Method for in situ carbon deposition measurement for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Kuhn, J.; Kesler, O.

2014-01-01

Previous methods to measure carbon deposition in solid oxide fuel cell (SOFC) anodes do not permit simultaneous electrochemical measurements. Electrochemical measurements supplemented with carbon deposition quantities create the opportunity to further understand how carbon affects SOFC performance and electrochemical impedance spectra (EIS). In this work, a method for measuring carbon in situ, named here as the quantification of gasified carbon (QGC), was developed. TGA experiments showed that carbon with a 100 h residence time in the SOFC was >99.8% gasified. Comparison of carbon mass measurements between the TGA and QGC show good agreement. In situ measurements of carbon deposition in SOFCs at varying molar steam/carbon ratios were performed to further validate the QGC method, and suppression of carbon deposition with increasing steam concentration was observed, in agreement with previous studies. The technique can be used to investigate in situ carbon deposition and gasification behavior simultaneously with electrochemical measurements for a variety of fuels and operating conditions, such as determining conditions under which incipient carbon deposition is reversible.

Electrochemical vapor deposition of semiconductors from gas phase with a solid membrane cell.

PubMed

Cho, Sung Ki; Fan, Fu-Ren F; Bard, Allen J

2015-05-27

We demonstrate the feasibility of semiconductor deposition via the electrochemical reduction of gaseous precursors by the use of an anhydrous proton-conducting membrane, the solid acid CsHSO4, at 165 °C. This membrane electrode assembly was operated within the oxidation of hydrogen on a porous Pt anode and the deposition of Si or Ge under bias at the cathode from chloride-based gaseous precursors; SiCl4 and GeCl4 in an Ar flow with a reduction potential over -1.0 V (vs RHE).

Real-time thermal imaging of solid oxide fuel cell cathode activity in working condition.

PubMed

Montanini, Roberto; Quattrocchi, Antonino; Piccolo, Sebastiano A; Amato, Alessandra; Trocino, Stefano; Zignani, Sabrina C; Faro, Massimiliano Lo; Squadrito, Gaetano

2016-09-01

Electrochemical methods such as voltammetry and electrochemical impedance spectroscopy are effective for quantifying solid oxide fuel cell (SOFC) operational performance, but not for identifying and monitoring the chemical processes that occur on the electrodes' surface, which are thought to be strictly related to the SOFCs' efficiency. Because of their high operating temperature, mechanical failure or cathode delamination is a common shortcoming of SOFCs that severely affects their reliability. Infrared thermography may provide a powerful tool for probing in situ SOFC electrode processes and the materials' structural integrity, but, due to the typical design of pellet-type cells, a complete optical access to the electrode surface is usually prevented. In this paper, a specially designed SOFC is introduced, which allows temperature distribution to be measured over all the cathode area while still preserving the electrochemical performance of the device. Infrared images recorded under different working conditions are then processed by means of a dedicated image processing algorithm for quantitative data analysis. Results reported in the paper highlight the effectiveness of infrared thermal imaging in detecting the onset of cell failure during normal operation and in monitoring cathode activity when the cell is fed with different types of fuels.

Real-time electrochemical impedance spectroscopy diagnosis of the solid oxide fuel cell for marine power applications

NASA Astrophysics Data System (ADS)

Nakajima, Hironori; Kitahara, Tatsumi

2017-11-01

We have investigated the behavior of an operating solid oxide fuel cell (SOFC) with supplying a simulated syngas to develop diagnosis method of the SOFC for marine power applications fueled with liquefied natural gas (LNG). We analyze the characteristics of a syngas-fueled intermediate temperature microtubular SOFC at 500 ∘C for accelerated deterioration by carbon deposition as a model case by electrochemical impedance spectroscopy (EIS) to in-situ find parameters useful for the real-time diagnosis. EIS analyses are performed by complex nonlinear least squares (CNLS) curve fitting to measured impedance spectra with an equivalent electric circuit model consisting of several resistances and capacitances attributed to the anode and cathode processes as well as Ohmic resistance of the cell. The characteristic changes of those circuit parameters by internal reforming and anode degradation are extracted, showing that they can be used for the real-time diagnosis of operating SOFCs.

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

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.

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.

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.

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.

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

Detailed Multi-dimensional Modeling of Direct Internal Reforming Solid Oxide Fuel Cells.

PubMed

Tseronis, K; Fragkopoulos, I S; Bonis, I; Theodoropoulos, C

2016-06-01

Fuel flexibility is a significant advantage of solid oxide fuel cells (SOFCs) and can be attributed to their high operating temperature. Here we consider a direct internal reforming solid oxide fuel cell setup in which a separate fuel reformer is not required. We construct a multidimensional, detailed model of a planar solid oxide fuel cell, where mass transport in the fuel channel is modeled using the Stefan-Maxwell model, whereas the mass transport within the porous electrodes is simulated using the Dusty-Gas model. The resulting highly nonlinear model is built into COMSOL Multiphysics, a commercial computational fluid dynamics software, and is validated against experimental data from the literature. A number of parametric studies is performed to obtain insights on the direct internal reforming solid oxide fuel cell system behavior and efficiency, to aid the design procedure. It is shown that internal reforming results in temperature drop close to the inlet and that the direct internal reforming solid oxide fuel cell performance can be enhanced by increasing the operating temperature. It is also observed that decreases in the inlet temperature result in smoother temperature profiles and in the formation of reduced thermal gradients. Furthermore, the direct internal reforming solid oxide fuel cell performance was found to be affected by the thickness of the electrochemically-active anode catalyst layer, although not always substantially, due to the counter-balancing behavior of the activation and ohmic overpotentials.

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.

High-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells

NASA Astrophysics Data System (ADS)

Kim, Si-Won; Bae, Yonggyun; Yoon, Kyung Joong; Lee, Jong-Ho; Lee, Jong-Heun; Hong, Jongsup

2018-02-01

To mitigate CO2 emissions, its reduction by high-temperature electrolysis using solid oxide cells is extensively investigated, for which excessive steam supply is assumed. However, such condition may degrade its feasibility due to massive energy required for generating hot steam, implying the needs for lowering steam demand. In this study, high-temperature electrolysis of CO2-enriched mixtures by using fuel-electrode supported La0.6Sr0.4CoO3/YSZ/Ni-YSZ solid oxide cells is considered to satisfy such needs. The effect of internal and external steam supply on its electrochemical performance and gas productivity is elucidated. It is shown that the steam produced in-situ inside the fuel-electrode by a reverse water gas shift reaction may decrease significantly the electrochemical resistance of dry CO2-fed operations, attributed to self-sustaining positive thermo-electrochemical reaction loop. This mechanism is conspicuous at low current density, whereas it is no longer effective at high current density in which total reactant concentrations for electrolysis is critical. To overcome such limitations, a small amount of external steam supply to the CO2-enriched feed stream may be needed, but this lowers the CO2 conversion and CO/H2 selectivity. Based on these results, it is discussed that there can be minimum steam supply sufficient for guaranteeing both low electrochemical resistance and high gas productivity.

Metal current collect protected by oxide film

DOEpatents

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

2004-05-25

Provided are low-cost, mechanically strong, highly electronically conductive current collects and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical devices having as current interconnects a ferritic steel felt or screen coated with a protective oxide film.

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

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.)

3D CFD ELECTROCHEMICAL AND HEAT TRANSFER MODEL OF AN INTERNALLY MANIFOLDED SOLID OXIDE ELECTROLYSIS CELL

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

Grant L. Hawkes; James E. O'Brien; Greg Tao

2011-11-01

A three-dimensional computational fluid dynamics (CFD) electrochemical model has been created to model high-temperature electrolysis cell performance and steam electrolysis in an internally manifolded planar solid oxide electrolysis cell (SOEC) stack. This design is being evaluated at the Idaho National Laboratory for hydrogen production from nuclear power and process heat. Mass, momentum, energy, and species conservation and transport are provided via the core features of the commercial CFD code FLUENT. A solid-oxide fuel cell (SOFC) model adds the electrochemical reactions and loss mechanisms and computation of the electric field throughout the cell. The FLUENT SOFC user-defined subroutine was modified formore » this work to allow for operation in the SOEC mode. Model results provide detailed profiles of temperature, operating potential, steam-electrode gas composition, oxygen-electrode gas composition, current density and hydrogen production over a range of stack operating conditions. Single-cell and five-cell results will be presented. Flow distribution through both models is discussed. Flow enters from the bottom, distributes through the inlet plenum, flows across the cells, gathers in the outlet plenum and flows downward making an upside-down ''U'' shaped flow pattern. Flow and concentration variations exist downstream of the inlet holes. Predicted mean outlet hydrogen and steam concentrations vary linearly with current density, as expected. Effects of variations in operating temperature, gas flow rate, oxygen-electrode and steam-electrode current density, and contact resistance from the base case are presented. Contour plots of local electrolyte temperature, current density, and Nernst potential indicate the effects of heat transfer, reaction cooling/heating, and change in local gas composition. Results are discussed for using this design in the electrolysis mode. Discussion of thermal neutral voltage, enthalpy of reaction, hydrogen production, cell thermal efficiency, cell electrical efficiency, and Gibbs free energy are discussed and reported herein.« less

Ultra-thin solid oxide fuel cells: Materials and devices

NASA Astrophysics Data System (ADS)

Kerman, Kian

Solid oxide fuel cells are electrochemical energy conversion devices utilizing solid electrolytes transporting O2- that typically operate in the 800 -- 1000 °C temperature range due to the large activation barrier for ionic transport. Reducing electrolyte thickness or increasing ionic conductivity can enable lower temperature operation for both stationary and portable applications. This thesis is focused on the fabrication of free standing ultrathin (<100 nm) oxide membranes of prototypical O 2- conducting electrolytes, namely Y2O3-doped ZrO2 and Gd2O3-doped CeO2. Fabrication of such membranes requires an understanding of thin plate mechanics coupled with controllable thin film deposition processes. Integration of free standing membranes into proof-of-concept fuel cell devices necessitates ideal electrode assemblies as well as creative processing schemes to experimentally test devices in a high temperature dual environment chamber. We present a simple elastic model to determine stable buckling configurations for free standing oxide membranes. This guides the experimental methodology for Y 2O3-doped ZrO2 film processing, which enables tunable internal stress in the films. Using these criteria, we fabricate robust Y2O3-doped ZrO2 membranes on Si and composite polymeric substrates by semiconductor and micro-machining processes, respectively. Fuel cell devices integrating these membranes with metallic electrodes are demonstrated to operate in the 300 -- 500 °C range, exhibiting record performance at such temperatures. A model combining physical transport of electronic carriers in an insulating film and electrochemical aspects of transport is developed to determine the limits of performance enhancement expected via electrolyte thickness reduction. Free standing oxide heterostructures, i.e. electrolyte membrane and oxide electrodes, are demonstrated. Lastly, using Y2O3-doped ZrO2 and Gd2O 3-doped CeO2, novel electrolyte fabrication schemes are explored to develop oxide alloys and nanoscale compositionally graded membranes that are thermomechanically robust and provide added interfacial functionality. The work in this thesis advances experimental state-of-the-art with respect to solid oxide fuel cell operation temperature, provides fundamental boundaries expected for ultrathin electrolytes, develops the ability to integrate highly dissimilar material (such as oxide-polymer) heterostructures, and introduces nanoscale compositionally graded electrolyte membranes that can lead to monolithic materials having multiple functionalities.

Implications of electronic short circuiting in plasma sprayed solid oxide fuel cells on electrode performance evaluation by electrochemical impedance spectroscopy

NASA Astrophysics Data System (ADS)

White, B. D.; Kesler, O.

Electronic short circuiting of the electrolyte in a solid oxide fuel cell (SOFC) arising from flaws in the plasma spray fabrication process has been found to have a significant effect on the perceived performance of the electrodes, as evaluated by electrochemical impedance spectroscopy (EIS). The presence of a short circuit has been found to lead to the underestimation of the electrode polarization resistance (R p) and hence an overestimation of electrode performance. The effect is particularly noticeable when electrolyte resistance is relatively high, for example during low to intermediate temperature operation, leading to an obvious deviation from the expected Arrhenius-type temperature dependence of R p. A method is developed for determining the real electrode performance from measurements of various cell properties, and strategies for eliminating the occurrence of short circuiting in plasma sprayed cells are identified.

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.

High performance cermet electrodes

DOEpatents

Isenberg, Arnold O.; Zymboly, Gregory E.

1986-01-01

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

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.

Fuel cell generator containing a gas sealing means

DOEpatents

Makiel, J.M.

1987-02-03

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

Inkjet-Printed Porous Silver Thin Film as a Cathode for a Low-Temperature Solid Oxide Fuel Cell.

PubMed

Yu, Chen-Chiang; Baek, Jong Dae; Su, Chun-Hao; Fan, Liangdong; Wei, Jun; Liao, Ying-Chih; Su, Pei-Chen

2016-04-27

In this work we report a porous silver thin film cathode that was fabricated by a simple inkjet printing process for low-temperature solid oxide fuel cell applications. The electrochemical performance of the inkjet-printed silver cathode was studied at 300-450 °C and was compared with that of silver cathodes that were fabricated by the typical sputtering method. Inkjet-printed silver cathodes showed lower electrochemical impedance due to their porous structure, which facilitated oxygen gaseous diffusion and oxygen surface adsorption-dissociation reactions. A typical sputtered nanoporous silver cathode became essentially dense after the operation and showed high impedance due to a lack of oxygen supply. The results of long-term fuel cell operation show that the cell with an inkjet-printed cathode had a more stable current output for more than 45 h at 400 °C. A porous silver cathode is required for high fuel cell performance, and the simple inkjet printing technique offers an alternative method of fabrication for such a desirable porous structure with the required thermal-morphological stability.

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.

Application of the monolithic solid oxide fuel cell to space power systems

NASA Astrophysics Data System (ADS)

Myles, Kevin M.; Bhattacharyya, Samit K.

1991-01-01

The monolithic solid-oxide fuel cell (MSOFC) is a promising electrochemical power generation device that is currently under development at Argonne National Laboratory. The extremely high power density of the MSOFC leads to MSOFC systems that have sufficiently high energy densities that they are excellent candidates for a number of space missions. The fuel cell can also be operated in reverse, if it can be coupled to an external power source, to regenerate the fuel and oxidant from the water product. This feature further enhances the potential mission applications of the MSOFC. In this paper, the current status of the fuel cell development is presented—the focus being on fabrication and currently achievable performance. In addition, a specific example of a space power system, featuring a liquid metal cooled fast spectrum nuclear reactor and a monolithic solid oxide fuel cell, is presented to demonstrate the features of an integrated system.

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.

Electrochemical enhancement of nitric oxide removal from simulated lean-burn engine exhaust via solid oxide fuel cells.

PubMed

Huang, Ta-Jen; Wu, Chung-Ying; Lin, Yu-Hsien

2011-07-01

A solid oxide fuel cell (SOFC) unit is constructed with Ni-YSZ as the anode, YSZ as the electrolyte, and La(0.6)Sr(0.4)CoO(3)-Ce(0.9)Gd(0.1)O(1.95) as the cathode. The SOFC operation is performed at 600 °C with a cathode gas simulating the lean-burn engine exhaust and at various fixed voltage, at open-circuit voltage, and with an inert gas flowing over the anode side, respectively. Electrochemical enhancement of NO decomposition occurs when an operating voltage is generated; higher O(2) concentration leads to higher enhancement. Smaller NO concentration results in larger NO conversion. Higher operating voltage and higher O(2) concentration can lead to both higher NO conversion and lower fuel consumption. The molar rate of the consumption of the anode fuel can be very much smaller than that of NO to N(2) conversion. This makes the anode fuel consumed in the SOFC-DeNO(x) process to be much less than the equivalent amount of ammonia consumed in the urea-based selective catalytic reduction process. Additionally, the NO conversion increases with the addition of propylene and SO(2) into the cathode gas. These are beneficial for the application of the SOFC-DeNO(x) technology on treating diesel and other lean-burn engine exhausts.

Innovative oxide materials for electrochemical energy conversion and oxygen separation

NASA Astrophysics Data System (ADS)

Belousov, V. V.

2017-10-01

Ion-conducting solid metal oxides are widely used in high-temperature electrochemical devices for energy conversion and oxygen separation. However, liquid metal oxides possessing unique electrochemical properties still remain of limited use. The review demonstrates the potential for practical applications of molten oxides. The transport properties of molten oxide materials are discussed. The emphasis is placed on the chemical diffusion of oxygen in the molten oxide membrane materials for electrochemical energy conversion and oxygen separation. The thermodynamics of these materials is considered. The dynamic polymer chain model developed to describe the oxygen ion transport in molten oxides is discussed. Prospects for further research into molten oxide materials are outlined. The bibliography includes 145 references.

Elementary reaction modeling of reversible CO/CO2 electrochemical conversion on patterned nickel electrodes

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Li, Wenying; Cai, Ningsheng

2018-03-01

CO/CO2 are the major gas reactant/product in the fuel electrode of reversible solid oxide cells (RSOC). This study proposes a two-charge-transfer-step mechanism to describe the reaction and transfer processes of CO-CO2 electrochemical conversion on a patterned Ni electrode of RSOC. An elementary reaction model is developed to couple two charge transfer reactions, C(Ni)+O2-(YSZ) ↔ CO(Ni)+(YSZ) +2e- and CO(Ni)+O2-(YSZ) ↔ CO2(Ni)+(YSZ)+2e-, with adsorption/desorption, surface chemical reactions and surface diffusion. This model well validates in both solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes by the experimental data from a patterned Ni electrode with 10 μm stripe width at different pCO (0-0.25 atm), pCO2 (0-0.35 atm) and operating temperature (600-700 °C). This model indicates SOEC mode is dominated by charge transfer step C(Ni)+O2-(YSZ)↔CO(Ni)+(YSZ) +2e-, while SOFC mode by CO(Ni)+ O2-(YSZ)↔CO2(Ni)+(YSZ)+2e- on the patterned Ni electrode. The sensitivity analysis shows charge transfer step is the major rate-determining step for RSOC, besides, surface diffusion of CO and CO2 as well as CO2 adsorption also plays a significant role in the electrochemical reaction of SOEC while surface diffusion of CO and CO2 desorption could be co-limiting in SOFC.

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.

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.

Investigation into the effects of sulfur on syngas reforming inside a solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Li, Ting Shuai; Xu, Min; Gao, Chongxin; Wang, Baoqing; Liu, Xiyun; Li, Baihai; Wang, Wei Guo

2014-07-01

The electrochemical performance and long-term durability of a solid oxide fuel cell have been evaluated with a simulated coal syngas containing 2 ppm H2S as fuel. The resulting impedance spectra indicate that no observable power loss is caused by the addition of 2 ppm H2S, and the cell shows stability of nearly 500 h at 0.625 A cm-2. The composition of mixed gas is analyzed both at a current load of 0.625 A cm-2 and open circuit state. Hydrogen and carbon monoxide are directly consumed as fuels at the anode side, whereas methane stays unchanged during the operation. It seems the internal carbohydrate reforming and impurity poisoning interacts and weakens the poisoning effects. The oxidation of H2 and the water gas shift reaction take advantages over methane reforming at the cell operational conditions.

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.

Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan J.; Sookhakian, Mehran; Baradaran, Saeid; Mahmoudian, Mohammad R.; Ebadi, Mehdi

2013-09-01

Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO.

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.

Surface protected lithium-metal-oxide electrodes

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho

2016-04-05

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

Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

DOEpatents

Borglum, Brian P.; Bessette, Norman F.

2000-01-01

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

Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1989-01-01

An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Oxide modified air electrode surface for high temperature electrochemical cells

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.

1992-01-01

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

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

NASA Astrophysics Data System (ADS)

Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

2011-07-01

The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

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.

Insights into electrochemical reactions from ambient pressure photoelectron spectroscopy.

PubMed

Stoerzinger, Kelsey A; Hong, Wesley T; Crumlin, Ethan J; Bluhm, Hendrik; Shao-Horn, Yang

2015-11-17

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces. X-ray photoelectron spectroscopy (XPS), also known as ESCA (electron spectroscopy for chemical analysis), has been used as a quantitative spectroscopic technique that measures the elemental composition, as well as chemical and electronic state of a material. Building from extensive ex situ characterization of electrochemical systems, initial in situ studies were conducted at or near ultrahigh vacuum (UHV) conditions (≤10(-6) Torr) to probe solid-state electrochemical systems. However, through the integration of differential-pumping stages, XPS can now operate at pressures in the torr range, comprising a technique called ambient pressure XPS (AP-XPS). In this Account, we briefly review the working principles and current status of AP-XPS. We use several recent in situ studies on model electrochemical components as well as operando studies performed by our groups at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory to illustrate that AP-XPS is both a chemically and an electrically specific tool since photoelectrons carry information on both the local chemistry and electrical potentials. The applications of AP-XPS to oxygen electrocatalysis shown in this Account span well-defined studies of (1) the oxide/oxygen gas interface, (2) the oxide/water vapor interface, and (3) operando measurements of half and full electrochemical cells. Using specially designed model devices, we can expose and isolate the electrode or interface of interest to the incident X-ray beam and AP-XPS analyzer to relate the electrical potentials to the composition/chemical state of the key components and interfaces. We conclude with an outlook on new developments of AP-XPS end stations, which may provide significant improvement in the observation of dynamics over a wide range of time scales, higher spatial resolution, and improved characterization of boundary or interface layers (solid/solid and liquid/solid).

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.

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.

High Performance Nano-Crystalline Oxide Fuel Cell Materials. Defects, Structures, Interfaces, Transport, and Electrochemistry

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

Barnett, Scott; Poeppelmeier, Ken; Mason, Tom

This project addresses fundamental materials challenges in solid oxide electrochemical cells, devices that have a broad range of important energy applications. Although nano-scale mixed ionically and electronically conducting (MIEC) materials provide an important opportunity to improve performance and reduce device operating temperature, durability issues threaten to limit their utility and have remained largely unexplored. Our work has focused on both (1) understanding the fundamental processes related to oxygen transport and surface-vapor reactions in nano-scale MIEC materials, and (2) determining and understanding the key factors that control their long-term stability. Furthermore, materials stability has been explored under the “extreme” conditions encounteredmore » in many solid oxide cell applications, i.e, very high or very low effective oxygen pressures, and high current density.« less

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M [Columbus, OH; Swartz, Scott L [Columbus, OH

2009-09-22

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M.; Swartz, Scott L.

2005-09-20

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

In situ, simultaneous thermal imaging and infrared molecular emission studies of solid oxide fuel cell electrodes

NASA Astrophysics Data System (ADS)

Kirtley, J. D.; Qadri, S. N.; Steinhurst, D. A.; Owrutsky, J. C.

2016-12-01

Various in situ probes of solid oxide fuel cells (SOFCs) have advanced recently to provide detailed, real time data regarding materials and chemical processes that relate to device performance and degradation. These techniques offer insights into complex fuel chemistry at the anode in particular, especially in the context of model predictions. However, cell-to-cell variations can hinder mechanistic interpretations of measurements from separate, independent techniques. The present study describes an in situ technique that for the first time simultaneously measures surface temperature changes using near infrared thermal imaging and gas species using Fourier-transform infrared emission spectra at the anodes of operating SOFCs. Electrolyte-supported SOFCs with Ni-based anodes are operated at 700 °C with internal, dry-reformed methane at 75% maximum current and at open circuit voltage (OCV) while electrochemical and optical measurements are collected. At OCV, more cooling is observed coincident with more CO reforming products. Under load, CO decreases while the anode cools less, especially near the current collectors. The extent of cooling is more sensitive to polarization for electrolyte-supported cells because their anodes are thinner relative to anode-supported cells. This study exemplifies how this duplex technique can be a useful probe of electrochemical processes in SOFCs.

Electrochemical catalyst recovery method

DOEpatents

Silva, L.J.; Bray, L.A.

1995-05-30

A method of recovering catalyst material from latent catalyst material solids includes: (a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; (b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; (c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and (d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications. 3 figs.

Electrochemical catalyst recovery method

DOEpatents

Silva, Laura J.; Bray, Lane A.

1995-01-01

A method of recovering catalyst material from latent catalyst material solids includes: a) combining latent catalyst material solids with a liquid acid anolyte solution and a redox material which is soluble in the acid anolyte solution to form a mixture; b) electrochemically oxidizing the redox material within the mixture into a dissolved oxidant, the oxidant having a potential for oxidation which is effectively higher than that of the latent catalyst material; c) reacting the oxidant with the latent catalyst material to oxidize the latent catalyst material into at least one oxidized catalyst species which is soluble within the mixture and to reduce the oxidant back into dissolved redox material; and d) recovering catalyst material from the oxidized catalyst species of the mixture. The invention is expected to be particularly useful in recovering spent catalyst material from petroleum hydroprocessing reaction waste products having adhered sulfides, carbon, hydrocarbons, and undesired metals, and as well as in other industrial applications.

Aqueous Electrochemical Mechanisms in Actinide Residue Processing

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

Morris, David E.; Burns, Carol J.; Smith, Wayne H.

2000-12-31

Plutonium and uranium residues (e.g., incinerator ash, combustibles, and sand/slag/crucibles) resulting from the purification and processing of nuclear materials constitute an enormous volume of ''lean'' processing waste and represent a significant fraction of the U. S. Department of Energy's (DOE) legacy waste from fifty years of nuclear weapons production activities. Much of this material is presently in storage at sites throughout the DOE weapons production complex (most notably Rocky Flats, Savannah River and Hanford) awaiting further processing and/or final disposition. The chemical and physical stability of much of this material has been called into question recently by the Defense Nuclearmore » Facility Safety Board (DNFSB) and resulted in the issuance of a mandate by the DNFSB to undertake a program to stabilize these materials [1]. The ultimate disposition for much of these materials is anticipated to be geologic repositories such as the proposed Waste Isolation Pilot Plant in New Mexico. However, in light of the mandate to stabilize existing residues and the probable concomitant increase in the volume of material to be disposed as a result of stabilization (e.g., from repackaging at lower residue densities), the projected storage volume for these wastes within anticipated geologic repositories will likely be exceeded simply to handle existing wastes. Additional processing of some of these residue waste streams to reduce radionuclide activity levels, matrix volume, or both is a potentially important strategy to achieve both stabilization and volume reduction so that the anticipated geologic repositories will provide adequate storage volume. In general, the plutonium and uranium that remains in solid residue materials exists in a very stable chemical form (e.g., as binary oxides), and the options available to remove the actinides are limited. However, there have been some demonstrated successes in this vain using aqueous phase electrochemical methods such as the Catalyzed Electrochemical Plutonium Oxide Dissolution (CEPOD) process pioneered by workers at Pacific Northwest National Laboratory in the mid-1970s [2]. The basis for most of these mediated electrochemical oxidation/reduction (MEO/R) processes is the generation of a dissolved electrochemical catalyst, such as Ag2+, which is capable of oxidizing or reducing solid-phase actinide species or actinide sorbates via 7 heterogeneous electron transfer to oxidation states that have significantly greater solubilities (e.g., PuO2(s) to PuO2 2+ (dissolved)). The solubilized actinide can then be recovered by ion exchange or other mechanisms. These aqueous electrochemical methods for residue treatment have been considered in many of the ''trade studies'' to evaluate options for stabilization of the various categories of residue materials. While some concerns generally arise (e.g., large secondary waste volumes could results since the process stream normally goes th rough anion exchange or precipitation steps to remove the actinide), the real utility and versatility of these methods should not be overlooked. They are low temperature, ambient pressure processes that operate in a non-corrosive environment. In principle, they can be designed to be highly selective for the actinides (i.e., no substrate degradation occurs), they can be utilized for many categories of residue materials with little or no modification in hardware or operating conditions, and they can conceivably be engineered to minimize secondary waste stream volume. However, some fundamental questions remain concerning the mechanisms through which these processes act, and how the processes might be optimized to maximize efficiency while minimizing secondary waste. In addition, given the success achieved to date on the limited set of residues, further research is merited to extend the range of applicability of these electrochemical methods to other residue and waste streams. The principal goal of the work described here is to develop a fundamental understanding of the heterogeneous electron transfer thermodynamics and kinetics that lie at the heart of the MEO/R processes for actinide solids and actinide species entrained in or surface-bound to residue substrates. This has been accomplished as described in detail below through spectroscopic characterization of actinide-bearing substrates and electrochemical investigations of electron transfer reactions between uranium- and plutonium- (or surrogates) bearing solids (dispersed actinide solid phases and actinides sorbed to inorganic and organic colloids) and polarizable electrode materials. In general, the actinide solids or substrate-supported species were chosen to represent relevant residue materials (e.g., incinerator ash, sand/slag/crucible, and combustibles).« less

High temperature lithium cells with solid polymer electrolytes

DOEpatents

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

2017-03-07

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

Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

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

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.

A High-Performing Direct Carbon Fuel Cell with a 3D Architectured Anode Operated Below 600 °C.

PubMed

Wu, Wei; Zhang, Yunya; Ding, Dong; He, Ting

2018-01-01

Direct carbon fuel cells (DCFCs) are highly efficient power generators fueled by abundant and cheap solid carbons. However, the limited triple-phase boundaries (TPBs) in the fuel electrode, due to the lack of direct contact among carbon, electrode, and electrolyte, inhibit the performance and result in poor fuel utilization. To address the challenges of low carbon oxidation activity and low carbon utilization, a highly efficient, 3D solid-state architected anode is developed to enhance the performance of DCFCs below 600 °C. The cell with the 3D textile anode framework, Gd:CeO 2 -Li/Na 2 CO 3 composite electrolyte, and Sm 0.5 Sr 0.5 CoO 3 cathode demonstrates excellent performance with maximum power densities of 143, 196, and 325 mW cm -2 at 500, 550, and 600 °C, respectively. At 500 °C, the cells can be operated steadily with a rated power density of ≈0.13 W cm -2 at a constant current density of 0.15 A cm -2 with a carbon utilization over 85.5%. These results, for the first time, demonstrate the feasibility of directly electrochemical oxidation of solid carbon at 500-600 °C, representing a promising strategy in developing high-performing fuel cells and other electrochemical systems via the integration of 3D architected electrodes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on the influences of reduction temperature on nickel-yttria-stabilized zirconia solid oxide fuel cell anode using nickel oxide-film electrode

NASA Astrophysics Data System (ADS)

Jiao, Zhenjun; Ueno, Ai; Suzuki, Yuji; Shikazono, Naoki

2016-10-01

In this study, the reduction processes of nickel oxide at different temperatures were investigated using nickel-film anode to study the influences of reduction temperature on the initial performances and stability of nickel-yttria-stabilized zirconia anode. Compared to conventional nickel-yttria-stabilized zirconia composite cermet anode, nickel-film anode has the advantage of direct observation at nickel-yttria-stabilized zirconia interface. The microstructural changes were characterized by scanning electron microscopy. The reduction process of nickel oxide is considered to be determined by the competition between the mechanisms of volume reduction in nickel oxide-nickel reaction and nickel sintering. Electrochemical impedance spectroscopy was applied to analyze the time variation of the nickel-film anode electrochemical characteristics. The anode performances and microstructural changes before and after 100 hours discharging and open circuit operations were analyzed. The degradation of nickel-film anode is considered to be determined by the co-effect between the nickel sintering and the change of nickel-yttria-stabilized zirconia interface bonding condition.

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

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.

Effect of PH 3 poisoning on a Ni-YSZ anode-supported solid oxide fuel cell under various operating conditions

NASA Astrophysics Data System (ADS)

Xu, Chunchuan; Zondlo, John W.; Gong, Mingyang; Liu, XingBo

The Ni-YSZ anode-supported solid oxide fuel cell (SOFC) can generate electrical power by using coal-derived syngas as the fuel. However, trace contamination of phosphine (PH 3) in the syngas can cause irreversible degradation in cell performance. A series of tests at 10 ppm PH 3 in the fuel gas was carried out under a variety of operating conditions, viz, with/without electrochemical reaction in syngas and with/without H 2O in H 2 fuel at 750 °C, 800 °C and 850 °C. The poisoning effects were evaluated by both electrochemical methods and chemical analyses. The post-mortem analyses of the SOFC anode were performed by means of XRD, SEM/EDS, and XPS. The results show that the degradation rate is larger at the higher cell working temperature using syngas with PH 3 in a 200 h test though PH 3 is more reactive with Ni in the anode at lower working temperature and produces a secondary nickel phosphide (Ni xP y) phase. The dominant compositions of Ni xP y on the cell anode are Ni 5P 2 with the presence of H 2O, and Ni 12P 5 without the presence of H 2O. The production of Ni xP y can be generated on the cell anode using syngas or dry H 2 fuel with 10 ppm PH 3 contaminant. Further, the appearance of Ni xP y phases is independent of the electrochemical reactions in the cell.

Electrochemical corrosion of a noble metal-bearing alloy-oxide composite

DOE PAGES

Chen, X.; Ebert, W. L.; Indacochea, J. E.

2017-04-27

The effects of added Ru and Pd on the microstructure and electrochemical behaviour of a composite material made by melting those metals with AISI 410 stainless steel, Zr, Mo, and lanthanide oxides were assessed using electrochemical and microscopic methods Furthermore, the lanthanide oxides reacted with Zr to form durable lanthanide zirconates and Mo alloyed with steel to form FeMoCr intermetallics. The noble metals alloyed with the steel to provide solid solution strengthening and inhibit carbide/nitride formation. In a passive film formed during electrochemical tests in acidic NaCl solution, but became less effective as corrosion progressed and regions over the intermetallicsmore » eventually failed.« less

Electrochemical characterization of Fe-air rechargeable oxide battery in planar solid oxide cell stacks

NASA Astrophysics Data System (ADS)

Fang, Qingping; Berger, Cornelius M.; Menzler, Norbert H.; Bram, Martin; Blum, Ludger

2016-12-01

Iron-air rechargeable oxide batteries (ROB) comprising solid oxide cells (SOC) as energy converters and Fe/metal-oxide redox couples were characterized using planar SOC stacks. The charge and discharge of the battery correspond to the operations in the electrolysis and fuel cell modes, respectively, but with a stagnant atmosphere consisting of hydrogen and steam. A novel method was employed to establish the stagnant atmosphere for battery testing during normal SOC operation without complicated modification to the test bench and stack/battery concept. Manipulation of the gas compositions during battery operation was not necessary, but the influence of the leakage current from the testing system had to be considered. Batteries incorporating Fe2O3/8YSZ, Fe2O3/CaO and Fe2O3/ZrO2 storage materials were characterized at 800 °C. A maximum charge capacity of 30.4 Ah per layer (with an 80 cm2 active cell area) with ∼0.5 mol Fe was reached with a current of 12 A. The charge capacity lost 11% after ∼130 ROB cycles due to the increased agglomeration of active materials and formation of a dense oxide layer on the surface. The round trip efficiencies of the tested batteries were ≤84% due to the large internal resistance. With state-of-the-art cells, the round trip efficiency can be further improved.

A thermodynamic approach for selecting operating conditions in the design of reversible solid oxide cell energy systems

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Kazempoor, Pejman; Braun, Robert J.

2016-01-01

Reversible solid oxide cell (ReSOC) systems are being increasingly considered for electrical energy storage, although much work remains before they can be realized, including cell materials development and system design optimization. These systems store electricity by generating a synthetic fuel in electrolysis mode and subsequently recover electricity by electrochemically oxidizing the stored fuel in fuel cell mode. System thermal management is improved by promoting methane synthesis internal to the ReSOC stack. Within this strategy, the cell-stack operating conditions are highly impactful on system performance and optimizing these parameters to suit both operating modes is critical to achieving high roundtrip efficiency. Preliminary analysis shows the thermoneutral voltage to be a useful parameter for analyzing ReSOC systems and the focus of this study is to quantitatively examine how it is affected by ReSOC operating conditions. The results reveal that the thermoneutral voltage is generally reduced by increased pressure, and reductions in temperature, fuel utilization, and hydrogen-to-carbon ratio. Based on the thermodynamic analysis, many different combinations of these operating conditions are expected to promote efficient energy storage. Pressurized systems can achieve high efficiency at higher temperature and fuel utilization, while non-pressurized systems may require lower stack temperature and suffer from reduced energy density.

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

DOE PAGES

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

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

Insights into electrode/electrolyte interfacial processes and the effect of nanostructured cobalt oxides loading on graphene-based hybrids by scanning electrochemical microscopy

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Carrizosa, Sara B.

2016-12-01

Nanostructured cobalt oxide polymorphs (CoO and Co3O4) deposited via electrodeposition allowed optimal loading on supercapacitive graphene nanosheets producing a set of graphene-based hybrids namely, CoO/GO, CoO/ErGO, Co3O4/GO, Co3O4/rGO, and Co3O4/ErGO, as pseudocapacitive electrochemical electrodes. We gained fundamental insights into the complex physicochemical interfacial processes at electrode surfaces and electrode/electrolyte (or solid/liquid) interfaces by scanning electrochemical microscopy operating in the feedback probe approach and imaging modes while monitoring and mapping the redox probe (re)activity behavior. We determined the various experimental descriptors including diffusion coefficient, electron transfer rate, and electroactive site distribution on electrodes. We emphasize the interplay of (1) heterogeneous basal and edge plane active sites, (2) graphene surface functional moieties (conducting/semiconducting), and (3) crystalline spinel cobalt oxides (semiconducting/insulating) coated graphene, reinforcing the available electron density of states in the vicinity of the Fermi level contributing to higher electroactivity, faster interfacial diffusion, and shorter distances for electron transfer, facilitated through molecular and chemical bridges obtained by electrodeposition as compared with the physical deposition.

Molecularly imprinted solid-phase extraction combined with electrochemical oxidation fluorimetry for the determination of methotrexate in human serum and urine

NASA Astrophysics Data System (ADS)

Chen, Suming; Zhang, Zhujun

2008-06-01

The method of synthesis and evaluation of molecularly imprinted polymers was reported. As a selective solid-phase extraction sorbent, the polymers were coupled with electrochemical fluorimetry detection for the efficient determination of methotrexate in serum and urine. Methotrexate was preconcentrated in the molecularly imprinted solid-phase extraction microcolumn packed with molecularly imprinted polymers, and then eluted. The eluate was detected by fluorescence spectrophotometer after electrochemical oxidation. The conditions of preconcentration, elution, electrochemical oxidation and determination were carefully studied. Under the selected experimental conditions, the calibration graph of the fluorescence intensity versus methotrexate concentration was linear from 4 × 10 -9 g mL -1 to 5 × 10 -7 g mL -1, and the detection limit was 8.2 × 10 -10 g mL -1 (3 σ). The relative standard deviation was 3.92% ( n = 7) for 1 × 10 -7 g mL -1 methotrexate. The experiments showed that the selectivity and sensitivity of fluorimetry could be greatly improved by the proposed method. This method has been successfully applied to the determination of methotrexate. At the same time, the binding characteristics of the polymers to the methotrexate were evaluated by batch and dynamic methods.

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

Masuda, Takuya; PRESTO, Japan Science and Technology Agency; Yoshikawa, Hideki

In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

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.

Micro-tubular solid oxide fuel cell based on a porous yttria-stabilized zirconia support

NASA Astrophysics Data System (ADS)

Panthi, Dhruba; Tsutsumi, Atsushi

2014-08-01

Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices owing to their high power generation efficiency and environmentally benign operation. Micro-tubular SOFCs, which have diameters ranging from a few millimeters to the sub-millimeter scale, offer several advantages over competing SOFCs such as high volumetric power density, good endurance against thermal cycling, and flexible sealing between fuel and oxidant streams. Herein, we successfully realized a novel micro-tubular SOFC design based on a porous yttria-stabilized zirconia (YSZ) support using multi-step dip coating and co-sintering methods. The micro-tubular SOFC consisted of Ni-YSZ, YSZ, and strontium-doped lanthanum manganite (LSM)-YSZ as the anode, electrolyte, and cathode, respectively. In addition, to facilitate current collection from the anode and cathode, Ni and LSM were applied as an anode current collector and cathode current collector, respectively. Micro-crystalline cellulose was selected as a pore former to achieve better shrinkage behavior of the YSZ support so that the electrolyte layer could be densified at a co-sintering temperature of 1300°C. The developed micro-tubular design showed a promising electrochemical performance with maximum power densities of 525, 442, and 354 mW cm-2 at 850, 800, and 750°C, respectively.

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.

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.

Co-flow planar SOFC fuel cell stack

DOEpatents

Chung, Brandon W.; Pham, Ai Quoc; Glass, Robert S.

2004-11-30

A co-flow planar solid oxide fuel cell stack with an integral, internal manifold and a casing/holder to separately seal the cell. This construction improves sealing and gas flow, and provides for easy manifolding of cell stacks. In addition, the stack construction has the potential for an improved durability and operation with an additional increase in cell efficiency. The co-flow arrangement can be effectively utilized in other electrochemical systems requiring gas-proof separation of gases.

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.

Influence of the charge double layer on solid oxide fuel cell stack behavior

NASA Astrophysics Data System (ADS)

Whiston, Michael M.; Bilec, Melissa M.; Schaefer, Laura A.

2015-10-01

While the charge double layer effect has traditionally been characterized as a millisecond phenomenon, longer timescales may be possible under certain operating conditions. This study simulates the dynamic response of a previously developed solid oxide fuel cell (SOFC) stack model that incorporates the charge double layer via an equivalent circuit. The model is simulated under step load changes. Baseline conditions are first defined, followed by consideration of minor and major deviations from the baseline case. This study also investigates the behavior of the SOFC stack with a relatively large double layer capacitance value, as well as operation of the SOFC stack under proportional-integral (PI) control. Results indicate that the presence of the charge double layer influences the SOFC stack's settling time significantly under the following conditions: (i) activation and concentration polarizations are significantly increased, or (ii) a large value of the double layer capacitance is assumed. Under normal (baseline) operation, on the other hand, the charge double layer effect diminishes within milliseconds, as expected. It seems reasonable, then, to neglect the charge double layer under normal operation. However, careful consideration should be given to potential variations in operation or material properties that may give rise to longer electrochemical settling times.

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

Joint with application in electrochemical devices

DOEpatents

Weil, K Scott [Richland, WA; Hardy, John S [Richland, WA

2010-09-14

A joint for use in electrochemical devices, such as solid oxide fuel cells (SOFCs), oxygen separators, and hydrogen separators, that will maintain a hermetic seal at operating temperatures of greater than 600.degree. C., despite repeated thermal cycling excess of 600.degree. C. in a hostile operating environment where one side of the joint is continuously exposed to an oxidizing atmosphere and the other side is continuously exposed to a wet reducing gas. The joint is formed of a metal part, a ceramic part, and a flexible gasket. The flexible gasket is metal, but is thinner and more flexible than the metal part. As the joint is heated and cooled, the flexible gasket is configured to flex in response to changes in the relative size of the metal part and the ceramic part brought about by differences in the coefficient of thermal expansion of the metal part and the ceramic part, such that substantially all of the tension created by the differences in the expansion and contraction of the ceramic and metal parts is absorbed and dissipated by flexing the flexible gasket.

Platinum Electrodeposition at Unsupported Electrochemically Reduced Nanographene Oxide for Enhanced Ammonia Oxidation

PubMed Central

2015-01-01

The electrochemical reduction of highly oxidized unsupported graphene oxide nanosheets and its platinum electrodeposition was done by the rotating disk slurry electrode technique. Avoiding the use of a solid electrode, graphene oxide was electrochemically reduced in a slurry solution with a scalable process without the use of a reducing agent. Graphene oxide nanosheets were synthesized from carbon platelet nanofibers to obtain highly hydrophilic layers of less than 250 nm in width. The graphene oxide and electrochemically reduced graphene oxide/Pt (erGOx/Pt) hybrid materials were characterized through different spectroscopy and microscopy techniques. Pt nanoparticles with 100 facets, clusters, and atoms at erGOx were identified by high resolution transmission electron microscopy (HRTEM). Cyclic voltammetry was used to characterize the electrocatalytic activity of the highly dispersed erGOx/Pt hybrid material toward the oxidation of ammonia, which showed a 5-fold current density increase when compared with commercially available Vulcan/Pt 20%. This is in agreement with having Pt (100) facets present in the HRTEM images of the erGOx/Pt material. PMID:24417177

Corner heating in rectangular solid oxide electrochemical cell generators

DOEpatents

Reichner, Philip

1989-01-01

Disclosed is an improvement in a solid oxide electrochemical cell generator 1 having a rectangular design with four sides that meet at corners, and containing multiplicity of electrically connected fuel cells 11, where a fuel gas is passed over one side of said cells and an oxygen containing gas is passed into said cells, and said fuel is burned to form heat, electricity, and an exhaust gas. The improvement comprises passing the exhaust gases over the multiplicity of cells 11 in such a way that more of the heat in said exhaust gases flows at the corners of the generator, such as through channels 19.

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

Energy-Efficient and Environmentally Friendly Solid Oxide Membrane Electrolysis Process for Magnesium Oxide Reduction: Experiment and Modeling

NASA Astrophysics Data System (ADS)

Guan, Xiaofei; Pal, Uday B.; Powell, Adam C.

2014-06-01

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM(La0.8Sr0.2MnO3-δ)-Inconel inert anode current collector for production of magnesium and oxygen directly from magnesium oxide at 1423 K (1150 °C). The electrochemical performance of the SOM cell was evaluated by means of various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scan, and electrolysis. Electronic transference numbers of the flux were measured to assess the magnesium dissolution in the flux during SOM electrolysis. The effects of magnesium solubility in the flux on the current efficiency and the SOM stability during electrolysis are discussed. An inverse correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed. Based on the experimental results, a new equivalent circuit of the SOM electrolysis process is presented. A general electrochemical polarization model of SOM process for magnesium and oxygen gas production is developed, and the maximum allowable applied potential to avoid zirconia dissociation is calculated as well. The modeling results suggest that a high electronic resistance of the flux and a relatively low electronic resistance of SOM are required to achieve membrane stability, high current efficiency, and high production rates of magnesium and oxygen.

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells.

PubMed

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A; Liu, Meilin

2011-06-21

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C(3)H(8), CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H(2)O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells

PubMed Central

Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A.; Liu, Meilin

2011-01-01

The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C3H8, CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity. PMID:21694705

Solid oxide fuel cell having monolithic core

DOEpatents

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

1983-10-12

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

CFD analysis of a solid oxide fuel cell with internal reforming: Coupled interactions of transport, heterogeneous catalysis and electrochemical processes

NASA Astrophysics Data System (ADS)

Janardhanan, Vinod M.; Deutschmann, Olaf

Direct internal reforming in solid oxide fuel cell (SOFC) results in increased overall efficiency of the system. Present study focus on the chemical and electrochemical process in an internally reforming anode supported SOFC button cell running on humidified CH 4 (3% H 2 O). The computational approach employs a detailed multi-step model for heterogeneous chemistry in the anode, modified Butler-Volmer formalism for the electrochemistry and Dusty Gas Model (DGM) for the porous media transport. Two-dimensional elliptic model equations are solved for a button cell configuration. The electrochemical model assumes hydrogen as the only electrochemically active species. The predicted cell performances are compared with experimental reports. The results show that model predictions are in good agreement with experimental observation except the open circuit potentials. Furthermore, the steam content in the anode feed stream is found to have remarkable effect on the resulting overpotential losses and surface coverages of various species at the three-phase boundary.

Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

PubMed

Zhu, Lin; Wei, Bo; Wang, Zhihong; Chen, Kongfa; Zhang, Haiwu; Zhang, Yaohui; Huang, Xiqiang; Lü, Zhe

2016-09-08

The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Activity and Stability of (Pr 1-xNd x) 2NiO 4+δ as Cathodes for Oxide Fuel Cells: Part VI. The Role of Cu Dopant on the Structure and Electrochemical Properties

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

Dogdibegovic, Emir; Yan, Jingbo; Cai, Qinsheng

Phase instability in praseodymium nickelates is a major concern for the long-term operations of solid oxide fuel cells since it may lead to the performance degradation. In this work, praseodymium nickelates (ex. Pr 2NiO 4+δ) have been stabilized via substitution on both Pr- and Ni-sites. Systematic studies over a wide range of compositions were conducted via long-term thermal annealing studies (T ≤ 870°C) and electrochemical tests in full cells. Proposed (Pr 0.50Nd 0.50) 2Ni 1-yCu yO 4+δ compositions (y = 0.05, 0.10, 0.20, and 0.30) showed the most promising results and serve as a comprehensive extension to our previous studiesmore » in this series of papers. A stable long-term performance was obtained for temperatures up to 790°C for 500 hours at 0.80 V with a minimal tradeoff between the activity (power density of 0.8–1.0 W cm -2 at 850°C) and performance stability. A preserved parent phase and suppressed performance degradation, when compared to Pr 2NiO 4+δ, make newly developed electrodes attractive candidates for the state-of-the-art solid oxide fuel cell applications.« less

Activity and Stability of (Pr 1-xNd x) 2NiO 4+δ as Cathodes for Oxide Fuel Cells: Part VI. The Role of Cu Dopant on the Structure and Electrochemical Properties

DOE PAGES

Dogdibegovic, Emir; Yan, Jingbo; Cai, Qinsheng; ...

2017-08-12

Phase instability in praseodymium nickelates is a major concern for the long-term operations of solid oxide fuel cells since it may lead to the performance degradation. In this work, praseodymium nickelates (ex. Pr 2NiO 4+δ) have been stabilized via substitution on both Pr- and Ni-sites. Systematic studies over a wide range of compositions were conducted via long-term thermal annealing studies (T ≤ 870°C) and electrochemical tests in full cells. Proposed (Pr 0.50Nd 0.50) 2Ni 1-yCu yO 4+δ compositions (y = 0.05, 0.10, 0.20, and 0.30) showed the most promising results and serve as a comprehensive extension to our previous studiesmore » in this series of papers. A stable long-term performance was obtained for temperatures up to 790°C for 500 hours at 0.80 V with a minimal tradeoff between the activity (power density of 0.8–1.0 W cm -2 at 850°C) and performance stability. A preserved parent phase and suppressed performance degradation, when compared to Pr 2NiO 4+δ, make newly developed electrodes attractive candidates for the state-of-the-art solid oxide fuel cell applications.« less

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

PubMed Central

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

2016-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Electrochemical incineration of wastes

NASA Technical Reports Server (NTRS)

Kaba, L.; Hitchens, G. D.; Bockris, J. O'M.

1989-01-01

A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

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.

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.

High-performance low-temperature solid oxide fuel cell with novel BSCF cathode

NASA Astrophysics Data System (ADS)

Liu, Q. L.; Khor, K. A.; Chan, S. H.

An anode-supported solid oxide fuel cell (SOFC), consisting of a dense 10 μm Gd 0.1Ce 0.9O 1.95 (GDC) electrolyte, a porous Ba 0.5Sr 0.5Co 0.8Fe 0.2O 3- δ (BSCF) cathode and a porous Ni-GDC cermet anode, is successfully assembled and electrochemically characterized. With humidified (3% water vapour) hydrogen as the fuel and air as the oxidant, the cell exhibits open-circuit voltages of 0.903 and 0.984 V when operating at 600 and 500 °C, respectively. The cell produces peak power densities of 1329, 863, 454, 208 and 83 mW cm -2 at 600, 550, 500, 450 and 400 °C, respectively. These results are impressive and demonstrate the potential of BSCF for use as the cathode material in new-generation SOFCs with GDC as the electrolyte. In addition, the sustained performance at temperatures below 600 °C warrants commercial exploitation of this SOFC in stationary and mobile applications.

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.

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

Apparatus and methods for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-04-25

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

Method for direct conversion of gaseous hydrocarbons to liquids

DOEpatents

Kong, Peter C.; Lessing, Paul A.

2006-03-07

A chemical reactor for direct conversion of hydrocarbons includes a dielectric barrier discharge plasma cell and a solid oxide electrochemical cell in fluid communication therewith. The discharge plasma cell comprises a pair of electrodes separated by a dielectric material and passageway therebetween. The electrochemical cell comprises a mixed-conducting solid oxide electrolyte membrane tube positioned between a porous cathode and a porous anode, and a gas inlet tube for feeding oxygen containing gas to the porous cathode. An inlet is provided for feeding hydrocarbons to the passageway of the discharge plasma cell, and an outlet is provided for discharging reaction products from the reactor. A packed bed catalyst may optionally be used in the reactor to increase efficiency of conversion. The reactor can be modified to allow use of a light source for directing ultraviolet light into the discharge plasma cell and the electrochemical cell.

Three dimensional electrochemical simulation of solid oxide fuel cell cathode based on microstructure reconstructed by marching cubes method

NASA Astrophysics Data System (ADS)

He, An; Gong, Jiaming; Shikazono, Naoki

2018-05-01

In the present study, a model is introduced to correlate the electrochemical performance of solid oxide fuel cell (SOFC) with the 3D microstructure reconstructed by focused ion beam scanning electron microscopy (FIB-SEM) in which the solid surface is modeled by the marching cubes (MC) method. Lattice Boltzmann method (LBM) is used to solve the governing equations. In order to maintain the geometries reconstructed by the MC method, local effective diffusivities and conductivities computed based on the MC geometries are applied in each grid, and partial bounce-back scheme is applied according to the boundary predicted by the MC method. From the tortuosity factor and overpotential calculation results, it is concluded that the MC geometry drastically improves the computational accuracy by giving more precise topology information.

Three-dimensional computational fluid dynamics modelling and experimental validation of the Jülich Mark-F solid oxide fuel cell stack

NASA Astrophysics Data System (ADS)

Nishida, R. T.; Beale, S. B.; Pharoah, J. G.; de Haart, L. G. J.; Blum, L.

2018-01-01

This work is among the first where the results of an extensive experimental research programme are compared to performance calculations of a comprehensive computational fluid dynamics model for a solid oxide fuel cell stack. The model, which combines electrochemical reactions with momentum, heat, and mass transport, is used to obtain results for an established industrial-scale fuel cell stack design with complex manifolds. To validate the model, comparisons with experimentally gathered voltage and temperature data are made for the Jülich Mark-F, 18-cell stack operating in a test furnace. Good agreement is obtained between the model and experiment results for cell voltages and temperature distributions, confirming the validity of the computational methodology for stack design. The transient effects during ramp up of current in the experiment may explain a lower average voltage than model predictions for the power curve.

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.

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.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, Terje

1986-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity

DOEpatents

Skotheim, T.

1984-09-28

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Synthesis and electrochemical performances of LiNiCuZn oxides as anode and cathode catalyst for low temperature solid oxide fuel cell.

PubMed

Jing, Y; Qin, H; Liu, Q; Singh, M; Zhu, B

2012-06-01

Low temperature solid oxide fuel cell (LTSOFC, 300-600 degrees C) is developed with advantages compared to conventional SOFC (800-1000 degrees C). The electrodes with good catalytic activity, high electronic and ionic conductivity are required to achieve high power output. In this work, a LiNiCuZn oxides as anode and cathode catalyst is prepared by slurry method. The structure and morphology of the prepared LiNiCuZn oxides are characterized by X-ray diffraction and field emission scanning electron microscopy. The LiNiCuZn oxides prepared by slurry method are nano Li0.28Ni0.72O, ZnO and CuO compound. The nano-crystallites are congregated to form ball-shape particles with diameter of 800-1000 nm. The LiNiCuZn oxides electrodes exhibits high ion conductivity and low polarization resistance to hydrogen oxidation reaction and oxygen reduction reaction at low temperature. The LTSOFC using the LiNiCuZn oxides electrodes demonstrates good cell performance of 1000 mW cm(-2) when it operates at 470 degrees C. It is considered that nano-composite would be an effective way to develop catalyst for LTSOFC.

Fabrication and electrochemical performance of nickel- and gadolinium-doped ceria-infiltrated La0·2Sr0·8TiO3 anodes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Min-Jin; Shin, Jae-Hwa; Ji, Mi-Jung; Hwang, Hae-Jin

2018-01-01

In this work, nickel and gadolinium-doped ceria (GDC)-infiltrated lanthanum strontium titanate (LST) anodes are fabricated, and their electrode performances under a hydrogen atmosphere is investigated in terms of the Ni:GDC ratios and cell operating temperature. The Ni/GDC-infiltrated LST anode exhibits excellent electrode performance in comparison with the Ni- or GDC-infiltrated anodes, which is attributed to the synergistic effect of an extended triple-phase boundary length by GDC and good catalytic activity for hydrogen oxidation because of the Ni particles. The polarization resistances (Rp) of Ni/GDC-infiltrated LST are 0.07, 0.08, and 0.12 Ω cm2 at 800, 750, and 700 °C, respectively, which are approximately three orders of magnitude lower than that of the LST anode (68.5 Ω cm2 at 700 °C). The effect of Ni and GDC on the electrochemical performance of LST was also investigated by using electrochemical impedance spectroscopy (EIS). The anode polarization resistance (Rp) is confirmed to be dependent on the content and dispersion state (microstructure) of the Ni and GDC nanoparticles.

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.

Modified cermet fuel electrodes for solid oxide electrochemical cells

DOEpatents

Ruka, Roswell J.; Spengler, Charles J.

1991-01-01

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

Modeling and optimization of proton-conducting solid oxide electrolysis cell: Conversion of CO2 into value-added products

NASA Astrophysics Data System (ADS)

Namwong, Lawit; Authayanun, Suthida; Saebea, Dang; Patcharavorachot, Yaneeporn; Arpornwichanop, Amornchai

2016-11-01

Proton-conducting solid oxide electrolysis cells (SOEC-H+) are a promising technology that can utilize carbon dioxide to produce syngas. In this work, a detailed electrochemical model was developed to predict the behavior of SOEC-H+ and to prove the assumption that the syngas is produced through a reversible water gas-shift (RWGS) reaction. The simulation results obtained from the model, which took into account all of the cell voltage losses (i.e., ohmic, activation, and concentration losses), were validated using experimental data to evaluate the unknown parameters. The developed model was employed to examine the structural and operational parameters. It is found that the cathode-supported SOEC-H+ is the best configuration because it requires the lowest cell potential. SOEC-H+ operated favorably at high temperatures and low pressures. Furthermore, the simulation results revealed that the optimal S/C molar ratio for syngas production, which can be used for methanol synthesis, is approximately 3.9 (at a constant temperature and pressure). The SOEC-H+ was optimized using a response surface methodology, which was used to determine the optimal operating conditions to minimize the cell potential and maximize the carbon dioxide flow rate.

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.

Thermal Modeling and Management of Solid Oxide Fuel Cells Operating with Internally Reformed Methane

NASA Astrophysics Data System (ADS)

Wu, Yiyang; Shi, Yixiang; Cai, Ningsheng; Ni, Meng

2018-06-01

A detailed three-dimensional mechanistic model of a large-scale solid oxide fuel cell (SOFC) unit running on partially pre-reformed methane is developed. The model considers the coupling effects of chemical and electrochemical reactions, mass transport, momentum and heat transfer in the SOFC unit. After model validation, parametric simulations are conducted to investigate how the methane pre-reforming ratio affects the transport and electrochemistry of the SOFC unit. It is found that the methane steam reforming reaction has a "smoothing effect", which can achieve more uniform distributions of gas compositions, current density and temperature among the cell plane. In the case of 1500 W/m2 power density output, adding 20% methane absorbs 50% of internal heat production inside the cell, reduces the maximum temperature difference inside the cell from 70 K to 22 K and reduces the cathode air supply by 75%, compared to the condition of completely pre-reforming of methane. Under specific operating conditions, the pre-reforming ratio of methane has an optimal range for obtaining a good temperature distribution and good cell performance.

Optimal design of solid oxide fuel cell, ammonia-water single effect absorption cycle and Rankine steam cycle hybrid system

NASA Astrophysics Data System (ADS)

Mehrpooya, Mehdi; Dehghani, Hossein; Ali Moosavian, S. M.

2016-02-01

A combined system containing solid oxide fuel cell-gas turbine power plant, Rankine steam cycle and ammonia-water absorption refrigeration system is introduced and analyzed. In this process, power, heat and cooling are produced. Energy and exergy analyses along with the economic factors are used to distinguish optimum operating point of the system. The developed electrochemical model of the fuel cell is validated with experimental results. Thermodynamic package and main parameters of the absorption refrigeration system are validated. The power output of the system is 500 kW. An optimization problem is defined in order to finding the optimal operating point. Decision variables are current density, temperature of the exhaust gases from the boiler, steam turbine pressure (high and medium), generator temperature and consumed cooling water. Results indicate that electrical efficiency of the combined system is 62.4% (LHV). Produced refrigeration (at -10 °C) and heat recovery are 101 kW and 22.1 kW respectively. Investment cost for the combined system (without absorption cycle) is about 2917 kW-1.

Cheap, High-Performance, and Wearable Mn Oxide Supercapacitors with Urea-LiClO4 Based Gel Electrolytes.

PubMed

Deng, Ming-Jay; Chen, Kai-Wen; Che, Yo-Cheng; Wang, I-Ju; Lin, Chih-Ming; Chen, Jin-Ming; Lu, Kueih-Tzu; Liao, Yen-Fa; Ishii, Hirofumi

2017-01-11

Here we report a simple, scalable, and low-cost method to enhance the electrochemical properties of Mn oxide electrodes for highly efficient and flexible symmetrical supercapacitors. The method involving printing on a printer, pencil-drawing, and electrodeposition is established to fabricate Mn oxide/Ni-nanotube/graphite/paper hybrid electrodes operating with a low-cost, novel urea-LiClO 4 /PVA as gel electrolyte for flexible solid-state supercapacitor (FSSC) devices. The Mn oxide nanofiber/Ni-nanotube/graphite/paper (MNNGP) electrodes in urea-LiClO 4 /PVA gel electrolyte show specific capacitance (C sp ) 960 F/g in voltage region 0.8 V at 5 mV/s and exhibit excellent rates of capacitance retention more than 85% after 5000 cycles. Moreover, the electrochemical behavior of the MNNGP electrodes in urea-LiClO 4 /PVA at operating temperatures 27-110 °C was investigated; the results show that the MNNGP electrodes in urea-LiClO 4 /PVA exhibit outstanding performance (1100 F/g), even at 90 °C. The assembled FSSC devices based on the MNNGP electrodes in urea-LiClO 4 /PVA exhibit great C sp (380 F/g in potential region of 2.0 V at 5 mV/s, exhibiting superior energy density 211.1 W h/kg) and great cycle stability (less than 15% loss after 5000 cycles at 25 mV/s). The oxidation-state change was examined by in situ X-ray absorption spectroscopy. FSSC devices would open new opportunities in developing novel portable, wearable, and roll-up electric devices owing to the cheap, high-performance, wide range of operating temperature, and simple procedures for large-area fabrication.

The aqueous electrochemistry of carbon-based surfaces-investigation by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Mühl, T.; Myhra, S.

2007-04-01

Electro-oxidation of carbon-based materials will lead to conversion of the solid to CO2/CO at the anode, with H2 being produced at the cathode. Recent voltammetric investigations of carbon nano-tubes and single crystal graphite have shown that only edge sites and other defect sites are electrochemically active. Local oxidation of diamond-like carbon films (DLC) by an STM tip in moist air followed by imaging allows correlation of topographical change with electro-chemical conditions and surface reactivity. The results may have implications for lithographic processing of carbon surfaces, and may have relevance for electrochemical H2 production.

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, T.

A polymer blend is disclosed of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Compositional control of continuously graded anode functional layer

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

In Situ Foaming of Porous (La 0.6 Sr 0.4 ) 0.98 (Co 0.2 Fe 0.8 ) O 3-δ (LSCF) Cathodes for Solid Oxide Fuel Cell Applications

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

Gandavarapu, Sodith; Sabolsky, Edward; Sabolsky, Katarzyna

2013-07-18

A binder system containing polyurethane precursors was used to in situ foam (direct foam) a (La{sub 0.6}Sr{sub 0.4}){sub 0.98} (Co{sub 0.2} Fe{sub 0.8}) O{sub 3-{ delta}} (LSCF) composition for solid oxide fuel cell (SOFC) cathode applications. The relation between in situ foaming parameters on the final microstructure and electrochemical properties was characterized by microscopy and electrochemical impedance spectroscopy (EIS), respectively. The optimal porous cathode architecture was formed with a 70 vol% solids loading within a polymer precursor composition with a volume ratio of 8:4:1 (isocyanate: PEG: surfactant) in a terpineol-based ink vehicle. The resultant microstructure displayed a broad pore sizemore » distribution with highly elongated pore structure.« less

Physical, mechanical and electrochemical characterization of all-perovskite intermediate temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Mohammadi, Alidad

Strontium- and magnesium-doped lanthanum gallate (LSGM) has been considered as a promising electrolyte for solid oxide fuel cell (SOFC) systems in recent years due to its high ionic conductivity and chemical stability over a wide range of oxygen partial pressures and temperatures. This research describes synthesis, physical and mechanical behavior, electrochemical properties, phase evolution, and microstructure of components of an all-perovskite anode-supported intermediate temperature solid oxide fuel cell (ITSOFC), based on porous La 0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) anode, La0.8Sr0.2Ga0.8Mg0.2O 2.8 (LSGM) electrolyte, and porous La0.6Sr0.4Fe 0.8Co0.2O3 (LSCF) cathode. The phase evolution of synthesized LSGM and LSCM powders has been investigated, and it has been confirmed that there is no reaction between LSGM and LSCM at sintering temperature. Using different amounts of poreformers and binders as well as controlling firing temperature, porosity of the anode was optimized while still retaining good mechanical integrity. The effect of cell operation conditions under dry hydrogen fuel on the SOFC open circuit voltage (OCV) and cell performance were also investigated. Characterization study of the synthesized LSGM indicates that sintering at 1500°C obtains higher electrical conductivity compared to the currently published results, while conductivity of pellets sintered at 1400°C and 1450°C would be slightly lower. The effect of sintering temperature on bulk and grain boundary resistivities was also discussed. The mechanical properties, such as hardness, Young's modulus, fracture toughness and modulus of rupture of the electrolyte were determined and correlated with scanning electron microscopy (SEM) morphological characterization. Linear thermal expansion and thermal expansion coefficient of LSGM were also measured.

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

Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

NASA Astrophysics Data System (ADS)

Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

2018-01-01

Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

Co-electrolysis of steam and CO2 in full-ceramic symmetrical SOECs: a strategy for avoiding the use of hydrogen as a safe gas.

PubMed

Torrell, M; García-Rodríguez, S; Morata, A; Penelas, G; Tarancón, A

2015-01-01

The use of cermets as fuel electrodes for solid oxide electrolysis cells requires permanent circulation of reducing gas, e.g. H2 or CO, so called safe gas, in order to avoid oxidation of the metallic phase. Replacing metallic based electrodes by pure oxides is therefore proposed as an advantage for the industrial application of solid oxide electrolyzers. In this work, full-ceramic symmetrical solid oxide electrolysis cells have been investigated for steam/CO2 co-electrolysis. Electrolyte supported cells with La(0.75)Sr(0.25)Cr(0.5)Mn(0.5)O3-δ reversible electrodes have been fabricated and tested in co-electrolysis mode using different fuel compositions, from pure H2O to pure CO2, at temperatures between 850-900 °C. Electrochemical impedance spectroscopy and galvanostatic measurements have been carried out for the mechanistic understanding of the symmetrical cell performance. The content of H2 and CO in the product gas has been measured by in-line gas micro-chromatography. The effect of employing H2 as a safe gas has also been investigated. Maximum density currents of 750 mA cm(-2) and 620 mA cm(-2) have been applied at 1.7 V for pure H2O and for H2O : CO2 ratios of 1 : 1, respectively. Remarkable results were obtained for hydrogen-free fuel compositions, which confirmed the interest of using ceramic oxides as a fuel electrode candidate to reduce or completely avoid the use of safe gas in operation minimizing the contribution of the reverse water shift reaction (RWSR) in the process. H2 : CO ratios close to two were obtained for hydrogen-free tests fulfilling the basic requirements for synthetic fuel production. An important increase in the operation voltage was detected under continuous operation leading to a dramatic failure by delaminating of the oxygen electrode.

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

NASA Astrophysics Data System (ADS)

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

2008-02-01

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

Promotion on electrochemical performance of a cation deficient SrCo0.7Nb0.1Fe0.2O3-δ perovskite cathode for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ding, Liming; Wang, Lixi; Ding, Dong; Zhang, Shihua; Ding, Xifeng; Yuan, Guoliang

2017-06-01

Solid oxide fuel cells (SOFCs) offer great promise for the most efficient and cost-effective conversion to electricity of a wide variety of fuels. The cathode materials with high electro-catalytic activity for oxygen reduction reaction is vital to the development of commercially-viable SOFCs to be operated at reduced temperatures. In present study, cobalt-based perovskite oxides SrxCo0.7Nb0.1Fe0.2O3-δ (SCNF, x = 0.95 and 1) were comparatively investigated as promising cathode materials for intermediate-temperature SOFCs. The SCNF compounds with a slight Sr deficiency (S0.95CNF) exhibited single phase of primitive cubic structure with Pm-3m symmetry. A small Sr deficiency is demonstrated to greatly enhance the electrochemical performance of stoichiometric SCNF cathode due to significantly increased oxygen vacancy. The polarization resistance of S0.95CNF at 700 °C was 0.11 Ω cm2, only about 61% of SCNF. The rate limiting step for oxygen reduction reaction (ORR) is demonstrated to be oxygen ion transfer within the bulk electrode and/or from electrode to electrolyte through the triple phase boundary. Full cells with the SCNF cathode present good performance and stable output at reduced temperatures, indicating the great potential for enhanced performance of Co-based cathodes with A-site deficiency.

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.

A Finite Length Cylinder Model for Mixed Oxide-Ion and Electron Conducting Cathodes Suited for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Jin, Xinfang; Wang, Jie; Jiang, Long; ...

2016-03-25

A physics-based model is presented to simulate the electrochemical behavior of mixed ion and electron conducting (MIEC) cathodes for intermediate-temperature solid oxide fuel cells. Analytic solutions for both transient and impedance models based on a finite length cylinder are derived. These solutions are compared to their infinite length counterparts. The impedance solution is also compared to experimental electrochemical impedance spectroscopy data obtained from both a traditional well-established La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) cathode and a new SrCo 0.9Nb 0.1O 3-δ (SCN) porous cathode. Lastly, the impedance simulations agree well with the experimental values, demonstrating that the new modelsmore » can be used to extract electro-kinetic parameters of MIEC SOFC cathodes.« less

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

NASA Astrophysics Data System (ADS)

1990-10-01

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

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.

Electroenzymatic oxidation of veratryl alcohol by lignin peroxidase.

PubMed

Lee, KiBeom; Moon, Seung-Hyeon

2003-05-08

This paper reports the formation of veratraldehyde by electroenzymatic oxidation of veratryl alcohol (3,4-dimethoxybenzyl alcohol) hybridizing both electrochemical and enzymatic reactions and using lignin peroxidase. The novel electroenzymatic method was found to be effective for replacement of hydrogen peroxide by an electrochemical reactor, which is essential for enzyme activity of lignin peroxidase. The effects of operating parameters such as enzyme dosage, pH, and electric potential were investigated. Further, the kinetics of veratryl alcohol oxidation in an electrochemical reactor were compared to oxidation when hydrogen peroxide was supplied externally.

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

Polymer blends for use in photoelectrochemical cells for conversion of solar energy to electricity and methods for manufacturing such blends

DOEpatents

Skotheim, Terje

1984-01-01

There is disclosed a polymer blend of a highly conductive polymer and a solid polymer electrolyte that is designed to achieve better charge transfer across the conductive film/polymer electrolyte interface of the electrochemical photovoltaic cell. The highly conductive polymer is preferably polypyrrole or poly-N-p-nitrophenylpyrrole and the solid polymer electrolyte is preferably polyethylene oxide or polypropylene oxide.

Flexible thin-film battery based on graphene-oxide embedded in solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Kammoun, M.; Berg, S.; Ardebili, H.

2015-10-01

Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending.Enhanced safety of flexible batteries is an imperative objective due to the intimate interaction of such devices with human organs such as flexible batteries that are integrated with touch-screens or embedded in clothing or space suits. In this study, the fabrication and testing of a high performance thin-film Li-ion battery (LIB) is reported that is both flexible and relatively safer compared to the conventional electrolyte based batteries. The concept is facilitated by the use of solid polymer nanocomposite electrolyte, specifically, composed of polyethylene oxide (PEO) matrix and 1 wt% graphene oxide (GO) nanosheets. The flexible LIB exhibits a high maximum operating voltage of 4.9 V, high capacity of 0.13 mA h cm-2 and an energy density of 4.8 mW h cm-3. The battery is encapsulated using a simple lamination method that is economical and scalable. The laminated battery shows robust mechanical flexibility over 6000 bending cycles and excellent electrochemical performance in both flat and bent configurations. Finite element analysis (FEA) of the LIB provides critical insights into the evolution of mechanical stresses during lamination and bending. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04339e

Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Diethelm, Stefan; Van herle, Jan

This study investigates the performance of a standard Ni-YSZ anode supported cell under ethanol steam reforming operating conditions. Therefore, the fuel cell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H 2, CO) in the fuel cell. The electrochemical properties of the fuel cell fed with four different fuel compositions were characterized between 710 and 860 °C by I- V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency. Results show that internal steam reforming of ethanol takes place significantly on Ni-YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water-gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.

Support tube for high temperature solid electrolyte electrochemical cell

DOEpatents

Ruka, Roswell J.; Rossing, Barry R.

1986-01-01

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

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

Solid electrolyte structure

DOEpatents

Fraioli, Anthony V.

1984-01-01

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

Palliative effects of H2 on SOFCs operating with carbon containing fuels

NASA Astrophysics Data System (ADS)

Reeping, Kyle W.; Bohn, Jessie M.; Walker, Robert A.

2017-12-01

Chlorine can accelerate degradation of solid oxide fuel cell (SOFC) Ni-based anodes operating on carbon containing fuels through several different mechanisms. However, supplementing the fuel with a small percentage of excess molecular hydrogen effectively masks the degradation to the catalytic activity of the Ni and carbon fuel cracking reaction reactions. Experiments described in this work explore the chemistry behind the "palliative" effect of hydrogen on SOFCs operating with chlorine-contaminated, carbon-containing fuels using a suite of independent, complementary techniques. Operando Raman spectroscopy is used to monitor carbon accumulation and, by inference, Ni catalytic activity while electrochemical techniques including electrochemical impedance spectroscopy and voltammetry are used to monitor overall cell performance. Briefly, hydrogen not only completely hides degradation observed with chlorine-contaminated carbon-containing fuels, but also actively removes adsorbed chlorine from the surface of the Ni, allowing for the methane cracking reaction to continue, albeit at a slower rate. When hydrogen is removed from the fuel stream the cell fails immediately due to chlorine occupation of methane/biogas reaction sites.

The Effect of Oxidation and Charge/Discharge rates on Li Plating in All-Solid-State Batteries

NASA Astrophysics Data System (ADS)

Yulaev, Alexander; Oleshko, Vladimir; Talin, A. Alec; Leite, Marina S.; Kolmakov, Andrei

All-solid-state Li-ion batteries (SSLIBs) is currently an extensive area of research due to their promising specific power and energy density properties. Moreover, SSLIBs significantly mitigate the safety risks of the thermal runaway that may occur in liquid electrolyte batteries. We fabricated a model SSLIB, which consists of LiCoO2 cathode layer, LiPON as an electrolyte, and a model ultra-thin carbon anode. Using in operando scanning electron microscopy in conjunction with electrochemical measurements, we found that depending on ambient oxidizing conditions and charging rate, the morphology of plated lithium alternates between quasi-1D and 3D microstructures. In addition, we were able to use an electron beam as a virtual nano-electrode to selectively control the nucleation rate and Li growth structure during the SSLIB charging with high spatial resolution. Finally, we determined the conditions when lithium may be oxidized even during battery cycling under UHV conditions, leading to significant capacity losses. We foresee that our work will provide deeper insights into a safe SSLIB performance under real world operating conditions.

Carbon fiber brush electrode as a novel substrate for atmospheric solids analysis probe (ASAP) mass spectrometry: Electrochemical oxidation of brominated phenols.

PubMed

Skopalová, Jana; Barták, Petr; Bednář, Petr; Tomková, Hana; Ingr, Tomáš; Lorencová, Iveta; Kučerová, Pavla; Papoušek, Roman; Borovcová, Lucie; Lemr, Karel

2018-01-25

A carbon fiber brush electrode (CFBE) was newly designed and used as a substrate for both controlled potential electrolysis and atmospheric solids analysis probe (ASAP) mass spectrometry. Electropolymerized and strongly adsorbed products of electrolysis were directly desorbed and ionized from the electrode surface. Electrochemical properties of the electrode investigated by cyclic voltammetry revealed large electroactive surface area (23 ± 3 cm 2 ) at 1.3 cm long array of carbon fibers with diameter 6-9 μm. Some products of electrochemical oxidation of pentabromophenol and 2,4,6-tribromophenol formed a compact layer on the carbon fibers and were analyzed using ASAP. Eleven new oligomeric products were identified including quinones and biphenoquinones. These compounds were not observed previously in electrolyzed solutions by liquid or gas chromatography/mass spectrometry. The thickness around 58 nm and 45 nm of the oxidation products layers deposited on carbon fibers during electrolysis of pentabromophenol and 2,4,6-tribromophenol, respectively, was estimated from atomic force microscopy analysis and confirmed by scanning electron microscopy with energy-dispersive X-ray spectroscopy measurements. Copyright © 2017 Elsevier B.V. All rights reserved.

Heterogeneous water oxidation: surface activity versus amorphization activation in cobalt phosphate catalysts.

PubMed

González-Flores, Diego; Sánchez, Irene; Zaharieva, Ivelina; Klingan, Katharina; Heidkamp, Jonathan; Chernev, Petko; Menezes, Prashanth W; Driess, Matthias; Dau, Holger; Montero, Mavis L

2015-02-16

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate-containing Co oxide (CoCat). X-ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5-8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high-TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high-TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte-exposed "outer surface", within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid oxide membrane-assisted controllable electrolytic fabrication of metal carbides in molten salt.

PubMed

Zou, Xingli; Zheng, Kai; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu

2016-08-15

Silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and tantalum carbide (TaC) have been electrochemically produced directly from their corresponding stoichiometric metal oxides/carbon (MOx/C) precursors by electrodeoxidation in molten calcium chloride (CaCl2). An assembled yttria stabilized zirconia solid oxide membrane (SOM)-based anode was employed to control the electrodeoxidation process. The SOM-assisted controllable electrochemical process was carried out in molten CaCl2 at 1000 °C with a potential of 3.5 to 4.0 V. The reaction mechanism of the electrochemical production process and the characteristics of these produced metal carbides (MCs) were systematically investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses clearly identify that SiC, TiC, ZrC, and TaC carbides can be facilely fabricated. SiC carbide can be controlled to form a homogeneous nanowire structure, while the morphologies of TiC, ZrC, and TaC carbides exhibit porous nodular structures with micro/nanoscale particles. The complex chemical/electrochemical reaction processes including the compounding, electrodeoxidation, dissolution-electrodeposition, and in situ carbonization processes in molten CaCl2 are also discussed. The present results preliminarily demonstrate that the molten salt-based SOM-assisted electrodeoxidation process has the potential to be used for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs, which can potentially be used for various applications.

High-temperature Raman spectroscopy of solid oxide fuel cell materials and processes.

PubMed

Pomfret, Michael B; Owrutsky, Jeffrey C; Walker, Robert A

2006-09-07

Chemical and material processes occurring in high temperature environments are difficult to quantify due to a lack of experimental methods that can probe directly the species present. In this letter, Raman spectroscopy is shown to be capable of identifying in-situ and noninvasively changes in material properties as well as the formation and disappearance of molecular species on surfaces at temperatures of 715 degrees C. The material, yttria-stabilized zirconia or YSZ, and the molecular species, Ni/NiO and nanocrystalline graphite, factor prominently in the chemistry of solid oxide fuel cells (SOFCs). Experiments demonstrate the ability of Raman spectroscopy to follow reversible oxidation/reduction kinetics of Ni/NiO as well as the rate of carbon disappearance when graphite, formed in-situ, is exposed to a weakly oxidizing atmosphere. In addition, the Raman active phonon mode of YSZ shows a temperature dependent shift that correlates closely with the expansion of the lattice parameter, thus providing a convenient internal diagnostic for identifying thermal gradients in high temperature systems. These findings provide direct insight into processes likely to occur in operational SOFCs and motivate the use of in-situ Raman spectroscopy to follow chemical processes in these high-temperature, electrochemically active environments.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, John P.; Young, John E.

1984-01-01

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

Composite anode La0.8Sr0.2MnO3 impregnated with cobalt oxide for steam electrolysis

NASA Astrophysics Data System (ADS)

Li, Shisong; Cheng, Jigui; Xie, Kui; Li, Peipei; Wu, Yucheng

2013-12-01

Oxygen-ion conducting solid oxide electrolyzer (SOE) has attracted a great deal of interest because it converts electrical energy into chemical energy directly. The oxygen evolution reaction (OER) is occurred at the anode of solid oxide electrolyzer as the O2- being oxidized and form O2 gas, which is considered as one of the major cause of overpotentials in steam electrolyzers. This paper investigates the electrolysis of steam based on cobalt oxide impregnated La0.8Sr0.2MnO3 (LSM) composite anode in an oxide-ion-conducting solid oxide electrolyzer. The conductivity of LSM is studied versus temperature and oxygen partial pressure and correlated to the electrochemical properties of the composite electrodes in symmetric cells at 800 °C. Different contents of Co3O4 (wt.1%, 2%, 4%, 6%, 8%, 10%) were impregnated into LSM electrode and it was found that the polarization resistance (Rp) of symmetric cells gradually improved from 1.16 Ω•cm2 (LSM) to 0.24 Ω•cm2 (wt.10%Co3O4-LSM). Steam electrolysis based on LSM and wt.6%Co3O4-LSM anode electrolyzers are tested at 800°C and the AC impedance spectroscopy results indicated that the Rp of high frequency process significantly decreased from1.1 Ω•cm2 (LSM) to 0.5 Ω•cm2 (wt.6%Co3O4-LSM) under 1.8V electrolysis voltage and the Rp of low frequency process decreased from 14.9 Ω•cm2 to 5.7 Ω•cm2. Electrochemical catalyst Co3O4 can efficiently improve the electrode and enhance the performance of high temperature solid oxide electrolyzer.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development of Anode-Supported Single Cells and Small Stacks for Intermediate Temperature Sofc at Kepri

NASA Astrophysics Data System (ADS)

Yoo, Y.-S.; Park, J.-W.; Park, J.-K.; Lim, H.-C.; Oh, J.-M.; Bae, J.-M.

Recent results on intermediate temperature-operating solid oxide fuel cells (IT-SOFC) are mainly focused on getting the higher performance of single cell at lower operating temperature, especially using planar type. We have started a project to develop 1 kW-class SOFC system for Residential Power Generation(RPG) application. For a 1 kW-class SOFC stack that can be operated at intermediate temperatures, we have developed anode-supported, planar type SOFC to have advantages for commercialization of SOFCs considering mass production and using cost-effective interconnects such as ferritic stainless steels. At higher temperature, performance of SOFC can be increased due to higher electrochemical activity of electrodes and lower ohmic losses, but the surface of metallic interconnects at cathode side is rapidly oxidized into resistive oxide scale. For efficient operation of SOFC at reduced temperature at, firstly we have developed alternative cathode materials of LSCF instead of LSM to get higher performance of electrodes, and secondly introduced functional-layered structure at anode side. The I-V and AC impedance characteristics of improved single cells and small stacks were evaluated at intermediate temperatures (650°C and 750°C) using hydrogen gas as a fuel.

Controlled Atmosphere High Temperature SPM for electrochemical measurements

NASA Astrophysics Data System (ADS)

Vels Hansen, K.; Sander, C.; Koch, S.; Mogensen, M.

2007-03-01

A new controlled atmosphere high temperature SPM has been designed and build for the purpose of performing electrochemical measurements on solid oxide fuel cell materials. The first tests show that images can be obtained at a surface temperature of 465°C in air with a standard AFM AC probe. The aim is to produce images at a surface temperature of 800°C with electrically conducting ceramic probes as working electrodes that can be positioned at desired locations at the surface for electrochemical measurements.

Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

PubMed

Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

2015-10-20

In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants.

Hybrid fibers made of molybdenum disulfide, reduced graphene oxide, and multi-walled carbon nanotubes for solid-state, flexible, asymmetric supercapacitors.

PubMed

Sun, Gengzhi; Zhang, Xiao; Lin, Rongzhou; Yang, Jian; Zhang, Hua; Chen, Peng

2015-04-07

One of challenges existing in fiber-based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two-dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS2 ) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy-related applications. Herein, by incorporating MoS2 and reduced graphene oxide (rGO) nanosheets into a well-aligned multi-walled carbon nanotube (MWCNT) sheet followed by twisting, MoS2 -rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid-state, flexible, asymmetric supercapacitors. This fiber-based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells

PubMed Central

Chen, Yun; Gerdes, Kirk; Song, Xueyan

2016-01-01

Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1−xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650–800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5–1.7 operated at 0.8 V at 750 °C. PMID:27605121

A distributed real-time model of degradation in a solid oxide fuel cell, part I: Model characterization

NASA Astrophysics Data System (ADS)

Zaccaria, V.; Tucker, D.; Traverso, A.

2016-04-01

Despite the high efficiency and flexibility of fuel cells, which make them an attractive technology for the future energy generation, their economic competitiveness is still penalized by their short lifetime, due to multiple degradation phenomena. As a matter of fact, electrochemical performance of solid oxide fuel cells (SOFCs) is reduced because of different degradation mechanisms, which depend on operating conditions, fuel and air contaminants, impurities in materials, and others. In this work, a real-time, one dimensional (1D) model of a SOFC is used to simulate the effects of voltage degradation in the cell. Different mechanisms are summarized in a simple empirical expression that relates degradation rate to cell operating parameters (current density, fuel utilization and temperature), on a localized basis. Profile distributions of different variables during cell degradation are analyzed. In particular, the effect of degradation on current density, temperature, and total resistance of the cell are investigated. An analysis of localized degradation effects shows how different parts of the cell degrade at a different time rate, and how the various profiles are redistributed along the cell as consequence of different degradation rates.

Degradation analysis of anode-supported intermediate temperature-solid oxide fuel cells under various failure modes

NASA Astrophysics Data System (ADS)

Lee, Tae-Hee; Park, Ka-Young; Kim, Ji-Tae; Seo, Yongho; Kim, Ki Buem; Song, Sun-Ju; Park, Byoungnam; Park, Jun-Young

2015-02-01

This study focuses on mechanisms and symptoms of several simulated failure modes, which may have significant influences on the long-term durability and operational stability of intermediate temperature-solid oxide fuel cells (IT-SOFCs), including fuel/oxidation starvation by breakdown of fuel/air supply components and wet and dry cycling atmospheres. Anode-supported IT-SOFCs consisting of a Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF)-Nd0.1Ce0.9O2-δ (NDC) composite cathode with an NDC electrolyte on a Ni-NDC anode substrate are fabricated via dry-pressings followed by the co-firing method. Comprehensive and systematic research based on the failure mode and effect analysis (FMEA) of anode-supported IT-SOFCs is conducted using various electrochemical and physiochemical analysis techniques to extend our understanding of the major mechanisms of performance deterioration under SOFC operating conditions. The fuel-starvation condition in the fuel-pump failure mode causes irreversible mechanical degradation of the electrolyte and cathode interface by the dimensional expansion of the anode support due to the oxidation of Ni metal to NiO. In contrast, the BSCF cathode shows poor stability under wet and dry cycling modes of cathode air due to the strong electroactivity of SrO with H2O. On the other hand, the air-depletion phenomena under air-pump failure mode results in the recovery of cell performance during the long-term operation without the visible microstructural transformation through the reduction of anode overvoltage.

Multiscale Transient and Steady-State Study of the Influence of Microstructure Degradation and Chromium Oxide Poisoning on Solid Oxide Fuel Cell Cathode Performance

NASA Astrophysics Data System (ADS)

Li, Guanchen; von Spakovsky, Michael R.; Shen, Fengyu; Lu, Kathy

2018-01-01

Oxygen reduction in a solid oxide fuel cell cathode involves a nonequilibrium process of coupled mass and heat diffusion and electrochemical and chemical reactions. These phenomena occur at multiple temporal and spatial scales, making the modeling, especially in the transient regime, very difficult. Nonetheless, multiscale models are needed to improve the understanding of oxygen reduction and guide cathode design. Of particular importance for long-term operation are microstructure degradation and chromium oxide poisoning both of which degrade cathode performance. Existing methods are phenomenological or empirical in nature and their application limited to the continuum realm with quantum effects not captured. In contrast, steepest-entropy-ascent quantum thermodynamics can be used to model nonequilibrium processes (even those far-from equilibrium) at all scales. The nonequilibrium relaxation is characterized by entropy generation, which can unify coupled phenomena into one framework to model transient and steady behavior. The results reveal the effects on performance of the different timescales of the varied phenomena involved and their coupling. Results are included here for the effects of chromium oxide concentrations on cathode output as is a parametric study of the effects of interconnect-three-phase-boundary length, oxygen mean free path, and adsorption site effectiveness. A qualitative comparison with experimental results is made.

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.

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

PubMed

Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung

2016-11-09

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

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

DOEpatents

Bowker, J.C.; Singh, P.

1989-08-29

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

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

DOEpatents

Bowker, Jeffrey C.; Singh, Prabhakar

1989-01-01

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

High-Density Magnetic Recording and Integrated Magneto-Optics: Materials and Devices; Symposium Held in San Francisco, California, on April 12-16 1998

DTIC Science & Technology

1998-04-01

Kido •Solution Flow System for Hydrothermal -Electrochemical Synthesis : New Opportunities for Multilayered Oxide Films 639 VI. Suchanek, T...FLOW SYSTEM FOR HYDROTHERMAL -ELECTROCHEMICAL SYNTHESIS : NEW OPPORTUNITIES FOR MULTTLAYERED OXIDE FILMS W. SUCHANEK, T. WATANABE, B. SAKURAI, M...ABSTRACT A solution flow system for hydrothermal -electrochemical synthesis has been constructed in our laboratory. This equipment can operate at 20

Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling.

PubMed

Xie, Jin; Sendek, Austin D; Cubuk, Ekin D; Zhang, Xiaokun; Lu, Zhiyi; Gong, Yongji; Wu, Tong; Shi, Feifei; Liu, Wei; Reed, Evan J; Cui, Yi

2017-07-25

Modern lithium ion batteries are often desired to operate at a wide electrochemical window to maximize energy densities. While pushing the limit of cutoff potentials allows batteries to provide greater energy densities with enhanced specific capacities and higher voltage outputs, it raises key challenges with thermodynamic and kinetic stability in the battery. This is especially true for layered lithium transition-metal oxides, where capacities can improve but stabilities are compromised as wider electrochemical windows are applied. To overcome the above-mentioned challenges, we used atomic layer deposition to develop a LiAlF 4 solid thin film with robust stability and satisfactory ion conductivity, which is superior to commonly used LiF and AlF 3 . With a predicted stable electrochemical window of approximately 2.0 ± 0.9 to 5.7 ± 0.7 V vs Li + /Li for LiAlF 4 , excellent stability was achieved for high Ni content LiNi 0.8 Mn 0.1 Co 0.1 O 2 electrodes with LiAlF 4 interfacial layer at a wide electrochemical window of 2.75-4.50 V vs Li + /Li.

Catalysis in high-temperature fuel cells.

PubMed

Föger, K; Ahmed, K

2005-02-17

Catalysis plays a critical role in solid oxide fuel cell systems. The electrochemical reactions within the cell--oxygen dissociation on the cathode and electrochemical fuel combustion on the anode--are catalytic reactions. The fuels used in high-temperature fuel cells, for example, natural gas, propane, or liquid hydrocarbons, need to be preprocessed to a form suitable for conversion on the anode-sulfur removal and pre-reforming. The unconverted fuel (economic fuel utilization around 85%) is commonly combusted using a catalytic burner. Ceramic Fuel Cells Ltd. has developed anodes that in addition to having electrochemical activity also are reactive for internal steam reforming of methane. This can simplify fuel preprocessing, but its main advantage is thermal management of the fuel cell stack by endothermic heat removal. Using this approach, the objective of fuel preprocessing is to produce a methane-rich fuel stream but with all higher hydrocarbons removed. Sulfur removal can be achieved by absorption or hydro-desulfurization (HDS). Depending on the system configuration, hydrogen is also required for start-up and shutdown. Reactor operating parameters are strongly tied to fuel cell operational regimes, thus often limiting optimization of the catalytic reactors. In this paper we discuss operation of an authothermal reforming reactor for hydrogen generation for HDS and start-up/shutdown, and development of a pre-reformer for converting propane to a methane-rich fuel stream.

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.

Method of doping interconnections for electrochemical cells

DOEpatents

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

1990-01-01

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

Synthesis, Characterization, and Optimization of Novel Solid Oxide Fuel Cell Anodes

NASA Astrophysics Data System (ADS)

Miller, Elizabeth C.

This dissertation presents research on the development of novel materials and fabrication procedures for solid oxide fuel cell (SOFC) anodes. The work discussed here is divided into three main categories: all-oxide anodes, catalyst exsolution oxide anodes, and Ni-infiltrated anodes. The all-oxide and catalyst exsolution anodes presented here are further classi?ed as Ni-free anodes operating at the standard 700-800°C SOFC temperature while the Ni-infiltrated anodes operate at intermediate temperatures (≤650°C). Compared with the current state-of-the-art Ni-based cermets, all-oxide, Ni-free SOFC anodes offer fewer coking issues in carbon-containing fuels, reduced degradation due to fuel contaminants, and improved stability during redox cycling. However, electrochemical performance has proven inferior to Ni-based anodes. The perovskite oxide Fe-substituted strontium titanate (STF) has shown potential as an anode material both as a single phase electrode and when combined with Gd-doped ceria (GDC) in a composite electrode. In this work, STF is synthesized using a modified Pechini processes with the aim of reducing STF particle size and increasing the electrochemically active area in the anode. The Pechini method produced particles ? 750 nm in diameter, which is signi°Cantly smaller than the typically micron-sized solid state reaction powder. In the first iteration of anode fabrication with the Pechini powder, issues with over-sintering of the small STF particles limited gas di?usion in the anode. However, after modifying the anode firing temperature, the Pechini cells produced power density comparable to solid state reaction based cells from previous work by Cho et al. Catalyst exsolution anodes, in which metal cations exsolve out of the lattice under reducing conditions and form nanoparticles on the oxide surface, are another Ni-free option for standard operating temperature SOFCs. Little information is known about the onset of nanoparticle formation, which presents opportunities for the new kinds of ex situ and in situ experiments performed in this thesis. Ex situ experiments involved reducing powder samples at SOFC operating temperatures under hydrogen gas and characterizing them via electron microscopy and X-ray diffraction (XRD). For the in situ experiments, powders were heated, then reduced at temperature, and catalyst exsolution was observed in real-time. Pechini-synthesized cerium oxide substituted with 2-5 mol% Pd was studied using in situ X-ray heating experiments at Argonne National Laboratory's Advanced Photon Source. In these experiments, the powder was subjected to several cycles of reduction and oxidation at 800°C, and Pd metal formation was confirmed through the appearance of Pd peaks in the X-ray spectra. Next, Fe- and Ru-substituted lanthanum strontium chromite (LSCrFeRu14) synthesized by solid state reaction was characterized with ex situ and in situ microscopy. Transmission electron microscopy (TEM) in situ heating experiments were conducted to observe Ru nanoparticle evolution under the reducing conditions of the TEM vacuum chamber. LSCrFeRu14 was heated to 750°C and observed over ˜ 90 min at temperature during which time nanoparticle formation, coarsening, and di?usion were observed. Experiments on both materials sought to understand the conditions and timing of nanoparticle formation in the anode, which is not necessarily apparent from electrochemical data. Reducing the operating temperature of SOFCs from the current state-of-the-art range of 700-800°C to ≤ 650°C has many advantages, among them increased long-term stability, reduced balance of plant costs, fewer interconnect/seal material issues, and decreased start-up times. In order to maintain good performance at reduced temperature, these intermediate temperature SOFCs require new materials including highly active alternatives to micron-scale Ni-YSZ composite anodes. The present work focuses on the development of IT-SOFCs with Sr0.8La 0.2TiO3 (SLT) anode supports, thin La1--xSr x Ga0.8Mg0.2O3 (x = 0.1, 0.2) dense electrolytes, and porous LSGM anode functional layers. The SLT support and the LSGM functional layer are infiltrated with nanoscale Ni, creating extensive electrochemically active triple phase boundary area. The scope of the work presented here encompasses every step of cell development including powder synthesis, optimization of firing conditions, and long-term stability testing. Using an optimized fabrication process, cells with power density > 1.2 W cm-2 were fabricated. Dry pressing and colloidal de-position were used to make the first generation of these cells, and once suitable times and temperatures were determined, the process was shifted to tape casting to make larger batches of uniform cells. After obtaining initial results of low anode polarization resistance and high power density, the long-term stability of the Ni-infiltrated anodes was examined. A coarsening model was developed using the data from accelerated degradation tests to predict cell performance over a typical device lifetime. This thesis encompasses a broad range of novel SOFC anode materials, each of which has its own strengths and weaknesses. Presenting several possible avenues for SOFC development provides a complete picture of the ?eld and its current focuses. The wide scope of this work offers multiple solutions for the SOFC community and demonstrates that SOFCs are a strong candidate for meeting the United States' need for energy conversion and storage.

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.

Designing a protonic ceramic fuel cell with novel electrochemically active oxygen electrodes based on doped Nd0.5Ba0.5FeO3-δ.

PubMed

Lyagaeva, Julia; Danilov, Nilolay; Tarutin, Arthem; Vdovin, Gennady; Medvedev, Dmitry; Demin, Anatoly; Tsiakaras, Panagiotis

2018-06-19

The Fe-based perovskite-structured Nd0.5Ba0.5FeO3-δ (NBF) system represents the basis for developing promising electrode materials for solid oxide fuel cells with proton-conducting electrolytes. This study aims at investigating the strategy of slight doping of neodymium-barium ferrite with some transition metals (M = Ni, Cu, Co) and examining the effect of this doping on the functional characteristics, such as phase structure, thermal expansion, total and ionic conductivity as well as electrochemical behavior, of Nd0.5Ba0.5Fe0.9M0.1O3-δ (NBFM) under testing in symmetrical cell (SC) and fuel cell (FC) modes of operation. Among the investigated dopants, cobalt (Co) is found to be the optimal dopant, resulting in an enhancement of transport properties and avoiding an undesirable increase in the thermal expansion coefficient. As a result, the electrode material made of NBFCo exhibits highest ionic conductivity and lowest polarization resistance in the SC mode of operation. Electrochemical characterization of the NBFCo cathode material in a protonic ceramic fuel cell (PCFC) followed by comparison of the obtained results with literature data demonstrates that NBFCo is an attractive cathode candidate for PCFC applications.

Hierarchical Ti-Nb oxide microspheres with synergic multiphase structure as ultra-long-life anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Guanqin; Wen, Zhongsheng; Du, Lulu; Yang, Yan-E.; Li, Song; Sun, Juncai; Ji, Shijun

2017-11-01

Titanium/niobium oxides have drawn wide attention due to their attractive high lithium-intercalation voltage avoiding the formation of solid electrochemical interface. However, their poor electronic conductivity hinders the commercial applications because of the low electrochemical kinetics in lithiating and de-lithiating process. In the study, new approach to improving the low conductivity of the conventional oxides in micrometers are tactically proposed via the synergic effect of highly mixed multiphase oxide nanocrystals. Ti-Nb oxide composite microspheres with hierarchical microstructure are fabricated successfully via a very facile method combined solvothermal process and calcination. Interconnected crystalline nanoparticles of TiO2, Nb2O5 and TiNb2O7 nanocrystals are involved in the obtained Ti-Nb oxides, demonstrating high structure stability during electrochemical reaction. Meanwhile, the ionic/electronic conductivity is remarkably enhanced by the defects of O2- vacancies and Ti3+/Nb4+ ions. The remained specific capacity of the multiphase Ti-Nb oxides is up to 185.3 mAh g-1 at 5 C with very weak capacity fade of 5.3% after 1800 cycles, showing a very long cycling stability.

High-Performanced Cathode with a Two-Layered R-P Structure for Intermediate Temperature Solid Oxide Fuel Cells.

PubMed

Huan, Daoming; Wang, Zhiquan; Wang, Zhenbin; Peng, Ranran; Xia, Changrong; Lu, Yalin

2016-02-01

Driven by the mounting concerns on global warming and energy crisis, intermediate temperature solid-oxide fuel cells (IT-SOFCs) have attracted special attention for their high fuel efficiency, low toxic gas emission, and great fuel flexibility. A key obstacle to the practical operation of IT-SOFCs is their sluggish oxygen reduction reaction (ORR) kinetics. In this work, we applied a new two-layered Ruddlesden-Popper (R-P) oxide, Sr3Fe2O7-δ (SFO), as the material for oxygen ion conducting IT-SOFCs. Density functional theory calculation suggested that SFO has extremely low oxygen ion formation energy and considerable energy barrier for O(2-) diffusion. Unfortunately, the stable SrO surface of SFO was demonstrated to be inert to O2 adsorption and dissociation reaction, and thus restricts its catalytic activity toward ORR. Based on this observation, Co partially substituted SFO (SFCO) was then synthesized and applied to improve its surface vacancy concentration to accelerate the oxygen adsorptive reduction reaction rate. Electrochemical performance results suggested that the cell using the SFCO single phase cathode has a peak power density of 685 mW cm(-2) at 650 °C, about 15% higher than those when using LSCF cathode. Operating at 200 mA cm(-2), the new cell using SFCO is quite stable within the 100-h' test.

Electrochemical processing of solid waste

NASA Technical Reports Server (NTRS)

Bockris, J. OM.; Hitchens, G. D.; Kaba, L.

1988-01-01

The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.

Enhanced lithium battery with polyethylene oxide-based electrolyte containing silane-Al2 O3 ceramic filler.

PubMed

Zewde, Berhanu W; Admassie, Shimelis; Zimmermann, Jutta; Isfort, Christian Schulze; Scrosati, Bruno; Hassoun, Jusef

2013-08-01

A solid polymer electrolyte prepared by using a solvent-free, scalable technique is reported. The membrane is formed by low-energy ball milling followed by hot-pressing of dry powdered polyethylene oxide polymer, LiCF3 SO3 salt, and silane-treated Al2 O3 (Al2 O3 -ST) ceramic filler. The effects of the ceramic fillers on the properties of the ionically conducting solid electrolyte membrane are characterized by using electrochemical impedance spectroscopy, XRD, differential scanning calorimeter, SEM, and galvanostatic cycling in lithium cells with a LiFePO4 cathode. We demonstrate that the membrane containing Al2 O3 -ST ceramic filler performs well in terms of ionic conductivity, thermal properties, and lithium transference number. Furthermore, we show that the lithium cells, which use the new electrolyte together with the LiFePO4 electrode, operate within 65 and 90 °C with high efficiency and long cycle life. Hence, the Al2 O3 -ST ceramic can be efficiently used as a ceramic filler to enhance the performance of solid polymer electrolytes in lithium batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improvement of performance in low temperature solid oxide fuel cells operated on ethanol and air mixtures using Cu-ZnO-Al2O3 catalyst layer

NASA Astrophysics Data System (ADS)

Morales, M.; Espiell, F.; Segarra, M.

2015-10-01

Anode-supported single-chamber solid oxide fuel cells with and without Cu-ZnO-Al2O3 catalyst layers deposited on the anode support have been operated on ethanol and air mixtures. The cells consist of gadolinia-doped ceria electrolyte, Ni-doped ceria anode, and La0.6Sr0.4CoO3-δ-doped ceria cathode. Catalyst layers with different Cu-ZnO-Al2O3 ratios are deposited and sintered at several temperatures. Since the performance of single-chamber fuel cells strongly depends on catalytic properties of electrodes for partial oxidation of ethanol, the cells are electrochemically characterized as a function of the temperature, ethanol-air molar ratio and gas flow rate. In addition, catalytic activities of supported anode, catalytic layer-supported anode and cathode for partial oxidation of ethanol are analysed. Afterwards, the effect of composition and sintering temperature of catalyst layer on the cell performance are determined. The results indicate that the cell performance can be significantly enhanced using catalyst layers of 30:35:35 and 40:30:30 wt.% Cu-ZnO-Al2O3 sintered at 1100 °C, achieving power densities above 50 mW cm-2 under 0.45 ethanol-air ratio at temperatures as low as 450 °C. After testing for 15 h, all cells present a gradual loss of power density, without carbon deposition, which is mainly attributed to the partial re-oxidation of Ni at the anode.

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

A carbon-air battery for high power generation.

PubMed

Yang, Binbin; Ran, Ran; Zhong, Yijun; Su, Chao; Tadé, Moses O; Shao, Zongping

2015-03-16

We report a carbon-air battery for power generation based on a solid-oxide fuel cell (SOFC) integrated with a ceramic CO2-permeable membrane. An anode-supported tubular SOFC functioned as a carbon fuel container as well as an electrochemical device for power generation, while a high-temperature CO2-permeable membrane composed of a CO3(2-) mixture and an O(2-) conducting phase (Sm(0.2)Ce(0.8)O(1.9)) was integrated for in situ separation of CO2 (electrochemical product) from the anode chamber, delivering high fuel-utilization efficiency. After modifying the carbon fuel with a reverse Boudouard reaction catalyst to promote the in situ gasification of carbon to CO, an attractive peak power density of 279.3 mW cm(-2) was achieved for the battery at 850 °C, and a small stack composed of two batteries can be operated continuously for 200 min. This work provides a novel type of electrochemical energy device that has a wide range of application potentials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper recovery and gold enrichment from waste printed circuit boards by mediated electrochemical oxidation.

PubMed

Fogarasi, Szabolcs; Imre-Lucaci, Florica; Imre-Lucaci, Arpád; Ilea, Petru

2014-05-30

The present study aims to develop an eco-friendly chemical-electrochemical process for the simultaneous recovery of copper and separation of a gold rich residue from waste printed circuit boards (WPCBs). The process was carried out by employing two different types of reactors coupled in series: a leaching reactor with a perforated rotating drum, for the dissolution of base metals and a divided electrochemical reactor for the regeneration of the leaching solution with the parallel electrowinning of copper. The process performances were evaluated on the basis of the dissolution efficiency, current efficiency and specific energy consumptions. Finally a process scale up was realized taking into consideration the optimal values of the operating parameters. The laboratory scale leaching plant allowed the recovery of a high purity copper deposit (99.04wt.%) at a current efficiency of 63.84% and specific energy consumption of 1.75kWh/kg cooper. The gold concentration in the remained solid residue was 25 times higher than the gold concentration in the initial WPCB samples. Copyright © 2014 Elsevier B.V. All rights reserved.

A simplified approach to predict performance degradation of a solid oxide fuel cell anode

NASA Astrophysics Data System (ADS)

Khan, Muhammad Zubair; Mehran, Muhammad Taqi; Song, Rak-Hyun; Lee, Jong-Won; Lee, Seung-Bok; Lim, Tak-Hyoung

2018-07-01

The agglomeration of nickel (Ni) particles in a Ni-cermet anode is a significant degradation phenomenon for solid oxide fuel cells (SOFCs). This work aims to predict the performance degradation of SOFCs due to Ni grain growth by using a simplified approach. Accelerated aging of Ni-scandia stabilized zirconia (SSZ) as an SOFC anode is carried out at 900 °C and subsequent microstructural evolution is investigated every 100 h up to 1000 h using scanning electron microscopy (SEM). The resulting morphological changes are quantified using a two-dimensional image analysis technique that yields the particle size, phase proportion, and triple phase boundary (TPB) point distribution. The electrochemical properties of an anode-supported SOFC are characterized using electrochemical impedance spectroscopy (EIS). The changes of particle size and TPB length in the anode as a function of time are in excellent agreement with the power-law coarsening model. This model is further combined with an electrochemical model to predict the changes in the anode polarization resistance. The predicted polarization resistances are in good agreement with the experimentally obtained values. This model for prediction of anode lifetime provides deep insight into the time-dependent Ni agglomeration behavior and its impact on the electrochemical performance degradation of the SOFC anode.

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.

Biotic and abiotic characterization of bioanodes formed on oxidized carbon electrodes as a basis to predict their performance.

PubMed

Cercado, Bibiana; Cházaro-Ruiz, Luis Felipe; Ruiz, Vianey; López-Prieto, Israel de Jesús; Buitrón, Germán; Razo-Flores, Elías

2013-12-15

Bioelectrochemical systems (BESs) are based on the catalytic activity of biofilm on electrodes, or the so-called bioelectrodes, to produce electricity and other valuable products. In order to increase bioanode performance, diverse electrode materials and modification methods have been implemented; however, the factors directly affecting performance are yet unclear. In this work carbon cloth electrodes were modified by thermal, chemical, and electrochemical oxidation to enhance oxygenated surface groups, to modify the electrode texture, and consequently the electron transfer rate and biofilm adhesion. The oxidized electrodes were physically, chemically, and electrochemically characterized, then bioanodes were formed at +0.1 V vs. Ag/AgCl using domestic wastewater amended with acetate. The bioanode performance was evaluated according to the current and charge generated. The efficacy of the treatments were in the order Thermal>Electrochemical>Untreated>Chemical oxidation. The maximum current observed with untreated electrode was 0.152±0.026 mA (380±92 mA m(-2)), and it was increased by 78% and 28% with thermal and electrochemical oxidized electrodes, respectively. Moreover, the volatile solids correlated significantly with the maximum current obtained, and the electrode texture was revealed as a critical factor for increasing the bioanode performance. Copyright © 2013 Elsevier B.V. All rights reserved.

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

PubMed

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

Comparative studies on single-layer reduced graphene oxide films obtained by electrochemical reduction and hydrazine vapor reduction

NASA Astrophysics Data System (ADS)

Wang, Zhijuan; Wu, Shixin; Zhang, Juan; Chen, Peng; Yang, Guocheng; Zhou, Xiaozhu; Zhang, Qichun; Yan, Qingyu; Zhang, Hua

2012-02-01

The comparison between two kinds of single-layer reduced graphene oxide (rGO) sheets, obtained by reduction of graphene oxide (GO) with the electrochemical method and hydrazine vapor reduction, referred to as E-rGO and C-rGO, respectively, is systematically studied. Although there is no morphology difference between the E-rGO and C-rGO films adsorbed on solid substrates observed by AFM, the reduction process to obtain the E-rGO and C-rGO films is quite different. In the hydrazine vapor reduction, the nitrogen element is incorporated into the obtained C-rGO film, while no additional element is introduced to the E-rGO film during the electrochemical reduction. Moreover, Raman spectra show that the electrochemical method is more effective than the hydrazine vapor reduction method to reduce the GO films. In addition, E-rGO shows better electrocatalysis towards dopamine than does C-rGO. This study is helpful for researchers to understand these two different reduction methods and choose a suitable one to reduce GO based on their experimental requirements.

Atomic layer deposition of ruthenium surface-coating on porous platinum catalysts for high-performance direct ethanol solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Jeong, Heon Jae; Kim, Jun Woo; Jang, Dong Young; Shim, Joon Hyung

2015-09-01

Pt-Ru bi-metallic catalysts are synthesized by atomic layer deposition (ALD) of Ru surface-coating on sputtered Pt mesh. The catalysts are evaluated in direct ethanol solid oxide fuel cells (DESOFCs) in the temperature range of 300-500 °C. Island-growth of the ALD Ru coating is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses. The performance of the DESOFCs is evaluated based on the current-voltage output and electrochemical impedance spectroscopy. Genuine reduction of the polarization impedance, and enhanced power output with improved surface kinetics are achieved with the optimized ALD Ru surface-coating compared to bare Pt. The chemical composition of the Pt/ALD Ru electrode surface after fuel cell operation is analyzed via XPS. Enhanced cell performance is clearly achieved, attributed to the effective Pt/ALD Ru bi-metallic catalysis, including oxidation of Cdbnd O by Ru, and de-protonation of ethanol and cleavage of C-C bonds by Pt, as supported by surface morphology analysis which confirms formation of a large amount of carbon on bare Pt after the ethanol-fuel-cell test.

Performance Impact Associated with Ni-Based SOFCs Fueled with Higher Hydrocarbon-Doped Coal Syngas

NASA Astrophysics Data System (ADS)

Hackett, Gregory A.; Gerdes, Kirk; Chen, Yun; Song, Xueyan; Zondlo, John

2015-03-01

Energy generation strategies demonstrating high efficiency and fuel flexibility are desirable in the contemporary energy market. When integrated with a gasification process, a solid oxide fuel cell (SOFC) can produce electricity at efficiencies exceeding 50 pct by consuming fuels such as coal, biomass, municipal solid waste, or other opportunity wastes. The synthesis gas derived from such fuel may contain trace species (including arsenic, lead, cadmium, mercury, phosphorus, sulfur, and tars) and low concentration organic species that adversely affect the SOFC performance. This work demonstrates the impact of exposure of the hydrocarbons ethylene, benzene, and naphthalene at various concentrations. The cell performance degradation rate is determined for tests exceeding 500 hours at 1073 K (800 °C). Cell performance is evaluated during operation with electrochemical impedance spectroscopy, and exposed samples are post-operationally analyzed by scanning electron microscopy/energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The short-term performance is modeled to predict performances to the desired 40,000-hours operational lifetime for SOFCs. Possible hydrocarbon interactions with the nickel anode are postulated, and acceptable hydrocarbon exposure limits are discussed.

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

PubMed

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

Solid oxide fuel cell generator

DOEpatents

Draper, Robert; George, Raymond A.; Shockling, Larry A.

1993-01-01

A solid oxide fuel cell generator has a pair of spaced apart tubesheets in a housing. At least two intermediate barrier walls are between the tubesheets and define a generator chamber between two intermediate buffer chambers. An array of fuel cells have tubes with open ends engaging the tubesheets. Tubular, axially elongated electrochemical cells are supported on the tubes in the generator chamber. Fuel gas and oxidant gas are preheated in the intermediate chambers by the gases flowing on the other side of the tubes. Gas leakage around the tubes through the tubesheets is permitted. The buffer chambers reentrain the leaked fuel gas for reintroduction to the generator chamber.

ELECTROCHEMISTRY AND ON-CELL REFORMATION MODELING FOR SOLID OXIDE FUEL CELL STACKS

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

Recknagle, Kurtis P.; Jarboe, Daniel T.; Johnson, Kenneth I.

2007-01-16

ABSTRACT Providing adequate and efficient cooling schemes for solid-oxide-fuel-cell (SOFC) stacks continues to be a challenge coincident with the development of larger, more powerful stacks. The endothermic steam-methane reformation reaction can provide cooling and improved system efficiency when performed directly on the electrochemically active anode. Rapid kinetics of the endothermic reaction typically causes a localized temperature depression on the anode near the fuel inlet. It is desirable to extend the endothermic effect over more of the cell area and mitigate the associated differences in temperature on the cell to alleviate subsequent thermal stresses. In this study, modeling tools validated formore » the prediction of fuel use, on-cell methane reforming, and the distribution of temperature within SOFC stacks, are employed to provide direction for modifying the catalytic activity of anode materials to control the methane conversion rate. Improvements in thermal management that can be achieved through on-cell reforming is predicted and discussed. Two operating scenarios are considered: one in which the methane fuel is fully pre-reformed, and another in which a substantial percentage of the methane is reformed on-cell. For the latter, a range of catalytic activity is considered and the predicted thermal effects on the cell are presented. Simulations of the cell electrochemical and thermal performance with and without on-cell reforming, including structural analyses, show a substantial decrease in thermal stresses for an on-cell reforming case with slowed methane conversion.« less

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.

Performance evaluation of a liquid tin anode solid oxide fuel cell operating under hydrogen, argon and coal

NASA Astrophysics Data System (ADS)

Khurana, Sanchit; LaBarbera, Mark; Fedkin, Mark V.; Lvov, Serguei N.; Abernathy, Harry; Gerdes, Kirk

2015-01-01

A liquid tin anode solid oxide fuel cell is constructed and investigated under different operating conditions. Electrochemical Impedance Spectroscopy (EIS) is used to reflect the effect of fuel feed as the EIS spectra changes significantly on switching the fuel from argon to hydrogen. A cathode symmetric cell is used to separate the impedance from the two electrodes, and the results indicate that a major contribution to the charge-transfer and mass-transfer impedance arises from the anode. The OCP of 0.841 V for the cell operating under argon as a metal-air battery indicates the formation of a SnO2 layer at the electrolyte/anode interface. The increase in the OCP to 1.1 V for the hydrogen fueled cell shows that H2 reduces the SnO2 film effectively. The effective diffusion coefficients are calculated using the Warburg element in the equivalent circuit model for the experimental EIS data, and the values of 1.9 10-3 cm2 s-1 at 700 °C, 2.3 10-3 cm2 s-1 at 800 °C and 3.5 10-3 cm2 s-1 at 900 °C indicate the system was influenced by diffusion of hydrogen in the system. Further, the performance degradation over time is attributed to the irreversible conversion of Sn to SnO2 resulting from galvanic polarization.

A novel family of Nb-doped Bi0.5Sr0.5FeO3-δ perovskite as cathode material for intermediate-temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Gao, Lei; Li, Qiang; Sun, Liping; Zhang, Xianfa; Huo, Lihua; Zhao, Hui; Grenier, Jean-Claude

2017-12-01

Cobalt-free provskite oxides Bi0.5Sr0.5Fe1-xNbxO3-δ (BSFNx, x = 0.05, 0.10 and 0.15) were prepared and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). In particular, the effects of Nb substitution on phase evolution, thermal expansion behavior and electrochemical performance were systematically investigated. The average thermal expansion coefficient (TEC) of BSFNx decreases from 13.3 × 10-6 K-1 at x = 0.05 to 12.6 × 10-6 K-1 at x = 0.15 within a temperature range of 50-800 °C. Among the BSFNx materials, Bi0.5Sr0.5Fe0.9Nb0.1O3-δ (BSFN0.10) oxide shows the best electrochemical performance. The polarization resistances (Rp) of BSFN0.10 cathode on CGO electrolyte are 0.038, 0.075 and 0.156 Ω cm2 at 700, 650 and 600 °C, respectively. Meanwhile the maximum power densities of the anode-supported single cells are 1.28, 1.54 and 1.34 W cm-2 at 700 °C for BSFNx cathodes with x = 0.05, 0.10, and 0.15, respectively. Furthermore, the relationship study of oxygen partial pressure dependence on Rp indicates that the oxygen reduction reaction (ORR) rate-limiting step is the oxygen adsorption-dissociation on the electrode surface. The desirable electrochemical performance demonstrates that BSFNx oxides are potential cathode materials for IT-SOFCs.

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.

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.

Electric-Loading Enhanced Kinetics in Oxide Ceramics: Pore Migration, Sintering and Grain Growth: Final Report

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

Chen, I-Wei

Solid oxide fuel cells and solid oxide electrolysis cells rely on solid electrolytes in which a large ionic current dominates. This project was initiated to investigate microstructural changes in such devices under electrochemical forces, because nominally insignificant processes may couple to the large ionic current to yield non-equilibrium phenomena that alter the microstructure. Our studies had focused on yttria-stabilized cubic zirconia (YSZ) widely used in these devices. The experiments have revealed enhanced grain growth at higher temperatures, pore and gas bubble migration at all temperatures, and the latter also lead to enhanced sintering of highly porous ceramics into fully densemore » ceramics at unprecedentedly low temperatures. These results have shed light on kinetic processes that fall completely outside the realm of classical ceramic processing. Other fast-oxygen oxide ceramics closely related to, and often used in conjunction with zirconia ceramics, have also be investigated, as are closely related scientific problems in zirconia ceramics. These include crystal structures, defects, diffusion kinetics, oxygen potentials, low temperature sintering, flash sintering, and coarsening theory, and all have resulted in greater clarity in scientific understanding. The knowledge is leveraged to provide new insight to electrode kinetics and near-electrode mixed conductivity and to new materials. In the following areas, our research has resulted in completely new knowledge that defines the state-of-the-art of the field. (a) Electrical current driven non-equilibrium phenomena, (b) Enhanced grain growth under electrochemically reducing conditions, (c) Development of oxygen potential polarization in electrically loaded electrolyte, (d) Low temperature sintering and grain growth, and (e) Structure, defects and cation kinetics of fluorite-structured oxides. Our research has also contributed to synthesis of new energy-relevant electrochemical materials and new understanding of flash sintering, which is a rapid sintering process initiated by a large electrical loading.« less

In situ and nonvolatile photoluminescence tuning and nanodomain writing demonstrated by all-solid-state devices based on graphene oxide.

PubMed

Tsuchiya, Takashi; Tsuruoka, Tohru; Terabe, Kazuya; Aono, Masakazu

2015-02-24

In situ and nonvolatile tuning of photoluminescence (PL) has been achieved based on graphene oxide (GO), the PL of which is receiving much attention because of various potential applications of the oxide (e.g., display, lighting, and nano-biosensor). The technique is based on in situ and nonvolatile tuning of the sp(2) domain fraction to the sp(3) domain fraction (sp(2)/sp(3) fraction) in GO through an electrochemical redox reaction achieved by solid electrolyte thin films. The all-solid-state variable PL device was fabricated by GO and proton-conducting mesoporous SiO2 thin films, which showed an extremely low PL background. The device successfully tuned the PL peak wavelength in a very wide range from 393 to 712 nm, covering that for chemically tuned GO, by adjusting the applied DC voltage within several hundred seconds. We also demonstrate the sp(2)/sp(3) fraction tuning using a conductive atomic force microscope. The device achieved not only writing, but also erasing of the sp(2)/sp(3)-fraction-tuned nanodomain (both directions operation). The combination of these techniques is applicable to a wide range of nano-optoelectronic devices including nonvolatile PL memory devices and on-demand rewritable biosensors that can be integrated into nano- and microtips which are transparent, ultrathin, flexible, and inexpensive.

Disinfection of biologically treated wastewater and prevention of biofouling by UV/electrolysis hybrid technology: influence factors and limits for domestic wastewater reuse.

PubMed

Haaken, Daniela; Dittmar, Thomas; Schmalz, Viktor; Worch, Eckhard

2014-04-01

Reuse of wastewater contributes significantly to an efficient and sustainable water usage. However, due to the presence of a multitude of pathogens (e.g. bacteria, viruses, worms, protozoa) in secondary effluents, disinfection procedures are indispensable. In decentralized wastewater treatment, UV irradiation represents one of the most common disinfection methods in addition to membrane processes and to a certain extent electrochemical procedures. However, the usage of UV disinfected secondary effluents for domestic (sanitary) or irrigation purposes bears a potential health risk due to the possible photo and dark repair of reversibly damaged bacteria. Against this background, the application of the UV/electrolysis hybrid technology for disinfection and prevention of bacterial reactivation in biologically treated wastewater was investigated in view of relevant influence factors and operating limits. Furthermore, the influence of electrochemically generated total oxidants on the formation of biofilms on quartz glass surfaces was examined, since its preventive avoidance contributes to an enhanced operational safety of the hybrid reactor. It was found that reactivation of bacteria in UV irradiated, biologically treated wastewater can be prevented by electrochemically produced total oxidants. In this regard, the influence of the initial concentration of the microbiological indicator organism Escherichia coli (E. coli) (9.3*10(2)-2.2*10(5) per 100 mL) and the influence of total suspended solids (TSS) in the range of 11-75 mg L(-1) was examined. The concentration of total oxidants necessary for prevention of bacterial regrowth increases linearly with the initial E. coli and TSS concentration. At an initial concentration of 933 E. coli per 100 mL, a total oxidants concentration of 0.4 mg L(-1) is necessary to avoid photo reactivation (at 4200 Lux), whereas 0.67 mg L(-1) is required if the E. coli concentration is enhanced by 2.4 log levels (cTSS = constant = 13 mg L(-1)). The prevention of dark repair is ensured with 25-50% lower concentration of total oxidants. An increase of the TSS concentration from 11 mg L(-1) to 75 mg L(-1) leads to a triplication of the need of total oxidants from 0.6 mg L(-1) to 1.8 mg L(-1) (3*10(5)E. coli per 100 mL). The energy consumption of the hybrid reactor varies from 0.17 kWh m(-3) to 0.94 kWh m(-3) depending on the TSS concentration (11-75 mg L(-1)). Furthermore, biofilm formation on quartz glass surfaces, of which the sleeves of UV lamps consist, can be suppressed by electrochemically produced total oxidants at a concentration of at least 1 mg L(-1) which ensures high operational safety of the hybrid reactor combined with large maintenance intervals. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Solid oxide electrochemical cell fabrication process

DOEpatents

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

1992-01-01

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

Graphene nanocomposites for electrochemical cell electrodes

DOEpatents

Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun

2015-11-19

A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

Intensive Study on the Catalytical Behavior of N-Methylphenothiazine as a Soluble Mediator to Oxidize the Li2O2 Cathode of the Li-O2 Battery.

PubMed

Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen

2017-02-01

Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.

High-temperature electrolysis of synthetic seawater using solid oxide electrolyzer cells

NASA Astrophysics Data System (ADS)

Lim, Chee Kuan; Liu, Qinglin; Zhou, Juan; Sun, Qiang; Chan, Siew Hwa

2017-02-01

A Ni-YSZ/YSZ/LSCF-GDC solid oxide electrolyzer cell (SOEC) is used to investigate the effects of seawater electrolysis for hydrogen production through electrolyzing steam produced from simulated seawater bath. Steam electrolysis using an SOEC with its fuel electrode contaminated by sea salt is also investigated. Steam produced from seawater is found to be free of contaminants, which are present in the seawater. Similar electrochemical performance is observed from the polarization curves and impedance spectra when using steam produced from pure water and seawater. Their short-term degradation rates are similar, which are registered at 15% 1000 h-1 for both cases. For the case of direct sea salt contamination in an SOEC's fuel electrode, both the uncontaminated and contaminated cells exhibit rather similar performance as observed from the polarization curves and impedance spectra. The difference in ASR values from the polarization curves and impedance spectra between the uncontaminated and contaminated cell are all within a 10% range. Rather similar short-term degradation rates of 15% 1000 h-1 and 16% 1000 h-1 are recorded for the uncontaminated and contaminated cells, respectively. Post-mortem analysis shows that the sea salt impregnated into the cell has been vaporized at a typical SOEC operating temperature of 800 °C over the period of operation.

Three-electrode metal oxide reduction cell

DOEpatents

Dees, Dennis W.; Ackerman, John P.

2008-08-12

A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

Three-Electrode Metal Oxide Reduction Cell

DOEpatents

Dees, Dennis W.; Ackerman, John P.

2005-06-28

A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

Enhancing Electrode Performance by Exsolved Nanoparticles: A Superior Cobalt-Free Perovskite Electrocatalyst for Solid Oxide Fuel Cells.

PubMed

Yang, Guangming; Zhou, Wei; Liu, Meilin; Shao, Zongping

2016-12-28

The successful development of low-cost, durable electrocatalysts for oxygen reduction reaction (ORR) at intermediate temperatures is critical for broad commercialization of solid oxide fuel cells. Here, we report our findings in design, fabrication, and characterization of a cobalt-free SrFe 0.85 Ti 0.1 Ni 0.05 O 3-δ cathode decorated with NiO nanoparticles. Exsolved from and well bonded to the parent electrode under well-controlled conditions, the NiO nanoparticles uniformly distributed on the surface of the parent electrode greatly enhance cathode performance, demonstrating ORR activity better than that of the benchmark cobalt-based Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ . Further, a process for regeneration of the NiO nanoparticles was also developed to mitigate potential performance degradation due to coarsening of NiO particles under practical operating conditions. As a general approach, this exsolution-dissolution of electrocatalytically active nanoparticles on an electrode surface may be applicable to the development of other high-performance cobalt-free cathodes for fuel cells and other electrochemical systems.

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.

Controlling Oxygen Mobility in Ruddlesden–Popper Oxides

PubMed Central

Lee, Dongkyu; Lee, Ho Nyung

2017-01-01

Discovering new energy materials is a key step toward satisfying the needs for next-generation energy conversion and storage devices. Among the various types of oxides, Ruddlesden–Popper (RP) oxides (A2BO4) are promising candidates for electrochemical energy devices, such as solid oxide fuel cells, owing to their attractive physicochemical properties, including the anisotropic nature of oxygen migration and controllable stoichiometry from oxygen excess to oxygen deficiency. Thus, understanding and controlling the kinetics of oxygen transport are essential for designing optimized materials to use in electrochemical energy devices. In this review, we first discuss the basic mechanisms of oxygen migration in RP oxides depending on oxygen nonstoichiometry. We then focus on the effect of changes in the defect concentration, crystallographic orientation, and strain on the oxygen migration in RP oxides. We also briefly review their thermal and chemical stability. Finally, we conclude with a perspective on potential research directions for future investigation to facilitate controlling oxygen ion migration in RP oxides. PMID:28772732

Treatment of winery wastewater by electrochemical methods and advanced oxidation processes.

PubMed

Orescanin, Visnja; Kollar, Robert; Nad, Karlo; Mikelic, Ivanka Lovrencic; Gustek, Stefica Findri

2013-01-01

The aim of this research was development of new system for the treatment of highly polluted wastewater (COD = 10240 mg/L; SS = 2860 mg/L) originating from vine-making industry. The system consisted of the main treatment that included electrochemical methods (electro oxidation, electrocoagulation using stainless steel, iron and aluminum electrode sets) with simultaneous sonication and recirculation in strong electromagnetic field. Ozonation combined with UV irradiation in the presence of added hydrogen peroxide was applied for the post-treatment of the effluent. Following the combined treatment, the final removal efficiencies of the parameters color, turbidity, suspended solids and phosphates were over 99%, Fe, Cu and ammonia approximately 98%, while the removal of COD and sulfates was 77% and 62%, respectively. A new approach combining electrochemical methods with ultrasound in the strong electromagnetic field resulted in significantly better removal efficiencies for majority of the measured parameters compared to the biological methods, advanced oxidation processes or electrocoagulation. Reduction of the treatment time represents another advantage of this new approach.

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.

Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

PubMed

Körbahti, Bahadır K; Taşyürek, Selin

2015-03-01

Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

Removal of arsenic, phosphates and ammonia from well water using electrochemical/chemical methods and advanced oxidation: a pilot plant approach.

PubMed

Orescanin, Visnja; Kollar, Robert; Nad, Karlo; Halkijevic, Ivan; Kuspilic, Marin; Findri Gustek, Stefica

2014-01-01

The purpose of this work was to develop a pilot plant purification system and apply it to groundwater used for human consumption, containing high concentrations of arsenic and increased levels of phosphates, ammonia, mercury and color. The groundwater used was obtained from the production well in the Vinkovci County (Eastern Croatia). Due to a complex composition of the treated water, the purification system involved a combined electrochemical treatment, using iron and aluminum electrode plates with simultaneous ozonation, followed by a post-treatment with UV, ozone and hydrogen peroxide. The removal of the contaminant with the waste sludge collected during the electrochemical treatment was also tested. The combined electrochemical and advanced oxidation treatment resulted in the complete removal of arsenic, phosphates, color, turbidity, suspended solids and ammonia, while the removal of other contaminants of interest was up to 96.7%. Comparable removal efficiencies were obtained by using waste sludge as a coagulant.

Influence of Adsorbed Hydroxyl and Carbon Monoxide on Potential-Induced Reconstruction of Au(100) as Examined by Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

years have witnessed substantial advances in our knowledge of metal reconstruction in electrochemical systems, primarily for low-index gold surfaces in...index gold surfaces, reconstruction can be formed or removed by applying electrode potentials corresponding to negative or positive electronic charge...potential and gold oxidation regions, for Au(100) in 0.1 M KOH, obtained in a conventional electrochemical cell (solid trace). The voltammetric

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

PubMed

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

2013-12-11

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

Electrodeposition for Electrochemical Energy Conversion and Storage Devices

NASA Astrophysics Data System (ADS)

Shaigan, Nima

Electrodeposition of metals, alloys, metal oxides, conductive polymers, and their composites plays a pivotal role in fabrication processes of some recently developed electrochemical energy devices, most particularly fuel cells, supercapacitors, and batteries. Unique nanoscale architectures of electrocatalysts for low temperature fuel cells, including proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC), can only be obtained through electrodeposition processes. Promising, cost-effective conductive/protective coatings for stainless steel interconnects used in solid oxide fuel cells (SOFCs) have been achieved employing a variety of electrodeposition techniques. In supercapacitors, anodic deposition of metal oxides, conductive polymers, and their composites is a versatile technique for fabrication of electrodes with distinctive morphology and exceptional specific capacitance. Electrodeposition is also very recently employed for preparation of Sn-based anodes for lithium ion batteries.

Measurement of phenols dearomatization via electrolysis: the UV-Vis solid phase extraction method.

PubMed

Vargas, Ronald; Borrás, Carlos; Mostany, Jorge; Scharifker, Benjamin R

2010-02-01

Dearomatization levels during electrochemical oxidation of p-methoxyphenol (PMP) and p-nitrophenol (PNP) have been determined through UV-Vis spectroscopy using solid phase extraction (UV-Vis/SPE). The results show that the method is satisfactory to determine the ratio between aromatic compounds and aliphatic acids and reaction kinetics parameters during treatment of wastewater, in agreement with results obtained from numerical deconvolution of UV-Vis spectra. Analysis of solutions obtained from electrolysis of substituted phenols on antimony-doped tin oxide (SnO(2)--Sb) showed that an electron acceptor substituting group favored the aromatic ring opening reaction, preventing formation of intermediate quinone during oxidation. (c) 2009 Elsevier Ltd. All rights reserved.

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

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.

Complete removal of AHPS synthetic dye from water using new electro-fenton oxidation catalyzed by natural pyrite as heterogeneous catalyst.

PubMed

Labiadh, Lazhar; Oturan, Mehmet A; Panizza, Marco; Hamadi, Nawfel Ben; Ammar, Salah

2015-10-30

The mineralization of a new azo dye - the (4-amino-3-hydroxy-2-p-tolylazo-naphthalene-1-sulfonic acid) (AHPS) - has been studied by a novel electrochemical advanced oxidation process (EAOP), consisting in electro-Fenton (EF) oxidation, catalyzed by pyrite as the heterogeneous catalyst - the so-called 'pyrite-EF'. This solid pyrite used as heterogeneous catalyst instead of a soluble iron salt, is the catalyst the system needs for production of hydroxyl radicals. Experiments were performed in an undivided cell equipped with a BDD anode and a commercial carbon felt cathode to electrogenerate in situ H2O2 and regenerate ferrous ions as catalyst. The effects on operating parameters, such as applied current, pyrite concentration and initial dye content, were investigated. AHPS decay and mineralization efficiencies were monitored by HPLC analyses and TOC measurements, respectively. Experimental results showed that AHPS was quickly oxidized by hydroxyl radicals (OH) produced simultaneously both on BDD surface by water discharge and in solution bulk from electrochemically assisted Fenton's reaction with a pseudo-first-order reaction. AHPS solutions with 175 mg L(-1) (100 mg L(-1) initial TOC) content were then almost completely mineralized in 8h. Moreover, the results demonstrated that, under the same conditions, AHPS degradation by pyrite electro-Fenton process was more powerful than the conventional electro-Fenton process. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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

Cell and current collector felt arrangement for solid oxide electrochemical cell combinations

DOEpatents

Reichner, Philip

1988-01-01

A solid electrolyte electrochemical cell combination 1 is made, comprising an annular, axially elongated, inner electrode 2 containing at least one interior gas feed conduit 3; annular solid electrolyte segments 4 around and covering portions of the inner electrode; annular outer electrode segments 6 around and covering portions of the electrolyte segments; electronically conducting, non-porous, interconnection material 5 disposed between electrolyte segments and in contact with the inner electrode, and electronically conducting, porous, metal fiber current collector felts 7 disposed on top of the non-porous interconnect material and outer electrode segments, where both the non-porous interconnect material and the porous metal felts are disposed circumferentially about the cell, transversely to the axial length of the cell and the inner electrode is continuous for the entire axial length of the cell combination.

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, Roswell J.; Basel, Richard A.

1996-01-01

A gas sensor measures O.sub.2 content of a reformable monitored gas containing hydrocarbons H.sub.2 O and/or CO.sub.2, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system.

Oxygen sensor for monitoring gas mixtures containing hydrocarbons

DOEpatents

Ruka, R.J.; Basel, R.A.

1996-03-12

A gas sensor measures O{sub 2} content of a reformable monitored gas containing hydrocarbons, H{sub 2}O and/or CO{sub 2}, preferably in association with an electrochemical power generation system. The gas sensor has a housing communicating with the monitored gas environment and carries the monitored gas through an integral catalytic hydrocarbon reforming chamber containing a reforming catalyst, and over a solid electrolyte electrochemical cell used for sensing purposes. The electrochemical cell includes a solid electrolyte between a sensor electrode that is exposed to the monitored gas, and a reference electrode that is isolated in the housing from the monitored gas and is exposed to a reference gas environment. A heating element is also provided in heat transfer communication with the gas sensor. A circuit that can include controls operable to adjust operations via valves or the like is connected between the sensor electrode and the reference electrode to process the electrical signal developed by the electrochemical cell. The electrical signal varies as a measure of the equilibrium oxygen partial pressure of the monitored gas. Signal noise is effectively reduced by maintaining a constant temperature in the area of the electrochemical cell and providing a monitored gas at chemical equilibria when contacting the electrochemical cell. The output gas from the electrochemical cell of the sensor is fed back into the conduits of the power generating system. 4 figs.

Hollow nanostructures of metal oxides as next generation electrode materials for supercapacitors.

PubMed

Sharma, Vikas; Singh, Inderjeet; Chandra, Amreesh

2018-01-22

Hollow nanostructures of copper oxides help to stabilize appreciably higher electrochemical characteristics than their solid counter parts of various morphologies. The specific capacitance values, calculated using cyclic voltammetry (CV) and charge-discharge (CD) studies, are found to be much higher than the values reported in literature for copper oxide particles showing  intriguing morphologies or even composites with trendy systems like CNTs, rGO, graphene, etc. The proposed cost-effective synthesis route makes these materials industrially viable for application in alternative energy storage devices. The improved electrochemical response can be attributed to effective access to the higher number of redox sites that become available on the surface, as well as in the cavity of the hollow particles. The ion transport channels also facilitate efficient de-intercalation, which results in the enhancement of cyclability and Coulombic efficiency. The charge storage mechanism in copper oxide structures is also proposed in the paper.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

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

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Devices capable of removing silicon and aluminum from gaseous atmospheres

DOEpatents

Spengler, Charles J.; Singh, Prabhakar

1989-01-01

An electrochemical device is made of a containment vessel (30) optional ceramic material within the containment vessel and including one or more electrochemical cells (10), the cells containing a porous exposed electrode (11) in contact with a solid electrolyte, where at least one of the exposed electrode, the containment vessel, and the optional ceramic material contains a deposit selected from metal oxide and metal salt capable of forming a metal oxide upon heating, where the metal is selected from the group consisting of Ce, Sm, Mg, Be, Ca, Sr, Ti, Zr, Hf, Y, La, Pr, Nb, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, U, and their mixtures.

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Cusick, Robert J.

1988-01-01

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

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.

Electrochemical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ electrolyte based proton-conducting SOFC solid oxide fuel cell with layered perovskite PrBaCo2O5+δ cathode

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xie, Yuanyuan; Xue, Xingjian

2011-03-01

BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBaCo2O5+δ (PBCO) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni-BZCYYb|BZCYYb|PBCO. The performance of the button cell was tested under intermediate-temperature range from 600 to 700 °C with humified H2 (∼3% H2O) as fuel and ambient air as oxidant. The results show that the open circuit potential of 0.983 V and the maximal power density of 490 mW cm-2 were achieved at 700 °C. By co-doping barium zirconate-cerate with Y and Yb, the conductivity of electrolyte was significantly improved. The polarization processes of the button cell were characterized using the complicated electrochemical impedance spectroscopy technique. The results indicate that the polarization resistances contributed from both charge migration processes and mass transfer processes increase with decreasing cell voltage loads. However the polarization resistance induced by mass transfer processes is negligible in the studied button cell.

Electrode design for direct-methane micro-tubular solid oxide fuel cell (MT-SOFC)

NASA Astrophysics Data System (ADS)

Rabuni, Mohamad Fairus; Li, Tao; Punmeechao, Puvich; Li, Kang

2018-04-01

Herein, a micro-structured electrode design has been developed via a modified phase-inversion method. A thin electrolyte integrated with a highly porous anode scaffold has been fabricated in a single-step process and developed into a complete fuel cell for direct methane (CH4) utilisation. A continuous and well-dispersed layer of copper-ceria (Cu-CeO2) was incorporated inside the micro-channels of the anode scaffold. A complete cell was investigated for direct CH4 utilisation. The well-organised micro-channels and nano-structured Cu-CeO2 anode contributed to an increase in electrochemical reaction sites that promoted charge-transfer as well as facilitating gaseous fuel distribution, resulting in outstanding performances. Excellent electrochemical performances have been achieved in both hydrogen (H2) and CH4 operation. The power density of 0.16 Wcm-2 at 750 °C with dry CH4 as fuel is one of the highest ever reported values for similar anode materials.

Performance and stability of a liquid anode high-temperature metal-air battery

NASA Astrophysics Data System (ADS)

Otaegui, L.; Rodriguez-Martinez, L. M.; Wang, L.; Laresgoiti, A.; Tsukamoto, H.; Han, M. H.; Tsai, C.-L.; Laresgoiti, I.; López, C. M.; Rojo, T.

2014-02-01

A High-Temperature Metal-Air Battery (HTMAB) that operates based on a simple redox reaction between molten metal and atmospheric oxygen at 600-1000 °C is presented. This innovative HTMAB concept combines the technology of conventional metal-air batteries with that of solid oxide fuel cells to provide a high energy density system for many applications. Electrochemical reversibility is demonstrated with 95% coulomb efficiency. Cell sealing has been identified as a key issue in order to determine the end-of-charge voltage, enhance coulomb efficiency and ensure long term stability. In this work, molten Sn is selected as anode material. Low utilization of the stored material due to precipitation of the SnO2 on the electrochemically active area limits the expected capacity, which should theoretically approach 903 mAh g-1. Nevertheless, more than 1000 charge/discharge cycles are performed during more than 1000 h at 800 °C, showing highly promising results of stability, reversibility and cyclability.

Electra-optical device including a nitrogen containing electrolyte

DOEpatents

Bates, J.B.; Dudney, N.J.; Gruzalski, G.R.; Luck, C.F.

1995-10-03

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.

Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors.

PubMed

Zang, Xining; Shen, Caiwei; Kao, Emmeline; Warren, Roseanne; Zhang, Ruopeng; Teh, Kwok Siong; Zhong, Junwen; Wei, Minsong; Li, Buxuan; Chu, Yao; Sanghadasa, Mohan; Schwartzberg, Adam; Lin, Liwei

2018-02-01

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS 2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g -1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg -1 -the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg -1 with stable operation over 10 000 cycles. A flexible solid-state supercapacitor prepared by transferring the TiS 2 -VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

A finite element analysis modeling tool for solid oxide fuel cell development: coupled electrochemistry, thermal and flow analysis in MARC®

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

Khaleel, Mohammad A.; Lin, Zijing; Singh, Prabhakar

2004-05-03

A 3D simulation tool for modeling solid oxide fuel cells is described. The tool combines the versatility and efficiency of a commercial finite element analysis code, MARC{reg_sign}, with an in-house developed robust and flexible electrochemical (EC) module. Based upon characteristic parameters obtained experimentally and assigned by the user, the EC module calculates the current density distribution, heat generation, and fuel and oxidant species concentration, taking the temperature profile provided by MARC{reg_sign} and operating conditions such as the fuel and oxidant flow rate and the total stack output voltage or current as the input. MARC{reg_sign} performs flow and thermal analyses basedmore » on the initial and boundary thermal and flow conditions and the heat generation calculated by the EC module. The main coupling between MARC{reg_sign} and EC is for MARC{reg_sign} to supply the temperature field to EC and for EC to give the heat generation profile to MARC{reg_sign}. The loosely coupled, iterative scheme is advantageous in terms of memory requirement, numerical stability and computational efficiency. The coupling is iterated to self-consistency for a steady-state solution. Sample results for steady states as well as the startup process for stacks with different flow designs are presented to illustrate the modeling capability and numerical performance characteristic of the simulation tool.« less

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

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.

Electrochemical alkaline Fe(VI) water purification and remediation.

PubMed

Licht, Stuart; Yu, Xingwen

2005-10-15

Fe(VI) is an unusual and strongly oxidizing form of iron, which provides a potentially less hazardous water-purifying agent than chlorine. A novel on-line electrochemical Fe(VI) water purification methodology is introduced. Fe(VI) addition had been a barrier to its effective use in water remediation, because solid Fe(VI) salts require complex (costly) syntheses steps and solutions of Fe(VI) decompose. Online electrochemical Fe(VI) water purification avoids these limitations, in which Fe(VI) is directly prepared in solution from an iron anode as the FeO42- ion, and is added to the contaminant stream. Added FeO42- decomposes, by oxidizing a wide range of water contaminants including sulfides (demonstrated in this study) and other sulfur-containing compounds, cyanides (demonstrated in this study), arsenic (demonstrated in this study), ammonia and other nitrogen-containing compounds (previously demonstrated), a wide range of organics (phenol demonstrated in this study), algae, and viruses (each previously demonstrated).

Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells.

PubMed

Kim, Junyoung; Sengodan, Sivaprakash; Kwon, Goeun; Ding, Dong; Shin, Jeeyoung; Liu, Meilin; Kim, Guntae

2014-10-01

We report on an excellent anode-supported H(+) -SOFC material system using a triple conducting (H(+) /O(2-) /e(-) ) oxide (TCO) as a cathode material for H(+) -SOFCs. Generally, mixed ionic (O(2-) ) and electronic conductors (MIECs) have been selected as the cathode material of H(+) -SOFCs. In an H(+) -SOFC system, however, MIEC cathodes limit the electrochemically active sites to the interface between the proton conducting electrolyte and the cathode. New approaches to the tailoring of cathode materials for H(+) -SOFCs should therefore be considered. TCOs can effectively extend the electrochemically active sites from the interface between the cathode and the electrolyte to the entire surface of the cathode. The electrochemical performance of NBSCF/BZCYYb/BZCYYb-NiO shows excellent long term stability for 500 h at 1023 K with high power density of 1.61 W cm(-2) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Broad Stability Investigation of Nb-Doped SrCoO 2.5+δ as a Reversible Oxygen Electrode for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Wang, Jie; Jiang, Long; Xiong, Xiaolei; ...

2016-06-10

The present work reports a systematic study on the structural, thermal, electrical and electrochemical stability of SrCo 1–xNb xO 2.5+δ series as a potential reversible oxygen-electrode for intermediate-temperature solid oxide fuel cells. The identified best composition is x = 0.10, which exhibits a stable pseudo primitive cubic structure at <700°C and a reversible oxygen redox reaction at 350°C. The conductivity of this material is p-type and also exhibits a peak at 350°C, implying that the electron hole conduction is closely associated with the oxygen nonstoichiometry. Electrochemical impedance spectroscopy analysis indicates a low polarization resistance rate-limited by a slower surface Omore » 2 dissociation step. Altogether, the material is thermally stable and oxygen redox reversible below 700°C, above which a catalytically less active brownmillerite SrCoO 2.5 is formed.« less

Integrating electrochemical oxidation into forward osmosis process for removal of trace antibiotics in wastewater.

PubMed

Liu, Pengxiao; Zhang, Hanmin; Feng, Yujie; Shen, Chao; Yang, Fenglin

2015-10-15

During the rejection of trace pharmaceutical contaminants from wastewater by forward osmosis (FO), disposal of the FO concentrate was still an unsolved issue. In this study, by integrating the advantages of forward osmosis and electrochemical oxidation, a forward osmosis process with the function of electrochemical oxidation (FOwEO) was established for the first time to achieve the aim of rejection of trace antibiotics from wastewater and treatment of the concentrate at the same time. Results demonstrated that FOwEO (current density J=1 mA cm(-2)) exhibited excellent rejections of antibiotics (>98%) regardless of different operation conditions, and above all, antibiotics in the concentrate were well degraded (>99%) at the end of experiment (after 3h). A synergetic effect between forward osmosis and electrochemical oxidation was observed in FOwEO, which lies in that antibiotic rejections by FO were enhanced due to the degradation of antibiotics in the concentrate, while the electrochemical oxidation capacity was improved in the FOwEO channel, of which good mass transfer and the assist of indirect oxidation owing to the reverse NaCl from draw solution were supposed to be the mechanism. This study demonstrated that the FOwEO has the capability to thoroughly remove trace antibiotics from wastewater. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Study on Zinc Oxide-Based Electrolytes in Low-Temperature Solid Oxide Fuel Cells.

PubMed

Xia, Chen; Qiao, Zheng; Feng, Chu; Kim, Jung-Sik; Wang, Baoyuan; Zhu, Bin

2017-12-28

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)-a legacy material in semiconductors but exceptionally novel to solid state ionics-are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO₂) electrolytes are respectively sandwiched between two Ni 0.8 Co 0.15 Al 0.05 Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158-482 mW cm -2 and high open circuit voltages (OCVs) of 1-1.06 V at 450-550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm -2 and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm -1 at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes.

Study on Zinc Oxide-Based Electrolytes in Low-Temperature Solid Oxide Fuel Cells

PubMed Central

Qiao, Zheng; Feng, Chu; Wang, Baoyuan; Zhu, Bin

2017-01-01

Semiconducting-ionic conductors have been recently described as excellent electrolyte membranes for low-temperature operation solid oxide fuel cells (LT-SOFCs). In the present work, two new functional materials based on zinc oxide (ZnO)—a legacy material in semiconductors but exceptionally novel to solid state ionics—are developed as membranes in SOFCs for the first time. The proposed ZnO and ZnO-LCP (La/Pr doped CeO2) electrolytes are respectively sandwiched between two Ni0.8Co0.15Al0.05Li-oxide (NCAL) electrodes to construct fuel cell devices. The assembled ZnO fuel cell demonstrates encouraging power outputs of 158–482 mW cm−2 and high open circuit voltages (OCVs) of 1–1.06 V at 450–550 °C, while the ZnO-LCP cell delivers significantly enhanced performance with maximum power density of 864 mW cm−2 and OCV of 1.07 V at 550 °C. The conductive properties of the materials are investigated. As a consequence, the ZnO electrolyte and ZnO-LCP composite exhibit extraordinary ionic conductivities of 0.09 and 0.156 S cm−1 at 550 °C, respectively, and the proton conductive behavior of ZnO is verified. Furthermore, performance enhancement of the ZnO-LCP cell is studied by electrochemical impedance spectroscopy (EIS), which is found to be as a result of the significantly reduced grain boundary and electrode polarization resistances. These findings indicate that ZnO is a highly promising alternative semiconducting-ionic membrane to replace the electrolyte materials for advanced LT-SOFCs, which in turn provides a new strategic pathway for the future development of electrolytes. PMID:29283395

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

NASA Astrophysics Data System (ADS)

Zhang, Long-shan; Gao, Jian-feng; Tian, Rui-fen; Xia, Chang-rong

2009-08-01

A porous NiO/yttria-stabilized zirconia anode substrate for tubular solid oxide fuel cells was prepared by gel casting technique. Nano-scale samaria-doped ceria (SDC) particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm(NO3)3 and Ce(NO3)3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm2 when it was fed with H2 fuel at 700 °C, but the power density increased to 400 mW/cm2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 °C. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Parallel Electrochemical Treatment System and Application for Identifying Acid-Stable Oxygen Evolution Electrocatalysts

DOE PAGES

Jones, Ryan J. R.; Shinde, Aniketa; Guevarra, Dan; ...

2015-01-05

There are many energy technologies require electrochemical stability or preactivation of functional materials. Due to the long experiment duration required for either electrochemical preactivation or evaluation of operational stability, parallel screening is required to enable high throughput experimentation. We found that imposing operational electrochemical conditions to a library of materials in parallel creates several opportunities for experimental artifacts. We discuss the electrochemical engineering principles and operational parameters that mitigate artifacts int he parallel electrochemical treatment system. We also demonstrate the effects of resistive losses within the planar working electrode through a combination of finite element modeling and illustrative experiments. Operationmore » of the parallel-plate, membrane-separated electrochemical treatment system is demonstrated by exposing a composition library of mixed metal oxides to oxygen evolution conditions in 1M sulfuric acid for 2h. This application is particularly important because the electrolysis and photoelectrolysis of water are promising future energy technologies inhibited by the lack of highly active, acid-stable catalysts containing only earth abundant elements.« less

Advanced air revitalization system modeling and testing

NASA Technical Reports Server (NTRS)

Dall-Baumann, Liese; Jeng, Frank; Christian, Steve; Edeer, Marybeth; Lin, Chin

1990-01-01

To support manned lunar and Martian exploration, an extensive evaluation of air revitalization subsystems (ARS) is being conducted. The major operations under study include carbon dioxide removal and reduction; oxygen and nitrogen production, storage, and distribution; humidity and temperature control; and trace contaminant control. A comprehensive analysis program based on a generalized block flow model was developed to facilitate the evaluation of various processes and their interaction. ASPEN PLUS was used in modelling carbon dioxide removal and reduction. Several life support test stands were developed to test new and existing technologies for their potential applicability in space. The goal was to identify processes which use compact, lightweight equipment and maximize the recovery of oxygen and water. The carbon dioxide removal test stands include solid amine/vacuum desorption (SAVD), regenerative silver oxide chemisorption, and electrochemical carbon dioxide concentration (EDC). Membrane-based carbon dioxide removal and humidity control, catalytic reduction of carbon dioxide, and catalytic oxidation of trace contaminants were also investigated.

Electrodeposition of Manganese-Nickel Oxide Films on a Graphite Sheet for Electrochemical Capacitor Applications.

PubMed

Lee, Hae-Min; Lee, Kangtaek; Kim, Chang-Koo

2014-01-09

Manganese-nickel (Mn-Ni) oxide films were electrodeposited on a graphite sheet in a bath consisting of manganese acetate and nickel chloride, and the structural, morphological, and electrochemical properties of these films were investigated. The electrodeposited Mn-Ni oxide films had porous structures covered with nanofibers. The X-ray diffractometer pattern revealed the presence of separate manganese oxide (g-MnO₂) and nickel oxide (NiO) in the films. The electrodeposited Mn-Ni oxide electrode exhibited a specific capacitance of 424 F/g in Na₂SO₄ electrolyte. This electrode maintained 86% of its initial specific capacitance over 2000 cycles of the charge-discharge operation, showing good cycling stability.

Directing Stem Cell Differentiation via Electrochemical Reversible Switching between Nanotubes and Nanotips of Polypyrrole Array.

PubMed

Wei, Yan; Mo, Xiaoju; Zhang, Pengchao; Li, Yingying; Liao, Jingwen; Li, Yongjun; Zhang, Jinxing; Ning, Chengyun; Wang, Shutao; Deng, Xuliang; Jiang, Lei

2017-06-27

Control of stem cell behaviors at solid biointerfaces is critical for stem-cell-based regeneration and generally achieved by engineering chemical composition, topography, and stiffness. However, the influence of dynamic stimuli at the nanoscale from solid biointerfaces on stem cell fate remains unclear. Herein, we show that electrochemical switching of a polypyrrole (Ppy) array between nanotubes and nanotips can alter surface adhesion, which can strongly influence mechanotransduction activation and guide differentiation of mesenchymal stem cells (MSCs). The Ppy array, prepared via template-free electrochemical polymerization, can be reversibly switched between highly adhesive hydrophobic nanotubes and poorly adhesive hydrophilic nanotips through an electrochemical oxidation/reduction process, resulting in dynamic attachment and detachment to MSCs at the nanoscale. Multicyclic attachment/detachment of the Ppy array to MSCs can activate intracellular mechanotransduction and osteogenic differentiation independent of surface stiffness and chemical induction. This smart surface, permitting transduction of nanoscaled dynamic physical inputs into biological outputs, provides an alternative to classical cell culture substrates for regulating stem cell fate commitment. This study represents a general strategy to explore nanoscaled interactions between stem cells and stimuli-responsive surfaces.

Solid oxide fuel cell operable over wide temperature range

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

2001-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

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

PubMed

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

2014-04-01

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

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.

Direct methane solid oxide fuel cells and their related applications

NASA Astrophysics Data System (ADS)

Lin, Yuanbo

Solid oxide fuel cells (SOFCs), renowned for their high electrical generation efficiency with low pollutant production, are promising for reducing global energy and environmental concerns. However, there are major barriers for SOFC commercialization. A primary challenge is reducing the capital cost of SOFC power plants to levels that can compete with other generation methods. While the focus of this thesis research was on operation of SOFCs directly with methane fuel, the underlying motivation was to make SOFCs more competitive by reducing their cost. This can be achieved by making SOFCs that reduce the size and complexity of the required "balance of plant". Firstly, direct operation of SOFCs on methane is desirable since it can eliminate the external reformer. However, effective means must be found to suppress deleterious anode coking in methane. In this thesis, the operating conditions under which SOFCs can operate stably and without anode coking were investigated in detail, and the underlying mechanisms of coking and degradation were determined. Furthermore, a novel design utilizing an inert anode barrier layer was developed and shown to substantially improve stability against coking. Secondly, the direct methane SOFCs were investigated for use as electrochemical partial oxidation (EPOx) reactors that can co-generate electricity and synthesis gas (CO+H2) from methane. The results indicated that conventional SOFCs work quite well as methane partial oxidation reactors, producing syngas at relatively high rates. While this approach would not decrease the cost of SOFC power plant, it would improve prospects for commercialization by increasing the value of the power plant, because two products, electricity and syngas, can be sold. Thirdly, SOFCs utilizing thin (La,Sr)(Ga,Mg)O3 electrolytes were demonstrated. This highly conductive material allows lower SOFC operation temperature, leading to the use of lower-cost materials for sealing, interconnection, and balance of plant. Deleterious electrolyte/electrode reactions and electrolyte La loss were avoided during high-temperature co-firing by using thin La-doped ceria barrier layers, allowing very high power densities at moderate operating temperatures. (La,Sr)(Ga,Mg)O3-(La,Sr)(Fe,Co)O3 composite cathodes were investigated and optimal processing parameters that yield low interfacial polarization resistance at intermediate temperature were determined.

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.

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.

Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

PubMed Central

Körbahti, Bahadır K.; Demirbüken, Pelin

2017-01-01

Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L), current density (2–10 mA/cm2), Na2SO4 concentration (0–20 g/L), and reaction temperature (25–45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction. PMID:29082225

High power density cell using nanostructured Sr-doped SmCoO3 and Sm-doped CeO2 composite powder synthesized by spray pyrolysis

NASA Astrophysics Data System (ADS)

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

2016-01-01

High power density solid oxide electrochemical cells were developed using nanostructure-controlled composite powder consisting of Sr-doped SmCoO3 (SSC) and Sm-doped CeO2 (SDC) for electrode material. The SSC-SDC nano-composite powder, which was synthesized by spray pyrolysis, had a narrow particle size distribution (D10, D50, and D90 of 0.59, 0.71, and 0.94 μm, respectively), and individual particles were spherical, composing of nano-size SSC and SDC fragments (approximately 10-15 nm). The application of the powder to a cathode for an anode-supported solid oxide fuel cell (SOFC) realized extremely fine cathode microstructure and excellent cell performance. The anode-supported SOFC with the SSC-SDC cathode achieved maximum power density of 3.65, 2.44, 1.43, and 0.76 W cm-2 at 800, 750, 700, and 650 °C, respectively, using humidified H2 as fuel and air as oxidant. This result could be explained by the extended electrochemically active region in the cathode induced by controlling the structure of the starting powder at the nano-order level.

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

PubMed

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

2015-07-29

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

Electrochemical performance of Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 cermet anodes with functionally graded structures for intermediate-temperature solid oxide fuel cell fueled with syngas

NASA Astrophysics Data System (ADS)

Miyake, Michihiro; Iwami, Makoto; Takeuchi, Mizue; Nishimoto, Shunsuke; Kameshima, Yoshikazu

2018-06-01

The electrochemical performance of layered Ni0.8Cu0.2/Ce0.8Gd0.2O1.9 (GDC) cermet anodes is investigated for intermediate-temperature solid oxide fuel cells (IT-SOFCs) at 600 °C using humidified (3% H2O) model syngas with a molar ratio of H2/CO = 3/2 as the fuel. From the results obtained, the electrochemical performance of the functionally graded multi-layered anodes is found to be superior to the mono-layered anodes. The test cell with a bi-layered anode consisting of 100 mass% Ni0.8Cu0.2/0 mass% GDC (10M/0E) and 70 mass% Ni0.8Cu0.2/30 mass% GDC (7M/3E) exhibits high power density. The test cell with a tri-layered anode consisting of 10M/0E, 7M/3E, and 50 mass% Ni0.8Cu0.2/50 mass% GDC (5M/5E) exhibits an even higher power density, suggesting that 10M/0E and 5M/5E layers contribute to the current collecting part and active part, respectively.

Post oxygen treatment characteristics of coke as an anode material for Li-ion batteries.

PubMed

Kim, Jae-Hun; Park, Min-Sik; Jo, Yong Nam; Yu, Ji-Sang; Jeong, Goojin; Kim, Young-Jun

2013-05-01

The effect of a oxygen treatment on the electrochemical characteristics of a soft carbon anode material for Li-ion batteries was investigated. After a coke carbonization process at 1000 degrees C in an argon atmosphere, the samples were treated under a flow of oxygen gas to obtain a mild oxidation effect. After this oxygen treatment, the coke samples exhibited an improved initial coulombic efficiency and cycle performance as compared to the carbonized sample. High-resolution transmission electron microscopy revealed that the carbonized cokes consisted of disordered and nanosized graphene layers and the surface of the modified carbon was significantly changed after the treatment. The chemical state of the cokes was analyzed using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The enhanced electrochemical properties of the surface modified cokes could be attributed to the mild oxidation effect induced by the oxygen treatment. The mild oxidation process could have led to the elimination of surface imperfections and the reinforcement of a solid electrolyte interphase film, which resulted in the improved electrochemical characteristics.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

NASA Astrophysics Data System (ADS)

Gupta, Sanju; Price, Carson

2015-10-01

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO)1, (PPy/ErGO)1, (PAni/GO)1 and (PPy/GO)1. The rationale design is to create thin films that possess interconnected graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, Cs, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent Cs of ≥350 F g-1 as compared with constituents (˜70 F g-1) at discharge current density of 0.3 A g-1 that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.

The surface evolution of La0.4Sr0.6TiO3+δ anode in solid oxide fuel cells: Understanding the sulfur-promotion effect

NASA Astrophysics Data System (ADS)

Yan, Ning; Zanna, Sandrine; Klein, Lorena H.; Roushanafshar, Milad; Amirkhiz, Babak S.; Zeng, Yimin; Rothenberg, Gadi; Marcus, Philippe; Luo, Jing-Li

2017-03-01

The ideal solid oxide fuel cells (SOFCs) can be powered by readily available hydrocarbon fuels containing impurities. While this is commonly recognized as a key advantage of SOFC, it also, together with the elevated operating temperature, becomes the main barrier impeding the in-situ or operando investigations of the anode surface chemistry. Here, using a well-designed quenching experiment, we managed to characterize the near-surface structure of La0.4Sr0.6TiO3+δ (LST) anode in SOFCs fuelled by H2S-containing methane. This new method enabled us to clearly observe the surface amorphization and sulfidation of LST under simulated SOFC operating conditions. The ∼1 nm-thick two dimensional sulfur-adsorbed layer was on top of the disordered LST, containing -S, -SH and elemental sulfur species. In SOFC test, such "poisoned" anode showed increased performances: a ten-fold enhanced power density enhancement (up to 30 mW cm-2) and an improved open circuit voltage (from 0.69 V to 1.17 V). Moreover, its anodic polarization resistance in methane decreased to 21.53 Ω cm2, a difference of 95% compared with the sulfur-free anode. Control experiments confirmed that once the adsorbed sulfur species were removed electrochemically, methane conversion slowed down simultaneously till full stop.

Performance and long term degradation of 7 W micro-tubular solid oxide fuel cells for portable applications

NASA Astrophysics Data System (ADS)

Torrell, M.; Morata, A.; Kayser, P.; Kendall, M.; Kendall, K.; Tarancón, A.

2015-07-01

Micro-tubular SOFCs have shown an astonishing thermal shock resistance, many orders of magnitude larger than planar SOFCs, opening the possibility of being used in portable applications. However, only few studies have been devoted to study the degradation of large-area micro-tubular SOFCs. This work presents microstructural, electrochemical and long term degradation studies of single micro-tubular cells fabricated by high shear extrusion, operating in the intermediate range of temperatures (T∼700 °C). A maximum power of 7 W per cell has been measured in a wide range of fuel utilizations between 10% and 60% at 700 °C. A degradation rate of 360 mW/1000 h (8%) has been observed for cells operated over more than 1500 h under fuel utilizations of 40%. Higher fuel utilizations lead to strong degradations associated to nickel oxidation/reduction processes. Quick thermal cycling with heating ramp rates of 30 °C /min yielded degradation rates of 440 mW/100 cycles (9%). These reasonable values of degradation under continuous and thermal cycling operation approach the requirements for many portable applications including auxiliary power units or consumer electronics opening this typically forbidden market to the SOFC technology.

Lubricant-impregnated surfaces for electrochemical applications, and devices and systems using same

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

Solomon, Brian Richmond; Chen, Xinwei; Chiang, Yet-Ming

In certain embodiments, the invention relates to an electrochemical device having a liquid lubricant impregnated surface. At least a portion of the interior surface of the electrochemical device includes a portion that includes a plurality of solid features disposed therein. The plurality of solid features define a plurality of regions therebetween. A lubricant is disposed in the plurality of regions which retain the liquid lubricant in the plurality of regions during operation of the device. An electroactive phase comes in contact with at least the portion of the interior surface. The liquid lubricant impregnated surface introduces a slip at themore » surface when the electroactive phase flows along the surface. The electroactive phase may be a yield stress fluid.« less

Fuel Cells and Electrochemical Energy Storage.

ERIC Educational Resources Information Center

Sammells, Anthony F.

1983-01-01

Discusses the nature of phosphoric acid, molten carbonate, and solid oxide fuel cells and major features and types of batteries used for electrical energy storage. Includes two tables presenting comparison of major battery features and summary of major material problems in the sodium-sulfur and lithium-alloy metal sulfide batteries. (JN)

Three dimensional CFD modeling and experimental validation of a single chamber solid oxide fuel cell fed by methane

NASA Astrophysics Data System (ADS)

Nguyen, H. T.; Le, M. V.; Nguyen, T. A.; Nguyen, T. A. N.

2017-06-01

The solid oxide fuel cell is one of the promising technologies for future energy demand. Solid oxide fuel cell operated in the single-chamber mode exhibits several advantages over conventional single oxide fuel cell due to the simplified, compact, sealing-free cell structure. There are some studies on simulating the behavior of this type of fuel cell but they mainly focus on the 2D model. In the present study, a three-dimensional numerical model of a single chamber solid oxide fuel cell (SOFC) is reported and solved using COMSOL Multiphysics software. Experiments of a planar button solid oxide fuel cell were used to verify the simulation results. The system is fed by methane and oxygen and operated at 700°C. The cathode is LSCF6482, the anode is GDC-Ni, the electrolyte is LDM and the operating pressure is 1 atm. There was a good agreement between the cell temperature and current voltage estimated from the model and measured from the experiment. The results indicate that the model is applicable for the single chamber solid oxide fuel cell and it can provide a basic for the design, scale up of single chamber solid oxide fuel cell system.

A metallic interconnect for a solid oxide fuel cell stack

NASA Astrophysics Data System (ADS)

England, Diane Mildred

A solid oxide fuel cell (SOFC) electrochemically converts the chemical energy of reaction into electrical energy. The commercial success of planar, SOFC stack technology has a number of challenges, one of which is the interconnect that electrically and physically connects the cathode of one cell to the anode of an adjacent cell in the SOFC stack and in addition, separates the anodic and cathodic gases. An SOFC stack operating at intermediate temperatures, between 600°C and 800°C, can utilize a metallic alloy as an interconnect material. Since the interconnect of an SOFC stack must operate in both air and fuel environments, the oxidation kinetics, adherence and electronic resistance of the oxide scales formed on commercial alloys were investigated in air and wet hydrogen under thermal cycling conditions to 800°C. The alloy, Haynes 230, exhibited the slowest oxidation kinetics and the lowest area-specific resistance as a function of oxidation time of all the alloys in air at 800°C. However, the area-specific resistance of the oxide scale formed on Haynes 230 in wet hydrogen was unacceptably high after only 500 hours of oxidation, which was attributed to the high resistivity of Cr2O3 in a reducing atmosphere. A study of the electrical conductivity of the minor phase manganese chromite, MnXCr3-XO4, in the oxide scale of Haynes 230, revealed that a composition closer to Mn2CrO4 had significantly higher electrical conductivity than that closer to MnCr 2O4. Haynes 230 was coated with Mn to form a phase closer to the Mn2CrO4 composition for application on the fuel side of the interconnect. U.S. Patent No. 6,054,231 is pending. Although coating a metallic alloy is inexpensive, the stringent economic requirements of SOFC stack technology required an alloy without coating for production applications. As no commercially available alloy, among the 41 alloys investigated, performed to the specifications required, a new alloy was created and designated DME-A2. The oxide scale formed on DME-A2 at 800°C exhibited extremely high electrical conductivity with respect to the commercially available alloys studied. This new alloy shows great promise for use as an interconnect material for a planar SOFC stack operating at intermediate temperatures.

The application of electrochemistry to pharmaceutical stability testing--comparison with in silico prediction and chemical forced degradation approaches.

PubMed

Torres, Susana; Brown, Roland; Szucs, Roman; Hawkins, Joel M; Zelesky, Todd; Scrivens, Garry; Pettman, Alan; Taylor, Mark R

2015-11-10

The aim of this study was to evaluate the use of electrochemistry to generate oxidative degradation products of a model pharmaceutical compound. The compound was oxidized at different potentials using an electrochemical flow-cell fitted with a glassy carbon working electrode, a Pd/H2 reference electrode and a titanium auxiliary electrode. The oxidative products formed were identified and structurally characterized by LC-ESI-MS/MS using a high resolution Q-TOF mass spectrometer. Results from electrochemical oxidation using electrolytes of different pH were compared to those from chemical oxidation and from accelerated stability studies. Additionally, oxidative degradation products predicted using an in silico commercially available software were compared to those obtained from the various experimental methods. The electrochemical approach proved to be useful as an oxidative stress test as all of the final oxidation products observed under accelerated stability studies could be generated; previously reported reactive intermediate species were not observed most likely because the electrochemical mechanism differs from the oxidative pathway followed under accelerated stability conditions. In comparison to chemical degradation tests electrochemical degradation has the advantage of being much faster and does not require the use of strong oxidizing agents. Moreover, it enables the study of different operating parameters in short periods of time and optimisation of the reaction conditions (pH and applied potential) to achieve different oxidative products mixtures. This technique may prove useful as a stress test condition for the generation of oxidative degradation products and may help accelerate structure elucidation and development of stability indicating analytical methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Structure and Dynamics Investigations of Sr/Ca-Doped LaPO 4 Proton Conductors

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

al-Wahish, Amal; al-Binni, U.; Tetard, L.

Proton conductors loom out of the pool of candidate materials with great potential to boost hydrogen alternatives to fossil-based resources for energy. Acceptor doped lanthanum orthophosphates are considered for solid oxide fuel cells (SOFCs) for their potential stability and conductivity at high temperature. By exploring the crystal and defect structure of x% Sr/Ca-doped LaPO 4 with different nominal Sr/Ca concentrations (x = 0 – 10) with Neutron powder diffraction (NPD) and X-ray powder diffraction (XRD), we confirm that Sr/Ca-doped LaPO 4 can exist as self-supported structures at high temperatures during solid oxide fuel cell operation. Thermal stability, surface topography, sizemore » distribution are also studied to better understand the proton conductivity for dry and wet compounds obtained at sintering temperatures ranging from 1200 to 1400 °C using a combination of scanning electron microscopy (SEM), Atomic Force Microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and electrochemical impedance spectroscopy (EIS). In conclusion, the results suggest that Sr doped samples exhibit the highest proton conductivity of our samples and illustrate the impact of material design and versatile characterization schemes on the development of proton conductors with superior functionality.« less

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.

Electrochemical surface modification of titanium in dentistry.

PubMed

Kim, Kyo-Han; Ramaswamy, Narayanan

2009-01-01

Titanium and its alloys have good biocompatibility with body cells and tissues and are widely used for implant applications. However, clinical procedures place more stringent and tough requirements on the titanium surface necessitating artificial surface treatments. Among the many methods of titanium surface modification, electrochemical techniques are simple and cheap. Anodic oxidation is the anodic electrochemical technique while electrophoretic and cathodic depositions are the cathodic electrochemical techniques. By anodic oxidation it is possible to obtain desired roughness, porosity and chemical composition of the oxide. Anodic oxidation at high voltages can improve the crystallinity of the oxide. The chief advantage of this technique is doping of the coating of the bath constituents and incorporation of these elements improves the properties of the oxide. Electrophoretic deposition uses hydroxyapatite (HA) powders dispersed in a suitable solvent at a particular pH. Under these operating conditions these particles acquire positive charge and coatings are obtained on the cathodic titanium by applying an external electric field. These coatings require a post-sintering treatment to improve the coating properties. Cathodic deposition is another type of electrochemical method where HA is formed in situ from an electrolyte containing calcium and phosphate ions. It is also possible to alter structure and/or chemistry of the obtained deposit. Nano-grained HA has higher surface energy and greater biological activity and therefore emphasis is being laid to produce these coatings by cathodic deposition.

Electrolytes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

The high operating temperature of solid oxide fuel cells (SOFCs), as compared to polymer electrolyte membrane fuel cells (PEMFCs), improves tolerance to impurities in the fuel, but also creates challenges in the development of suitable materials for the various fuel cell components. In response to these challenges, intermediate temperature solid oxide fuel cells (IT-SOFCs) are being developed to reduce high-temperature material requirements, which will extend useful lifetime, improve durability and reduce cost, while maintaining good fuel flexibility. A major challenge in reducing the operating temperature of SOFCs is the development of solid electrolyte materials with sufficient conductivity to maintain acceptably low ohmic losses during operation. In this paper, solid electrolytes being developed for solid oxide fuel cells, including zirconia-, ceria- and lanthanum gallate-based materials, are reviewed and compared. The focus is on the conductivity, but other issues, such as compatibility with electrode materials, are also discussed.

Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in a SiO2-CaO-MgO-Al2O3 molten slag at 1723 K.

PubMed

Gao, Yunming; Yang, Chuanghuang; Zhang, Canlei; Qin, Qingwei; Chen, George Z

2017-06-21

Production of metallic iron through molten oxide electrolysis using inert electrodes is an alternative route for fast ironmaking without CO 2 emissions. The fact that many inorganic oxides melt at ultrahigh temperatures (>1500 K) challenges conventional electro-analytical techniques used in aqueous, organic and molten salt electrolytes. However, in order to design a feasible and effective electrolytic process, it is necessary to best understand the electrochemical properties of iron ions in molten oxide electrolytes. In this work, a magnesia-stabilised zirconia (MSZ) tube with a closed end was used to construct an integrated three-electrode cell with a "MSZ|Pt|O 2 (air)" assembly functioning as the solid electrolyte, the reference electrode and also the counter electrode. Electrochemical reduction of iron ions was systematically investigated on an iridium (Ir) wire working electrode in a SiO 2 -CaO-MgO-Al 2 O 3 molten slag at 1723 K by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis (PE). The results show that the electroreduction of the Fe 2+ ion to Fe on the Ir electrode in the molten slag follows a single two-electron transfer step, and the rate of the process is diffusion controlled. The peak current on the obtained CVs is proportional to the concentration of the Fe 2+ ion in the molten slag and the square root of scan rate. The diffusion coefficient of Fe 2+ ions in the molten slag containing 5 wt% FeO at 1723 K was derived to be (3.43 ± 0.06) × 10 -6 cm 2 s -1 from CP analysis. However, a couple of subsequent processes, i.e. alloy formation on the Ir electrode surface and interdiffusion, were found to affect the kinetics of iron deposition. An ECC mechanism is proposed to account for the CV observations. The findings from this work confirm that zirconia-based solid electrolytes can play an important role in electrochemical fundamental research in high temperature molten slag electrolytes.

Promotion of Oxygen Reduction by Exsolved Silver Nanoparticles on a Perovskite Scaffold for Low-Temperature Solid Oxide Fuel Cells.

PubMed

Zhu, Yinlong; Zhou, Wei; Ran, Ran; Chen, Yubo; Shao, Zongping; Liu, Meilin

2016-01-13

Solid oxide fuel cells (SOFCs) have potential to be the cleanest and most efficient electrochemical energy conversion devices with excellent fuel flexibility. To make SOFC systems more durable and economically competitive, however, the operation temperature must be significantly reduced, which depends sensitively on the development of highly active electrocatalysts for oxygen reduction reaction (ORR) at low temperatures. Here we report a novel silver nanoparticle-decorated perovskite oxide, prepared via a facile exsolution process from a Sr0.95Ag0.05Nb0.1Co0.9O3-δ (SANC) perovskite precursor, as a highly active and robust ORR electrocatalyst for low-temperature SOFCs. The exsolved Sr0.95Ag0.05Nb0.1Co0.9O3-δ (denoted as e-SANC) electrode is very active for ORR, achieving a very low area specific resistance (∼0.214 Ω cm(2) at 500 °C). An anode-supported cell with the new heterostructured cathode demonstrates very high peak power density (1116 mW cm(-2) at 500 °C) and stable operation for 140 h at a current density of 625 mA cm(-2). The superior ORR activity and stability are attributed to the fast oxygen surface exchange kinetics and the firm adhesion of the Ag nanoparticles to the Sr0.95Nb0.1Co0.9O3-δ (SNC0.95) support. Moreover, the e-SANC cathode displays improved tolerance to CO2. These unique features make the new heterostructured material a highly promising cathode for low-temperature SOFCs.

Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

NASA Astrophysics Data System (ADS)

Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

2017-12-01

Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

Microwave-assisted synthesis and electrochemical evaluation of VO 2 (B) nanostructures

DOE PAGES

Ashton, Thomas E.; Borras, David Hevia; Iadecola, Antonella; ...

2015-12-01

Understanding how intercalation materials change during electrochemical operation is paramount to optimising their behaviour and function and in situ characterisation methods allow us to observe these changes without sample destruction. Here, we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave assisted route which exhibits a larger electrochemical capacity (232 mAh g -1) compared to VO 2 (B) prepared by a solvothermal route (197 mAh g -1). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during batterymore » operation.« less

Simulation of thermal stresses in anode-supported solid oxide fuel cell stacks. Part II: Loss of gas-tightness, electrical contact and thermal buckling

NASA Astrophysics Data System (ADS)

Nakajo, Arata; Wuillemin, Zacharie; Van herle, Jan; Favrat, Daniel

Structural stability issues in planar solid oxide fuel cells arise from the mismatch between the coefficients of thermal expansion of the components. The stress state at operating temperature is the superposition of several contributions, which differ depending on the component. First, the cells accumulate residual stresses due to the sintering phase during the manufacturing process. Further, the load applied during assembly of the stack to ensure electric contact and flatten the cells prevents a completely stress-free expansion of each component during the heat-up. Finally, thermal gradients cause additional stresses in operation. The temperature profile generated by a thermo-electrochemical model implemented in an equation-oriented process modelling tool (gPROMS) was imported into finite-element software (ABAQUS) to calculate the distribution of stress and contact pressure on all components of a standard solid oxide fuel cell repeat unit. The different layers of the cell in exception of the cathode, i.e. anode, electrolyte and compensating layer were considered in the analysis to account for the cell curvature. Both steady-state and dynamic simulations were performed, with an emphasis on the cycling of the electrical load. The study includes two different types of cell, operation under both thermal partial oxidation and internal steam-methane reforming and two different initial thicknesses of the air and fuel compressive sealing gaskets. The results generated by the models are presented in two papers: Part I focuses on cell cracking. In the present paper, Part II, the occurrences of loss of gas-tightness in the compressive gaskets and/or electrical contact in the gas diffusion layer were identified. In addition, the dependence on temperature of both coefficients of thermal expansion and Young's modulus of the metallic interconnect (MIC) were implemented in the finite-element model to compute the plastic deformation, while the possibilities of thermal buckling were analysed in a dedicated and separate model. The value of the minimum stable thickness of the MIC is large, even though significantly affected by the operating conditions. This phenomenon prevents any unconsidered decrease of the thickness to reduce the thermal inertia of the stack. Thermal gradients and the shape of the temperature profile during operation induce significant decreases of the contact pressure on the gaskets near the fuel manifold, at the inlet or outlet, depending on the flow configuration. On the contrary, the electrical contact was ensured independently of the operating point and history, even though plastic strain developed in the gas diffusion layer.

Electra-optical device including a nitrogen containing electrolyte

DOEpatents

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

1995-01-01

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.

Thin film battery and method for making same

DOEpatents

Bates, J.B.; Dudney, N.J.; Gruzalski, G.R.; Luck, C.F.

1994-08-16

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.

Thin film battery and method for making same

DOEpatents

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

1994-01-01

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.

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G. Bryan; Chiba, Zoher; Lewis, Patricia R.; Nelson, Norvell; Steward, G. Anthony

1999-01-01

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO.sub.2. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement.

Method of low temperature operation of an electrochemical cell array

DOEpatents

Singh, P.; Ruka, R.J.; Bratton, R.J.

1994-04-26

A method is described for operating an electrochemical cell generator apparatus containing a generator chamber containing an array of cells having interior and exterior electrodes with solid electrolyte between the electrodes, where a hot gas contacts the outside of the cells and the generating chamber normally operates at over 850 C, where N[sub 2] gas is fed to contact the interior electrode of the cells in any case when the generating chamber temperature drops for whatever reason to within the range of from 550 C to 800 C, to eliminate cracking within the cells. 2 figures.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

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.

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.

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, A.O.

1987-03-10

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection. 1 fig.

Bipolar plating of metal contacts onto oxide interconnection for solid oxide electrochemical cell

DOEpatents

Isenberg, Arnold O.

1987-01-01

Disclosed is a method of forming an adherent metal deposit on a conducting layer of a tube sealed at one end. The tube is immersed with the sealed end down into an aqueous solution containing ions of the metal to be deposited. An ionically conducting aqueous fluid is placed inside the tube and a direct current is passed from a cathode inside the tube to an anode outside the tube. Also disclosed is a multi-layered solid oxide fuel cell tube which consists of an inner porous ceramic support tube, a porous air electrode covering the support tube, a non-porous electrolyte covering a portion of the air electrode, a non-porous conducting interconnection covering the remaining portion of the electrode, and a metal deposit on the interconnection.

An electrochemical study of a liquid crystal used in information displays

NASA Technical Reports Server (NTRS)

Oglesby, D. M.; Kern, J. B.; Robertson, J. B.

1974-01-01

The operational lifetime of liquid crystal displays were investigated. Electrochemical reaction at the electrodes of the display can cause failure after 2000 to 3000 hours of operation. Studies using cyclic voltametry of electrochemical reactions of N (p-methoxybenzilidene p-butylaniline (MBBA), a nematic liquid crystal were made. These studies indicate the presence of a reversible reduction of MBBA at the cathode, and that the reduction product undergoes a further reaction leading to products which are not reversibly oxidized. It is concluded that the degradation of the liquid crystal in displays can be reduced with a suitable frequency of alternating voltage.

Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.

PubMed

Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni

2015-11-01

Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability and Performance of Oxygen Electrodes for Reversible Solid Oxide Cells

NASA Astrophysics Data System (ADS)

Railsback, Justin Gary

Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources requires that large scale energy storage be implemented to ensure grid stability. Pumped hydro storage is currently the only technology available for large scale energy storage; however, pumped hydro remains geographically confined and susceptible to seasonal fluctuations and offers limited discharge hours. Recent system level models predict that reversible solid oxide cells may be a competitive solution, but two key advancements are required to realize the technology: low cell resistance (<0.2 O•cm2 at <650 °C), particularly low polarization resistance at the oxygen electrode, and low degradation rate (<0.5%/khr for 50,000 hours). The oxygen electrode is typically the largest contributor to the total cell resistance, and when a cell is operated in electrolysis the oxygen electrode is known to degrade quickly. This work focuses on both aspects of the oxygen electrode. A Pr2NiO4 based electrode is developed that has improved phase stability and good polarization resistance ( 0.1 O•cm2 at 650 °C). The electrode is prepared by wet chemical impregnation (infiltration) of Pr2NiO4 precursors into a La0.9Sr 0.1Ga0.8Mg0.2O3 scaffold. Electrochemical data for a number cells is presented and the number of infiltrations is optimized. Preliminary life tests and x-ray data are presented. Pressurization of the oxygen electrode is predicted to decrease its polarization resistance and pressurization of the reversible solid oxide cell system is desirable to achieve high round-trip efficiency. The electrochemical performance of mixed electronic-ionic conducting electrodes has not been reported above 1 atm. Four candidate electrodes are examined under pressurization up to 10 atm: Pr2NiO4 infiltrated La0.9Sr0.1 Ga0.8Mg0.2O3, Sm0.5Sr 0.5CoO3 infiltrated Ce0.9Gd0.1O 2, single phase La0.6Sr0.4Co0.2Fe 0.8O3, and single phase Nd2NiO4. The role of the ion conduction mechanism (vacancy or interstitial) is explored in relation to the decrease in polarization resistance with increased pressure. Current switched life-tests designed to emulate reversible solid oxide cell operating conditions were performed for a range of current densities and overpotentials on three candidate systems: composite La0.7Sr 0.3MnO3-Zr0.84Y0.16O2, single phase La0.6Sr0.4Co0.2Fe0.8O 3, and La2NiO4 infiltrated La0.9Sr 0.1Ga0.8Mg0.2O3. The degradation mode of each system is determined by impedance spectroscopy and post-test microstructural analysis. Operating regions of improved stability are identified for each system based on the measured degradation rates. Overpotential is determined to be the major controlling factor in La0.7Sr0.3MnO 3-Zr0.84Y0.16O2. Analysis and modeling for predicting the long term degradation of an infiltrated electrode is presented. Coarsening of the nanoscale features is thought to be the main contributor to degradation under annealing for infiltrated electrodes and so a combined electrochemical - coarsening model is presented to understand the limitations of such an electrode. The model is fit to prior results to better understand the trade-off between coarsening rate and initial good performance. A figure of merit is presented for selecting materials for infiltration that takes into account the coarsening behavior.

Performance of electrochemical oxidation and photocatalysis in terms of kinetics and energy consumption. New insights into the p-cresol degradation.

PubMed

Escudero, Carlos J; Iglesias, Olalla; Dominguez, Sara; Rivero, Maria J; Ortiz, Inmaculada

2017-06-15

This work reports the comparative performance of two Advanced Oxidation Processes (AOPs), electrochemical oxidation and photocatalysis, as individual technological alternatives for the treatment of effluents containing p-cresol. First, the influence of operating parameters in the oxidation and mineralization yield was carried out together with kinetic analysis. Boron Doped Diamond (BDD), RuO 2 and Pt as anodic materials, Na 2 SO 4 and NaCl as supporting electrolytes and different current densities were evaluated in electrochemical oxidation whereas the effect of TiO 2 concentration and radiation was studied in the photocatalytic degradation. Then, the parameter Electrical Energy per Order (E EO ) was calculated to compare the energy consumption in both AOPs, concluding that under the studied conditions the electrochemical treatment with BDD, Na 2 SO 4 and 125 A m -2 showed the best energy efficiency, with an E EO of 5.83 kW h m -3 order -1 for p-cresol and 58.05 kW h m -3 order -1 for DOC removal, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anodes for protonic ceramic fuel cells (PCFCs) =

NASA Astrophysics Data System (ADS)

Nasani, Narendar

One of the more promising possibilities for future "green" electrical energy generation is the protonic ceramic fuel cell (PCFC). PCFCs offer a low-pollution technology to generate electricity electrochemically with high efficiency. Reducing the operating temperature of solid oxide fuel cells (SOFCs) to the 500-700°C range is desirable to reduce fabrication costs and improve overall longevity. This aim can be achieved by using protonic ceramic fuel cells (PCFCs) due to their higher electrolyte conductivity at these temperatures than traditional ceramic oxide-ion conducting membranes. This thesis deals with the state of the art Ni-BaZr0.85Y0.15O3-delta cermet anodes for PCFCs. The study of PCFCs is in its initial stage and currently only a few methods have been developed to prepare suitable anodes via solid state mechanical mixing of the relevant oxides or by combustion routes using nitrate precursors. This thesis aims to highlight the disadvantages of these traditional methods of anode preparation and to, instead, offer a novel, efficient and low cost nitrate free combustion route to prepare Ni-BaZr0.85Y0.15O3-delta cermet anodes for PCFCs. A wide range of techniques mainly X-ray diffraction (XRD), scanning electron microscopy (SEM), environmental scanning electron microscopy, (ESEM) and electrochemical impedance spectroscopy (EIS) were employed in the cermet anode study. The work also offers a fundamental examination of the effect of porosity, redox cycling behaviour, involvement of proton conducting oxide phase in PCFC cermet anodes and finally progresses to study the electrochemical performance of a state of the art anode supported PCFC. The polarisation behaviour of anodes has been assessed as a function of temperature (T), water vapour (pH2O), hydrogen partial pressures (pH2) and phase purity for electrodes of comparable microstructure. The impedance spectra generally show two arcs at high frequency R2 and low frequency R3 at 600 °C, which correspond to the electrode polarisation resistance. Work shows that the R2 and R3 terms correspond to proton transport and dissociative H2 adsorption on electrode surface, respectively. The polarization resistance of the cermet anode (Rp) was shown to be significantly affected by porosity, with the PCFC cermet anode with the lowest porosity exhibiting the lowest Rp under standard operating conditions. This result highlights that porogens are not required for peak performance in PCFC anodes, a result contrary to that of their oxide-ion conducting anode counterparts. In-situ redox cycling studies demonstrate that polarisation behaviour was drastically impaired by redox cycling. In-situ measurements using an environmental scanning electron microscopy (ESEM) reveal that degradation proceeds due to volume expansion of the Ni-phase during the re-oxidation stage of redox cycling.The anode supported thin BCZY44 based protonic ceramic fuel cell, formed using a peak performing Ni-BaZr0.85Y0.15O3-delta cermet anode with no porogen, shows promising results in fuel cell testing conditions at intermediate temperatures with good durability and an overall performance that exceeds current literature data.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Solid oxide fuel cell generator with removable modular fuel cell stack configurations

DOEpatents

Gillett, J.E.; Dederer, J.T.; Zafred, P.R.; Collie, J.C.

1998-04-21

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack. 8 figs.

Solid oxide fuel cell generator with removable modular fuel cell stack configurations

DOEpatents

Gillett, James E.; Dederer, Jeffrey T.; Zafred, Paolo R.; Collie, Jeffrey C.

1998-01-01

A high temperature solid oxide fuel cell generator produces electrical power from oxidation of hydrocarbon fuel gases such as natural gas, or conditioned fuel gases, such as carbon monoxide or hydrogen, with oxidant gases, such as air or oxygen. This electrochemical reaction occurs in a plurality of electrically connected solid oxide fuel cells bundled and arrayed in a unitary modular fuel cell stack disposed in a compartment in the generator container. The use of a unitary modular fuel cell stack in a generator is similar in concept to that of a removable battery. The fuel cell stack is provided in a pre-assembled self-supporting configuration where the fuel cells are mounted to a common structural base having surrounding side walls defining a chamber. Associated generator equipment may also be mounted to the fuel cell stack configuration to be integral therewith, such as a fuel and oxidant supply and distribution systems, fuel reformation systems, fuel cell support systems, combustion, exhaust and spent fuel recirculation systems, and the like. The pre-assembled self-supporting fuel cell stack arrangement allows for easier assembly, installation, maintenance, better structural support and longer life of the fuel cells contained in the fuel cell stack.

Solid oxide fuel cells, and air electrode and electrical interconnection materials therefor

DOEpatents

Bates, J. Lambert

1992-01-01

In one aspect of the invention, an air electrode material for a solid oxide fuel cell comprises Y.sub.1-a Q.sub.a MnO.sub.3, where "Q" is selected from the group consisting of Ca and Sr or mixtures thereof and "a" is from 0.1 to 0.8. Preferably, "a" is from 0.4 to 0.7. In another aspect of the invention, an electrical interconnection material for a solid oxide fuel cell comprises Y.sub.1-b Ca.sub.b Cr.sub.1-c Al.sub.c O.sub.3, where "b" is from 0.1 to 0.6 and "c" is from 0 to 9.3. Preferably, "b" is from 0.3 to 0.5 and "c" is from 0.05 to 0.1. A composite solid oxide electrochemical fuel cell incorporating these materials comprises: a solid oxide air electrode and an adjacent solid oxide electrical interconnection which commonly include the cation Y, the air electrode comprising Y.sub.1-a Q.sub.a MnO.sub.3, where "Q" is selected from the group consisting of Ca and Sr or mixtures thereof and "a" is from 0.1 to 0.8, the electrical interconnection comprising Y.sub.1-b Ca.sub.b Cr.sub.1-c Al.sub.c O.sub.3, where "b" is from 0.1 to 0.6 and "c" is from 0.0 to 0.3; a yttrium stabilized solid electrolyte comprising (1-d)ZrO.sub.2 -(d)Y.sub.2 O.sub.3 where "d" is from 0.06 to 0.5; and a solid fuel electrode comprising X-ZrO.sub.2, where "X" is an elemental metal.

Solid oxide fuel cells, and air electrode and electrical interconnection materials therefor

DOEpatents

Bates, J.L.

1992-09-01

In one aspect of the invention, an air electrode material for a solid oxide fuel cell comprises Y[sub 1[minus]a]Q[sub a]MnO[sub 3], where Q is selected from the group consisting of Ca and Sr or mixtures thereof and a' is from 0.1 to 0.8. Preferably, a' is from 0.4 to 0.7. In another aspect of the invention, an electrical interconnection material for a solid oxide fuel cell comprises Y[sub 1[minus]b]Ca[sub b]Cr[sub 1[minus]c]Al[sub c]O[sub 3], where b' is from 0.1 to 0.6 and c' is from 0 to 9.3. Preferably, b' is from 0.3 to 0.5 and c' is from 0.05 to 0.1. A composite solid oxide electrochemical fuel cell incorporating these materials comprises: a solid oxide air electrode and an adjacent solid oxide electrical interconnection which commonly include the cation Y, the air electrode comprising Y[sub 1[minus]a]Q[sub a]MnO[sub 3], where Q is selected from the group consisting of Ca and Sr or mixtures thereof and a' is from 0.1 to 0.8, the electrical interconnection comprising Y[sub 1[minus]b]Ca[sub b]Cr[sub 1[minus]c]Al[sub c]O[sub 3], where b' is from 0.1 to 0.6 and c' is from 0.0 to 0.3; a yttrium stabilized solid electrolyte comprising (1[minus]d)ZrO[sub 2]-(d)Y[sub 2]O[sub 3] where d' is from 0.06 to 0.5; and a solid fuel electrode comprising X-ZrO[sub 2], where X' is an elemental metal. 5 figs.

High Performance Proton-Conducting Solid Oxide Fuel Cells with a Layered Perovskite GdBaCuCoO5+ x Cathode

NASA Astrophysics Data System (ADS)

Zhang, Xiaozhen; Jiang, Yuhua; Hu, Xuebing; Sun, Liangliang; Ling, Yihan

2018-03-01

Proton-conducting solid oxide fuel cell (H-SOFC) based on layered perovskite type GdBaCuCoO5+x (GBCC) cathode was fabricated with in situ drop-coating BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte membrane. The influences of Cu doping into Co sites of GdBaCo2O5+ x on the electrical conductivity and conduction mechanism, thermal expansion property and electrochemical performance of cathode materials and corresponding single cell were investigated. Results show that the electrical conductivity decreased and the conduction mechanism would gradually transform to the semiconductor-like behavior. A high maximum power density of 480 mW cm-2 was obtained for the anode supported NiO-BZCY/NiO-BZCY/BZCY/GBCC single cells with wet H2 fuel at 700 °C. The corresponding polarization resistance was as low as 0.17 Ω cm2. The excellent electrochemical performance of as-prepared single cell indicates that GBCC is a good candidate of cathode materials for H-SOFCs.

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.

Aluminum Complexes of N2O23- Formazanate Ligands Supported by Phosphine Oxide Donors.

PubMed

Maar, Ryan R; Rabiee Kenaree, Amir; Zhang, Ruizhong; Tao, Yichen; Katzman, Benjamin D; Staroverov, Viktor N; Ding, Zhifeng; Gilroy, Joe B

2017-10-16

The synthesis and characterization of a new family of phosphine oxide supported aluminum formazanate complexes (7a,b, 8a, 9a) are reported. X-ray diffraction studies showed that the aluminum atoms in the complexes adopt an octahedral geometry in the solid state. The equatorial positions are occupied by an N 2 O 2 3- formazanate ligand, and the axial positions are occupied by L-type phosphine oxide donors. UV-vis absorption spectroscopy revealed that the complexes were strongly absorbing (ε ≈ 30000 M -1 cm -1 ) between 500 and 700 nm. The absorption maxima in this region were simulated using time-dependent density functional theory. With the exception of 3-cyano-substituted complex 7b, which showed maximum luminescence intensity in the presence of excess phosphine oxide, the title complexes are nonemissive in solution and the solid state. The electrochemical properties of the complexes were probed using cyclic voltammetry. Each complex underwent sequential one-electron oxidations in potential ranges of -0.12 to 0.29 V and 0.62 to 0.97 V, relative to the ferrocene/ferrocenium redox couple. Electrochemical reduction events were observed at potentials between -1.34 and -1.75 V. In combination with tri-n-propylamine as a coreactant, complex 7b acted as an electrochemiluminescence emitter with a maximum electrochemiluminescence intensity at a wavelength of 735 nm, red-shifted relative to the photoluminescence maximum of the same compound.

La0.8Sr0.2Co0.8Ni0.2O3-δ impregnated oxygen electrode for H2O/CO2 co-electrolysis in solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Zheng, Haoyu; Tian, Yunfeng; Zhang, Lingling; Chi, Bo; Pu, Jian; Jian, Li

2018-04-01

High-temperature H2O/CO2 co-electrolysis through reversible solid oxide electrolysis cell (SOEC) provides potentially a feasible and eco-friendly way to convert electrical energy into chemicals stored in syngas. In this work, La0.8Sr0.2Co0.8Ni0.2O3-δ (LSCN) impregnated Gd0.1Ce0.9O1.95 (GDC)-(La0.8Sr0.2)0.95MnO3-δ (LSM) composite oxygen electrode is studied as high-performance electrode for H2O/CO2 co-electrolysis. The LSCN impregnated cell exhibits competitive performance with the peak power density of 1057 mW cm-2 at 800 °C in solid oxide fuel cell (SOFC) mode; in co-electrolysis mode, the current density can reach 1.60 A cm-2 at 1.5 V at 800 °C with H2O/CO2 ratio of 2/1. With LSCN nanoparticles dispersed on the surface of GDC-LSM to maximize the reaction active sites, the LSCN impregnated cell shows significant enhanced electrochemical performance at both SOEC and SOFC modes. The influence of feed gas composition (H2O-H2-CO2) and operating voltages on the performance of co-electrolysis are discussed in detail. The cell shows a very stable performance without obvious degradation for more than 100 h. Post-test characterization is analyzed in detail by multiple measurements.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, Joseph E.

1987-01-01

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

Recent advances in nanostructured Nb-based oxides for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Yan, Litao; Rui, Xianhong; Chen, Gen; Xu, Weichuan; Zou, Guifu; Luo, Hongmei

2016-04-01

For the past five years, nanostructured niobium-based oxides have emerged as one of the most prominent materials for batteries, supercapacitors, and fuel cell technologies, for instance, TiNb2O7 as an anode for lithium-ion batteries (LIBs), Nb2O5 as an electrode for supercapacitors (SCs), and niobium-based oxides as chemically stable electrochemical supports for fuel cells. Their high potential window can prevent the formation of lithium dendrites, and their rich redox chemistry (Nb5+/Nb4+, Nb4+/Nb3+) makes them very promising electrode materials. Their unique chemical stability under acid conditions is favorable for practical fuel-cell operation. In this review, we summarized recent progress made concerning the use of niobium-based oxides as electrodes for batteries (LIBs, sodium-ion batteries (SIBs), and vanadium redox flow batteries (VRBs)), SCs, and fuel cell applications. Moreover, crystal structures, charge storage mechanisms in different crystal structures, and electrochemical performances in terms of the specific capacitance/capacity, rate capability, and cycling stability of niobium-based oxides are discussed. Insights into the future research and development of niobium-based oxide compounds for next-generation electrochemical devices are also presented. We believe that this review will be beneficial for research scientists and graduate students who are searching for promising electrode materials for batteries, SCs, and fuel cells.

Recent advances in nanostructured Nb-based oxides for electrochemical energy storage.

PubMed

Yan, Litao; Rui, Xianhong; Chen, Gen; Xu, Weichuan; Zou, Guifu; Luo, Hongmei

2016-04-28

For the past five years, nanostructured niobium-based oxides have emerged as one of the most prominent materials for batteries, supercapacitors, and fuel cell technologies, for instance, TiNb2O7 as an anode for lithium-ion batteries (LIBs), Nb2O5 as an electrode for supercapacitors (SCs), and niobium-based oxides as chemically stable electrochemical supports for fuel cells. Their high potential window can prevent the formation of lithium dendrites, and their rich redox chemistry (Nb(5+)/Nb(4+), Nb(4+)/Nb(3+)) makes them very promising electrode materials. Their unique chemical stability under acid conditions is favorable for practical fuel-cell operation. In this review, we summarized recent progress made concerning the use of niobium-based oxides as electrodes for batteries (LIBs, sodium-ion batteries (SIBs), and vanadium redox flow batteries (VRBs)), SCs, and fuel cell applications. Moreover, crystal structures, charge storage mechanisms in different crystal structures, and electrochemical performances in terms of the specific capacitance/capacity, rate capability, and cycling stability of niobium-based oxides are discussed. Insights into the future research and development of niobium-based oxide compounds for next-generation electrochemical devices are also presented. We believe that this review will be beneficial for research scientists and graduate students who are searching for promising electrode materials for batteries, SCs, and fuel cells.

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.

Electrochemically influenced cation inter-diffusion and Co 3O 4 formation on La 0.6Sr 0.4CoO 3 infiltrated into SOFC cathodes

DOE PAGES

Song, Xueyan; Lee, Shiwoo; Chen, Yun; ...

2015-06-18

Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm 2O 3-doped CeO 2 (SDC) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La 0.6Sr 0.4CoO 3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibitmore » comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co 3O 4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co 3O 4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

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

PubMed

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

2015-01-14

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

Spontaneous oscillations of cell voltage, power density, and anode exit CO concentration in a PEM fuel cell.

PubMed

Lu, Hui; Rihko-Struckmann, Liisa; Sundmacher, Kai

2011-10-28

The spontaneous oscillations of the cell voltage and output power density of a PEMFC (with PtRu/C anode) using CO-containing H(2) streams as anodic fuels have been observed during galvanostatic operating. It is ascribed to the dynamic coupling of the CO adsorption (poisoning) and the electrochemical CO oxidation (reactivating) processes in the anode chamber of the single PEMFC. Accompanying the cell voltage and power density oscillations, the discrete CO concentration oscillations at the anode outlet of the PEMFC were also detected, which directly confirms the electrochemical CO oxidation taking place in the anode chamber during galvanostatic operating. This journal is © the Owner Societies 2011

Electrochemical oxidation of COD from real textile wastewaters: Kinetic study and energy consumption.

PubMed

Zou, Jiaxiu; Peng, Xiaolan; Li, Miao; Xiong, Ying; Wang, Bing; Dong, Faqin; Wang, Bin

2017-03-01

In the present study, the electrochemical oxidation of real wastewaters discharged by textile industry was carried out using a boron-doped diamond (BDD) anode. The effect of operational variables, such as applied current density (20-100 mA·cm -2 ), NaCl concentration added to the real wastewaters (0-3 g·L -1 ), and pH value (2.0-10.0), on the kinetics of COD oxidation and on the energy consumption was carefully investigated. The obtained experimental results could be well matched with a proposed kinetic model, in which the indirect oxidation mediated by electrogenerated strong oxidants would be described through a pseudo-first-order kinetic constant k. Values of k exhibited a linear increase with increasing applied current density and decreasing pH value, and an exponential increase with NaCl concentration. Furthermore, high oxidation kinetics resulted in low specific energy consumption, but this conclusion was not suitable to the results obtained under different applied current density. Under the optimum operational conditions, it only took 3 h to complete remove the COD in the real textile wastewaters and the specific energy consumption could be as low as 11.12 kWh·kg -1  COD. The obtained results, low energy consumption and short electrolysis time, allowed to conclude that the electrochemical oxidation based on BDD anodes would have practical industrial application for the treatment of real textile wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

An innovative architectural design to enhance the electrochemical performance of La2NiO4+δ cathodes for solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Sharma, Rakesh K.; Burriel, Mónica; Dessemond, Laurent; Martin, Vincent; Bassat, Jean-Marc; Djurado, Elisabeth

2016-06-01

An architectural design of the cathode microstructure based on combining electrostatic spray deposition (ESD) and screen-printing (SP) techniques has demonstrated to be an innovative strategy to enhance the electrochemical properties of La2NiO4+δ (LNO) as oxygen electrode on Ce0.9Gd0.1O2-δ (CGO) electrolyte for solid oxide fuel cells. For this purpose, the influence of the ESD process parameters on the microstructure has been systematically investigated. Electrochemical performances of four selected cathode microstructures are investigated: (i) 3-D coral nanocrystalline (average particle size ∼ 100 nm) LNO film grown by ESD; (ii) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) grown by ESD with a continuous nanometric dense interface; (iii) porous screen-printed LNO film (average particle size ∼ 400 nm); and (iv) 3-D coral nanocrystalline film (average particle size ∼ 150 nm) with a continuous nanometric dense interface prepared by ESD topped by a LNO current collector prepared by SP. A significant reduction in the polarization resistance (Rpol) is obtained (0.08 Ω cm2 at 700 °C) for 3-D coral topped by the SP layer. Moreover LNO is found to be stable and compatible with CGO up to 800 °C for only 10 days duration in air, making it potentially suitable for SOFCs cathode application.

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

Solid oxide fuel cell steam reforming power system

DOEpatents

Chick, Lawrence A.; Sprenkle, Vincent L.; Powell, Michael R.; Meinhardt, Kerry D.; Whyatt, Greg A.

2013-03-12

The present invention is a Solid Oxide Fuel Cell Reforming Power System that utilizes adiabatic reforming of reformate within this system. By utilizing adiabatic reforming of reformate within the system the system operates at a significantly higher efficiency than other Solid Oxide Reforming Power Systems that exist in the prior art. This is because energy is not lost while materials are cooled and reheated, instead the device operates at a higher temperature. This allows efficiencies higher than 65%.

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.

Sintered electrode for solid oxide fuel cells

DOEpatents

Ruka, Roswell J.; Warner, Kathryn A.

1999-01-01

A solid oxide fuel cell fuel electrode is produced by a sintering process. An underlayer is applied to the electrolyte of a solid oxide fuel cell in the form of a slurry, which is then dried. An overlayer is applied to the underlayer and then dried. The dried underlayer and overlayer are then sintered to form a fuel electrode. Both the underlayer and the overlayer comprise a combination of electrode metal such as nickel, and stabilized zirconia such as yttria-stabilized zirconia, with the overlayer comprising a greater percentage of electrode metal. The use of more stabilized zirconia in the underlayer provides good adhesion to the electrolyte of the fuel cell, while the use of more electrode metal in the overlayer provides good electrical conductivity. The sintered fuel electrode is less expensive to produce compared with conventional electrodes made by electrochemical vapor deposition processes. The sintered electrodes exhibit favorable performance characteristics, including good porosity, adhesion, electrical conductivity and freedom from degradation.

Sintered electrode for solid oxide fuel cells

DOEpatents

Ruka, R.J.; Warner, K.A.

1999-06-01

A solid oxide fuel cell fuel electrode is produced by a sintering process. An underlayer is applied to the electrolyte of a solid oxide fuel cell in the form of a slurry, which is then dried. An overlayer is applied to the underlayer and then dried. The dried underlayer and overlayer are then sintered to form a fuel electrode. Both the underlayer and the overlayer comprise a combination of electrode metal such as nickel, and stabilized zirconia such as yttria-stabilized zirconia, with the overlayer comprising a greater percentage of electrode metal. The use of more stabilized zirconia in the underlayer provides good adhesion to the electrolyte of the fuel cell, while the use of more electrode metal in the overlayer provides good electrical conductivity. The sintered fuel electrode is less expensive to produce compared with conventional electrodes made by electrochemical vapor deposition processes. The sintered electrodes exhibit favorable performance characteristics, including good porosity, adhesion, electrical conductivity and freedom from degradation. 4 figs.

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

La(0.4)Ba(0.6)Fe(0.8)Zn(0.2)O(3-delta) as cathode in solid oxide fuel cells for simultaneous NO reduction and electricity generation.

PubMed

Zhou, Renjie; Bu, Yunfei; Xu, Dandan; Zhong, Qin

2014-01-01

A perovskite-type oxide La(0.4)Ba(0.6)Fe(0.8)Zn(0.2)O(3-delta) (LBFZ) was investigated as the cathode material for simultaneous NO reduction and electricity generation in solid oxide fuel cells (SOFCs). The microstructure of LBFZ was demonstrated by X-ray diffraction and scanning electron microscopy. The results showed that a single cubic perovskite LBFZ was formed after calcined at 1100 degrees C. Meanwhile, the solid-state reaction between LBFZ and Ce(0.8)Sm(0.2)O(1.9) (SDC) at 900 degrees C was negligible. To measure the electrochemical properties, SOFC units were constructed with Sm(0.9)Sr(0.1)Cr(0.5)Fe(0.5)O3 as the anode, SDC as the electrolyte and LBFZ as the cathode. The maximum power density increased with the increasing NO concentration and temperature. The cell resistance is mainly due to the cathodic polarization resistance.

Interfacial material for solid oxide fuel cell

DOEpatents

Baozhen, Li; Ruka, Roswell J.; Singhal, Subhash C.

1999-01-01

Solid oxide fuel cells having improved low-temperature operation are disclosed. In one embodiment, an interfacial layer of terbia-stabilized zirconia is located between the air electrode and electrolyte of the solid oxide fuel cell. The interfacial layer provides a barrier which controls interaction between the air electrode and electrolyte. The interfacial layer also reduces polarization loss through the reduction of the air electrode/electrolyte interfacial electrical resistance. In another embodiment, the solid oxide fuel cell comprises a scandia-stabilized zirconia electrolyte having high electrical conductivity. The scandia-stabilized zirconia electrolyte may be provided as a very thin layer in order to reduce resistance. The scandia-stabilized electrolyte is preferably used in combination with the terbia-stabilized interfacial layer. The solid oxide fuel cells are operable over wider temperature ranges and wider temperature gradients in comparison with conventional fuel cells.

Liquid-Solid Dual-Gate Organic Transistors with Tunable Threshold Voltage for Cell Sensing.

PubMed

Zhang, Yu; Li, Jun; Li, Rui; Sbircea, Dan-Tiberiu; Giovannitti, Alexander; Xu, Junling; Xu, Huihua; Zhou, Guodong; Bian, Liming; McCulloch, Iain; Zhao, Ni

2017-11-08

Liquid electrolyte-gated organic field effect transistors and organic electrochemical transistors have recently emerged as powerful technology platforms for sensing and simulation of living cells and organisms. For such applications, the transistors are operated at a gate voltage around or below 0.3 V because prolonged application of a higher voltage bias can lead to membrane rupturing and cell death. This constraint often prevents the operation of the transistors at their maximum transconductance or most sensitive regime. Here, we exploit a solid-liquid dual-gate organic transistor structure, where the threshold voltage of the liquid-gated conduction channel is controlled by an additional gate that is separated from the channel by a metal-oxide gate dielectric. With this design, the threshold voltage of the "sensing channel" can be linearly tuned in a voltage window exceeding 0.4 V. We have demonstrated that the dual-gate structure enables a much better sensor response to the detachment of human mesenchymal stem cells. In general, the capability of tuning the optimal sensing bias will not only improve the device performance but also broaden the material selection for cell-based organic bioelectronics.

Small organic molecule based flow battery

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

Huskinson, Brian; Marshak, Michael; Aziz, Michael J.

The invention provides an electrochemical cell based on a new chemistry for a flow battery for large scale, e.g., gridscale, electrical energy storage. Electrical energy is stored chemically at an electrochemical electrode by the protonation of small organic molecules called quinones to hydroquinones. The proton is provided by a complementary electrochemical reaction at the other electrode. These reactions are reversed to deliver electrical energy. A flow battery based on this concept can operate as a closed system. The flow battery architecture has scaling advantages over solid electrode batteries for large scale energy storage.

Binder Jetting: A Novel Solid Oxide Fuel-Cell Fabrication Process and Evaluation

NASA Astrophysics Data System (ADS)

Manogharan, Guha; Kioko, Meshack; Linkous, Clovis

2015-03-01

With an ever-growing concern to find a more efficient and less polluting means of producing electricity, fuel cells have constantly been of great interest. Fuel cells electrochemically convert chemical energy directly into electricity and heat without resorting to combustion/mechanical cycling. This article studies the solid oxide fuel cell (SOFC), which is a high-temperature (100°C to 1000°C) ceramic cell made from all solid-state components and can operate under a wide range of fuel sources such as hydrogen, methanol, gasoline, diesel, and gasified coal. Traditionally, SOFCs are fabricated using processes such as tape casting, calendaring, extrusion, and warm pressing for substrate support, followed by screen printing, slurry coating, spray techniques, vapor deposition, and sputter techniques, which have limited control in substrate microstructure. In this article, the feasibility of engineering the porosity and configuration of an SOFC via an additive manufacturing (AM) method known as binder jet printing was explored. The anode, cathode and oxygen ion-conducting electrolyte layers were fabricated through AM sequentially as a complete fuel cell unit. The cell performance was measured in two modes: (I) as an electrolytic oxygen pump and (II) as a galvanic electricity generator using hydrogen gas as the fuel. An analysis on influence of porosity was performed through SEM studies and permeability testing. An additional study on fuel cell material composition was conducted to verify the effects of binder jetting through SEM-EDS. Electrical discharge of the AM fabricated SOFC and nonlinearity of permeability tests show that, with additional work, the porosity of the cell can be modified for optimal performance at operating flow and temperature conditions.

Electrode design for low temperature direct-hydrocarbon solid oxide fuel cells

DOEpatents

Chen, Fanglin; Zhao, Fei; Liu, Qiang

2015-10-06

In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

Electrode Design for Low Temperature Direct-Hydrocarbon Solid Oxide Fuel Cells

NASA Technical Reports Server (NTRS)

Liu, Qiang (Inventor); Chen, Fanglin (Inventor); Zhao, Fei (Inventor)

2015-01-01

In certain embodiments of the present disclosure, a solid oxide fuel cell is described. The solid oxide fuel cell includes a hierarchically porous cathode support having an impregnated cobaltite cathode deposited thereon, an electrolyte, and an anode support. The anode support includes hydrocarbon oxidation catalyst deposited thereon, wherein the cathode support, electrolyte, and anode support are joined together and wherein the solid oxide fuel cell operates a temperature of 600.degree. C. or less.

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.

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.

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G.B.; Chiba, Z.; Lewis, P.R.; Nelson, N.; Steward, G.A.

1999-06-15

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO[sub 2]. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement. 2 figs.

Instrumentation for air quality measurements.

NASA Technical Reports Server (NTRS)

Loewenstein, M.

1973-01-01

Comparison of the new generation of air quality monitoring instruments with some more traditional methods. The first generation of air quality measurement instruments, based on the use of oxidant coulometric cells, nitrogen oxide colorimetry, carbon monoxide infrared analyzers, and other types of detectors, is compared with new techniques now coming into wide use in the air monitoring field and involving the use of chemiluminescent reactions, optical absorption detectors, a refinement of the carbon monoxide infrared analyzer, electrochemical cells based on solid electrolytes, and laser detectors.

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.

Electrochemistry of the Zinc-Silver Oxide System. Part 2: Practical Measurements of Energy Conversion Using Commercial Miniature Cells.

ERIC Educational Resources Information Center

Smith, Michael J.; Vincent, Colin A.

1989-01-01

Summarizes the quantitative relationships pertaining to the operation of electrochemical cells. Energy conversion efficiency, cycle efficiency, battery power, and energy/power density of two types of zinc-silver oxide cells are discussed. (YP)

Studying the characteristics of a 5 kW power installation on solid-oxide fuel cells with steam reforming of natural gas

NASA Astrophysics Data System (ADS)

Munts, V. A.; Volkova, Yu. V.; Plotnikov, N. S.; Dubinin, A. M.; Tuponogov, V. G.; Chernishev, V. A.

2015-11-01

The results from tests of a 5 kW power plant on solid-oxide fuel cells (SOFCs), in which natural gas is used as fuel, are presented. The installation's process circuit, the test procedure, and the analysis of the obtained results are described. The characteristics of the power plant developed by the Ural Industrial Company are investigated in four steady-state modes of its operation: with the SOFC nominal power capacity utilized by 40% (2 kW), 60% (3 kW), 90% (4.5 kW) and 110% (5.4 kW) (the peaking mode). The electrical and thermodynamic efficiencies are calculated for all operating modes, and the most efficient mode, in which the electrical efficiency reached almost 70%, is determined. The air excess coefficient and heat loss with flue gases q 2 are determined, and it is revealed that the heat loss q 5 decreases from 40 to 25% with increasing the load. Thermal balances are drawn up for the following components of the system the reformer, the SOFC battery, the catalytic burner for afterburning anode gases, the heat exchanger for heating the cathode air and the mixture of natural gas and steam, and the actual fuel utilization rates in the electrochemical generator are calculated. An equation for the resulting natural gas steam reforming reaction was obtained based on the results from calculating the equilibrium composition of reforming products for the achieved temperatures at the reformer outlet t 3.

Method of low temperature operation of an electrochemical cell array

DOEpatents

Singh, Prabhakar; Ruka, Roswell J.; Bratton, Raymond J.

1994-01-01

In the method of operating an electrochemical cell generator apparatus containing a generator chamber (20) containing an array of cells (12) having interior and exterior electrodes with solid electrolyte between the electrodes, where a hot gas (F) contacts the outside of the cells (12) and the generating chamber normally operates at over 850.degree. C., where N.sub.2 gas is fed to contact the interior electrode of the cells (12) in any case when the generating chamber (20) temperature drops for whatever reason to within the range of from 550.degree. C. to 800.degree. C., to eliminate cracking within the cells (12).

Effect of Electrode Configuration on Nitric Oxide Gas Sensor Behavior.

PubMed

Cui, Ling; Murray, Erica P

2015-09-23

The influence of electrode configuration on the impedancemetric response of nitric oxide (NO) gas sensors was investigated for solid electrochemical cells [Au/yttria-stabilized zirconia (YSZ)/Au)]. Fabrication of the sensors was carried out at 1050 °C in order to establish a porous YSZ electrolyte that enabled gas diffusion. Two electrode configurations were studied where Au wire electrodes were either embedded within or wrapped around the YSZ electrolyte. The electrical response of the sensors was collected via impedance spectroscopy under various operating conditions where gas concentrations ranged from 0 to 100 ppm NO and 1%-18% O₂ at temperatures varying from 600 to 700 °C. Gas diffusion appeared to be a rate-limiting mechanism in sensors where the electrode configuration resulted in longer diffusion pathways. The temperature dependence of the NO sensors studied was independent of the electrode configuration. Analysis of the impedance data, along with equivalent circuit modeling indicated the electrode configuration of the sensor effected gas and ionic transport pathways, capacitance behavior, and NO sensitivity.

Electrochemical investigation of mixed metal oxide nanocomposite electrode for low temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Abbas, Ghazanfar; Raza, Rizwan; Ashfaq Ahmad, M.; Ajmal Khan, M.; Jafar Hussain, M.; Ahmad, Mukhtar; Aziz, Hammad; Ahmad, Imran; Batool, Rida; Altaf, Faizah; Zhu, Bin

2017-10-01

Zinc-based nanostructured nickel (Ni) free metal oxide electrode material Zn0.60/Cu0.20Mn0.20 oxide (CMZO) was synthesized by solid state reaction and investigated for low temperature solid oxide fuel cell (LTSOFC) applications. The crystal structure and surface morphology of the synthesized electrode material were examined by XRD and SEM techniques respectively. The particle size of ZnO phase estimated by Scherer’s equation was 31.50 nm. The maximum electrical conductivity was found to be 12.567 S/cm and 5.846 S/cm in hydrogen and air atmosphere, respectively at 600∘C. The activation energy of the CMZO material was also calculated from the DC conductivity data using Arrhenius plots and it was found to be 0.060 and 0.075 eV in hydrogen and air atmosphere, respectively. The CMZO electrode-based fuel cell was tested using carbonated samarium doped ceria composite (NSDC) electrolyte. The three layers 13 mm in diameter and 1 mm thickness of the symmetric fuel cell were fabricated by dry pressing. The maximum power density of 728.86 mW/cm2 was measured at 550∘C.

Molecular and ionic-scale chemical mechanisms behind the role of nitrocyl group in the electrochemical removal of heavy metals from sludge

PubMed Central

Hasan, S. W.; Ahmed, I.; Housani, A. A.; Giwa, A.

2016-01-01

The chemical basis for improved removal rates of toxic heavy metals such as Zn and Cu from wastewater secondary sludge has been demonstrated in this study. Instead of using excess corrosive chemicals as the source of free nitrous acid (FNA) for improved solubility of heavy metals in the sludge (in order to enhance electrokinetics), an optimized use of aqua regia has been proposed as an alternative. Fragments of nitrocyl group originated from aqua regia are responsible for the disruption of biogenic mixed liquor volatile suspended solids (MLVSS) and this disruption resulted in enhanced removal of exposed and oxidized metal ions. A diversity of nitric oxide (NO), peroxy nitrous acid, and peroxy nitroso group are expected to be introduced in the mixed liquor by the aqua regia for enhanced electrochemical treatment. The effects of pectin as a post treatment on the Zn removal from sludge were also presented for the first time. Results revealed 63.6% Cu and 93.7% Zn removal efficiencies, as compared to 49% Cu and 74% Zn removal efficiencies reported in a recent study. Also, 93.3% reduction of time-to-filter (TTF), and 95 mL/g of sludge volume index (SVI) were reported. The total operating cost obtained was USD 1.972/wet ton. PMID:27550724

Sol-Gel Synthesis, Electrochemical Characterization, and Stability Testing of Ti0.7W0.3O2 Nanoparticles for Catalyst Support Applications in Proton-Exchange Membrane Fuel Cells

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

Subban, Chinmayee V.; Zhou, Qin; Hu, Anthony

2010-11-19

The materials currently used in proton-exchange membrane fuel cells (PEMFCs) require complex control of operating conditions to make them sufficiently durable to permit commercial deployment. One of the major materials challenges to allow simplification of fuel cell operating strategies is the discovery of catalyst supports that are much more stable to oxidative decomposition than currently used carbon blacks. Here we report the synthesis and characterization of Ti 0.7W 0.3O 2 nanoparticles (approximately 50 nm diameter), a promising doped metal oxide that is a candidate for such a durable catalyst support. The synthesized nanoparticles were platinized, characterized by electrochemical testing, andmore » evaluated for stability under PEMFC and other oxidizing acidic conditions. Ti 0.7W 0.3O 2 nanoparticles show no evidence of decomposition when heated in a Nafion solution for 3 weeks at 80 °C. In contrast, when heated in sulfuric, nitric, perchloric, or hydrochloric acid, the oxide reacts to form salts such as titanylsulfatehydrate from sulfuric acid. Electrochemical tests show that rates of hydrogen oxidation and oxygen reduction by platinum nanoparticles supported on Ti 0.7W 0.3O 2 are comparable to those of commercial Pt on carbon black.« less

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.

Lead paste recycling based on conversion into battery grade oxides. Electrochemical tests and industrial production of new batteries

NASA Astrophysics Data System (ADS)

Fusillo, G.; Rosestolato, D.; Scura, F.; Cattarin, S.; Mattarozzi, L.; Guerriero, P.; Gambirasi, A.; Brianese, N.; Staiti, P.; Guerriero, R.; La Sala, G.

2018-03-01

We present the preparation and characterization of pure lead monoxide obtained through recycling of the lead paste recovered from exhausted lead acid batteries. The recycling is based on a hydrometallurgical procedure reported in a STC Patent, that includes simple chemical operations (desulphurisation, leaching, precipitation, filtration) and a final thermal conversion. Materials obtained by treatment at 600 °C consist predominantly of β-PbO. The electrochemical behaviour of Positive Active Mass (PAM) prepared from different materials (or mixtures) is then investigated and compared. An optimized oxide material, obtained by prolonged (8 h) thermal treatment at 600 °C, consists of pure β-PbO and appears suitable for preparation of battery elements, alone or in mixture with a small fraction (10%-30%) of traditional industrial leady oxide. The resulting battery performances are similar to those obtained from pure leady oxide. In comparison with traditional recycling processes, the proposed method guarantees lower energy consumption, limited environmental impact and reduced operating risk for industry workers.

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.

Multi-length scale tomography for the determination and optimization of the effective microstructural properties in novel hierarchical solid oxide fuel cell anodes

NASA Astrophysics Data System (ADS)

Lu, Xuekun; Taiwo, Oluwadamilola O.; Bertei, Antonio; Li, Tao; Li, Kang; Brett, Dan J. L.; Shearing, Paul R.

2017-11-01

Effective microstructural properties are critical in determining the electrochemical performance of solid oxide fuel cells (SOFCs), particularly when operating at high current densities. A novel tubular SOFC anode with a hierarchical microstructure, composed of self-organized micro-channels and sponge-like regions, has been fabricated by a phase inversion technique to mitigate concentration losses. However, since pore sizes span over two orders of magnitude, the determination of the effective transport parameters using image-based techniques remains challenging. Pioneering steps are made in this study to characterize and optimize the microstructure by coupling multi-length scale 3D tomography and modeling. The results conclusively show that embedding finger-like micro-channels into the tubular anode can improve the mass transport by 250% and the permeability by 2-3 orders of magnitude. Our parametric study shows that increasing the porosity in the spongy layer beyond 10% enhances the effective transport parameters of the spongy layer at an exponential rate, but linearly for the full anode. For the first time, local and global mass transport properties are correlated to the microstructure, which is of wide interest for rationalizing the design optimization of SOFC electrodes and more generally for hierarchical materials in batteries and membranes.

Robust adaptive control for a hybrid solid oxide fuel cell system

NASA Astrophysics Data System (ADS)

Snyder, Steven

2011-12-01

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices. They offer a number of advantages beyond those of most other fuel cells due to their high operating temperature (800-1000°C), such as internal reforming, heat as a byproduct, and faster reaction kinetics without precious metal catalysts. Mitigating fuel starvation and improving load-following capabilities of SOFC systems are conflicting control objectives. However, this can be resolved by the hybridization of the system with an energy storage device, such as an ultra-capacitor. In this thesis, a steady-state property of the SOFC is combined with an input-shaping method in order to address the issue of fuel starvation. Simultaneously, an overall adaptive system control strategy is employed to manage the energy sharing between the elements as well as to maintain the state-of-charge of the energy storage device. The adaptive control method is robust to errors in the fuel cell's fuel supply system and guarantees that the fuel cell current and ultra-capacitor state-of-charge approach their target values and remain uniformly, ultimately bounded about these target values. Parameter saturation is employed to guarantee boundedness of the parameters. The controller is validated through hardware-in-the-loop experiments as well as computer simulations.

Cyclic-Voltammetry-Based Solid-State Gas Sensor for Methane and Other VOC Detection.

PubMed

Gross, Pierre-Alexandre; Jaramillo, Thomas; Pruitt, Beth

2018-05-15

We present the fabrication, characterization, and testing of an electrochemical volatile organic compound (VOC) sensor operating in gaseous conditions at room temperature. It is designed to be microfabricated and to prove the sensing principle based on cyclic voltammetry (CV). It is composed of a working electrode (WE), a counter electrode (CE), a reference electrode (RE), and a Nafion solid-state electrolyte. Nafion is a polymer that conducts protons (H + ) generated from redox reactions from the WE to the CE. The sensor needs to be activated prior to exposure to gases, which consists of hydrating the Nafion layer to enable its ion conduction properties. During testing, we have shown that our sensor is not only capable of detecting methane, but it can also quantify its concentration in the gas flow as well as differentiate its signal from carbon monoxide (CO). These results have been confirmed by exposing the sensor to two different concentrations of methane (50% and 10% of methane diluted in N 2 ), as well as pure CO. Although the signal is positioned in the H ads region of Pt, because of thermodynamic reasons it cannot be directly attributed to methane oxidation into CO 2 . However, its consistency suggests the presence of a methane-related oxidation process that can be used for detection, identification, and quantification purposes.

Recent Advances in Metal Chalcogenides (MX; X = S, Se) Nanostructures for Electrochemical Supercapacitor Applications: A Brief Review

PubMed Central

Theerthagiri, Jayaraman; Durai, Govindarajan; Rana, Abu ul Hassan Sarwar; Sangeetha, Kirubanandam; Kuppusami, Parasuraman; Kim, Hyun-Seok

2018-01-01

Supercapacitors (SCs) have received a great deal of attention and play an important role for future self-powered devices, mainly owing to their higher power density. Among all types of electrical energy storage devices, electrochemical supercapacitors are considered to be the most promising because of their superior performance characteristics, including short charging time, high power density, safety, easy fabrication procedures, and long operational life. An SC consists of two foremost components, namely electrode materials, and electrolyte. The selection of appropriate electrode materials with rational nanostructured designs has resulted in improved electrochemical properties for high performance and has reduced the cost of SCs. In this review, we mainly spotlight the non-metallic oxide, especially metal chalcogenides (MX; X = S, Se) based nanostructured electrode materials for electrochemical SCs. Different non-metallic oxide materials are highlighted in various categories, such as transition metal sulfides and selenides materials. Finally, the designing strategy and future improvements on metal chalcogenide materials for the application of electrochemical SCs are also discussed. PMID:29671823

Electrochemical oxidation coupled with liquid chromatography and mass spectrometry to study the oxidative stability of active pharmaceutical ingredients in solution: A comparison of off-line and on-line approaches.

PubMed

Torres, Susana; Brown, Roland; Zelesky, Todd; Scrivens, Garry; Szucs, Roman; Hawkins, Joel M; Taylor, Mark R

2016-11-30

Stability studies of pharmaceutical drug products and pharmaceutical active substances are important to research and development in order to fully understand and maintain product quality and safety throughout its shelf-life. Oxidative forced degradation studies are among the different types of stability studies performed by the pharmaceutical industry in order to understand the intrinsic stability of drug molecules. We have been comparing the use of electrochemistry as an alternative oxidative forced degradation method to traditional forced degradation and accelerated stability studies. Using the electrochemical degradation approach the substrate oxidation takes place in a commercially available electrochemical cell and the effluent of the cell can be either a) directly infused into the mass spectrometer or b) injected in a chromatographic column for separation of the different products formed prior to the mass spectrometry analysis. To enable the study of large numbers of different experimental conditions and molecules we developed a new dual pump automated electrochemical screening platform. This system used a HPLC pump and autosampler to load and wash the electrochemical cell and deliver the oxidized sample plug to a second injection loop. This system enabled the automatic sequential analyses of large numbers of different solutions under varied experimental conditions without need for operator intervention during the run sequence. Here we describe the system and evaluate its performance using a test molecule with well characterized stability and compare results to those obtained using an off-line electrochemistry approach. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural design considerations for micromachined solid-oxide fuel cells

NASA Astrophysics Data System (ADS)

Srikar, V. T.; Turner, Kevin T.; Andrew Ie, Tze Yung; Spearing, S. Mark

Micromachined solid-oxide fuel cells (μSOFCs) are among a class of devices being investigated for portable power generation. Optimization of the performance and reliability of such devices requires robust, scale-dependent, design methodologies. In this first analysis, we consider the structural design of planar, electrolyte-supported, μSOFCs from the viewpoints of electrochemical performance, mechanical stability and reliability, and thermal behavior. The effect of electrolyte thickness on fuel cell performance is evaluated using a simple analytical model. Design diagrams that account explicitly for thermal and intrinsic residual stresses are presented to identify geometries that are resistant to fracture and buckling. Analysis of energy loss due to in-plane heat conduction highlights the importance of efficient thermal isolation in microscale fuel cell design.

Electrochemical removal of tannins from aqueous solutions

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

Buso, A.; Balbo, L.; Giomo, M.

2000-02-01

The application of electrochemical methods to remove tannins from wastewater was investigated. Gallotannic acid was used as the reference substance. Electrochemical experiments were performed using platinum electrodes. Macroscale potentiostatic or galvanostatic electrolyses were carried out with sodium sulfate or sodium chloride as supporting electrolytes, to analyze direct and indirect oxidation processes. Operating variables such as pH and chloride concentration were considered to determine their influence on the efficiency and energy consumption of the process. The simulation of a pilot plant was carried out with a mathematical model, the parameters of which were determined by fitting of experimental profiles. The resultsmore » of a preliminary investigation on the oxidation-coagulation process using sacrificial electrodes are also reported.« less

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.

Freestanding Gold/Graphene-Oxide/Manganese Oxide Microsupercapacitor Displaying High Areal Energy Density.

PubMed

Morag, Ahiud; Becker, James Y; Jelinek, Raz

2017-07-10

Microsupercapacitors are touted as one of the promising "next frontiers" in energy-storage research and applications. Despite their potential, significant challenges still exist in terms of physical properties and electrochemical performance, particularly attaining high energy density, stability, ease of synthesis, and feasibility of large-scale production. We present new freestanding microporous electrodes comprising self-assembled scaffold of gold and reduced graphene oxide (rGO) nanowires coated with MnO 2 . The electrodes exhibited excellent electrochemical characteristics, particularly superior high areal capacitance. Moreover, the freestanding Au/rGO scaffold also served as the current collector, obviating the need for an additional electrode support required in most reported supercapacitors, thus enabling low volume and weight devices with a high overall device specific energy. Stacked symmetrical solid-state supercapacitors were fabricated using the Au/rGO/MnO 2 electrodes in parallel configurations showing the advantage of using freestanding electrodes in the fabrication of low-volume devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced methane steam reforming activity and electrochemical performance of Ni0.9Fe0.1-supported solid oxide fuel cells with infiltrated Ni-TiO2 particles

PubMed Central

Li, Kai; Jia, Lichao; Wang, Xin; Pu, Jian; Chi, Bo; Li, Jian

2016-01-01

Ni0.9Fe0.1 alloy-supported solid oxide fuel cells with NiTiO3 (NTO) infiltrated into the cell support from 0 to 4 wt.% are prepared and investigated for CH4 steam reforming activity and electrochemical performance. The infiltrated NiTiO3 is reduced to TiO2-supported Ni particles in H2 at 650 °C. The reforming activity of the Ni0.9Fe0.1-support is increased by the presence of the TiO2-supported Ni particles; 3 wt.% is the optimal value of the added NTO, corresponding to the highest reforming activity, resistance to carbon deposition and electrochemical performance of the cell. Fueled wet CH4 at 100 mL min−1, the cell with 3 wt.% of NTO demonstrates a peak power density of 1.20 W cm−2 and a high limiting current density of 2.83 A cm−2 at 650 °C. It performs steadily for 96 h at 0.4 A cm−2 without the presence of deposited carbon in the Ni0.9Fe0.1-support and functional anode. Five polarization processes are identified by deconvoluting and data-fitting the electrochemical impedance spectra of the cells under the testing conditions; and the addition of TiO2-supported Ni particles into the Ni0.9Fe0.1-support reduces the polarization resistance of the processes ascribed to CH4 steam reforming and gas diffusion in the Ni0.9Fe0.1-support and functional anode. PMID:27775092

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on-off" ratio in electrochemical activity at elevated temperatures. Overall, solution pH and conductivity were altered by an order of magnitude and device performance (ability to store charge) decreased by over 70%. After demonstration of a model responsive electrolyte in an aqueous system, ionic liquid (IL) based electrolytes were developed as a means of controlling the electrochemical performance in the non-aqueous environments that batteries, specifically Li-ion, require. Here, two systems were developed: (1) an electrolyte comprising poly(ethylene oxide) (PEO), the IL, [EMIM][BF4], and a lithium salt and (2) an electrolyte comprising poly(benzyl methacrylate) (PBzMA), the IL, [EMIM][TFSI], and a lithium salt. In each system, the polymer-IL phase separation inhibited device operation at elevated temperatures. For the PEO/IL electrolyte, the thermally induced liquid-liquid phase separation was shown to decrease the ionic conductivity, thereby affecting the concentration of ions at the electrode. Additionally, an increasing charge transfer resistance associated with the phase separated polymer coating the porous electrode was shown to limit electrochemical activity significantly. For the PBzMA/IL electrolyte, the solid-liquid phase separation did not show a change in conductivity, but did cause a drastic increase in charge transfer resistance, effectively shutting off Li-ion battery operation at high temperatures. Such responsive mixtures provide a transformative approach to regulating electrochemical processes, which is necessary to achieve inherently safe operation in large format energy storage with EDLCs, supercapacitors and Li-ion batteries.

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.

Scanning electrochemical microscopy of graphene/polymer hybrid thin films as supercapacitors: Physical-chemical interfacial processes

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

Gupta, Sanju, E-mail: sanju.gupta@wku.edu; Price, Carson

2015-10-15

Hybrid electrode comprising an electric double-layer capacitor of graphene nanosheets and a pseudocapacitor of the electrically conducting polymers namely, polyaniline; PAni and polypyrrole; PPy are constructed that exhibited synergistic effect with excellent electrochemical performance as thin film supercapacitors for alternative energy. The hybrid supercapacitors were prepared by layer-by-layer (LbL) assembly based on controlled electrochemical polymerization followed by reduction of graphene oxide electrochemically producing ErGO, for establishing intimate electronic contact through nanoscale architecture and chemical stability, producing a single bilayer of (PAni/ErGO){sub 1}, (PPy/ErGO){sub 1}, (PAni/GO){sub 1} and (PPy/GO){sub 1}. The rationale design is to create thin films that possess interconnectedmore » graphene nanosheets (GNS) with polymer nanostructures forming well-defined tailored interfaces allowing sufficient surface adsorption and faster ion transport due to short diffusion distances. We investigated their electrochemical properties and performance in terms of gravimetric specific capacitance, C{sub s}, from cyclic voltammograms. The LbL-assembled bilayer films exhibited an excellent C{sub s} of ≥350 F g{sup −1} as compared with constituents (∼70 F g{sup −1}) at discharge current density of 0.3 A g{sup −1} that outperformed many other hybrid supercapacitors. To gain deeper insights into the physical-chemical interfacial processes occurring at the electrode/electrolyte interface that govern their operation, we have used scanning electrochemical microscopy (SECM) technique in feedback and probe approach modes. We present our findings from viewpoint of reinforcing the role played by heterogeneous electrode surface composed of nanoscale graphene sheets (conducting) and conducting polymers (semiconducting) backbone with ordered polymer chains via higher/lower probe current distribution maps. Also targeted is SECM imaging that allowed to determine electrochemical (re)activity of surface ion adsorption sites density at solid/liquid interface.« less

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 study of alternative methods for reclaiming oxygen from carbon dioxide and water by a solid-electrolyte process for spacecraft applications

NASA Technical Reports Server (NTRS)

1971-01-01

Two alternative technical approaches were studied for application of an electrochemical process using a solid oxide electrolyte (zirconia stabilized by yttria or scandia) to oxygen reclamation from carbon dioxide and water, for spacecraft life support systems. Among the topics considered are the advisability of proceeding to engineering prototype development and fabrication of a full scale model for the system concept, the optimum choice of method or approach to be carried into prototype development, and the technical problem areas which exist.

Excimer laser assisted very fast exfoliation and reduction of graphite oxide at room temperature under air ambient for Supercapacitors electrode

NASA Astrophysics Data System (ADS)

Malek Hosseini, S. M. B.; Baizaee, S. M.; Naderi, Hamid Reza; Dare Kordi, Ali

2018-01-01

Excimer laser was used for reduction and exfoliation of graphite oxide (GO) at room temperature under air ambient. The prepared excimer laser reduced graphite oxide (XLRGO) is characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), nitrogen adsorption/desorption (BET method), X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and UV-vis absorption techniques for surface, structural functional groups and band gap analysis. Electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge-discharge, electrochemical impedance spectroscopy (EIS) and continues cyclic voltammetry (CCV) in 0.5 M Na2SO4 as electrolyte. Electrochemical investigations revealed that XLRGO electrode has enhanced supercapacitive performance including specific capacitance of 299 F/g at a scan rate of 2 mV/s. Furthermore, CCV measurement showed that XLRGO electrode kept 97.8% of its initial capacitance/capacity after 4000 cycles. The obtained results from electrochemical investigations confirm that the reduction of GO by using an excimer laser produces high-quality graphene for supercapacitor applications without the need for additional operations.

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

DOE PAGES

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.; ...

2018-02-09

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

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

Ahluwalia, Rajesh K.; Papadias, Dionissios D.; Kariuki, Nancy N.

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potentialmore » limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.« less

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

PubMed Central

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

2016-01-01

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

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

PubMed

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

2016-06-06

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

Low resistance fuel electrodes

DOEpatents

Maskalick, Nichols J.; Folser, George R.

1989-01-01

An electrode 6 bonded to a solid, ion conducting electrolyte 5 is made, where the electrode 6 comprises a ceramic metal oxide 18, metal particles 17, and heat stable metal fibers 19, where the metal fibers provide a matrix structure for the electrode. The electrolyte 5 can be bonded to an air electrode cathode 4, to provide an electrochemical cell 2, preferably of tubular design.

Layered method of electrode for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1991-07-30

A process for fabricating a fuel electrode comprising: slurry dipping to form layers which are structurally graded from all or mostly all stabilized zirconia at a first layer, to an outer most layer of substantially all metal powder, such an nickel. Higher performaance fuel electrodes may be achieved if sinter active stabilized zirconia doped for electronic conductivity is used.

Study on the electrochemical corrosion behavior of industrial boilers

NASA Astrophysics Data System (ADS)

Wu, Xiaoyang; Huang, Song; Zhang, Wenpin; Feng, Qiang; Huang, Yong

2018-06-01

In this paper, industrial boilers are used as the research object, and Boilerentiodynamic polarization analysis of boiler steel is used to study the electrochemical corrosion behavior in the boiler water. The electrochemical corrosion nature and morphology of the samples were tested through experiments. The study shows: the corrosion resistance of the samples will decrease significantly with the increase of the operating time of boilers. Dissolved solids and Cl- in the boiler water will destroy the original protective film, of which the increase of its content is the main reason for the deterioration of the material properties.

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

NASA Astrophysics Data System (ADS)

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

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

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.

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

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

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

2015-01-15

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

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Jiang, Long; Wang, Jie; Xiong, Xiaolei; ...

2016-01-21

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

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

Jiang, Long; Wang, Jie; Xiong, Xiaolei

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Investigation of nanoporous platinum thin films fabricated by reactive sputtering: Application as micro-SOFC electrode

NASA Astrophysics Data System (ADS)

Jung, WooChul; Kim, Jae Jin; Tuller, Harry L.

2015-02-01

Highly porous Pt thin films, with nano-scale porosity, were fabricated by reactive sputtering. The strategy involved deposition of thin film PtOx at room temperature, followed by the subsequent decomposition of the oxide by rapid heat treatment. The resulting films exhibited percolating Pt networks infiltrated with interconnected nanosized pores, critical for superior solid oxide fuel cell cathode performance. This approach is particularly attractive for micro-fabricated solid oxide fuel cells, since it enables fabrication of the entire cell stack (anode/electrolyte/cathode) within the sputtering chamber, without breaking vacuum. In this work, the morphological, crystallographic and chemical properties of the porous electrode were systematically varied by control of deposition conditions. Oxygen reduction reaction kinetics were investigated by means of electrochemical impedance spectroscopy, demonstrating the critical role of nano-pores in achieving satisfactory micro-SOFC cathode performance.

Amperometric urea biosensors based on sulfonated graphene/polyaniline nanocomposite

PubMed Central

Das, Gautam; Yoon, Hyon Hee

2015-01-01

An electrochemical biosensor based on sulfonated graphene/polyaniline nanocomposite was developed for urea analysis. Oxidative polymerization of aniline in the presence of sulfonated graphene oxide was carried out by electrochemical methods in an aqueous environment. The structural properties of the nanocomposite were characterized by Fourier-transform infrared, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy techniques. The urease enzyme-immobilized sulfonated graphene/polyaniline nanocomposite film showed impressive performance in the electroanalytical detection of urea with a detection limit of 0.050 mM and a sensitivity of 0.85 (μA · cm−2·mM−1. The biosensor achieved a broad linear range of detection (0.12–12.3 mM) with a notable response time of approximately 5 seconds. Moreover, the fabricated biosensor retained 81% of its initial activity (based on sensitivity) after 15 days of storage at 4°C. The ease of fabrication coupled with the low cost and good electrochemical performance of this system holds potential for the development of solid-state biosensors for urea detection. PMID:26346240

Fluorinated reduced graphene oxide as a protective layer on the metallic lithium for application in the high energy batteries.

PubMed

Bobnar, Jernej; Lozinšek, Matic; Kapun, Gregor; Njel, Christian; Dedryvère, Rémi; Genorio, Boštjan; Dominko, Robert

2018-04-11

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials. The FGI on the metallic lithium exhibit two roles, firstly it acts as a Li-ion conductive layer and electronic insulator and secondly, it effectively suppresses the formation of high surface area lithium (HSAL). An enhanced electrochemical performance of the full cell battery system with two different types of cathodes was shown in the carbonate or in the ether based electrolytes. The presented results indicate a potential application in future secondary Li-metal batteries.

Development of a Novel Efficient Solid-Oxide Hybrid for Co-generation of Hydrogen and Electricity Using Nearby Resources for Local Application

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

Tao, Greg, G.; Virkar, Anil, V.; Bandopadhyay, Sukumar

2009-06-30

Developing safe, reliable, cost-effective, and efficient hydrogen-electricity co-generation systems is an important step in the quest for national energy security and minimized reliance on foreign oil. This project aimed to, through materials research, develop a cost-effective advanced technology cogenerating hydrogen and electricity directly from distributed natural gas and/or coal-derived fuels. This advanced technology was built upon a novel hybrid module composed of solid-oxide fuel-assisted electrolysis cells (SOFECs) and solid-oxide fuel cells (SOFCs), both of which were in planar, anode-supported designs. A SOFEC is an electrochemical device, in which an oxidizable fuel and steam are fed to the anode and cathode,more » respectively. Steam on the cathode is split into oxygen ions that are transported through an oxygen ion-conducting electrolyte (i.e. YSZ) to oxidize the anode fuel. The dissociated hydrogen and residual steam are exhausted from the SOFEC cathode and then separated by condensation of the steam to produce pure hydrogen. The rationale was that in such an approach fuel provides a chemical potential replacing the external power conventionally used to drive electrolysis cells (i.e. solid oxide electrolysis cells). A SOFC is similar to the SOFEC by replacing cathode steam with air for power generation. To fulfill the cogeneration objective, a hybrid module comprising reversible SOFEC stacks and SOFC stacks was designed that planar SOFECs and SOFCs were manifolded in such a way that the anodes of both the SOFCs and the SOFECs were fed the same fuel, (i.e. natural gas or coal-derived fuel). Hydrogen was produced by SOFECs and electricity was generated by SOFCs within the same hybrid system. A stand-alone 5 kW system comprising three SOFEC-SOFC hybrid modules and three dedicated SOFC stacks, balance-of-plant components (including a tailgas-fired steam generator and tailgas-fired process heaters), and electronic controls was designed, though an overall integrated system assembly was not completed because of limited resources. An inexpensive metallic interconnects fabrication process was developed in-house. BOP components were fabricated and evaluated under the forecasted operating conditions. Proof-of-concept demonstration of cogenerating hydrogen and electricity was performed, and demonstrated SOFEC operational stability over 360 hours with no significant degradation. Cost analysis was performed for providing an economic assessment of the cost of hydrogen production using the targeted hybrid technology, and for guiding future research and development.« less

ESM of ionic and electrochemical phenomena on the nanoscale

DOE PAGES

Kalinin, Sergei V.; Kumar, Amit; Balke, Nina; ...

2011-01-01

Operation of energy storage and conversion devices is ultimately controlled by series of intertwined ionic and electronic transport processes and electrochemical reactions at surfaces and interfaces, strongly mediated by strain and mechanical processes. In a typical fuel cell, these include chemical species transport in porous cathode and anode materials, gas-solid electrochemical reactions at grains and triple-phase boundaries (TPBs), ionic and electronic flows in multicomponent electrodes, and chemical and electronic potential drops at internal interfaces in electrodes and electrolytes. Furthermore, all these phenomena are sensitively affected by the microstructure of materials from device level to the atomic scales. Similar spectrum ofmore » length scales and phenomena underpin operation of other energy systems including primary and secondary batteries, as well as hybrid systems such flow and metal-air/water batteries.« less

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.

Analysis of cerium-composite polymer-electrolyte membranes during and after accelerated oxidative-stability test

NASA Astrophysics Data System (ADS)

Shin, Dongwon; Han, Myungseong; Shul, Yong-Gun; Lee, Hyejin; Bae, Byungchan

2018-02-01

The oxidative stability of membranes constructed from a composite of pristine sulfonated poly(arylene ether sulfone) and cerium was investigated by conducting an accelerated oxidative-stability test at the open-circuit voltage (OCV). The membranes were analyzed in situ through OCV and impedance measurements, cyclic voltammetry, and linear-sweep voltammetry to monitor the electrochemical properties during the stability test. Although the high-frequency resistance of a composite membrane was slightly higher than that of a pristine membrane because of the exchange of protons from the sulfonic acid with cerium ions, the composite membrane maintained its potential for much longer than the pristine membrane. The effect of the cerium ions as radical scavengers was confirmed by analyzing the drain water and chemical structure after operation. These post-operation analyses confirmed that cerium ions improved the oxidative stability of the hydrocarbon-based polymer during fuel-cell operation. It is clear that the cerium-based radical scavengers prevented chemical degradation of the polymer membrane as well as the electrode in terms of hydrogen cross-over, polymer-chain scission, and the electrochemical surface area, while they rarely diffused outward from the membrane.

Enhanced electrochemical performance and carbon anti-coking ability of solid oxide fuel cells with silver modified nickel-yttrium stabilized zirconia anode by electroless plating

NASA Astrophysics Data System (ADS)

Wu, Xiaoyan; Tian, Yu; Zhang, Jun; Zuo, Wei; Kong, Xiaowei; Wang, Jinghui; Sun, Kening; Zhou, Xiaoliang

2016-01-01

In this paper, silver (Ag) particles are introduced into the conventional Ni/YSZ anode by utilizing electroless plating method to improve its carbon anti-coking ability in hydrocarbons. The experimental results show that electrochemical performances of the decorated cells in H2, CH4 and C2H6 are all increased as compared to the cell with unmodified Ni/YSZ anode, which are verified by impedance spectrums as well. The durability experiment is carried out for as long as 24 h at the current density of 0.33 A/cm2 where the modified anode is subjected to dry C2H6 indicating the anti-coking ability of the anode is greatly improved. Scanning electron microscope shows that the slight decreasing in the cell terminal voltage can be attributed to the minimized carbon deposition which maybe resulted from the aggregation of silver particles at high temperature. Energy-dispersive X-ray spectroscopy line scanning results after long-term stability operation of the anode suggest that the carbon deposition can be depressed effectively both inside the anode and on the surface of the anode. Therefore, the results show that silver is a promising candidate material for modifying the Ni/YSZ anode with regard to improving electrochemical performance and suppressing the carbon deposition when taking the hydrocarbons as fuels.

In operando infrared spectroscopy of lithium polysulfides using a novel spectro-electrochemical cell

NASA Astrophysics Data System (ADS)

Saqib, Najmus; Ohlhausen, Gretchen M.; Porter, Jason M.

2017-10-01

A new in operando spectro-electrochemical Li-S cell has been demonstrated. The novel design allows investigations of the liquid electrolyte phase, in a commercial coin cell geometry, at C rates much higher than conventional in situ cells. We use ATR FT-IR spectroscopy, coupled with a previously developed polysulfide diagnostic to quantify the evolution of lithium polysulfides during the discharge and charge cycles of a Li-S cell. The trends observed in the polysulfide order and concentration with respect to state of charge are consistent with prevailing understanding of the electrochemical mechanisms of Li-S battery operation. During discharge, we observe the reduction of elemental sulfur to dissolved Li2S8 polysulfides, and their cascading conversion to smaller polysulfides until insoluble species (Li2S2 and Li2S) are formed. During cell charging, we observe the oxidation of insoluble polysulfides to larger, soluble polysulfides (Li2Sn , n > 3), and infer an eventual recovery of crystalline sulfur, from changes in polysulfides. Long-term evolution of polysulfides is observed over 7 discharge/charge cycles. Capacity fading is evident in the decay of polysulfide order and concentration at the same state of charge between cycles. Sulfur is not recovered by charging the cell in the latter cycles, and the active material is lost as solid Li2S .

Development of Ni-Ba(Zr,Y)O3 cermet anodes for direct ammonia-fueled solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Miyazaki, Kazunari; Okanishi, Takeou; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

2017-10-01

In this study, the availability of Ni-Ba(Zr,Y)O3-δ (BZY) cermet for the anode of direct ammonia-fueled solid oxide fuel cells (SOFCs) is evaluated. In this device, the anodes need to be active for the catalytic ammonia decomposition as well as the electrochemical hydrogen oxidation. In the catalytic activity test, ammonia decomposes completely over Ni-BZY at ca. 600 °C, while higher temperature is required to accomplish the complete decomposition over the conventional SOFC anode of Ni-yttria-stabilized zirconia cermet. The high activity of Ni-BZY is attributed to the high basicity of BZY and the high resistance to hydrogen poisoning effect. The electrochemical property of Ni-BZY anode is also evaluated with the anode-supported cell of Ni-BZY|BZY|Pt at 600-700 °C with feeding ammonia or hydrogen as a fuel. Since the residence time of ammonia fuel in the thick Ni-BZY anode is long, the difference in the cell performance between two fuels is relatively small. Furthermore, it is proved that the steam concentration in the fuel strongly affects the cell performance. We find that this factor is important to satisfy the above mentioned requirements for the anode of direct ammonia-fueled SOFCs. Throughout this study, it is concluded that Ni-BZY cermet will be a promising anode.

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.

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.

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

PubMed

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

PubMed Central

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-01-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

DOE PAGES

Qiu, Bao; Zhang, Minghao; Wu, Lijun; ...

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high asmore » 301 mAh g –1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g –1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.« less

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, J.E.

1985-05-20

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

Electrochemical pesticide detection with AutoDip--a portable platform for automation of crude sample analyses.

PubMed

Drechsel, Lisa; Schulz, Martin; von Stetten, Felix; Moldovan, Carmen; Zengerle, Roland; Paust, Nils

2015-02-07

Lab-on-a-chip devices hold promise for automation of complex workflows from sample to answer with minimal consumption of reagents in portable devices. However, complex, inhomogeneous samples as they occur in environmental or food analysis may block microchannels and thus often cause malfunction of the system. Here we present the novel AutoDip platform which is based on the movement of a solid phase through the reagents and sample instead of transporting a sequence of reagents through a fixed solid phase. A ball-pen mechanism operated by an external actuator automates unit operations such as incubation and washing by consecutively dipping the solid phase into the corresponding liquids. The platform is applied to electrochemical detection of organophosphorus pesticides in real food samples using an acetylcholinesterase (AChE) biosensor. Minimal sample preparation and an integrated reagent pre-storage module hold promise for easy handling of the assay. Detection of the pesticide chlorpyrifos-oxon (CPO) spiked into apple samples at concentrations of 10(-7) M has been demonstrated. This concentration is below the maximum residue level for chlorpyrifos in apples defined by the European Commission.

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

Safety shutdown separators

DOEpatents

Carlson, Steven Allen; Anakor, Ifenna Kingsley; Farrell, Greg Robert

2015-06-30

The present invention pertains to electrochemical cells which comprise (a) an anode; (b) a cathode; (c) a solid porous separator, such as a polyolefin, xerogel, or inorganic oxide separator; and (d) a nonaqueous electrolyte, wherein the separator comprises a porous membrane having a microporous coating comprising polymer particles which have not coalesced to form a continuous film. This microporous coating on the separator acts as a safety shutdown layer that rapidly increases the internal resistivity and shuts the cell down upon heating to an elevated temperature, such as 110.degree. C. Also provided are methods for increasing the safety of an electrochemical cell by utilizing such separators with a safety shutdown layer.

Direct Logistic Fuel JP-8 Conversion in a Liquid Tin Anode Solid Oxide Fuel Cell (LTA-SOFC)

DTIC Science & Technology

2008-04-09

GeSnOOSn sgl [1] As governed by the Nernst equation Open Circuit Voltage (OCV) is inversely proportional to temperature. The OCV of...inherently stable at 1,000°C. The LTA-SOFC electrochemical reaction is based on the following thermodynamic equation . C1000T kJ 311 42 o)(2... equation 1 is 0.8V at 1000°C, using an oxygen partial pressure of one. This equation gives the OCV for a LTA–SOFC functioning as a battery. The tin oxide

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

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.

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

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

Raza, Rizwan, E-mail: razahussaini786@gmail.com; Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044; Ahmed, Akhlaq

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

Anode materials for electrochemical waste destruction

NASA Technical Reports Server (NTRS)

Molton, Peter M.; Clarke, Clayton

1990-01-01

Electrochemical Oxidation (ECO) offers promise as a low-temperature, atmospheric pressure method for safe destruction of hazardous organic chemical wastes in water. Anode materials tend to suffer corrosion in the intensely oxidizing environment of the ECO cell. There is a need for cheaper, more resistant materials. In this experiment, a system is described for testing anode materials, with examples of several common anodes such as stainless steel, graphite, and platinized titanium. The ECO system is simple and safe to operate and the experiment can easily be expanded in scope to study the effects of different solutions, temperatures, and organic materials.

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy.

PubMed

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Kubicek, Markus; Götsch, Thomas; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Klötzer, Bernhard; Fleig, Jürgen

2017-10-18

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO 2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H 2 ) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO 3-δ and (La,Sr)CrO 3-δ based perovskite-type electrodes was studied during electrochemical CO 2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO 2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO 2 reduction. In contrast to water splitting, the CO 2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view.

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy

PubMed Central

2017-01-01

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H2) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO3−δ and (La,Sr)CrO3−δ based perovskite-type electrodes was studied during electrochemical CO2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO2 reduction. In contrast to water splitting, the CO2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view. PMID:28933825

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, L.J.H.; Singh, P.; Ruka, R.J.; Vasilow, T.R.; Bratton, R.J.

1997-11-11

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators. 4 figs.

Low cost stable air electrode material for high temperature solid oxide electrolyte electrochemical cells

DOEpatents

Kuo, Lewis J. H.; Singh, Prabhakar; Ruka, Roswell J.; Vasilow, Theodore R.; Bratton, Raymond J.

1997-01-01

A low cost, lanthanide-substituted, dimensionally and thermally stable, gas permeable, electrically conductive, porous ceramic air electrode composition of lanthanide-substituted doped lanthanum manganite is provided which is used as the cathode in high temperature, solid oxide electrolyte fuel cells and generators. The air electrode composition of this invention has a much lower fabrication cost as a result of using a lower cost lanthanide mixture, either a natural mixture or an unfinished lanthanide concentrate obtained from a natural mixture subjected to incomplete purification, as the raw material in place of part or all of the higher cost individual lanthanum. The mixed lanthanide primarily contains a mixture of at least La, Ce, Pr, and Nd, or at least La, Ce, Pr, Nd and Sm in its lanthanide content, but can also include minor amounts of other lanthanides and trace impurities. The use of lanthanides in place of some or all of the lanthanum also increases the dimensional stability of the air electrode. This low cost air electrode can be fabricated as a cathode for use in high temperature, solid oxide fuel cells and generators.

Electrodes for solid state gas sensor

DOEpatents

Mukundan, Rangachary [Santa Fe, NM; Brosha, Eric L [Los Alamos, NM; Garzon, Fernando [Santa Fe, NM

2007-05-08

A mixed potential electrochemical sensor for the detection of gases has a ceria-based electrolyte with a surface for exposing to the gases to be detected, and with a reference wire electrode and a sensing wire electrode extending through the surface and fixed within the electrolyte as the electrolyte is compressed and sintered. The electrochemical sensor is formed by placing a wire reference electrode and a wire sensing electrode in a die, where each electrode has a first compressed planar section and a second section depending from the first section with the second section of each electrode extending axially within the die. The die is filled with an oxide-electrolyte powder and the powder is pressed within the die with the wire electrodes. The wire-electrodes and the pressed oxide-electrolyte powder are sintered to form a ceramic electrolyte base with a reference wire electrode and a sensing wire electrode depending therefrom.

Electrodes for solid state gas sensor

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

Mukundan, Rangachary; Brosha, Eric L; Garzon, Fernando

2007-05-08

A mixed potential electrochemical sensor for the detection of gases has a ceria-based electrolyte with a surface for exposing to the gases to be detected, and with a reference wire electrode and a sensing wire electrode extending through the surface and fixed within the electrolyte as the electrolyte is compressed and sintered. The electrochemical sensor is formed by placing a wire reference electrode and a wire sensing electrode in a die, where each electrode has a first compressed planar section and a second section depending from the first section with the second section of each electrode extending axially within themore » die. The die is filled with an oxide-electrolyte powder and the powder is pressed within the die with the wire electrodes. The wire-electrodes and the pressed oxide-electrolyte powder are sintered to form a ceramic electrolyte base with a reference wire electrode and a sensing wire electrode depending therefrom.« less

Electrodes for solid state gas sensor

DOEpatents

Mukundan, Rangachary; Brosha, Eric L.; Garzon, Fernando

2003-08-12

A mixed potential electrochemical sensor for the detection of gases has a ceria-based electrolyte with a surface for exposing to the gases to be detected, and with a reference wire electrode and a sensing wire electrode extending through the surface and fixed within the electrolyte as the electrolyte is compressed and sintered. The electrochemical sensor is formed by placing a wire reference electrode and a wire sensing electrode in a die, where each electrode has a first compressed planar section and a second section depending from the first section with the second section of each electrode extending axially within the die. The die is filled with an oxide-electrolyte powder and the powder is pressed within the die with the wire electrodes. The wire-electrodes and the pressed oxide-electrolyte powder are sintered to form a ceramic electrolyte base with a reference wire electrode and a sensing wire electrode depending therefrom.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels.

PubMed

Singh, Meenesh R; Clark, Ezra L; Bell, Alexis T

2015-11-10

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

NASA Astrophysics Data System (ADS)

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-11-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells.

PubMed

Blanc, Frédéric; Leskes, Michal; Grey, Clare P

2013-09-17

Electrochemical cells, in the form of batteries (or supercapacitors) and fuel cells, are efficient devices for energy storage and conversion. These devices show considerable promise for use in portable and static devices to power electronics and various modes of transport and to produce and store electricity both locally and on the grid. For example, high power and energy density lithium-ion batteries are being developed for use in hybrid electric vehicles where they improve the efficiency of fuel use and help to reduce greenhouse gas emissions. To gain insight into the chemical reactions involving the multiple components (electrodes, electrolytes, interfaces) in the electrochemical cells and to determine how cells operate and how they fail, researchers ideally should employ techniques that allow real-time characterization of the behavior of the cells under operating conditions. This Account reviews the recent use of in situ solid-state NMR spectroscopy, a technique that probes local structure and dynamics, to study these devices. In situ NMR studies of lithium-ion batteries are performed on the entire battery, by using a coin cell design, a flat sealed plastic bag, or a cylindrical cell. The battery is placed inside the NMR coil, leads are connected to a potentiostat, and the NMR spectra are recorded as a function of state of charge. (7)Li is used for many of these experiments because of its high sensitivity, straightforward spectral interpretation, and relevance to these devices. For example, (7)Li spectroscopy was used to detect intermediates formed during electrochemical cycling such as LixC and LiySiz species in batteries with carbon and silicon anodes, respectively. It was also used to observe and quantify the formation and growth of metallic lithium microstructures, which can cause short circuits and battery failure. This approach can be utilized to identify conditions that promote dendrite formation and whether different electrolytes and additives can help prevent dendrite formation. The in situ method was also applied to monitor (by (11)B NMR) electrochemical double-layer formation in supercapacitors in real time. Though this method is useful, it comes with challenges. The separation of the contributions from the different cell components in the NMR spectra is not trivial because of overlapping resonances. In addition, orientation-dependent NMR interactions, including the spatial- and orientation-dependent bulk magnetic susceptibility (BMS) effects, can lead to resonance broadening. Efforts to understand and mitigate these BMS effects are discussed in this Account. The in situ NMR investigation of fuel cells initially focused on the surface electrochemistry at the electrodes and the electrochemical oxidation of methanol and CO to CO2 on the Pt cathode. On the basis of the (13)C and (195)Pt NMR spectra of the adsorbates and electrodes, CO adsorbed on Pt and other reaction intermediates and complete oxidation products were detected and their mode of binding to the electrodes investigated. Appropriate design and engineering of the NMR hardware has allowed researchers to integrate intact direct methanol fuel cells into NMR probes. Chemical transformations of the circulating methanol could be followed and reaction intermediates could be detected in real time by either (2)H or (13)C NMR spectroscopy. By use of the in situ NMR approach, factors that control fuel cell performance, such as methanol cross over and catalyst performance, were identified.

Evaluation of Ca3Co2O6 as cathode material for high-performance solid-oxide fuel cell

PubMed Central

Wei, Tao; Huang, Yun-Hui; Zeng, Rui; Yuan, Li-Xia; Hu, Xian-Luo; Zhang, Wu-Xing; Jiang, Long; Yang, Jun-You; Zhang, Zhao-Liang

2013-01-01

A cobalt-based thermoelectric compound Ca3Co2O6 (CCO) has been developed as new cathode material with superior performance for intermediate-temperature (IT) solid-oxide fuel cell (SOFC). Systematic evaluation has been carried out. Measurement of thermal expansion coefficient (TEC), thermal-stress (σ) and interfacial shearing stress (τ) with the electrolyte show that CCO matches well with several commonly-used IT electrolytes. Maximum power density as high as 1.47 W cm−2 is attained at 800°C, and an additional thermoelectric voltage of 11.7 mV is detected. The superior electrochemical performance, thermoelectric effect, and comparable thermal and mechanical behaviors with the electrolytes make CCO to be a promising cathode material for SOFC. PMID:23350032

Proton Conduction in Grain-Boundary-Free Oxygen-Deficient BaFeO2.5+δ Thin Films

PubMed Central

Benes, Alexander; Molinari, Alan; Kruk, Robert; Brötz, Joachim; Chellali, Reda; Hahn, Horst

2017-01-01

Reduction of the operating temperature to an intermediate temperature range between 350 °C and 600 °C is a necessity for Solid Oxide Fuel/Electrolysis Cells (SOFC/SOECs). In this respect the application of proton-conducting oxides has become a broad area of research. Materials that can conduct protons and electrons at the same time, to be used as electrode catalysts on the air electrode, are especially rare. In this article we report on the proton conduction in expitaxially grown BaFeO2.5+δ (BFO) thin films deposited by pulsed laser deposition on Nb:SrTiO3 substrates. By using Electrochemical Impedance Spectroscopy (EIS) measurements under different wet and dry atmospheres, the bulk proton conductivity of BFO (between 200 °C and 300 °C) could be estimated for the first time (3.6 × 10−6 S cm−1 at 300 °C). The influence of oxidizing measurement atmosphere and hydration revealed a strong dependence of the conductivity, most notably at temperatures above 300 °C, which is in good agreement with the hydration behavior of BaFeO2.5 reported previously. PMID:29286321

Elimination of ethanethiol released from municipal wastes by absorption sequencing electrochemical oxidation.

PubMed

Gong, Xiao; Yang, Xu; Zheng, Haoyue; Wu, Zucheng

2017-07-01

As a typical municipal waste landfill gas, ethanethiol can become an air pollutant because of its low odor threshold concentration and toxicity to human beings. A hybrid process of absorption combined with electrochemical oxidation to degrade ethanethiol was investigated. The ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF 4 ) was employed as an absorbent to capture ethanethiol from the air stream. Electrochemical oxidation demonstrated that ethanethiol could be oxidized on a β-PbO 2 anode modified with fluoride, while [BMIM]BF 4 was used as an electrolyte. After a reaction time of 90 min under a current density of 50 mA/cm 2 , ethanethiol could be thoroughly destructed by the successive attack of hydroxyl radicals (·OH) electrogenerated on the surface of the β-PbO 2 anode, while the sulfur atoms in ethanethiol were ultimately converted to sulfate ions [Formula: see text]. The reaction mechanism is proposed, and the operating condition is also estimated with a kinetic model. This hybrid process could be a promising way to remove thiol compounds from municipal waste landfill gases.

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

Structural and electrochemical characterization and surface modification of layered solid solution oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Wu, Yan

Lithium ion batteries are widely used to power portable electronic devices such as cell phones and laptop computers due to their high energy density. However, the currently used layered LiCoO2 cathode could deliver only 50 % of its theoretical capacity in practical lithium ion cells (140 mAh/g) due to the chemical and structural instabilities at deep charge with (1-x) < 0.5 in Li1-xCoO2. Also, cobalt is relatively expensive and toxic. These difficulties have generated enormous interest in alternative cathode hosts. In this regard, solid solutions between layered Li[Li1/3Mn2/3]O2 (commonly designated as Li2MnO3) and LiMO2 (M = Mn, Ni, Co)) have become appealing as some of them exhibit much higher capacity (˜ 250 mAh/g on charging to 4.8 V) with lower cost and better safety compared to LiCoO 2. This dissertation investigates the (1-z) Li[Li1/3Mn 2/3]O2 - (z) Li[Mn0.5-yNi0.5-yCo 2y]O2 (y = 1/12, 1/6 and 1/3 and 0.25 = z = 0.75) layered oxide cathodes, which belong to a solid solution series between layered Li[Li 1/3Mn2/3]O2 and Li[Mn0.5-yNi0.5-y Co2y]O2, with an aim to develop a better understanding of the charge-discharge mechanisms and optimize the electrochemical performance of these materials. To accomplish this, the structural and electrochemical characterization of the (1- z) Li[Li1/3Mn2/3]O2 - (z) Li[Mn 0.5-yNi0.5-yCo2y]O2 cathodes is carried out. It is found that the amount of oxygen loss is related to the lithium content in the transition metal layer, and the Co and Mn4+ contents play a role in influencing the electrochemical behavior. In addition, the chemically delithiated samples are found to transform to O1 or P3 structure with a vanishing of the superlattice reflections arising from cationic ordering in the transition metal layer due to the incorporation of protons from the chemical delithiation medium, while the electrochemically charged samples retain the initial O3 structure. These layered solid solution oxides exhibit high irreversible capacity (IRC) loss (difference between first charge and discharge capacity) values (up to 100 mAh/g), which have been reduced significantly by modifying the cathode surface with other materials like Al2O3, AlPO 4, and F-. For example, compared to an IRC of 75 mAh/g and a first discharge capacity of 253 mAh/g for the pristine Li[Li0.2 Mn0.54Ni0.13Co0.13]O2 (y = 1/6 and z = 0.4), the 3 wt. % Al2O3 modified sample exhibits a lower IRC of 41 mAh/g and a higher first discharge capacity of 285 mAh/g, which is two times higher than that achieved with the LiCoO 2 cathode. A careful and systematic analysis of the experimentally observed capacity and IRC values suggest that part of the oxide ion vacancies created during first charge is retained in the layered lattice in contrast to the idealized model (elimination of all oxide ion vacancies) proposed in the literature. The surface modification helps to retain even more number of oxide ion vacancies in the lattice, which leads to a lower IRC and higher discharge capacity values. Additionally, bulk cationic and anionic substitutions of Al3+ and F- in Li[Li0.17Mn0.58Ni0.25 ]O2 (y = 0 and z = 0.5) are found to sensitively decrease the amount of oxygen loss from the lattice.

Occurrence and behaviour of dissolved, nano-particulate and micro-particulate iron in waste waters and treatment systems: new insights from electrochemical analysis.

PubMed

Matthies, R; Aplin, A C; Horrocks, B R; Mudashiru, L K

2012-04-01

Cyclic-, Differential Pulse- and Steady-state Microdisc Voltammetry (CV, DPV, SMV) techniques have been used to quantify the occurrence and fate of dissolved Fe(ii)/Fe(iii), nano-particulate and micro-particulate iron over a 12 month period in a series of net-acidic and net-alkaline coal mine drainages and passive treatment systems. Total iron in the mine waters is typically 10-100 mg L(-1), with values up to 2100 mg L(-1). Between 30 and 80% of the total iron occurs as solid phase, of which 20 to 80% is nano-particulate. Nano-particulate iron comprises 20 to 70% of the nominally "dissolved" (i.e. <0.45 μm) iron. Since coagulation and sedimentation are the only processes required to remove solid phase iron, these data have important implications for the generation or consumption of acidity during water treatment. In most waters, the majority of truly dissolved iron occurs as Fe(ii) (average 64 ± 22%). Activities of Fe(ii) do not correlate with pH and geochemical modelling shows that no Fe(ii) mineral is supersaturated. Removal of Fe(ii) must proceed via oxidation and hydrolysis. Except in waters with pH < 4.4, activities of Fe(iii) are strongly and negatively correlated with pH. Geochemical modelling suggests that the activity of Fe(iii) is controlled by the solubility of hydrous ferric oxides and oxyhydroxysulfates, supported by scanning and transmission electron microscopic analysis of solids. Nevertheless, the waters are generally supersaturated with respect to ferrihydrite and schwertmannite, and are not at redox equilibrium, indicating the key role of oxidation and hydrolysis kinetics on water treatment. Typically 70-100% of iron is retained in the treatment systems. Oxidation, hydrolysis, precipitation, coagulation and sedimentation occur in all treatment systems and - independent of water chemistry and the type of treatment system - hydroxides and oxyhydroxysulfates are the main iron sinks. The electrochemical data thus reveal the rationale for incomplete iron retention in individual systems and can thus inform future design criteria. The successful application of this low cost and rapid electrochemical method demonstrates its significant potential for real-time, on-site monitoring of iron-enriched waters and may in future substitute traditional analytical methods.

Caracterizacion y optimizacion electroquimica de dispositivos electrocromicos duales basados en polimeros conductores

NASA Astrophysics Data System (ADS)

Padilla Martinez, Javier

The aim of this thesis is to emphasize the existing relations between electrochemical processes, or electrochemical magnitudes, and colour changes. The work is focused on two aspects: individual spectroelectrochemical characterization of the constituent materials followed by an electrochemical and optical study of the performance of the dual system constructed with those materials. The objective is the optimization of both electrochemical and optical processes in dual conducting polymer systems, obtaining experimental methodologies able to characterize, predict, and finally design optimal dual electrochromic devices. The first part of the study is focused on the development of the proper methodology to obtain an optical characterization of any electrochromic material as a function of its electrochemical properties. Materials used were poly((3,4-ethylenedioxy)thiophene) (PEDOT) and poly-(3,6-bis(2-(3,4-ethylenedioxy)thienyl)-N-methylcarbazole) (PBEDOT-NMCz). PEDOT films are coloured under reduction, while PBEDOT-NMCz are coloured under oxidation, showing complementary colouration, and so they can be used to construct a dual electrochromic device. Based on the obtained experimental results, a theoretical study was undertaken to establish the optical responses of a system comprising several electrochromic layers. The theoretically obtained relations were experimentally proved. Relations obtained allow the prediction of the maximum contrast configuration for a dual system, as a function of the individual electrochemical properties of each constituent material. The system studied was PEDOT/PBEDOT-NMCz. The third chapter deals with the proposal and development of a new experimental methodology able to register the individual oxidation states of each electrode during operation of a dual device, obtaining then direct information about device performance. This methodology allows the study of the influence of different physical and chemical variables, like ratio of redox charge between both constituent films, applied potential to the device and initial oxidation state of the constituent polymer films, on the device performance. The final objective of this work is the construction of electrochromic devices that can be use in real applications out of research or academic contexts. It is necessary then, for safety purposes, to use solid electrolytes in the cell. For final applications it is also required to construct devices of appropriate dimensions. In the fourth chapter, the construction and study of large dimensions and solid state devices for the system PEDOT/PBEDOT-NMCz was carried out. The information obtained in previous sections was used to determine maximum contrast combinations. Problems related to electrodeposition of conducting polymers on large surfaces (around 30 cm2) are discussed, together with the optimization of switching speeds when a solid electrolyte is used. Finally the ability to tune colour states and retain them in the absence of an external potential applied was studied and discussed. The last section deals with the study of two new cathodically colouring polymers, poly(3-(Biphenyl-4-ylmethoxymethyl)-3,4-dihydro-2H-thieno(3,4-b)-(1,2)dioxepine) (BPMOM-ProDOT) and poly-dibenzylProDOT (PDiBz-ProDOT), which have been reported to show larger contrasts than PEDOT. For this reason, dual cells were constructed and checked by combination of these two polymers with PBEDOT-NMCz. The methodology previously developed and used to characterize PEDOT and PBEDOT-NMCz was applied to these polymers. The developed theoretical equations were used to determine the maximum contrast for both systems. Finally, the use of standard optical magnitudes as photopic values is emphasized. Photopic values are standardized by the Commission Internationale de l'Eclairage (CIE), and correspond to real sensations perceived by the human eye, whose sensitivity is different for each wavelength. In this sense the use of photopic values, instead of values corresponding to a single wavelength, is encouraged. (Abstract shortened by UMI.)

Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

PubMed Central

Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

2016-01-01

The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy.

PubMed

Maher, Robert C; Shearing, Paul R; Brightman, Edward; Brett, Dan J L; Brandon, Nigel P; Cohen, Lesley F

2016-01-01

The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single-step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

DOE PAGES

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua; ...

2015-05-07

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

Using “Tender” x-ray ambient pressure x-Ray photoelectron spectroscopy as a direct probe of solid-liquid interface

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

Axnanda, Stephanus; Crumlin, Ethan J.; Mao, Baohua

We report a new method to probe the solid-liquid interface through the use of a thin liquid layer on a solid surface. An ambient pressure XPS (AP-XPS) endstation that is capable of detecting high kinetic energy photoelectrons (7 keV) at a pressure up to 110 Torr has been constructed and commissioned. Additionally, we have deployed a “dip & pull” method to create a stable nanometers-thick aqueous electrolyte on platinum working electrode surface. Combining the newly constructed AP-XPS system, “dip & pull” approach, with a “tender” X-ray synchrotron source (2 keV–7 keV), we are able to access the interface between liquidmore » and solid dense phases with photoelectrons and directly probe important phenomena occurring at the narrow solid-liquid interface region in an electrochemical system. Using this approach, we have performed electrochemical oxidation of the Pt electrode at an oxygen evolution reaction (OER) potential. Under this potential, we observe the formation of both Pt²⁺ and Pt⁴⁺ interfacial species on the Pt working electrode in situ. We believe this thin-film approach and the use of “tender” AP-XPS highlighted in this study is an innovative new approach to probe this key solid-liquid interface region of electrochemistry.« less

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.

All-solid-state asymmetric supercapacitors based on Fe-doped mesoporous Co3O4 and three-dimensional reduced graphene oxide electrodes with high energy and power densities.

PubMed

Zhang, Cheng; Wei, Jun; Chen, Leiyi; Tang, Shaolong; Deng, Mingsen; Du, Youwei

2017-10-19

An asymmetric supercapacitor offers opportunities to effectively utilize the full potential of the different potential windows of the two electrodes for a higher operating voltage, resulting in an enhanced specific capacitance and significantly improved energy without sacrificing the power delivery and cycle life. To achieve high energy and power densities, we have synthesized an all-solid-state asymmetric supercapacitor with a wider voltage range using Fe-doped Co 3 O 4 and three-dimensional reduced graphene oxide (3DrGO) as the positive and negative electrodes, respectively. In contrast to undoped Co 3 O 4 , the increased density of states and modified charge spatial separation endow the Fe-doped Co 3 O 4 electrode with greatly improved electrochemical capacitive performance, including high specific capacitance (1997 F g -1 and 1757 F g -1 at current densities of 1 and 20 A g -1 , respectively), excellent rate capability, and superior cycling stability. Remarkably, the optimized all-solid-state asymmetric supercapacitor can be cycled reversibly in a wide range of 0-1.8 V, thus delivering a high energy density (270.3 W h kg -1 ), high power density (9.0 kW kg -1 at 224.2 W h kg -1 ), and excellent cycling stability (91.8% capacitance retention after 10 000 charge-discharge cycles at a constant current density of 10 A g -1 ). The superior capacitive performance suggests that such an all-solid-state asymmetric supercapacitor shows great potential for developing energy storage systems with high levels of energy and power delivery.

On-Chip Electrolytic Chemistry for the Tuning of Graphene Devices

NASA Astrophysics Data System (ADS)

Schmucker, Scott; Ruppalt, Laura; Culbertson, James; Do, Jae Won; Lyding, Joseph; Robinson, Jeremy; Cress, Cory

2015-03-01

The inherent interfacial nature of two-dimensional materials has motivated the tuning of these films by choice of substrate or chemical functionalization. Such parameters are generally selected during fabrication, and therefore remain static during device operation. However, the possibility of dynamic chemistry in a tunable solid-state system will enable the development of new devices which fully leverage the rich chemistry of graphenic materials. Here, we fabricate a novel device for localized, dynamic doping and functionalization of graphene that is compatible with CMOS processing. The device is enabled by a top-gated, solid electrochemical cell designed with calcium fluoride (CaF2) substituting the oxide of a traditional MOSFET. When the CaF2 is gated, F flows from cathode to anode, segregating Ca and F. In this work, one electrode is graphene. When saturated with fluorine, graphene undergoes covalent modification, becoming a wide-bandgap semiconductor. In contrast, when functionalized with calcium or dilute fluorine, graphene is electron or hole doped, respectively. With transport, Raman, and XPS, we demonstrate this lithographically localized and reversible modulation of graphene's electronic and chemical character.

A New Composite Electrode Applied for Studying the Electrochemistry of Insoluble Particles: α-HgS.

PubMed

Yang, Minjun; Compton, Richard G

2018-05-22

The redox chemistry of solid α-HgS particles is revealed using a carbon/PVDF composite containing α-HgS, carbon black, polyvinylidene fluoride (PVDF). The electrochemical behaviour of the carbon/PVDF composite is first characterised with three water insoluble organic solids. Then the reduction of solid α-HgS particles is investigated and found to occur at a high negative potential, -1.82 V versus saturated mercury sulphate reference electrode, to form metallic mercury and sulphide ions. The subsequent oxidation of metallic mercury and sulphide occurs at +0.24 and -0.49 V versus MSE respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous carbonaceous electrode structure and method for secondary electrochemical cell

DOEpatents

Kaun, Thomas D.

1977-03-08

Positive and negative electrodes are provided as rigid, porous carbonaceous matrices with particulate active material fixedly embedded. Active material such as metal chalcogenides, solid alloys of alkali metal or alkaline earth metals along with other metals and their oxides in particulate form are blended with a thermosetting resin and a solid volatile to form a paste mixture. Various electrically conductive powders or current collector structures can be blended or embedded into the paste mixture which can be molded to the desired electrode shape. The molded paste is heated to a temperature at which the volatile transforms into vapor to impart porosity as the resin begins to cure into a rigid solid structure.

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.

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

PubMed

Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

2014-07-07

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Degradation of aniline by electrochemical activation of peroxydisulfate at MWCNT cathode: The proofed concept of nonradical oxidation process.

PubMed

Nie, Chunyang; Ao, Zhimin; Duan, Xiaoguang; Wang, Chengying; Wang, Shaobin; An, Taicheng

2018-05-07

Enhanced elimination of aniline in aqueous solution was achieved by coupling electrosorption of aniline and electrochemical activation of peroxydisulfate (PDS) at multi-walled carbon nanotube (MWCNT) cathode, in which a synergistic effect occurred. It was found that PDS could be effectively activated under a small voltage at MWCNT cathode owing to the specific pore structures of MWCNTs. A nonradical oxidation pathway instead of radical-based oxidation was proposed from the cathodic activation of PDS, wherein PDS molecules with a modified electronic structure was suggested to be the principal reactive species. Meanwhile, the influences of various operation parameters such as electrode potential, PDS concentration, presence of chloride ions on the elimination efficiency, and the stability of MWCNT electrode were also attempted. Therefore, the electrochemical activation of PDS by MWCNT cathode is a promising energy-saving method for the treatment of organic pollutants in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Impact of operating conditions on the acetylene contamination in the cathode of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhai, Yunfeng; St-Pierre, Jean

2017-12-01

Realistically, proton exchange membrane fuel cells (PEMFCs) are operated under varying operating conditions that potentially impact the acetylene contamination reactions. In this paper, the effects of the cell operating conditions on the acetylene contamination in PEMFCs are investigated under different current densities and temperatures with different acetylene concentrations in the cathode. Electrochemical impedance spectroscopy is applied during the constant-current operation to analyze the impacts of the operating conditions on the acetylene electrochemical reactions. The experimental results indicate that higher acetylene concentrations, higher current densities and lower cell temperatures decrease the cell performance more. In particular, cathode poisoning becomes more severe at medium cell current densities. The cell cathode potentials at such current densities are not sufficient to completely oxidize the intermediate or sufficiently low to completely reduce the adsorbed acetylene. Based on these investigations, the possible condition-dependent limitations of the acetylene concentration and cell operating voltage are proposed for insight into the acetylene contamination mitigation stratagem. Regarding the barrier conditions, the acetylene reactions change abruptly, and adjusting the cell operation parameters to change the acetylene adsorbate and intermediate accumulation conditions to induce complete oxidation or reduction conditions may mitigate the severe acetylene contamination effects on PEMFCs.

Development of a tritium monitor combined with an electrochemical tritium pump using a proton conducting oxide

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

Tanaka, M.; Sugiyama, T.

2015-03-15

The detection of low level tritium is one of the key issues for tritium management in tritium handling facilities. Such a detection can be performed by tritium monitors based on proton conducting oxide technique. We tested a tritium monitoring system composed of a commercial proportional counter combined with an electrochemical hydrogen pump equipped with CaZr{sub 0.9}In{sub 0.1}O{sub 3-α} as proton conducting oxide. The hydrogen pump operated at 973 K under electrolysis conditions using tritiated water vapor (HTO). The proton conducting oxide extracts tritium molecules (HT) from HTO and tritium concentration is measured by the proportional counter. The advantage of themore » proposed tritium monitoring system is that it is able to convert HTO into molecular hydrogen.« less

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

DOE PAGES

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

2015-03-25

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

Poisoning of Ni-Based anode for proton conducting SOFC by H2S, CO2, and H2O as fuel contaminants

NASA Astrophysics Data System (ADS)

Sun, Shichen; Awadallah, Osama; Cheng, Zhe

2018-02-01

It is well known that conventional solid oxide fuel cells (SOFCs) based on oxide ion conducting electrolyte (e.g., yttria-stabilized zirconia, YSZ) and nickel (Ni) - ceramic cermet anodes are susceptible to poisoning by trace amount of hydrogen sulfide (H2S) while not significantly impacted by the presence of carbon dioxide (CO2) and moisture (H2O) in the fuel stream unless under extreme operating conditions. In comparison, the impacts of H2S, CO2, and H2O on proton-conducting SOFCs remain largely unexplored. This study aims at revealing the poisoning behaviors caused by H2S, CO2, and H2O for proton-conducting SOFCs. Anode-supported proton-conducting SOFCs with BaZe0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb) electrolyte and Ni-BZCYYb anode and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode as well as Ni-BZCYYb/BZCYYb/Ni-BZCYYb anode symmetrical cells were subjected to low ppm-level H2S or low percentage-level CO2 or H2O in the hydrogen fuel, and the responses in cell electrochemical behaviors were recorded. The results suggest that, contrary to conventional SOFCs that show sulfur poisoning and CO2 and H2O tolerance, such proton-conducting SOFCs with Ni-BZCYYb cermet anode seem to be poisoned by all three types of "contaminants". Beyond that, the implications of the experimental observations on understanding the fundamental mechanism of anode hydrogen electrochemical oxidation reaction in proton conducting SOFCs are also discussed.

Electrochemical Oxidation of EDTA in Nuclear Wastewater Using Platinum Supported on Activated Carbon Fibers

PubMed Central

Zhao, Bo; Zhu, Wenkun; Mu, Tao; Hu, Zuowen; Duan, Tao

2017-01-01

A novel Pt/ACF (Pt supported on activated carbon fibers) electrode was successfully prepared with impregnation and electrodeposition method. Characterization of the electrodes indicated that the Pt/ACF electrode had a larger effective area and more active sites. Electrochemical degradation of ethylenediaminetetra-acetic acid (EDTA) in aqueous solution with Pt/ACF electrodes was investigated. The results showed that the 3% Pt/ACF electrode had a better effect on EDTA removal. The operational parameters influencing the electrochemical degradation of EDTA with 3% Pt/ACF electrode were optimized and the optimal removal of EDTA and chemical oxygen demand (COD) were 94% and 60% after 100 min on condition of the electrolyte concentration, initial concentration of EDTA, current density and initial value of pH were 0.1 mol/L, 300 mg/L, 40 mA/cm2 and 5.0, respectively. The degradation intermediates of EDTA in electrochemical oxidation with 3% Pt/ACF electrode were identified by gas chromatography-mass spectrum (GC-MS). PMID:28754016

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

Enhanced Electrochemical Activity and Chromium Tolerance of the Nucleation-Agent-Free La2Ni0.9Fe0.1O4+δ Cathode by Gd0.1Ce0.9O1.95 Incorporation

NASA Astrophysics Data System (ADS)

Ling, Yihan; Xie, Huixin; Liu, Zijing; Du, Xiaoni; Chen, Hui; Ou, Xuemei; Zhao, Ling; Budiman, Riyan Achmad

2018-07-01

For the sake of improving the electrochemical activity and chromium tolerance of the K2NiF4-type oxide, La2NiO4+δ (LNO), with nonnucleation agents like Mn and Sr elements, the electrochemical performance and degradation were comparatively studied at two cathodes La2Ni0.9Fe0.1O4+δ (LNF) and LNF-40wt%Gd0.1Ce0.9O1.95 (LNF-GDC) on the GDC electrolyte, where 5wt%Cr2O3 incorporation provides Cr-containing atmosphere. Compared with non-doped LNO, LNF shows a higher interstitial oxygen concentration (δ = 0.298) and a lower electrical conductivity, where bivalent Ni ion, {Ni}_{Ni}^{ × }, and trivalent Ni ion, {Ni}_{Ni}^{ \\cdot }, and trivalent Fe ion on Ni-site, {Fe}_{Ni}^{ \\cdot }, were observed from the XPS measurements. LNF-GDC shows greatly reduced interfacial polarization resistances (Rp), which are only half of those of LNF, indicating a better electrochemical performance. More importantly, no significant degradation of LNF-GDC in performance has been observed under exposure of Cr-containing atmosphere at 700 °C for 350 h, while Rp of LNF increased by nearly 20%, suggesting LNF by GDC incorporation can enhance the electrochemical performance as well as chromium tolerance for intermediate temperature solid oxide fuel cells (IT-SOFCs).

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

Enhanced Electrochemical Activity and Chromium Tolerance of the Nucleation-Agent-Free La2Ni0.9Fe0.1O4+δ Cathode by Gd0.1Ce0.9O1.95 Incorporation

NASA Astrophysics Data System (ADS)

Ling, Yihan; Xie, Huixin; Liu, Zijing; Du, Xiaoni; Chen, Hui; Ou, Xuemei; Zhao, Ling; Budiman, Riyan Achmad

2018-03-01

For the sake of improving the electrochemical activity and chromium tolerance of the K2NiF4-type oxide, La2NiO4+δ (LNO), with nonnucleation agents like Mn and Sr elements, the electrochemical performance and degradation were comparatively studied at two cathodes La2Ni0.9Fe0.1O4+δ (LNF) and LNF-40wt%Gd0.1Ce0.9O1.95 (LNF-GDC) on the GDC electrolyte, where 5wt%Cr2O3 incorporation provides Cr-containing atmosphere. Compared with non-doped LNO, LNF shows a higher interstitial oxygen concentration (δ = 0.298) and a lower electrical conductivity, where bivalent Ni ion, {Ni}_{Ni}^{ × } , and trivalent Ni ion, {Ni}_{Ni}^{ \\cdot } , and trivalent Fe ion on Ni-site, {Fe}_{Ni}^{ \\cdot } , were observed from the XPS measurements. LNF-GDC shows greatly reduced interfacial polarization resistances (Rp), which are only half of those of LNF, indicating a better electrochemical performance. More importantly, no significant degradation of LNF-GDC in performance has been observed under exposure of Cr-containing atmosphere at 700 °C for 350 h, while Rp of LNF increased by nearly 20%, suggesting LNF by GDC incorporation can enhance the electrochemical performance as well as chromium tolerance for intermediate temperature solid oxide fuel cells (IT-SOFCs).

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.

Emerging Applications of Liquid Metals Featuring Surface Oxides

PubMed Central

2014-01-01

Gallium and several of its alloys are liquid metals at or near room temperature. Gallium has low toxicity, essentially no vapor pressure, and a low viscosity. Despite these desirable properties, applications calling for liquid metal often use toxic mercury because gallium forms a thin oxide layer on its surface. The oxide interferes with electrochemical measurements, alters the physicochemical properties of the surface, and changes the fluid dynamic behavior of the metal in a way that has, until recently, been considered a nuisance. Here, we show that this solid oxide “skin” enables many new applications for liquid metals including soft electrodes and sensors, functional microcomponents for microfluidic devices, self-healing circuits, shape-reconfigurable conductors, and stretchable antennas, wires, and interconnects. PMID:25283244

Effect of tungsten on the corrosion behavior of sulfuric acid-resistant steels for flue gas desulfurization system

NASA Astrophysics Data System (ADS)

Ji, Woo-Soo; Jang, Young-Wook; Kim, Jung-Gu

2011-06-01

Flue gas desulfurization systems (FGDs) are operated in severely corrosive environments that cause sulfuric acid dew-point corrosion. The corrosion behavior of low-alloy steels was tested using electrochemical techniques (electrochemical impedance spectroscopy, potentiodynamic tests, potentiostatic tests), and the corrosion products were analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy. The electrochemical results showed that alloying W with small amounts of Sb, Cu, and Co improves the corrosion resistance of steels. The results of surface analyses showed that the surface of the steels alloyed with W consisted of W oxides and higher amounts of Sb and Cu oxides. This suggests that the addition of W promotes the formation of a protective WO3 film, in addition to Sb2O5 and CuO films on the surface.

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.

Composite fuel electrode La(0.2)Sr(0.8)TiO(3-δ)-Ce(0.8)Sm(0.2)O(2-δ) for electrolysis of CO2 in an oxygen-ion conducting solid oxide electrolyser.

PubMed

Li, Yuanxin; Zhou, Jianer; Dong, Dehua; Wang, Yan; Jiang, J Z; Xiang, Hongfa; Xie, Kui

2012-11-28

Composite Ni-YSZ fuel electrodes are able to operate only under strongly reducing conditions for the electrolysis of CO(2) in oxygen-ion conducting solid oxide electrolysers. In an atmosphere without a flow of reducing gas (i.e., carbon monoxide), a composite fuel electrode based on redox-reversible La(0.2)Sr(0.8)TiO(3+δ) (LSTO) provides a promising alternative. The Ti(3+) was approximately 0.3% in the oxidized LSTO (La(0.2)Sr(0.8)TiO(3.1)), whereas the Ti(3+) reached approximately 8.0% in the reduced sample (La(0.2)Sr(0.8)TiO(3.06)). The strong adsorption of atmospheric oxygen in the form of superoxide ions led to the absence of Ti(3+) either on the surface of oxidized LSTO or the reduced sample. Reduced LSTO showed typical metallic behaviour from 50 to 700 °C in wet H(2); and the electrical conductivity of LSTO reached approximately 30 S cm(-1) at 700 °C. The dependence of [Ti(3+)] concentration in LSTO on P(O(2)) was correlated to the applied potentials when the electrolysis of CO(2) was performed with the LSTO composite electrode. The electrochemical reduction of La(0.2)Sr(0.8)TiO(3+δ) was the main process but was still present up to 2 V at 700 °C during the electrolysis of CO(2); however, the electrolysis of CO(2) at the fuel electrode became dominant at high applied voltages. The current efficiency was approximately 36% for the electrolysis of CO(2) at 700 °C and a 2 V applied potential.

In-situ study of the gas-phase composition and temperature of an intermediate-temperature solid oxide fuel cell anode surface fed by reformate natural gas

NASA Astrophysics Data System (ADS)

Santoni, F.; Silva Mosqueda, D. M.; Pumiglia, D.; Viceconti, E.; Conti, B.; Boigues Muñoz, C.; Bosio, B.; Ulgiati, S.; McPhail, S. J.

2017-12-01

An innovative experimental setup is used for in-depth and in-operando characterization of solid oxide fuel cell anodic processes. This work focuses on the heterogeneous reactions taking place on a 121 cm2 anode-supported cell (ASC) running with a H2, CH4, CO2, CO and steam gas mixture as a fuel, using an operating temperature of 923 K. The results have been obtained by analyzing the gas composition and temperature profiles along the anode surface in different conditions: open circuit voltage (OCV) and under two different current densities, 165 mA cm-2 and 330 mA cm-2, corresponding to 27% and 54% of fuel utilization, respectively. The gas composition and temperature analysis results are consistent, allowing to monitor the evolution of the principal chemical and electrochemical reactions along the anode surface. A possible competition between CO2 and H2O in methane internal reforming is shown under OCV condition and low current density values, leading to two different types of methane reforming: Steam Reforming and Dry Reforming. Under a current load of 40 A, the dominance of exothermic reactions leads to a more marked increase of temperature in the portion of the cell close to the inlet revealing that current density is not uniform along the anode surface.

Synthesis and (spectro)electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives.

PubMed

Kowalski, Konrad; Karpowicz, Rafał; Mlostoń, Grzegorz; Miesel, Dominique; Hildebrandt, Alexander; Lang, Heinrich; Czerwieniec, Rafał; Therrien, Bruno

2015-04-07

Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (1, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of 1 gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1-oxide (2, sulfoxide) and 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1,1-dioxide (3, sulfone), respectively. The molecular structures of 1 and 3 in the solid state were determined by single crystal X-ray crystallography. The oxidation of sulphide 1 to sulfone 3, plays only a minor role on the overall structure of the two compounds. Electrochemical (cyclic voltammetry (= CV), square wave voltammetry (= SWV)) and spectroelectrochemical (in situ UV-Vis/NIR spectroscopy) studies were carried out. The CV and SWV measurements showed that an increase of the sulphur atom oxidation from -2 in 1 to +2 in 3 causes an anodic shift of the ferrocenyl-based oxidation potentials of about 100 mV. The electrochemical oxidation of 1-3 generates mixed-valent cations 1(+)-3(+). These monooxidised species display low-energy electronic absorption bands between 1000 and 3000 nm assigned to IVCT (= Inter-Valence Charge Transfer) electronic transitions. Accordingly, the mixed-valent cations 1(+)-3(+) are classified as weakly coupled class II systems according to Robin and Day.

Three-Dimensional Expanded Graphene-Metal Oxide Film via Solid-State Microwave Irradiation for Aqueous Asymmetric Supercapacitors.

PubMed

Yang, MinHo; Lee, Kyoung G; Lee, Seok Jae; Lee, Sang Bok; Han, Young-Kyu; Choi, Bong Gill

2015-10-14

Carbon-based electrochemical double-layer capacitors and pseudocapacitors, consisting of a symmetric configuration of electrodes, can deliver much higher power densities than batteries, but they suffer from low energy densities. Herein, we report the development of high energy and power density supercapacitors using an asymmetric configuration of Fe2O3 and MnO2 nanoparticles incorporated into 3D macroporous graphene film electrodes that can be operated in a safe and low-cost aqueous electrolyte. The gap in working potential windows of Fe2O3 and MnO2 enables the stable expansion of the cell voltage up to 1.8 V, which is responsible for the high energy density (41.7 Wh kg(-1)). We employ a household microwave oven to simultaneously create conductivity, porosity, and the deposition of metal oxides on graphene films toward 3D hybrid architectures, which lead to a high power density (13.5 kW kg(-1)). Such high energy and power densities are maintained for over 5000 cycles, even during cycling at a high current density of 16.9 A g(-1).

Solid oxide fuel cell cathode infiltrate particle size control and oxygen surface exchange resistance determination

NASA Astrophysics Data System (ADS)

Burye, Theodore E.

Over the past decade, nano-sized Mixed Ionic Electronic Conducting (MIEC) -- micro-sized Ionic Conducting (IC) composite cathodes produced by the infiltration method have received much attention in the literature due to their low polarization resistance (RP) at intermediate (500-700°C) operating temperatures. Small infiltrated MIEC oxide nano-particle size and low intrinsic MIEC oxygen surface exchange resistance (Rs) have been two critical factors allowing these Nano-Micro-Composite Cathodes (NMCCs) to achieve high performance and/or low temperature operation. Unfortunately, previous studies have not found a reliable method to control or reduce infiltrated nano-particle size. In addition, controversy exists on the best MIEC infiltrate composition because: 1) Rs measurements on infiltrated MIEC particles are presently unavailable in the literature, and 2) bulk and thin film Rs measurements on nominally identical MIEC compositions often vary by up to 3 orders of magnitude. Here, two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, were developed to systematically produce a reduction in the average La0.6Sr0.4Co0.8Fe 0.2O3-delta (LSCF) infiltrated nano-particle size from 50 nm to 22 nm. This particle size reduction reduced the SOFC operating temperature, (defined as the temperature where RP=0.1 Ocm 2) from 650°C to 540°C. In addition, Rs values for infiltrated MIEC particles were determined for the first time through finite element modeling calculations on 3D Focused Ion Beam-Scanning Electron Microscope (FIB-SEM) reconstructions of electrochemically characterized infiltrated electrodes.

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.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

2013-03-07

We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

Electrochemical device for syngas and liquid fuels production

DOEpatents

Braun, Robert J.; Becker, William L.; Penev, Michael

2017-04-25

The invention relates to methods for creating high value liquid fuels such as gasoline, diesel, jet and alcohols using carbon dioxide and water as the starting raw materials and a system for using the same. These methods combine a novel solid oxide electrolytic cell (SOEC) for the efficient and clean conversion of carbon dioxide and water to hydrogen and carbon monoxide, uniquely integrated with a gas-to-liquid fuels producing method.

Tailoring the electrode-electrolyte interface of Solid Oxide Fuel Cells (SOFC) by laser micro-patterning to improve their electrochemical performance

NASA Astrophysics Data System (ADS)

Cebollero, J. A.; Lahoz, R.; Laguna-Bercero, M. A.; Larrea, A.

2017-08-01

Cathode activation polarisation is one of the main contributions to the losses of a Solid Oxide Fuel Cell. To reduce this loss we use a pulsed laser to modify the surface of yttria stabilized zirconia (YSZ) electrolytes to make a corrugated micro-patterning in the mesoscale. The beam of the laser source, 5 ns pulse width and emitting at λ = 532 nm (green region), is computer-controlled to engrave the selected micro-pattern on the electrolyte surface. Several laser scanning procedures and geometries have been tested. Finally, we engrave a square array with 28 μm of lattice parameter and 7 μm in depth on YSZ plates. With these plates we prepare LSM-YSZ/YSZ/LSM-YSZ symmetrical cells (LSM: La1-xSrxMnO3) and determine their activation polarisation by Electrochemical Impedance Spectroscopy (EIS). To get good electrode-electrolyte contact after sintering it is necessary to use pressure-assisted sintering with low loads (about 5 kPa), which do not modify the electrode microstructure. The decrease in polarisation with respect to an unprocessed cell is about 30%. EIS analysis confirms that the reason for this decrease is an improvement in the activation processes at the electrode-electrolyte interface.

Vibrational characterisation of a crystallised oligoaniline: a model compound of polyaniline

NASA Astrophysics Data System (ADS)

Quillard, Sophie; Corraze, Benoı̂t; Boyer, Marie Isabelle; Fayad, Elias; Louarn, Guy; Froyer, Gérard

2001-09-01

We present a detailed study on the vibrational properties of N,N‧-diphenyl-1,4-phenylenediamine in different crystalline forms. A new triclinic form of the molecule has been obtained through appropriate recrystallization procedure. This polymorphism of the crystalline state was associated to different vibrational features. These results are discussed with regards to the possible conformations of the molecule. In order to complete the study, thin solid films of these materials were also elaborated by vacuum sublimation of the molecule, upon selected conditions of rate, deposition and thickness. Spectroscopic measurements of these layers are showed and compared to those obtained on the crystalline solid forms. We performed convenient oxidation processes of this neutral N,N‧-diphenyl-1,4-phenylenediamine (powder and thin solid film) leading to the formation of the correspondent radical cation species. A comparison with radical cation generated in solution by electrochemical oxidative method is done. Vibrational characterisations of this doped oligomer were achieved in each case and finally, the observed differences are discussed in terms of conformation.

Coating of tips for electrochemical scanning tunneling microscopy by means of silicon, magnesium, and tungsten oxides

NASA Astrophysics Data System (ADS)

Salerno, Marco

2010-09-01

Different combinations of metal tips and oxide coatings have been tested for possible operation in electrochemical scanning tunneling microscopy. Silicon and magnesium oxides have been thermally evaporated onto gold and platinum-iridium tips, respectively. Two different thickness values have been explored for both materials, namely, 40 and 120 nm for silicon oxide and 20 and 60 nm for magnesium oxide. Alternatively, tungsten oxide has been grown on tungsten tips via electrochemical anodization. In the latter case, to seek optimal results we have varied the pH of the anodizing electrolyte between one and four. The oxide coated tips have been first inspected by means of scanning electron microscopy equipped with microanalysis to determine the morphological results of the coating. Second, the coated tips have been electrically characterized ex situ for stability in time by means of cyclic voltammetry in 1 M aqueous KCl supporting electrolyte, both bare and supplemented with K3[Fe(CN)6] complex at 10 mM concentration in milliQ water as an analyte. Only the tungsten oxide coated tungsten tips have shown stable electrical behavior in the electrolyte. For these tips, the uncoated metal area has been estimated from the electrical current levels, and they have been successfully tested by imaging a gold grating in situ, which provided stable results for several hours. The successful tungsten oxide coating obtained at pH=4 has been assigned to the WO3 form.

Coating of tips for electrochemical scanning tunneling microscopy by means of silicon, magnesium, and tungsten oxides.

PubMed

Salerno, Marco

2010-09-01

Different combinations of metal tips and oxide coatings have been tested for possible operation in electrochemical scanning tunneling microscopy. Silicon and magnesium oxides have been thermally evaporated onto gold and platinum-iridium tips, respectively. Two different thickness values have been explored for both materials, namely, 40 and 120 nm for silicon oxide and 20 and 60 nm for magnesium oxide. Alternatively, tungsten oxide has been grown on tungsten tips via electrochemical anodization. In the latter case, to seek optimal results we have varied the pH of the anodizing electrolyte between one and four. The oxide coated tips have been first inspected by means of scanning electron microscopy equipped with microanalysis to determine the morphological results of the coating. Second, the coated tips have been electrically characterized ex situ for stability in time by means of cyclic voltammetry in 1 M aqueous KCl supporting electrolyte, both bare and supplemented with K(3)[Fe(CN)(6)] complex at 10 mM concentration in milliQ water as an analyte. Only the tungsten oxide coated tungsten tips have shown stable electrical behavior in the electrolyte. For these tips, the uncoated metal area has been estimated from the electrical current levels, and they have been successfully tested by imaging a gold grating in situ, which provided stable results for several hours. The successful tungsten oxide coating obtained at pH=4 has been assigned to the WO(3) form.

Methane–oxygen electrochemical coupling in an ionic liquid: a robust sensor for simultaneous quantification†

PubMed Central

Wang, Zhe; Guo, Min; Baker, Gary A.; Stetter, Joseph R.; Lin, Lu; Mason, Andrew J.

2017-01-01

Current sensor devices for the detection of methane or natural gas emission are either expensive and have high power requirements or fail to provide a rapid response. This report describes an electrochemical methane sensor utilizing a non-volatile and conductive pyrrolidinium-based ionic liquid (IL) electrolyte and an innovative internal standard method for methane and oxygen dual-gas detection with high sensitivity, selectivity, and stability. At a platinum electrode in bis(trifluoromethylsulfonyl)imide (NTf2)-based ILs, methane is electro-oxidized to produce CO2 and water when an oxygen reduction process is included. The in situ generated CO2 arising from methane oxidation was shown to provide an excellent internal standard for quantification of the electrochemical oxygen sensor signal. The simultaneous quantification of both methane and oxygen in real time strengthens the reliability of the measurements by cross-validation of two ambient gases occurring within a single sample matrix and allows for the elimination of several types of random and systematic errors in the detection. We have also validated this IL-based methane sensor employing both conventional solid macroelectrodes and flexible microfabricated electrodes using single- and double-potential step chronoamperometry. PMID:25093213

Electrochemical Detectors in HPLC and Ion Chromatography.

PubMed

Horvai, George; Pungor, ErnÕ

1989-01-01

Back in 1952, the renowned Polish electrochemist Wiktor Kemula introduced chromato-polarography, 1 i.e., polaro-graphic detection for liquid chromatography. This technique continued to develop slowly until the early 1970s (for a review see Reference 2) when modem high-performance liquid chromatography (HPLC) emerged. This new, highly efficient chromatographc method could only be. used with detectors ensuring low dispersion. It was not easy to modify the dropping mercury electrode cells to satisfy this requirement. However, at the same time, electroanalytical chemists, who already had much experience in using carbon-based electrodes for oxidative detection in flow analysis, put forward the idea of oxidative amperometric detection in liquid chromatography. 3,4 In this technique, solid or quasi-solid (paste) electrodes were used and this made possible the construction of miniaturized cells with just a few microliter volume.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

PubMed Central

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-01-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices. PMID:26504215

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

DOE PAGES

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-10-26

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO 2 reduction on silver and coppermore » cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H 2 and CO) and Hythane (H 2 and CH 4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C 2H 4 have high profitability indices.« less

Performance and Structural Evolution of Nano-Scale Infiltrated Solid Oxide Fuel Cell Cathodes

NASA Astrophysics Data System (ADS)

Call, Ann Virginia

Nano-structured mixed ionic and electronic conducting (MIEC) materials have garnered intense interest in electrode development for solid oxide fuel cells due to their high surface areas which allow for effective catalytic activity and low polarization resistances. In particular, composite solid oxide fuel cell (SOFC) cathodes consisting of ionic conducting scaffolds infiltrated with MIEC nanoparticles have exhibited some of the lowest reported polarization resistances. In order for cells utilizing nanostructured moRPhologies to be viable for commercial implementation, more information on their initial performance and long term stability is necessary. In this study, symmetric cell cathodes were prepared via wet infiltration of Sr0.5Sm 0.5CoO3 (SSC) nano-particles via a nitrate process into porous Ce0.9Gd0.1O1.95 (GDC) scaffolds to be used as a model system to investigate performance and structural evolution. Detailed analysis of the cells and cathodes was carried out using electrochemical impedance spectroscopy (EIS). Initial polarization resistances (RP) as low as 0.11 O cm2 at 600ºC were obtained for these SSC-GDC cathodes, making them an ideal candidate for studying high performance nano-structured electrodes. The present results show that the infiltrated cathode microstructure has a direct impact on the initial performance of the cell. Small initial particle sizes and high infiltration loadings (up to 30 vol% SSC) improved initial RP. A simple microstructure-based electrochemical model successfully explained these trends in RP. Further understanding of electrode performance was gleaned from fitting EIS data gathered under varying temperatures and oxygen partial pressures to equivalent circuit models. Both RQ and Gerischer impedance elements provided good fits to the main response in the EIS data, which was associated with the combination of oxygen surface exchange and oxygen diffusion in the electrode. A gas diffusion response was also observed at relatively low pO2. The cells were subjected to life testing at temperatures between 650°C and 800°C for as long as 1500 h. EIS measurements, carried out periodically during the life tests, were done in air at 600°C, a typical expected intermediate-temperature SOFC operating temperature. These were accelerated tests because the aging temperatures > 600ºC should accelerate most degradation processes such as nano-particle coarsening. Long-term RP versus time data was fitted to a combined surface resistance and coarsening kinetics model, and a t0.25 power law coarsening model was found to provide the best fits to the data, suggesting that surface diffusion is the dominant mass transport pathway in SSC-GDC infiltrated cathodes. That is, cathode degradation was due primarily to the coarsening-induced decrease in active SSC surface area. Scanning electron microscopy (SEM) performed after electrochemical life testing confirmed the extent of coarsening of the SSC nanoparticles. The model is used to make predictions regarding long-term stability of infiltrated SSC electrodes, and is also compared with prior results on a similar perovskite MIEC electrode, LSCF. An important new finding is that increasing infiltration loadings yields a marked decrease in the long term degradation rate. Predictions based on accelerated life tests found the lowest possible operating temperature while achieving a degradation rate of 0.5% per kh is 595°C, corresponding to an initial particle size of 40 nm.

Detailed Multi‐dimensional Modeling of Direct Internal Reforming Solid Oxide Fuel Cells

PubMed Central

Tseronis, K.; Fragkopoulos, I.S.; Bonis, I.

2016-01-01

Abstract Fuel flexibility is a significant advantage of solid oxide fuel cells (SOFCs) and can be attributed to their high operating temperature. Here we consider a direct internal reforming solid oxide fuel cell setup in which a separate fuel reformer is not required. We construct a multidimensional, detailed model of a planar solid oxide fuel cell, where mass transport in the fuel channel is modeled using the Stefan‐Maxwell model, whereas the mass transport within the porous electrodes is simulated using the Dusty‐Gas model. The resulting highly nonlinear model is built into COMSOL Multiphysics, a commercial computational fluid dynamics software, and is validated against experimental data from the literature. A number of parametric studies is performed to obtain insights on the direct internal reforming solid oxide fuel cell system behavior and efficiency, to aid the design procedure. It is shown that internal reforming results in temperature drop close to the inlet and that the direct internal reforming solid oxide fuel cell performance can be enhanced by increasing the operating temperature. It is also observed that decreases in the inlet temperature result in smoother temperature profiles and in the formation of reduced thermal gradients. Furthermore, the direct internal reforming solid oxide fuel cell performance was found to be affected by the thickness of the electrochemically‐active anode catalyst layer, although not always substantially, due to the counter‐balancing behavior of the activation and ohmic overpotentials. PMID:27570502

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

PubMed

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

2014-12-01

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

Investigation of aluminosilicate refractory for solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Gentile, Paul Steven

Stationary solid oxide fuel cells (SOFCs) have been demonstrated to provide clean and reliable electricity through electro-chemical conversion of various fuel sources (CH4 and other light hydrocarbons). To become a competitive conversion technology the costs of SOFCs must be reduced to less than $400/kW. Aluminosilicate represents a potential low cost alternative to high purity alumina for SOFC refractory applications. The objectives of this investigation are to: (1) study changes of aluminosilicate chemistry and morphology under SOFC conditions, (2) identify volatile silicon species released by aluminosilicates, (3) identify the mechanisms of aluminosilicate vapor deposition on SOFC materials, and (4) determine the effects of aluminosilicate vapors on SOFC electrochemical performance. It is shown thermodynamically and empirically that low cost aluminosilicate refractory remains chemically and thermally unstable under SOFC operating conditions between 800°C and 1000°C. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) of the aluminosilicate bulk and surface identified increased concentrations of silicon at the surface after exposure to SOFC gases at 1000°C for 100 hours. The presence of water vapor accelerated surface diffusion of silicon, creating a more uniform distribution. Thermodynamic equilibrium modeling showed aluminosilicate remains stable in dry air, but the introduction of water vapor indicative of actual SOFC gas streams creates low temperature (<1000°C) silicon instability due to the release of Si(OH)4 and SiO(OH) 2. Thermal gravimetric analysis and transpiration studies identified a discrete drop in the rate of silicon volatility before reaching steady state conditions after 100-200 hours. Electron microscopy observed the preferential deposition of vapors released from aluminosilicate on yttria stabilized zirconia (YSZ) over nickel. The adsorbent consisted of alumina rich clusters enclosed in an amorphous siliceous layer. Silicon penetrated the YSZ along grain boundaries, isolating grains in an insulating glassy phase. XPS did not detect spectra shifts or peak broadening associated with formation of new Si-Zr-Y-O phases. SOFC electrochemical performance testing at 800-1000°C attributed rapid degradation (0.1% per hour) of cells exposed to aluminosilicate vapors in the fuel stream predominately to ohmic polarization. EDS identified silicon concentrations above impurity levels at the electrolyte/active anode interface.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

PubMed

Badalyan, Artavazd; Stahl, Shannon S

2016-07-21

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1–2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2′-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2′-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

NASA Astrophysics Data System (ADS)

Badalyan, Artavazd; Stahl, Shannon S.

2016-07-01

The electrochemical oxidation of alcohols is a major focus of energy and chemical conversion efforts, with potential applications ranging from fuel cells to biomass utilization and fine-chemical synthesis. Small-molecule electrocatalysts for processes of this type are promising targets for further development, as demonstrated by recent advances in nickel catalysts for electrochemical production and oxidation of hydrogen. Complexes with tethered amines that resemble the active site of hydrogenases have been shown both to catalyse hydrogen production (from protons and electrons) with rates far exceeding those of such enzymes and to mediate reversible electrocatalytic hydrogen production and oxidation with enzyme-like performance. Progress in electrocatalytic alcohol oxidation has been more modest. Nickel complexes similar to those used for hydrogen oxidation have been shown to mediate efficient electrochemical oxidation of benzyl alcohol, with a turnover frequency of 2.1 per second. These compounds exhibit poor reactivity with ethanol and methanol, however. Organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidine N-oxyl), are the most widely studied electrocatalysts for alcohol oxidation. These catalysts exhibit good activity (1-2 turnovers per second) with a wide range of alcohols and have great promise for electro-organic synthesis. Their use in energy-conversion applications, however, is limited by the high electrode potentials required to generate the reactive oxoammonium species. Here we report (2,2‧-bipyridine)Cu/nitroxyl co-catalyst systems for electrochemical alcohol oxidation that proceed with much faster rates, while operating at an electrode potential a half-volt lower than that used for the TEMPO-only process. The (2,2‧-bipyridine)Cu(II) and TEMPO redox partners exhibit cooperative reactivity and exploit the low-potential, proton-coupled TEMPO/TEMPOH redox process rather than the high-potential TEMPO/TEMPO+ process. The results show how electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

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

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.

Computational analysis of species transport and electrochemical characteristics of a MOLB-type SOFC

NASA Astrophysics Data System (ADS)

Hwang, J. J.; Chen, C. K.; Lai, D. Y.

A multi-physics model coupling electrochemical kinetics with fluid dynamics has been developed to simulate the transport phenomena in mono-block-layer built (MOLB) solid oxide fuel cells (SOFC). A typical MOLB module is composed of trapezoidal flow channels, corrugated positive electrode-electrolyte-negative electrode (PEN) plates, and planar inter-connecters. The control volume-based finite difference method is employed for calculation, which is based on the conservation of mass, momentum, energy, species, and electric charge. In the porous electrodes, the flow momentum is governed by a Darcy model with constant porosity and permeability. The diffusion of reactants follows the Bruggman model. The chemistry within the plates is described via surface reactions with a fixed surface-to-volume ratio, tortuosity and average pore size. Species transports as well as the local variations of electrochemical characteristics, such as overpotential and current density distributions in the electrodes of an MOLB SOFC, are discussed in detail.

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

PubMed

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

2013-05-01

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

Calcium alloy as active material in secondary electrochemical cell

DOEpatents

Roche, Michael F.; Preto, Sandra K.; Martin, Allan E.

1976-01-01

Calcium alloys such as calcium-aluminum and calcium-silicon, are employed as active material within a rechargeable negative electrode of an electrochemical cell. Such cells can use a molten salt electrolyte including calcium ions and a positive electrode having sulfur, sulfides, or oxides as active material. The calcium alloy is selected to prevent formation of molten calcium alloys resulting from reaction with the selected molten electrolytic salt at the cell operating temperatures.

High-performance wearable supercapacitors fabricated with surface activated continuous filament graphite fibers

NASA Astrophysics Data System (ADS)

Jia, Dedong; Yu, Xin; Chen, Tinghan; Wang, Shu; Tan, Hua; Liu, Hong; Wang, Zhong Lin; Li, Linlin

2017-08-01

Generally, carbon or graphite fibers (GFs) are used as the supporting materials for the preparation of flexible supercapacitors (SCs) by assembling various electrochemically active nanomaterials on them. A facile and rapid electrochemical oxidation method with a voltage of 3 V in a mixed H2SO4-HNO3 solution for 2-15 min is proposed to active continuous filament GFs. Detailed structural characterization, SEM, TEM, XRD, Raman and XPS demonstrate that the GFs-8 (oxidized for 8 min) possessing high specific surface area which provided numerous electrochemical sites and a large number of oxygen-containing functional groups producing pseudocapacitance. Cyclic voltammetric (CV), galvanostatic charge-discharge measurements and electrochemical impedance spectroscopy (EIS) are conducted to test the capacitive of GFs and activated GFs. The capacitance of GFs-8 reaches as high as 570 mF cm-1 at the current density of 1 mA cm-1 in LiCl electrolyte, a 1965-fold enhancement with respect to the pristine GFs (0.29 mF cm-1). The fabricated fiber solid-state supercapacitors (SSCs) provide high energy density of 0.68 mWh cm-3 at the power density 3.3 W cm-3 and have excellent durability with 90% capacitance retention after 10000 cycles. In addition, such fiber SSCs features flexibility and mechanical stability, which may have wide applications in wearable electronic devices.

Lowering the temperature of solid oxide fuel cells.

PubMed

Wachsman, Eric D; Lee, Kang Taek

2011-11-18

Fuel cells are uniquely capable of overcoming combustion efficiency limitations (e.g., the Carnot cycle). However, the linking of fuel cells (an energy conversion device) and hydrogen (an energy carrier) has emphasized investment in proton-exchange membrane fuel cells as part of a larger hydrogen economy and thus relegated fuel cells to a future technology. In contrast, solid oxide fuel cells are capable of operating on conventional fuels (as well as hydrogen) today. The main issue for solid oxide fuel cells is high operating temperature (about 800°C) and the resulting materials and cost limitations and operating complexities (e.g., thermal cycling). Recent solid oxide fuel cells results have demonstrated extremely high power densities of about 2 watts per square centimeter at 650°C along with flexible fueling, thus enabling higher efficiency within the current fuel infrastructure. Newly developed, high-conductivity electrolytes and nanostructured electrode designs provide a path for further performance improvement at much lower temperatures, down to ~350°C, thus providing opportunity to transform the way we convert and store energy.

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.

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

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-12-11

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

Electrode including porous particles with embedded active material for use in a secondary electrochemical cell

DOEpatents

Vissers, Donald R.; Nelson, Paul A.; Kaun, Thomas D.; Tomczuk, Zygmunt

1978-04-25

Particles of carbonaceous matrices containing embedded electrode active material are prepared for vibratory loading within a porous electrically conductive substrate. In preparing the particles, active materials such as metal chalcogenides, solid alloys of alkali or alkaline earth metals along with other metals and their oxides in powdered or particulate form are blended with a thermosetting resin and particles of a volatile to form a paste mixture. The paste is heated to a temperature at which the volatile transforms into vapor to impart porosity at about the same time as the resin begins to cure into a rigid, solid structure. The solid structure is then comminuted into porous, carbonaceous particles with the embedded active material.

Method of preparing porous, active material for use in electrodes of secondary electrochemical cells

DOEpatents

Vissers, Donald R.; Nelson, Paul A.; Kaun, Thomas D.; Tomczuk, Zygmunt

1977-01-01

Particles of carbonaceous matrices containing embedded electrode active material are prepared for vibratory loading within a porous electrically conductive substrate. In preparing the particles, active materials such as metal chalcogenides, solid alloys of alkali or alkaline earth metals along with other metals and their oxides in powdered or particulate form are blended with a thermosetting resin and particles of a volatile to form a paste mixture. The paste is heated to a temperature at which the volatile transforms into vapor to impart porosity at about the same time as the resin begins to cure into a rigid, solid structure.The solid structure is then comminuted into porous, carbonaceous particles with the embedded active material.

Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

NASA Astrophysics Data System (ADS)

Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

2000-03-01

The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the oxides on the Zr and Zry-2 samples which presumably originates from the electrolyte.

Stable, fast and high-energy-density LiCoO2 cathode at high operation voltage enabled by glassy B2O3 modification

NASA Astrophysics Data System (ADS)

Zhou, Aijun; Wang, Weihang; Liu, Qin; Wang, Yi; Yao, Xu; Qing, Fangzhu; Li, Enzhu; Yang, Tingting; Zhang, Long; Li, Jingze

2017-09-01

In this work, commercial LiCoO2 is modified with a glassy B2O3 by solution mixing with H3BO3 followed by post-calcination in order to enhance its high-voltage electrochemical performance. The glassy B2O3 coating/additive is believed to serve as an effective physiochemical buffer and protection between LiCoO2 and liquid electrolyte, which can suppress the high-voltage induced electrolyte decomposition and active material dissolution. During the early cycling and due to the electrochemical force, the as-coated B2O3 glasses which have 3D open frameworks tend to accommodate some mobile Li+ and form a more chemically-resistant and ion-conductive lithium boron oxide (LBO) interphase as a major component of the solid electrolyte interphase (SEI), which consequently enables much easier Li+ diffusion/transfer at the solid-liquid interfaces upon further cycling. Due to the synergetic effects of B2O3 coating/modification, the high-voltage capacity and energy density of the B2O3-modified LiCoO2 cathode are promisingly improved by 35% and 30% after 100 cycles at 1 C within 3.0-4.5 V vs. Li/Li+. Meanwhile, the high-rate performance of the B2O3-modified electrode is even more greatly improved, showing a capacity of 105 mAh g-1 at 10 C while the bare electrode has dropped to no more than 30 mAh g-1 under this rate condition.

Cobalt doped lanthanum chromite material suitable for high temperature use

DOEpatents

Ruka, Roswell J.

1986-01-01

A high temperature, solid electrolyte electrochemical cell, subject to thermal cycling temperatures of between about 25.degree. C. and about 1200.degree. C., capable of electronic interconnection to at least one other electrochemical cell and capable of operating in an environment containing oxygen and a fuel, is made; where the cell has a first and second electrode with solid electrolyte between them, where an improved interconnect material is applied along a portion of a supporting electrode; where the interconnect is made of a chemically modified lanthanum chromite, containing cobalt as the important additive, which interconnect allows for adjustment of the thermal expansion of the interconnect material to more nearly match that of other cell components, such as zirconia electrolyte, and is stable in oxygen containing atmospheres such as air and in fuel environments.

First-principles density functional calculation of electrochemical stability of fast Li ion conducting garnet-type oxides.

PubMed

Nakayama, Masanobu; Kotobuki, Masashi; Munakata, Hirokazu; Nogami, Masayuki; Kanamura, Kiyoshi

2012-07-28

The research and development of rechargeable all-ceramic lithium batteries are vital to realize their considerable advantages over existing commercial lithium ion batteries in terms of size, energy density, and safety. A key part of such effort is the development of solid-state electrolyte materials with high Li(+) conductivity and good electrochemical stability; lithium-containing oxides with a garnet-type structure are known to satisfy the requirements to achieve both features. Using first-principles density functional theory (DFT), we investigated the electrochemical stability of garnet-type Li(x)La(3)M(2)O(12) (M = Ti, Zr, Nb, Ta, Sb, Bi; x = 5 or 7) materials against Li metal. We found that the electrochemical stability of such materials depends on their composition and structure. The electrochemical stability against Li metal was improved when a cation M was chosen with a low effective nuclear charge, that is, with a high screening constant for an unoccupied orbital. In fact, both our computational and experimental results show that Li(7)La(3)Zr(2)O(12) and Li(5)La(3)Ta(2)O(12) are inert to Li metal. In addition, the linkage of MO(6) octahedra in the crystal structure affects the electrochemical stability. For example, perovskite-type La(1/3)TaO(3) was found, both experimentally and computationally, to react with Li metal owing to the corner-sharing MO(6) octahedral network of La(1/3)TaO(3), even though it has the same constituent elements as garnet-type Li(5)La(3)Ta(2)O(12) (which is inert to Li metal and features isolated TaO(6) octahedra).

A solid oxide photoelectrochemical cell with UV light-driven oxygen storage in mixed conducting electrodes

PubMed Central

Walch, Gregor; Rotter, Bernhard; Brunauer, Georg Christoph; Esmaeili, Esmaeil; Opitz, Alexander Karl; Kubicek, Markus; Summhammer, Johann; Ponweiser, Karl

2017-01-01

A single crystalline SrTiO3 working electrode in a zirconia-based solid oxide electrochemical cell is illuminated by UV light at temperatures of 360–460 °C. In addition to photovoltaic effects, this leads to the build-up of a battery-type voltage up to more than 300 mV. After switching off UV light, this voltage only slowly decays. It is caused by UV-induced oxygen incorporation into the mixed conducting working electrode and thus by changes of the oxygen stoichiometry δ in SrTiO3–δ under UV illumination. These changes of the oxygen content could be followed in time-dependent voltage measurements and also manifest themselves in time-dependent resistance changes during and after UV illumination. Discharge currents measured after UV illumination reveal that a large fraction of the existing oxygen vacancies in SrTiO3 become filled under UV light. Additional measurements on cells with TiO2 thin film electrodes show the broader applicability of this novel approach for transforming light into chemical energy and thus the feasibility of solid oxide photoelectrochemical cells (SOPECs) in general and of a “light-charged oxygen battery” in particular. PMID:28261480

Caco-2 cell-based electrochemical biosensor for evaluating the antioxidant capacity of Asp-Leu-Glu-Glu isolated from dry-cured Xuanwei ham.

PubMed

Xing, Lujuan; Ge, Qingfeng; Jiang, Donglei; Gao, Xiaoge; Liu, Rui; Cao, Songmin; Zhuang, Xinbo; Zhou, Guanghong; Zhang, Wangang

2018-05-15

A cell-based electrochemical biosensor was developed to determine the antioxidant activity of Asp-Leu-Glu-Glu (DLEE) isolated from dry-cured Chinese Xuanwei ham. A platinized gold electrode (Pt NPs/GE) covered with silver nanowires (Ag NWs) was fabricated to detect H 2 O 2 using redox signaling via cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Under optimal condition, the detection limit of the modified electrode was 0.12μM with a linear relationship from 0.2 to 2μM, which showed relatively outstanding catalytic effects towards the reduction of H 2 O 2 . Furthermore, the generation of reactive oxygen species (ROS) in the cell can be used to indirectly assess changes in intercellular oxidative stress by detecting variations in electrochemical signals. A 3D cell culture of alginate/graphene oxide (NaAlg/GO) was used to encapsulate and immobilize Caco-2 cells. Based on ROS generation and electrochemical results, we found that DLEE could effectively reduce oxidative stress level in Caco-2 cells under external stimulation. DLEE showed high antioxidant activity with a relative antioxidant capacity (RAC) rate of 88.17% at 1.5mg/mL. Finally, an efficient electrochemical biosensor was established using the active 3D Caco-2 cell platform. This system is sensitive and simple to operate with the property to evaluate the antioxidant activity of peptides by the detection of H 2 O 2 in cell membrane. In summary, this work describes a new method for assessing antioxidant capacity of peptide DLEE using cell-based electrochemical signaling with a rapid screening pattern. Copyright © 2018 Elsevier B.V. All rights reserved.

Application of infiltrated LSCM-GDC oxide anode in direct carbon/coal fuel cells.

PubMed

Yue, Xiangling; Arenillas, Ana; Irvine, John T S

2016-08-15

Hybrid direct carbon/coal fuel cells (HDCFCs) utilise an anode based upon a molten carbonate salt with an oxide conducting solid electrolyte for direct carbon/coal conversion. They can be fuelled by a wide range of carbon sources, and offer higher potential chemical to electrical energy conversion efficiency and have the potential to decrease CO2 emissions compared to coal-fired power plants. In this study, the application of (La, Sr)(Cr, Mn)O3 (LSCM) and (Gd, Ce)O2 (GDC) oxide anodes was explored in a HDCFC system running with two different carbon fuels, an organic xerogel and a raw bituminous coal. The electrochemical performance of the HDCFC based on a 1-2 mm thick 8 mol% yttria stabilised zirconia (YSZ) electrolyte and the GDC-LSCM anode fabricated by wet impregnation procedures was characterized and discussed. The infiltrated oxide anode showed a significantly higher performance than the conventional Ni-YSZ anode, without suffering from impurity formation under HDCFC operation conditions. Total polarisation resistance (Rp) reached 0.8-0.9 Ω cm(2) from DCFC with an oxide anode on xerogel and bituminous coal at 750 °C, with open circuit voltage (OCV) values in the range 1.1-1.2 V on both carbon forms. These indicated the potential application of LSCM-GDC oxide anode in HDCFCs. The chemical compatibility of LSCM/GDC with carbon/carbonate investigation revealed the emergence of an A2BO4 type oxide in place of an ABO3 perovskite structure in the LSCM in a reducing environment, due to Li attack as a result of intimate contact between the LSCM and Li2CO3, with GDC being stable under identical conditions. Such reaction between LSCM and Li2CO3 was not observed on a LSCM-YSZ pellet treated with Li-K carbonate in 5% H2/Ar at 700 °C, nor on a GDC-LSCM anode after HDCFC operation. The HDCFC durability tests of GDC-LSCM oxide on a xerogel and on raw bituminous coal were performed under potentiostatic operation at 0.7 V at 750 °C. The degradation mechanisms were addressed, especially on raw coal.