Sarbjit S.; Munnings, Christopher; Bhatt, Anand I.; Hollenkamp, Anthony F.

2014-01-01

Electrochemical cells and systems play a key role in a wide range of industry sectors. These devices are critical enabling technologies for renewable energy; energy management, conservation, and storage; pollution control/monitoring; and greenhouse gas reduction. A large number of electrochemical energy technologies have been developed in the past. These systems continue to be optimized in terms of cost, life time, and performance, leading to their continued expansion into existing and emerging market sectors. The more established technologies such as deep-cycle batteries and sensors are being joined by emerging technologies such as fuel cells, large format lithium-ion batteries, electrochemical reactors; ion transport membranes and supercapacitors. This growing demand (multi billion dollars) for electrochemical energy systems along with the increasing maturity of a number of technologies is having a significant effect on the global research and development effort which is increasing in both in size and depth. A number of new technologies, which will have substantial impact on the environment and the way we produce and utilize energy, are under development. This paper presents an overview of several emerging electrochemical energy technologies along with a discussion some of the key technical challenges. PMID:25309898

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.

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.

Hierarchical VOOH hollow spheres for symmetrical and asymmetrical supercapacitor devices.

PubMed

Jing, Xuyang; Wang, Cong; Feng, Wenjing; Xing, Na; Jiang, Hanmei; Lu, Xiangyu; Zhang, Yifu; Meng, Changgong

2018-01-01

Hierarchical VOOH hollow spheres with low crystallinity composed of nanoparticles were prepared by a facile and template-free method, which involved a precipitation of precursor microspheres in aqueous solution at room temperature and subsequent hydrothermal reaction. Quasi-solid-state symmetric and asymmetric supercapacitor (SSC and ASC) devices were fabricated using hierarchical VOOH hollow spheres as the electrodes, and the electrochemical properties of the VOOH//VOOH SSC device and the VOOH//AC ASC device were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). Results demonstrated that the electrochemical performance of the VOOH//AC ASC device was better than that of the VOOH//VOOH SSC device. After 3000 cycles, the specific capacitance of the VOOH//AC ASC device retains 83% of the initial capacitance, while the VOOH//VOOH SSC device retains only 7.7%. Findings in this work proved that hierarchical VOOH hollow spheres could be a promising candidate as an ideal electrode material for supercapacitor devices.

Hierarchical VOOH hollow spheres for symmetrical and asymmetrical supercapacitor devices

NASA Astrophysics Data System (ADS)

Jing, Xuyang; Wang, Cong; Feng, Wenjing; Xing, Na; Jiang, Hanmei; Lu, Xiangyu; Zhang, Yifu; Meng, Changgong

2018-01-01

Hierarchical VOOH hollow spheres with low crystallinity composed of nanoparticles were prepared by a facile and template-free method, which involved a precipitation of precursor microspheres in aqueous solution at room temperature and subsequent hydrothermal reaction. Quasi-solid-state symmetric and asymmetric supercapacitor (SSC and ASC) devices were fabricated using hierarchical VOOH hollow spheres as the electrodes, and the electrochemical properties of the VOOH//VOOH SSC device and the VOOH//AC ASC device were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). Results demonstrated that the electrochemical performance of the VOOH//AC ASC device was better than that of the VOOH//VOOH SSC device. After 3000 cycles, the specific capacitance of the VOOH//AC ASC device retains 83% of the initial capacitance, while the VOOH//VOOH SSC device retains only 7.7%. Findings in this work proved that hierarchical VOOH hollow spheres could be a promising candidate as an ideal electrode material for supercapacitor devices.

Electrochemical characteristics of flexible micro supercapacitors with reduced graphene oxide-carbon nanotubes composite electrodes

NASA Astrophysics Data System (ADS)

Yang, Kyungwhan; Cho, Kyoungah; Kim, Sangsig

2018-06-01

In this study, we fabricate solid-state flexible micro-supercapacitors (MSCs) with reduced graphene oxide-carbon nanotube (rGO-CNT) composite electrodes and investigate the electrochemical characteristics by comparing with those of an MSC with rGO electrodes. Regarding the resistance-capacitance time constant and IR drop, the addition of CNTs into the rGO electrodes shows a significant effect owing to both the decrease in the resistance and the increase in the permeability of the electrolytes. Compared to the rGO MSCs, the rGO-CNT MSCs show an excellent areal capacitance of 2.6 mF/cm2, a smaller IR drop of 11 mV, a lower RC time constant of 6 ms, and faster charging/discharging rates with a high scan rate ability up to 100 V/s. The mechanical stability of the flexible rGO-CNT MSCs is verified by 1000 bending cycles. In addition, the electrochemical characteristics of the flexible rGO-CNT MSCs are maintained regardless of the MSC array type.

All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels.

PubMed

Kang, Yu Jin; Chun, Sang-Jin; Lee, Sung-Suk; Kim, Bo-Yeong; Kim, Jung Hyeun; Chung, Haegeun; Lee, Sun-Young; Kim, Woong

2012-07-24

We demonstrate all-solid-state flexible supercapacitors with high physical flexibility, desirable electrochemical properties, and excellent mechanical integrity, which were realized by rationally exploiting unique properties of bacterial nanocellulose, carbon nanotubes, and ionic liquid based polymer gel electrolytes. This deliberate choice and design of main components led to excellent supercapacitor performance such as high tolerance against bending cycles and high capacitance retention over charge/discharge cycles. More specifically, the performance of our supercapacitors was highly retained through 200 bending cycles to a radius of 3 mm. In addition, the supercapacitors showed excellent cyclability with C(sp) (~20 mF/cm(2)) reduction of only <0.5% over 5000 charge/discharge cycles at the current density of 10 A/g. Our demonstration could be an important basis for material design and development of flexible supercapacitors.

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte.

PubMed

Gao, Tao; Li, Xiaogang; Wang, Xiwen; Hu, Junkai; Han, Fudong; Fan, Xiulin; Suo, Liumin; Pearse, Alex J; Lee, Sang Bok; Rubloff, Gary W; Gaskell, Karen J; Noked, Malachi; Wang, Chunsheng

2016-08-16

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layered Lepidocrocite Type Structure Isolated by Revisiting the Sol–Gel Chemistry of Anatase TiO 2 : A New Anode Material for Batteries

DOE PAGES

Ma, Jiwei; Reeves, Kyle G.; Porras Gutierrez, Ana-Gabriela; ...

2017-09-19

Searches for new electrode materials for batteries must comply on financial and environmental costs to be useful in practical devices. The sol-gel chemistry has been widely used to design and implemented new concepts for the emergence of advanced materials such as hydride organic-inorganic composites. Here, we show that the simple reaction system including titanium alkoxide and water can be used to stabilize a new class of electrode materials. By investigating the crystallization path of anatase TiO2, an X-ray amorphous intermediate phase has been identified whose local structure probed by the pair distribution function, 1H solid-state NMR and DFT calculations, consistsmore » of a layered-type structure as found in the lepido-crocite. This phase presents the following general formula Ti 2-x⟂ xO 4-4x(OH) 4x.nH 2O (x ~ 0.5) where the substitution of oxide by hydroxide anions leads to the formation of titanium vacancies (•) and H 2O molecules are located in interlayers. Solid-state 1H NMR has enabled to characterize three main hydroxide environments that are Ti⟂-OH, Ti 2⟂ 2-OH and Ti3⟂-OH and layered H 2O molecules. The electrochemical properties of this phase were further investigated versus lithium and is shown to be very promising with reversible capacities of around 200 mAh.g -1 and an operating voltage of 1.55 V. We further showed that the lithium intercalation proceeds via a solid-solution mechanism. 7Li solid-state NMR and DFT calculations allowed to identify lithium host sites that are located at the titanium vacancies and interlayer space with lithium being solvated by structural water molecules. The easy fabrication, the absence of lithium and easier recycling and the encouraging properties makes this class of materials very attractive for competitive electrodes for batteries. We thus demonstrate that the revisit of an “old” chemistry with advanced characterization tools allows discovering new materials of technological relevance.« less

Layered Lepidocrocite Type Structure Isolated by Revisiting the Sol–Gel Chemistry of Anatase TiO 2 : A New Anode Material for Batteries

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

Ma, Jiwei; Reeves, Kyle G.; Porras Gutierrez, Ana-Gabriela

Searches for new electrode materials for batteries must comply on financial and environmental costs to be useful in practical devices. The sol-gel chemistry has been widely used to design and implemented new concepts for the emergence of advanced materials such as hydride organic-inorganic composites. Here, we show that the simple reaction system including titanium alkoxide and water can be used to stabilize a new class of electrode materials. By investigating the crystallization path of anatase TiO2, an X-ray amorphous intermediate phase has been identified whose local structure probed by the pair distribution function, 1H solid-state NMR and DFT calculations, consistsmore » of a layered-type structure as found in the lepido-crocite. This phase presents the following general formula Ti 2-x⟂ xO 4-4x(OH) 4x.nH 2O (x ~ 0.5) where the substitution of oxide by hydroxide anions leads to the formation of titanium vacancies (•) and H 2O molecules are located in interlayers. Solid-state 1H NMR has enabled to characterize three main hydroxide environments that are Ti⟂-OH, Ti 2⟂ 2-OH and Ti3⟂-OH and layered H 2O molecules. The electrochemical properties of this phase were further investigated versus lithium and is shown to be very promising with reversible capacities of around 200 mAh.g -1 and an operating voltage of 1.55 V. We further showed that the lithium intercalation proceeds via a solid-solution mechanism. 7Li solid-state NMR and DFT calculations allowed to identify lithium host sites that are located at the titanium vacancies and interlayer space with lithium being solvated by structural water molecules. The easy fabrication, the absence of lithium and easier recycling and the encouraging properties makes this class of materials very attractive for competitive electrodes for batteries. We thus demonstrate that the revisit of an “old” chemistry with advanced characterization tools allows discovering new materials of technological relevance.« less

Architecture and method for a burst buffer using flash technology

DOEpatents

Tzelnic, Percy; Faibish, Sorin; Gupta, Uday K.; Bent, John; Grider, Gary Alan; Chen, Hsing-bung

2016-03-15

A parallel supercomputing cluster includes compute nodes interconnected in a mesh of data links for executing an MPI job, and solid-state storage nodes each linked to a respective group of the compute nodes for receiving checkpoint data from the respective compute nodes, and magnetic disk storage linked to each of the solid-state storage nodes for asynchronous migration of the checkpoint data from the solid-state storage nodes to the magnetic disk storage. Each solid-state storage node presents a file system interface to the MPI job, and multiple MPI processes of the MPI job write the checkpoint data to a shared file in the solid-state storage in a strided fashion, and the solid-state storage node asynchronously migrates the checkpoint data from the shared file in the solid-state storage to the magnetic disk storage and writes the checkpoint data to the magnetic disk storage in a sequential fashion.

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

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

DOE PAGES

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.; ...

2015-08-10

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation dynamics in the anisotropic deposition and stripping of bulk magnesium electrodes during electrochemical cycling

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

Wetzel, David J.; Malone, Marvin A.; Haasch, Richard T.

Rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, though little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pitmore » densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. Finally, the passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.« less

Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

PubMed

Wetzel, David J; Malone, Marvin A; Haasch, Richard T; Meng, Yifei; Vieker, Henning; Hahn, Nathan T; Gölzhäuser, Armin; Zuo, Jian-Min; Zavadil, Kevin R; Gewirth, Andrew A; Nuzzo, Ralph G

2015-08-26

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 μm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li7La3Zr2O12 Solid Electrolytes

PubMed Central

2016-01-01

Several “Beyond Li-Ion Battery” concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li7La3Zr2O12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet (Ia3̅d, No. 230) to “non-garnet” (I4̅3d, No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10–4 S cm–1 to 1.2 × 10–3 S cm–1, which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm2, the lowest reported value for LLZO so far. These results illustrate that understanding the structure–properties relationships in this class of materials allows practical obstacles to its utilization to be readily overcome. PMID:27110064

Structural and Electrochemical Consequences of Al and Ga Cosubstitution in Li7La3Zr2O12 Solid Electrolytes.

PubMed

Rettenwander, Daniel; Redhammer, Günther; Preishuber-Pflügl, Florian; Cheng, Lei; Miara, Lincoln; Wagner, Reinhard; Welzl, Andreas; Suard, Emmanuelle; Doeff, Marca M; Wilkening, Martin; Fleig, Jürgen; Amthauer, Georg

2016-04-12

Several "Beyond Li-Ion Battery" concepts such as all solid-state batteries and hybrid liquid/solid systems envision the use of a solid electrolyte to protect Li-metal anodes. These configurations are very attractive due to the possibility of exceptionally high energy densities and high (dis)charge rates, but they are far from being realized practically due to a number of issues including high interfacial resistance and difficulties associated with fabrication. One of the most promising solid electrolyte systems for these applications is Al or Ga stabilized Li 7 La 3 Zr 2 O 12 (LLZO) based on high ionic conductivities and apparent stability against reduction by Li metal. Nevertheless, the fabrication of dense LLZO membranes with high ionic conductivity and low interfacial resistances remains challenging; it definitely requires a better understanding of the structural and electrochemical properties. In this study, the phase transition from garnet ( Ia 3̅ d , No. 230) to "non-garnet" ( I 4̅3 d , No. 220) space group as a function of composition and the different sintering behavior of Ga and Al stabilized LLZO are identified as important factors in determining the electrochemical properties. The phase transition was located at an Al:Ga substitution ratio of 0.05:0.15 and is accompanied by a significant lowering of the activation energy for Li-ion transport to 0.26 eV. The phase transition combined with microstructural changes concomitant with an increase of the Ga/Al ratio continuously improves the Li-ion conductivity from 2.6 × 10 -4 S cm -1 to 1.2 × 10 -3 S cm -1 , which is close to the calculated maximum for garnet-type materials. The increase in Ga content is also associated with better densification and smaller grains and is accompanied by a change in the area specific resistance (ASR) from 78 to 24 Ω cm 2 , the lowest reported value for LLZO so far. These results illustrate that understanding the structure-properties relationships in this class of materials allows practical obstacles to its utilization to be readily overcome.

Bipolar stacked quasi-all-solid-state lithium secondary batteries with output cell potentials of over 6 V

PubMed Central

Matsuo, Takahiro; Gambe, Yoshiyuki; Sun, Yan; Honma, Itaru

2014-01-01

Designing a lithium ion battery (LIB) with a three-dimensional device structure is crucial for increasing the practical energy storage density by avoiding unnecessary supporting parts of the cell modules. Here, we describe the superior secondary battery performance of the bulk all-solid-state LIB cell and a multilayered stacked bipolar cell with doubled cell potential of 6.5 V, for the first time. The bipolar-type solid LIB cell runs its charge/discharge cycle over 200 times in a range of 0.1–1.0 C with negligible capacity decrease despite their doubled output cell potentials. This extremely high performance of the bipolar cell is a result of the superior battery performance of the single cell; the bulk all-solid-state cell has a charge/discharge cycle capability of over 1500 although metallic lithium and LiFePO4 are employed as anodes and cathodes, respectively. The use of a quasi-solid electrolyte consisting of ionic liquid and Al2O3 nanoparticles is considered to be responsible for the high ionic conductivity and electrochemical stability at the interface between the electrodes and the electrolyte. This paper presents the effective applications of SiO2, Al2O3, and CeO2 nanoparticles and various Li+ conducting ionic liquids for the quasi-solid electrolytes and reports the best ever known cycle performances. Moreover, the results of this study show that the bipolar stacked three-dimensional device structure would be a smart choice for future LIBs with higher cell energy density and output potential. In addition, our report presents the advantages of adopting a three-dimensional cell design based on the solid-state electrolytes, which is of particular interest in energy-device engineering for mobile applications. PMID:25124398

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

Optofluidic devices with integrated solid-state nanopores

PubMed Central

Hawkins, Aaron R.; Schmidt, Holger

2016-01-01

This review (with 90 refs.) covers the state of the art in optofluidic devices with integrated solid-state nanopores for use in detection and sensing. Following an introduction into principles of optofluidics and solid-state nanopore technology, we discuss features of solid-state nanopore based assays using optofluidics. This includes the incorporation of solid-state nanopores into optofluidic platforms based on liquid-core anti-resonant reflecting optical waveguides (ARROWs), methods for their fabrication, aspects of single particle detection and particle manipulation. We then describe the new functionalities provided by solid-state nanopores integrated into optofluidic chips, in particular acting as smart gates for correlated electro-optical detection and discrimination of nanoparticles. This enables the identification of viruses and λ-DNA, particle trajectory simulations, enhancing sensitivity by tuning the shape of nanopores. The review concludes with a summary and an outlook. PMID:27046940

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

Checkerboard deposition of lithium manganese oxide spinel (LiMn2O4) by RF magnetron sputtering on a stainless steel in all-solid-state thin film battery

NASA Astrophysics Data System (ADS)

Hsueh, T. H.; Yu, Y. Q.; Jan, D. J.; Su, C. H.; Chang, S. M.

2018-03-01

All-solid-state thin film lithium batteries (TFLBs) are the most competitive low-power sources to be applied in various kinds of micro-electro-mechanical systems and have been draw a lot of attention in academic research. In this paper, the checkerboard deposition of all-solid-state TFLB was composed of thin film lithium metal anode, lithium phosphorus oxynitride (LiPON) solid electrolyte, and checkerboard deposition of lithium manganese oxide spinel (LiMn2O4) cathode. The LiPON and LiMn2O4 were deposited by a radio frequency magnetron sputtering system, and the lithium metal was deposited by a thermal evaporation coater. The electrochemical characterization of this lithium battery showed the first discharge capacity of 107.8 μAh and the capacity retention was achieved 95.5% after 150 charge-discharge cycles between 4.3V and 3V at a current density of 11 μA/cm2 (0.5C). Obviously, the checkerboard of thin film increased the charge exchange rate; also this lithium battery exhibited high C-rate performance, with better capacity retention of 82% at 220 μA/cm2 (10C).

New Horizons in Electrochemical Science and Technology. Report of the Committee on Electrochemical Aspects of Energy Conservation and Production.

ERIC Educational Resources Information Center

National Academy of Sciences - National Research Council, Washington, DC. National Materials Advisory Board.

Electrochemical phenomena play a fundamental role in providing essential materials and devices for modern society. This report reviews the status of current knowledge of electrochemical science and technology and makes recommendations for future research and development in this multidisciplinary field. The report identifies new technological…

Fabrication and characterization of solid oxide cells for energy conversion and storage

NASA Astrophysics Data System (ADS)

Yang, Chenghao

2011-12-01

There has been an increasing interest in clean and renewable energy generation for highlighted energy and environmental concerns. Solid oxide cells (SOCs) have been considered as one of the promising technologies, since they can be operated efficiently both in electrolysis mode by generating hydrogen through steam electrolysis and fuel cell mode by electrochemically combining fuel with oxidant. The present work is devoted to performing a fundamental study of SOC in both fuel cell mode for power generation and electrolysis mode for fuel production. The research work on SOCs that can be operated reversibly for power generation and fuel production has been conducted in the following six projects: (1) High performance solid oxide electrolysis cell (SOEC) Fabrication of novel structured SOEC oxygen electrode with the conventional and commercial solid oxide fuel cell materials by screen-printing and infiltration fabrication methods. The microstructure, electrochemical properties and durability of SOECs has been investigated. It was found that the LSM infiltrated cell has an area specific resistance (ASR) of 0.20 Ω cm2 at 900°C at open circuit voltage with 50% absolute humidity (AH), which is relatively lower than that of the cell with LSM-YSZ oxygen electrode made by a conventional mixing method. Electrolysis cell with LSM infiltrated oxygen electrode has demonstrated stable performance under electrolysis operation with 0.33 A/cm2 and 50 vol.% AH at 800°C. (2) Advanced performance high temperature micro-tubular solid oxide fuel cell (MT-SOFC) Phase-inversion, dip-coating, high temperature co-sintering process and impregnation method were used to fabricate micro-tubular solid oxide fuel cell. The micro-structure of the micro-tubular fuel cell will be investigated and the power output and thermal robustness has been evaluated. High performance and rapid start-up behavior have been achieved, indicates that the MT-SOFC developed in this work can be a promising technology for portable applications. (3) Promising intermediate temperature micro-tubular solid oxide fuel cells for portable power supply applications Maximum power densities of 0.5, 0.38 and 0.27 W/cm2 have been obtained using H2-15% H2O as fuel at 550, 600 and 650°C, respectively. Quick thermal cycles performed on the intermediate temperature MT-SOFC stability demonstrate that the cell has robust performance stability for portable applications. (4) Micro-tubular solid oxide cell (MT-SOC) for steam electrolysis The electrochemical properties of MT-SOC will be investigated in detail in electrolysis mode. The mechanism of the novel hydrogen electrode structure benefiting the cell performance will be demonstrated systematically. The high electrochemical performance of the MT-SOC in electrolysis mode indicates that MT-SOC can provide an efficient hydrogen generation process. (5) Micro-tubular solid oxide cell (MT-SOC) for steam and CO2 co-electrolysis The MT-SOC will be operated in co-electrolysis mode for steam and CO 2, which will provide an efficient approach to generate syngas (H2+CO) without consuming fossil fuels. This can potentially provide an alternative superior approach for carbon sequestration which has been a critical issue facing the sustainability of our society. (6) Steam and CO2 co-electrolysis using solid oxide cells fabricated by freeze-drying tape-casting Tri-layer scaffolds have been prepared by freeze-drying tape casting process and the electrode catalysts are obtained by infiltrating the porous electrode substrates. Button cells will be tested for co-electrolysis of steam and CO2. The mechanism and efficiency of steam and CO2 co-electrolysis will be systemically investigated. In conclusion, SOCs have been fabricated with conventional materials and evaluated, but their performance has been found to be limited in either SOFC or SOEC mode. The cell performance has been significantly improved by employing an infiltrated LSM-YSZ electrode, due to dramatically decreased polarization resistance. However, mass transport limitation has been observed, particularly in electrolysis mode. By utilizing micro-tubular SOCs with novel hydrogen electrode produced via a phase inversion method, mass transport limitation has been mitigated. Finally, mass transport has been further improved by using cells with electrodes fabricated through a freeze-drying tape-casting method. (Abstract shortened by UMI.)

Lithium1.3Aluminum0.3Titanium1.7Phosphate as a solid state Li-ion conductor: Issues with microcracking and stability in aqueous solutions

NASA Astrophysics Data System (ADS)

Jackman, Spencer D.

Lithium aluminum titanium phosphate (LATP) with formula Li1.3Al0.3Ti1.7(PO4)3 was analyzed and tested to better understand its applicability as a solid state ion conducting ceramic material for electrochemical applications. Sintered samples were obtained from Ceramatec, Inc. in Salt Lake City and characterized in terms of density, phase-purity, fracture toughness, Young's modulus, thermal expansion behavior, mechanical strength, a.c. and d.c. ionic conductivity, and susceptibility to static and electrochemical corrosion in aqueous Li salt solutions. It was shown that LATP is prone to microcrack generation because of high thermal expansion anisotropy. A.c. impedance spectra of high-purity LATP of varying grain sizes showed that microcracking had a negative impact on the ionic conduction of Li along grain boundaries, with fine-grained (1.7±0.7 µm) LATP having twice the ionic conductivity of the same purity of coarse-grained (4.8±1.9 µm) LATP at 50°C. LATP with detectible secondary phases had lower ionic conductivity for similar grain sizes, as would be expected. The Young's modulus of fine-grained LATP was measured to be 115 GPa, and the highest biaxial strength was 191±11 MPa when tested in mineral oil, 144±13 MPa as measured in air, and 26±7 MPa after exposure to deionized water, suggesting that LATP undergoes stress-corrosion cracking. After exposure to LiOH, the strength was 76±19 MPa. This decrease in strength was observed despite there being no measureable change in a.c. impedance spectra, X-ray diffraction, or sample mass, suggesting phosphate glasses at grain boundaries. The chemical and electrochemical stability of high-purity LATP in aqueous electrochemical cells was evaluated using LiOH, LiCl, LiNO3, and LiCOOCH3 salts as the Li source. LATP was found to be most stable between pH 8-9, with the longest cell operating continuously at 25 mA cm-2 for 625 hours at 40°C in LiCOOCH3. At pH values outside of the 7-10 range, eventual membrane degradation was observed in all aqueous systems under electrochemical conditions. While LATP was surprisingly resistant to static corrosion in a hot, aqueous LiOH solution, electrochemical degradation was observed at the cathode due to subsurface pitting. Strength measurements were more instructive than impedance measurements in detecting this degradation.

High speed chalcogenide glass electrochemical metallization cells with various active metals.

PubMed

Hughes, Mark A; Burgess, Alexander; Hinder, Steven; Gholizadeh, A Baset; Craig, Christopher; Hewak, Daniel W

2018-08-03

We fabricated electrochemical metallization cells using a GaLaSO solid electrolyte, an InSnO inactive electrode and active electrodes consisting of various metals (Cu, Ag, Fe, Cu, Mo, Al). Devices with Ag and Cu active metals showed consistent and repeatable resistive switching behaviour, and had a retention of 3 and >43 days, respectively; both had switching speeds of <5 ns. Devices with Cr and Fe active metals displayed incomplete or intermittent resistive switching, and devices with Mo and Al active electrodes displayed no resistive switching ability. Deeper penetration of the active metal into the GaLaSO layer resulted in greater resistive switching ability of the cell. The off-state resistivity was greater for more reactive active metals which may be due to a thicker intermediate layer.

Development of Brazing Technology for Use in High- Temperature Gas Separation Equipment

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

Weil, K.S.; Hardy, J.S.; Kim, J.Y.

2003-04-23

The development of high-temperature electrochemical devices such as oxygen and hydrogen separators, fuel gas reformers, solid oxide fuel cells, and chemical sensors is part of a rapidly expanding segment of the solid state technology market. These devices employ an ionic conducting ceramic as the active membrane that establishes the electrochemical potential of the device, either under voltage (i.e. to carry out gas separation) or under chemical gradient (to develop an electrical potential and thereby generate electrical power). Because the device operates under an ionic gradient that develops across the electrolyte, hermiticity across this layer is paramount. That is, not onlymore » must this thin ceramic membrane be dense with no interconnected porosity, but it must be connected to the rest of the device, typically constructed from a heat resistant alloy, with a high-temperature, gas-tight seal. A significant engineering challenge in fabricating these devices is how to effectively join the thin electrochemically active membrane to the metallic body of the device such that the resulting seal is hermetic, rugged, and stable during continuous high temperature operation. Active metal brazing is the typical method of joining ceramic and metal engineering components. It employs a braze alloy that contains one or more reactive elements, often titanium, which will chemically reduce the ceramic faying surface and greatly improve its wetting behavior and adherence with the braze. However, recent studies of these brazes for potential use in fabricating high-temperature electrochemical devices revealed problems with interfacial oxidation and subsequent joint failure [1,2]. Specifically, it was found that the introduction of the ceramic electrolyte and/or heat resistant metal substrate dramatically affects the inherent oxidation behavior of the braze, often in a deleterious manner. These conclusions pointed to the need for an oxidation resistant, high-temperature ceramic-to-metal braze and consequently lead to the development of the novel reactive air brazing (RAB) concept. The goal in RAB is to reactively modify one or both oxide faying surfaces with an oxide compound dissolved in a molten noble metal alloy such that the newly formed surface is readily wetted by the remaining liquid filler material. In many respects, this concept is similar to active metal brazing, except that joining can be conducted in air and the final joint will be resistant to oxidation at high temperature. Potentially, there are a number of metal oxide-noble metal systems that can be considered for RAB, including Ag-CuO, Ag-V2O5, and Pt-Nb2O5. Our current interest is in determining whether the Ag-CuO system is suitable for air brazing functional ceramic-to-metal joints such as those needed in practical electrochemical devices. In a series of studies, the wetting behavior of the Ag-CuO braze was investigated with respect to a number of potential hydrogen separation, oxygen separation, and fuel cell electrolyte membrane materials and heat resistant metal systems, including: alumina, (La0.6Sr0.4)(Co0.2Fe0.8)O3, (La0.8Sr0.2)FeO3, YSZ, fecralloy, and Crofer-22APU. Selected findings from these studies as well as from our work on joint strength and durability during high-temperature exposure testing will be discussed.« less

Space Electrochemical Research and Technology

NASA Technical Reports Server (NTRS)

1991-01-01

The proceedings of NASA's third Space Electrochemical Research and Technology (SERT) conference are presented. The objective of the conference was to assess the present status and general thrust of research and development in those areas of electrochemical technology required to enable NASA missions in the next century. The conference provided a forum for the exchange of ideas and opinions of those actively involved in the field, in order to define new opportunities for the application of electrochemical processes in future NASA missions. Papers were presented in three technical areas: the electrochemical interface, the next generation in aerospace batteries and fuel cells, and electrochemistry for nonenergy storage applications.

The Electrochemical Properties of Sr(Ti,Fe)O 3-δ for Anodes in Solid Oxide Fuel Cells

DOE PAGES

Nenning, Andreas; Volgger, Lukas; Miller, Elizabeth; ...

2017-02-18

Reduction-stable mixed ionic and electronic conductors such as Sr(Ti,Fe)O 3-δ (STF) are promising materials for application in anodes of solid oxide fuel cells. The defect chemistry of STF and its properties as solid oxide fuel cell (SOFC) cathode have been studied thoroughly, while mechanistic investigations of its electrochemical properties as SOFC anode material are still scarce. In this study, thin film model electrodes of STF with 30% and 70% Fe content were investigated in H 2+H 2O atmosphere by electrochemical impedance spectroscopy. Lithographically patterned thin film Pt current collectors were applied on top or beneath the STF thin films tomore » compensate for the low electronic conductivity under reducing conditions. Oxygen exchange resistances, electronic and ionic conductivities and chemical capacitances were quantified and discussed in a defect chemical model. Increasing Fe content increases the electro-catalytic activity of the STF surface as well as the electronic and ionic conductivity. Current collectors on top also increase the electrochemical activity due to a highly active Pt-atmosphere-STF triple phase boundary. Furthermore, the electrochemical activity depends decisively on the H 2:H 2O mixing ratio and the polarization. Lastly, Fe 0 nanoparticles may evolve on the surface in hydrogen rich atmospheres and increase the hydrogen adsorption rate.« less

Ion conducting organic/inorganic hybrid polymers

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Kinder, James D. (Inventor)

2010-01-01

This invention relates to a series of organic/inorganic hybrid polymers that are easy to fabricate into dimensionally stable films with good ion-conductivity over a wide range of temperatures for use in a variety of applications. The polymers are prepared by the reaction of amines, preferably diamines and mixtures thereof with monoamines with epoxy-functionalized alkoxysilanes. The products of the reaction are polymerized by hydrolysis of the alkoxysilane groups to produce an organic-containing silica network. Suitable functionality introduced into the amine and alkoxysilane groups produce solid polymeric membranes which conduct ions for use in fuel cells, high-performance solid state batteries, chemical sensors, electrochemical capacitors, electro-chromic windows or displays, analog memory devices and the like.

Bottom-up electrochemical preparation of solid-state carbon nanodots directly from nitriles/ionic liquids using carbon-free electrodes and the applications in specific ferric ion detection and cell imaging

NASA Astrophysics Data System (ADS)

Niu, Fushuang; Xu, Yuanhong; Liu, Mengli; Sun, Jing; Guo, Pengran; Liu, Jingquan

2016-03-01

Carbon nanodots (C-dots), a new type of potential alternative to conventional semiconductor quantum dots, have attracted numerous attentions in various applications including bio-chemical sensing, cell imaging, etc., due to their chemical inertness, low toxicity and flexible functionalization. Various methods including electrochemical (EC) methods have been reported for the synthesis of C-dots. However, complex procedures and/or carbon source-containing electrodes are often required. Herein, solid-state C-dots were simply prepared by bottom-up EC carbonization of nitriles (e.g. acetonitrile) in the presence of an ionic liquid [e.g. 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)], using carbon-free electrodes. Due to the positive charges of BMIM+ on the C-dots, the final products presented in a precipitate form on the cathode, and the unreacted nitriles and BMIMPF6 can be easily removed by simple vacuum filtration. The as-prepared solid-state C-dots can be well dispersed in an aqueous medium with excellent photoluminescence properties. The average size of the C-dots was found to be 3.02 +/- 0.12 nm as evidenced by transmission electron microscopy. Other techniques such as UV-vis spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were applied for the characterization of the C-dots and to analyze the possible generation mechanism. These C-dots have been successfully applied in efficient cell imaging and specific ferric ion detection.Carbon nanodots (C-dots), a new type of potential alternative to conventional semiconductor quantum dots, have attracted numerous attentions in various applications including bio-chemical sensing, cell imaging, etc., due to their chemical inertness, low toxicity and flexible functionalization. Various methods including electrochemical (EC) methods have been reported for the synthesis of C-dots. However, complex procedures and/or carbon source-containing electrodes are often required. Herein, solid-state C-dots were simply prepared by bottom-up EC carbonization of nitriles (e.g. acetonitrile) in the presence of an ionic liquid [e.g. 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6)], using carbon-free electrodes. Due to the positive charges of BMIM+ on the C-dots, the final products presented in a precipitate form on the cathode, and the unreacted nitriles and BMIMPF6 can be easily removed by simple vacuum filtration. The as-prepared solid-state C-dots can be well dispersed in an aqueous medium with excellent photoluminescence properties. The average size of the C-dots was found to be 3.02 +/- 0.12 nm as evidenced by transmission electron microscopy. Other techniques such as UV-vis spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy and atomic force microscopy were applied for the characterization of the C-dots and to analyze the possible generation mechanism. These C-dots have been successfully applied in efficient cell imaging and specific ferric ion detection. Electronic supplementary information (ESI) available: Fig. S1. TEM image of the products generated via an electrochemical method using pure BMIMBF4 aqueous solution as the electrolyte; Fig. S2. TEM and HRTEM (inset) images of the water-dispersed solution of C-dots generated from the EC process using electrolytes with a BMIMPF6/3-methylaminopropionitrile volume ratio of 1 : 9 Fig. S3. The effect of pH on the fluorescence intensity (I) of the C-dots; experimental details for detection of Fe3+ in tap water; Fig. S4. Calibration curve for detection of Fe3+ in tap water using the standard addition method. See DOI: 10.1039/c6nr00023a

First-Principles Investigation of Electronic Properties in Sodium-Ion Electrolytes for Solid-State Battery Materials

NASA Astrophysics Data System (ADS)

Rush, Larry E., Jr.

This thesis mainly focuses on characterizing and understanding the electronic properties of sodium-ion electrolytes using first-principles calculations. The core of these calculations is built upon a functional understanding of the relationship between quantum mechanics and the crystalline geometries that contribute to unique properties of materials such as diffusion mechanisms of ions within solid-state materials, conductivity, and ground state structures. The goal of this body of work is to understand how this relationship can give us insight into materials that might have use in an emerging field within battery technology. Sodium-ion solid-state batteries are an auspicious technology because nature has provided us with widely distributed precursor materials in such a way that removes geopolitical constraints in its construction and distribution. This is extremely important to individuals (and a collection of individuals) who want to expedite the wide use of clean and renewable energy from a societal perspective. An example is Morocco's initiative to generate 52% of its total energy consumption from clean and renewable energy sources to eliminate dependencies on foreign countries to supply energy resources. Sodium-ion solid-state batteries are an inexpensive option for large-scale grid storage, so this could play a role in providing a cost-effective option for Morocco. The challenging part is to sift through the large chemical space of sodium-ion solid-state electrolytes to find optimal materials for battery technology, and that is what motivates this body of work.

Insights into the Surface Reactivity of Cermet and Perovskite Electrodes in Oxidizing, Reducing, and Humid Environments.

PubMed

Paloukis, Fotios; Papazisi, Kalliopi M; Dintzer, Thierry; Papaefthimiou, Vasiliki; Saveleva, Viktoriia A; Balomenou, Stella P; Tsiplakides, Dimitrios; Bournel, Fabrice; Gallet, Jean-Jacques; Zafeiratos, Spyridon

2017-08-02

Understanding the surface chemistry of electrode materials under gas environments is important in order to control their performance during electrochemical and catalytic applications. This work compares the surface reactivity of Ni/YSZ and La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , which are commonly used types of electrodes in solid oxide electrochemical devices. In situ synchrotron-based near-ambient pressure photoemission and absorption spectroscopy experiments, assisted by theoretical spectral simulations and combined with microscopy and electrochemical measurements, are used to monitor the effect of the gas atmosphere on the chemical state, the morphology, and the electrical conductivity of the electrodes. It is shown that the surface of both electrode types readjusts fast to the reactive gas atmosphere and their surface composition is notably modified. In the case of Ni/YSZ, this is followed by evident changes in the oxidation state of nickel, while for La 0.75 Sr 0.25 Cr 0.9 Fe 0.1 O 3 , a fine adjustment of the Cr valence and strong Sr segregation is observed. An important difference between the two electrodes is their capacity to maintain adsorbed hydroxyl groups on their surface, which is expected to be critical for the electrocatalytic properties of the materials. The insight gained from the surface analysis may serve as a paradigm for understanding the effect of the gas environment on the electrochemical performance and the electrical conductivity of the electrodes.

NOx Sensor Development

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

Woo, L Y; Glass, R S

NO{sub x} compounds, specifically NO and NO{sub 2}, are pollutants and potent greenhouse gases. Compact and inexpensive NO{sub x} sensors are necessary in the next generation of diesel (CIDI) automobiles to meet government emission requirements and enable the more rapid introduction of more efficient, higher fuel economy CIDI vehicles. Because the need for a NO{sub x} sensor is recent and the performance requirements are extremely challenging, most are still in the development phase. Currently, there is only one type of NO{sub x} sensor that is sold commercially, and it seems unlikely to meet more stringent future emission requirements. Automotive exhaustmore » sensor development has focused on solid-state electrochemical technology, which has proven to be robust for in-situ operation in harsh, high-temperature environments (e.g., the oxygen stoichiometric sensor). Solid-state sensors typically rely on yttria-stabilized zirconia (YSZ) as the oxygen-ion conducting electrolyte and then target different types of metal or metal-oxide electrodes to optimize the response. Electrochemical sensors can be operated in different modes, including amperometric (a current is measured) and potentiometric (a voltage is measured), both of which employ direct current (dc) measurements. Amperometric operation is costly due to the electronics necessary to measure the small sensor signal (nanoampere current at ppm NO{sub x} levels), and cannot be easily improved to meet the future technical performance requirements. Potentiometric operation has not demonstrated enough promise in meeting long-term stability requirements, where the voltage signal drift is thought to be due to aging effects associated with electrically driven changes, both morphological and compositional, in the sensor. Our approach involves impedancemetric operation, which uses alternating current (ac) measurements at a specified frequency. The approach is described in detail in previous reports and several publications. Briefly, impedancemetric operation has shown the potential to overcome the drawbacks of other approaches, including higher sensitivity towards NO{sub x}, better long-term stability, potential for subtracting out background interferences, total NO{sub x} measurement, and lower cost materials and operation. Past LLNL research and development efforts have focused on characterizing different sensor materials and understanding complex sensing mechanisms. Continued effort has led to improved prototypes with better performance, including increased sensitivity (to less than 5 ppm) and long-term stability, with more appropriate designs for mass fabrication, including incorporation of an alumina substrate with an imbedded heater. Efforts in the last year to further improve sensor robustness have led to successful engine dynamometer testing with prototypes mounted directly in the engine manifold. Previous attempts had required exhaust gases to be routed into a separate furnace for testing due to mechanical failure of the sensor from engine vibrations. A more extensive cross-sensitivity study was also undertaken this last year to examine major noise factors including fluctuations in water, oxygen, and temperature. The quantitative data were then used to develop a strategy using numerical algorithms to improve sensor accuracy. The ultimate goal is the transfer of this technology to a supplier for commercialization. Due to the recent economic downturn, suppliers are demanding more comprehensive data and increased performance analysis before committing their resources to take the technology to market. Therefore, our NO{sub x} sensor work requires a level of technology development more thorough and extensive than ever before. The objectives are: (1) Develop an inexpensive, rapid-response, high-sensitivity and selective electrochemical sensor for oxides of nitrogen (NO{sub x}) for compression-ignition, direct-injection (CIDI) exhaust gas monitoring; (2) Explore and characterize novel, effective sensing methodologies based on impedance measurements and designs and manufacturing methods that could be compatible with mass fabrication; and (3) Collaborate with industry in order to (ultimately) transfer the technology to a supplier for commercialization.« less

From Two-Phase to Three-Phase: The New Electrochemical Interface by Oxide Electrocatalysts

NASA Astrophysics Data System (ADS)

Xu, Zhichuan J.

2018-03-01

Electrochemical reactions typically occur at the interface between a solid electrode and a liquid electrolyte. The charge exchange behaviour between these two phases determines the kinetics of electrochemical reactions. In the past few years, significant advances have been made in the development of metal oxide electrocatalysts for fuel cell and electrolyser reactions. However, considerable gaps remain in the fundamental understanding of the charge transfer pathways and the interaction between the metal oxides and the conducting substrate on which they are located. In particular, the electrochemical interfaces of metal oxides are significantly different from the traditional (metal) ones, where only a conductive solid electrode and a liquid electrolyte are considered. Oxides are insulating and have to be combined with carbon as a conductive mediator. This electrode configuration results in a three-phase electrochemical interface, consisting of the insulating oxide, the conductive carbon, and the liquid electrolyte. To date, the mechanistic insights into this kind of non-traditional electrochemical interface remain unclear. Consequently conventional electrochemistry concepts, established on classical electrode materials and their two-phase interfaces, are facing challenges when employed for explaining these new electrode materials. [Figure not available: see fulltext.

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.

A compact 300 kV solid-state high-voltage nanosecond generator for dielectric wall accelerator

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

Shen, Yi; Wang, Wei; Liu, Yi

2015-05-15

Compact solid-state system is the main development trend in pulsed power technologies. A compact solid-state high-voltage nanosecond pulse generator with output voltage of 300 kV amplitude, 10 ns duration (FWHM), and 3 ns rise-time was designed for a dielectric wall accelerator. The generator is stacked by 15 planar-plate Blumlein pulse forming lines (PFL). Each Blumlein PFL consists of two solid-state planar transmission lines, a GaAs photoconductive semiconductor switch, and a laser diode trigger. The key components of the generator and the experimental results are reported in this paper.

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

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

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

Low-cost superior solid-state symmetric supercapacitors based on hematite nanocrystals.

PubMed

Peng, Shaomin; Yu, Lin; Lan, Bang; Sun, Ming; Cheng, Gao; Liao, Shuhuan; Cao, Han; Deng, Yulin

2016-11-22

We present a facile method for the fabrication of hematite nanocrystal-carbon cloth (Fe 2 O 3 -CC) composite. Hierarchical manganite is chosen as the sacrificial precursor, that does not contribute to the component of final iron oxide but can be in situ dissolved by the acid produced from the Fe 3+ hydrolysis. This method effectively enhances the specific surface area and conductivity of hematite (Fe 2 O 3 ) by attaching Fe 2 O 3 nanocrystals (around 5 nm) firmly on the surface of carbon fibers. The obtained Fe 2 O 3 -CC can be directly used as a binder-free electrode for a supercapacitor. Interestingly, the composite electrode exhibits synergistic electrochemical capacitance (electrochemical double-layer capacitance and pseudo-capacitance). It manifests a very high areal capacitance of 1.66 F cm -2 (1660 F g -1 ) at 2 mA cm -2 and excellent cycling performance at large current densities (88.6% retention at 30 mA cm -2 after 5000 cycles) in a three-electrode testing system, which is among the best performances reported in the literature. Importantly, when fabricated as a solid-state flexible symmetric supercapacitor it still shows a maximum energy density of 8.74 mW h cm -3 and power density of 253.9 mW cm -3 . Additionally, its good flexibility makes it suitable for portable devices.

Low-cost superior solid-state symmetric supercapacitors based on hematite nanocrystals

NASA Astrophysics Data System (ADS)

Peng, Shaomin; Yu, Lin; Lan, Bang; Sun, Ming; Cheng, Gao; Liao, Shuhuan; Cao, Han; Deng, Yulin

2016-12-01

We present a facile method for the fabrication of hematite nanocrystal-carbon cloth (Fe2O3-CC) composite. Hierarchical manganite is chosen as the sacrificial precursor, that does not contribute to the component of final iron oxide but can be in situ dissolved by the acid produced from the Fe3+ hydrolysis. This method effectively enhances the specific surface area and conductivity of hematite (Fe2O3) by attaching Fe2O3 nanocrystals (around 5 nm) firmly on the surface of carbon fibers. The obtained Fe2O3-CC can be directly used as a binder-free electrode for a supercapacitor. Interestingly, the composite electrode exhibits synergistic electrochemical capacitance (electrochemical double-layer capacitance and pseudo-capacitance). It manifests a very high areal capacitance of 1.66 F cm-2 (1660 F g-1) at 2 mA cm-2 and excellent cycling performance at large current densities (88.6% retention at 30 mA cm-2 after 5000 cycles) in a three-electrode testing system, which is among the best performances reported in the literature. Importantly, when fabricated as a solid-state flexible symmetric supercapacitor it still shows a maximum energy density of 8.74 mW h cm-3 and power density of 253.9 mW cm-3. Additionally, its good flexibility makes it suitable for portable devices.

Carbon black as an alternative cathode material for electrical energy recovery and transfer in a microbial battery.

PubMed

Zhang, Xueqin; Guo, Kun; Shen, Dongsheng; Feng, Huajun; Wang, Meizhen; Zhou, Yuyang; Jia, Yufeng; Liang, Yuxiang; Zhou, Mengjiao

2017-08-01

Rather than the conventional concept of viewing conductive carbon black (CB) to be chemically inert in microbial electrochemical cells (MECs), here we confirmed the redox activity of CB for its feasibility as an electron sink in the microbial battery (MB). Acting as the cathode of a MB, the solid-state CB electrode showed the highest electron capacity equivalent of 18.58 ± 0.46 C/g for the unsintered one and the lowest capacity of 2.29 ± 0.48 C/g for the one sintered under 100% N 2 atmosphere. The capacity vibrations of CBs were strongly in coincidence with the abundances of C=O moiety caused by different pretreatments and it implied one plausible mechanism based on CB's surface functionality for its electron capturing. Once subjected to electron saturation, CB could be completely regenerated by different strategies in terms of electrochemical discharging or donating electrons to biologically-catalyzed nitrate reduction. Surface characterization also revealed that CB's regeneration fully depended on the reversible shift of C=O moiety, further confirming the functionality-based mechanism for CB's feasibility as the role of MB's cathode. Moreover, resilience tests demonstrated that CB cathode was robust for the multi-cycles charging-discharging operations. These results imply that CB is a promising alternative material for the solid-state cathode in MBs.

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

DOE PAGES

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.; ...

2018-03-30

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

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

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

Physical principles and current status of emerging non-volatile solid state memories

NASA Astrophysics Data System (ADS)

Wang, L.; Yang, C.-H.; Wen, J.

2015-07-01

Today the influence of non-volatile solid-state memories on persons' lives has become more prominent because of their non-volatility, low data latency, and high robustness. As a pioneering technology that is representative of non-volatile solidstate memories, flash memory has recently seen widespread application in many areas ranging from electronic appliances, such as cell phones and digital cameras, to external storage devices such as universal serial bus (USB) memory. Moreover, owing to its large storage capacity, it is expected that in the near future, flash memory will replace hard-disk drives as a dominant technology in the mass storage market, especially because of recently emerging solid-state drives. However, the rapid growth of the global digital data has led to the need for flash memories to have larger storage capacity, thus requiring a further downscaling of the cell size. Such a miniaturization is expected to be extremely difficult because of the well-known scaling limit of flash memories. It is therefore necessary to either explore innovative technologies that can extend the areal density of flash memories beyond the scaling limits, or to vigorously develop alternative non-volatile solid-state memories including ferroelectric random-access memory, magnetoresistive random-access memory, phase-change random-access memory, and resistive random-access memory. In this paper, we review the physical principles of flash memories and their technical challenges that affect our ability to enhance the storage capacity. We then present a detailed discussion of novel technologies that can extend the storage density of flash memories beyond the commonly accepted limits. In each case, we subsequently discuss the physical principles of these new types of non-volatile solid-state memories as well as their respective merits and weakness when utilized for data storage applications. Finally, we predict the future prospects for the aforementioned solid-state memories for the next generation of data-storage devices based on a comparison of their performance. [Figure not available: see fulltext.

Application of Smart Solid State Sensor Technology in Aerospace Applications

NASA Technical Reports Server (NTRS)

Hunter, Gary W.; Xu, Jennifer C.; Dungan, L.K.; Makel, D.; Ward, B.; Androjna, D.

2008-01-01

Aerospace applications require a range of chemical sensing technologies to monitor conditions in both space vehicles and aircraft operations. One example is the monitoring of oxygen. For example, monitoring of ambient oxygen (O2) levels is critical to ensuring the health, safety, and performance of humans living and working in space. Oxygen sensors can also be incorporated in detection systems to determine if hazardous leaks are occurring in space propulsion systems and storage facilities. In aeronautic applications, O2 detection has been investigated for fuel tank monitoring. However, as noted elsewhere, O2 is not the only species of interest in aerospace applications with a wide range of species of interest being relevant to understand an environmental or vehicle condition. These include combustion products such as CO, HF, HCN, and HCl, which are related to both the presence of a fire and monitoring of post-fire clean-up operations. This paper discusses the development of an electrochemical cell platform based on a polymer electrolyte, NAFION, and a three-electrode configuration. The approach has been to mature this basic platform for a range of applications and to test this system, combined with "Lick and Stick" electronics, for its viability to monitor an environment related to astronaut crew health and safety applications with an understanding that a broad range of applications can be addressed with a core technology.

Solid-state X-band Combiner Study

NASA Technical Reports Server (NTRS)

Pitzalis, O., Jr.; Russell, K. J.

1979-01-01

The feasibility of developing solid-state amplifiers at 4 and 10 GHz for application in spacecraft altimeters was studied. Bipolar-transistor, field-effect-transistor, and Impatt-diode amplifier designs based on 1980 solid-state technology are investigated. Several output power levels of the pulsed, low-duty-factor amplifiers are considered at each frequency. Proposed transistor and diode amplifier designs are illustrated in block diagrams. Projections of size, weight, and primary power requirements are given for each design.

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Clean Energy Manufacturing Initiative Solid-State Lighting

ScienceCinema

Thomas, Sunil; Edmond, John; Krames, Michael; Rama

2018-05-30

The importance of U.S. manufacturing for clean energy technologies, such as solid-state lighting (SSL), is paramount to increasing competitiveness in a global marketplace. SSLs are poised to drive the lighting market, worldwide. In order to continue that competitiveness and support further innovation, the time to invest in U.S. manufacturing of clean energy technologies is now. Across the country, companies developing innovative clean energy technologies find competitive advantages to manufacturing in the U.S. The Department of Energy's Building Technology Office SSL Manufacturing Roadmap is just one example of how we support manufacturing through convening industry perspectives on opportunities to significantly reduce risk, improve quality, increase yields, and lower costs.

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

NASA Astrophysics Data System (ADS)

Kitaura, Hirokazu; Zhou, Haoshen

2015-08-01

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g-1 at 10 mA g-1 (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step.

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range

PubMed Central

Kitaura, Hirokazu; Zhou, Haoshen

2015-01-01

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g−1 at 10 mA g−1 (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step. PMID:26293134

All-solid-state lithium-oxygen battery with high safety in wide ambient temperature range.

PubMed

Kitaura, Hirokazu; Zhou, Haoshen

2015-08-21

There is need to develop high energy storage devices with high safety to satisfy the growing industrial demands. Here, we show the potential to realize such batteries by assembling a lithium-oxygen cell using an inorganic solid electrolyte without any flammable liquid or polymer materials. The lithium-oxygen battery using Li1.575Al0.5Ge1.5(PO4)3 solid electrolyte was examined in the pure oxygen atmosphere from room temperature to 120 °C. The cell works at room temperature and first full discharge capacity of 1420 mAh g(-1) at 10 mA g(-1) (based on the mass of carbon material in the air electrode) was obtained. The charge curve started from 3.0 V, and that the majority of it lay below 4.2 V. The cell also safely works at high temperature over 80 °C with the improved battery performance. Furthermore, fundamental data of the electrochemical performance, such as cyclic voltammogram, cycle performance and rate performance was obtained and this work demonstrated the potential of the all-solid-state lithium-oxygen battery for wide temperature application as a first step.

Next-Generation Electrochemical Energy Materials for Intermediate Temperature Molten Oxide Fuel Cells and Ion Transport Molten Oxide Membranes.

PubMed

Belousov, Valery V

2017-02-21

High temperature electrochemical devices such as solid oxide fuel cells (SOFCs) and oxygen separators based on ceramic materials are used for efficient energy conversion. These devices generally operate in the temperature range of 800-1000 °C. The high operating temperatures lead to accelerated degradation of the SOFC and oxygen separator materials. To solve this problem, the operating temperatures of these electrochemical devices must be lowered. However, lowering the temperature is accompanied by decreasing the ionic conductivity of fuel cell electrolyte and oxygen separator membrane. Therefore, there is a need to search for alternative electrolyte and membrane materials that have high ionic conductivity at lower temperatures. A great many opportunities exist for molten oxides as electrochemical energy materials. Because of their unique electrochemical properties, the molten oxide innovations can offer significant benefits for improving energy efficiency. In particular, the newly developed electrochemical molten oxide materials show high ionic conductivities at intermediate temperatures (600-800 °C) and could be used in molten oxide fuel cells (MOFCs) and molten oxide membranes (MOMs). The molten oxide materials containing both solid grains and liquid channels at the grain boundaries have advantages compared to the ceramic materials. For example, the molten oxide materials are ductile, which solves a problem of thermal incompatibility (difference in coefficient of thermal expansion, CTE). Besides, the outstanding oxygen selectivity of MOM materials allows us to separate ultrahigh purity oxygen from air. For their part, the MOFC electrolytes show the highest ionic conductivity at intermediate temperatures. To evaluate the potential of molten oxide materials for technological applications, the relationship between the microstructure of these materials and their transport and mechanical properties must be revealed. This Account summarizes the latest results on oxygen ion transport in potential MOM materials and MOFC electrolytes. In addition, we consider the rapid oxygen transport in a molten oxide scale formed on a metal surface during catastrophic oxidation and show that the same transport could be used beneficially in MOMs and MOFCs. A polymer model explaining the oxygen transport in molten oxides is also considered. Understanding the oxygen transport mechanisms in oxide melts is important for the development of new generation energy materials, which will contribute to more efficient operation of electrochemical devices at intermediate temperatures. Here we highlight the progress made in developing this understanding. We also show the latest advances made in search of alternative molten oxide materials having high mixed ion electronic and ionic conductivities for use in MOMs and MOFCs, respectively. Prospects for further research are presented.