Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

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

Hermann, S.D.; Gese, N.J.; Wurth, L.A.

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide.more » In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.« less

Non-consumable anode and lining for aluminum electrolytic reduction cell

DOEpatents

Beck, Theodore R.; Brooks, Richard J.

1994-01-01

An oxidation resistant, non-consumable anode, for use in the electrolytic reduction of alumina to aluminum, has a composition comprising copper, nickel and iron. The anode is part of an electrolytic reduction cell comprising a vessel having an interior lined with metal which has the same composition as the anode. The electrolyte is preferably composed of a eutectic of AlF.sub.3 and either (a) NaF or (b) primarily NaF with some of the NaF replaced by an equivalent molar amount of KF or KF and LiF.

Increasing the Energy Efficiency of Aluminum-Reduction Cells Using Modified Cathodes

NASA Astrophysics Data System (ADS)

Jianping, Peng; Yang, Song; Yuezhong, Di; Yaowu, Wang; Naixiang, Feng

2017-10-01

A cathode with an inclined surface (5°) and increased bar collector height (230 mm high) was incorporated into two 300-kA industrial aluminum-reduction cells. The voltage of the cells with the modified cathode was reduced by approximately 200 mV when compared with that of a conventional cell with a flat cathode. Through the use of simulations, the reduction in the cell voltage was attributed to the cathode modification (40 mV) and a reduced electrolyte level of 0.5 cm (160 mV). As a result of reduced anode cathode distance (ACD), the ledge toe was extended to the anode shadow by 12 cm. This caused a large inverted horizontal current and a velocity increase. The ledge profile returned to the desired position when the cells were insulated more effectively, and the metal velocity and metal crest in the modified cells were reduced accordingly.

The Effect of Structural Modifications on Ionic Conductivity in Newly-Designed Polyester Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Jung, Yuki; Coates, Geoff; Balsara, Nitash

2015-03-01

Gaining a fundamental understanding of the relationship between molecular structure and ionic conductivity of polymer electrolytes is an essential step toward designing next generation materials for battery applications. In this study, we use a systematic set of newly-designed polyesters with varying side-chain lengths and oxygen functional groups to elucidate the effects of structural modifications on the conductive properties of the corresponding electrolytes. Mixtures of polyesters and lithium bis(trifluromethanesulfonyl)imide (LiTFSI) were characterized using ac impedance spectroscopy to measure the ionic conductivity at various temperatures and salt concentrations. The relative conductivities of these electrolytes in the dilute limit are directly comparable to results of molecular dynamics simulations performed using the same polymers. The simulations correspond well with the experimental results, and provide molecular level insight about the solvation environment of the lithium ions and how the ions transport through these polyesters.

Anion permselective membrane

NASA Technical Reports Server (NTRS)

Hodgdon, R. B.; Waite, W. A.; Alexander, S. S.

1984-01-01

Two polymer ion exchange membranes were synthesized to fulfill the needs of both electrical resistivity and anolyte/catholyte separation for utility load leveling utilizing the DOE/NASA mixed electrolyte REDOX battery. Both membranes were shown to meet mixed electrolyte utility load leveling criteria. Several modifications of an anion exchange membrane failed to meet utility load leveling REDOX battery criteria using the unmixed electrolyte REDOX cell.

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.

Electrochemical surface modification of carbon mesh anode to improve the performance of air-cathode microbial fuel cells.

PubMed

Luo, Jianmei; Chi, Meiling; Wang, Hongyu; He, Huanhuan; Zhou, Minghua

2013-12-01

A convenient and promising alternative to surface modification of carbon mesh anode was fulfilled by electrochemical oxidation in the electrolyte of nitric acid or ammonium nitrate at ambient temperature. It was confirmed that such an anode modification method was low cost and effective not only in improving the efficiency of power generation in microbial fuel cells (MFCs) for synthetic wastewater treatment, but also helping to reduce the period for MFCs start-up. The MFCs with anode modification in electrolyte of nitric acid performed the best, achieving a Coulombic efficiency enhancement of 71 %. As characterized, the electrochemical modification resulted in the decrease of the anode potential and internal resistance but the increase of current response and nitrogen-containing and oxygen-containing functional groups on the carbon surface, which might contribute to the enhancement on the performances of MFCs.

Polymer membranes as separators for supercapacitors

NASA Astrophysics Data System (ADS)

Szubzda, Bronisław; Szmaja, Aleksandra; Ozimek, Mariusz; Mazurkiewicz, Sławomir

2014-12-01

The purpose of the studies described was to examine the influence of low-energy plasma modification of polyamide and polypropylene polymer nonwoven fabrics on the usable properties of supercapacitors when using these fabrics as the separator material. To achieve this goal the following investigations were carried out: testing the time required for electrolyte saturation of separators and the conductivity of the electrolyte contained in the separator, as well as electrochemical examinations of supercapacitor models in which the modified fabric separators were used. The tests conducted fully confirm the usability of this modification for cleaning the surface and improving the wettability of separators by the electrolyte, which in turn results in a significant decrease of the internal resistance of the supercapacitor, thus increasing the usable power of the device.

Electrolyte treatment for aluminum reduction

DOEpatents

Brown, Craig W.; Brooks, Richard J.; Frizzle, Patrick B.; Juric, Drago D.

2002-01-01

A method of treating an electrolyte for use in the electrolytic reduction of alumina to aluminum employing an anode and a cathode, the alumina dissolved in the electrolyte, the treating improving wetting of the cathode with molten aluminum during electrolysis. The method comprises the steps of providing a molten electrolyte comprised of ALF.sub.3 and at least one salt selected from the group consisting of NaF, KF and LiF, and treating the electrolyte by providing therein 0.004 to 0.2 wt. % of a transition metal or transition metal compound for improved wettability of the cathode with molten aluminum during subsequent electrolysis to reduce alumina to aluminum.

Combination for electrolytic reduction of alumina

DOEpatents

Brown, Craig W.; Brooks, Richard J.; Frizzle, Patrick B.; Juric, Drago D.

2002-04-30

An electrolytic bath for use during the electrolytic reduction of alumina to aluminum. The bath comprises molten electrolyte having the following ingredients: AlF.sub.3 and at least one salt selected from the group consisting of NaF, KF, and LiF; and about 0.004 wt. % to about 0.2 wt. %, based on total weight of the molten electrolyte, of at least one transition metal or at least one compound of the metal or both. The compound is, a fluoride; oxide, or carbonate. The metal is nickel, iron, copper, cobalt, or molybdenum. The bath is employed in a combination including a vessel for containing the bath and at least one non-consumable anode and at least one dimensionally stable cathode in the bath. Employing the instant bath during electrolytic reduction of alumina to aluminum improves the wetting of aluminum on a cathode by reducing or eliminating the formation of non-metallic deposits on the cathode.

Unusual Passivation Ability of Superconcentrated Electrolytes toward Hard Carbon Negative Electrodes in Sodium-Ion Batteries.

PubMed

Takada, Koji; Yamada, Yuki; Watanabe, Eriko; Wang, Jianhui; Sodeyama, Keitaro; Tateyama, Yoshitaka; Hirata, Kazuhisa; Kawase, Takeo; Yamada, Atsuo

2017-10-04

The passivation of negative electrodes is key to achieving prolonged charge-discharge cycling with Na-ion batteries. Here, we report the unusual passivation ability of superconcentrated Na-salt electrolytes. For example, a 50 mol % sodium bis(fluorosulfonyl)amide (NaFSA)/succinonitrile (SN) electrolyte enables highly reversible Na + insertion into a hard carbon negative electrode without any electrolyte additive, functional binder, or electrode pretreatment. Importantly, an anion-derived passivation film is formed via preferential reduction of the anion upon charging, which can effectively suppress further electrolyte reduction. As a structural characteristic of the electrolyte, most anions are coordinated to multiple Na + cations at high concentration, which shifts the lowest unoccupied molecular orbitals of the anions downward, resulting in preferential anion reduction. The present work provides a new understanding of the passivation mechanism with respect to the coordination state of the anion.

Evaluation of selected chemical processes for production of low-cost silicon. Quarterly progress report, 15 Dec 1975--31 Mar 1976

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

Blocher, J.M. Jr; Browning, M.F.; Wilson, W.J.

1976-04-08

Plant construction costs and manufacturing costs were estimmated for the production of solar-grade silicon by the reduction of silicon tetrachloride in a fluidized bed of seed particles, and several modifications of the iodide process using either thermal decomposition on heated filaments (rods) or hydrogen reduction in a fluidized bed of seed particles. Energy consumption data for the zinc reduction process and each of the iodide process options are given and all appear to be acceptable from the standpoint of energy pay back. Information is presented on the experimental zinc reduction of SiCl4 and electrolytic recovery of zinc from ZnCl2. Allmore » of the experimental work performed thus far has supported the initial assumption as to technical feasibility of producing semiconductor silicon by the zinc reduction or iodide processes proposed. The results of a more thorough thermodynamic evaluation of the iodination of silicon oxide/carbon mixtures are presented which explain apparent inconsistencies in an earlier cursory examination of the system.« less

Modular cathode assemblies and methods of using the same for electrochemical reduction

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

Wiedmeyer, Stanley G.; Barnes, Laurel A.; Williamson, Mark A.

Modular cathode assemblies are useable in electrolytic reduction systems and include a basket through which fluid electrolyte may pass and exchange charge with a material to be reduced in the basket. The basket can be divided into upper and lower sections to provide entry for the material. Example embodiment cathode assemblies may have any shape to permit modular placement at any position in reduction systems. Modular cathode assemblies include a cathode plate in the basket, to which unique and opposite electrical power may be supplied. Example embodiment modular cathode assemblies may have standardized electrical connectors. Modular cathode assemblies may bemore » supported by a top plate of an electrolytic reduction system. Electrolytic oxide reduction systems are operated by positioning modular cathode and anode assemblies at desired positions, placing a material in the basket, and charging the modular assemblies to reduce the metal oxide.« less

Modular cathode assemblies and methods of using the same for electrochemical reduction

DOEpatents

Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L

2014-12-02

Modular cathode assemblies are useable in electrolytic reduction systems and include a basket through which fluid electrolyte may pass and exchange charge with a material to be reduced in the basket. The basket can be divided into upper and lower sections to provide entry for the material. Example embodiment cathode assemblies may have any shape to permit modular placement at any position in reduction systems. Modular cathode assemblies include a cathode plate in the basket, to which unique and opposite electrical power may be supplied. Example embodiment modular cathode assemblies may have standardized electrical connectors. Modular cathode assemblies may be supported by a top plate of an electrolytic reduction system. Electrolytic oxide reduction systems are operated by positioning modular cathode and anode assemblies at desired positions, placing a material in the basket, and charging the modular assemblies to reduce the metal oxide.

Apparatus for the electrolytic production of metals

DOEpatents

Sadoway, Donald R.

1993-01-01

Improved electrolytic cells for producing metals by the electrolytic reduction of a compound dissolved in a molten electrolyte are disclosed. In the improved cells, at least one electrode includes a protective layer comprising an oxide of the cell product metal formed upon an alloy of the cell product metal and a more noble metal. In the case of an aluminum reduction cell, the electrode can comprise an alloy of aluminum with copper, nickel, iron, or combinations thereof, upon which is formed an aluminum oxide protective layer.

Bath for electrolytic reduction of alumina and method therefor

DOEpatents

Brown, Craig W.; Brooks, Richard J.; Frizzle, Patrick B.; Juric, Drago D.

2001-07-10

An electrolytic bath for use during the electrolytic reduction of alumina to aluminum. The bath comprises a molten electrolyte having the following ingredients: (a) AlF.sub.3 and at least one salt selected from the group consisting of NaF, KF, and LiF; and (b) about 0.004 wt. % to about 0.2 wt. %, based on total weight of the molten electrolyte, of at least one transition metal or at least one compound of the metal or both. The compound may be, for example, a fluoride, oxide, or carbonate. The metal can be nickel, iron, copper, cobalt, or molybdenum. The bath can be employed in a combination that includes a vessel for containing the bath and at least one non-consumable anode and at least one dimensionally stable cathode in the bath. Employing the bath of the present invention during electrolytic reduction of alumina to aluminum can improve the wetting of aluminum on a cathode by reducing or eliminating the formation of non-metallic deposits on the cathode.

Preventing Corrosion by Controlling Cathodic Reaction Kinetics

DTIC Science & Technology

2016-03-25

electrochemical reaction rates of processes that drive corrosion, e.g. the oxygen reduction reaction (ORR). To this end, we have used reactive...elements on the kinetics of oxygen reduction reaction catalyzed on titanium oxide in order to develop new approaches for controlling galvanic corrosion... consumption of anions in reactions with metal cations can deplete the electrolyte. However, in the atmospheric electrolyte, the electrolyte

Adsorptive behaviour of mercury on algal biomass: competition with divalent cations and organic compounds.

PubMed

Carro, Leticia; Barriada, José L; Herrero, Roberto; Sastre de Vicente, Manuel E

2011-08-15

Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed. Copyright © 2011 Elsevier B.V. All rights reserved.

Titanium surface modification by microarc oxidation in electrolyte based on wollastonite and hydroxyapatite

NASA Astrophysics Data System (ADS)

Sharkeev, Yu. P.; Sedelnikova, M. B.; Komarova, E. G.; Khlusov, I. A.

2015-11-01

An investigation of titanium surface modification by microarc oxidation in the electrolyte based on wollastonite and hydroxyapatite was presented. The dependences of the coating properties on the microarc oxidation parameters were found. A variation of the process parameters allowed producing wollastonite-calcium phosphate coatings with aplate-like structure, thickness 25-30 µm, roughness 2.5-5.0 µm, and adhesion strength 57 MPa. The optimum microarc oxidation parameters such as the electrical voltage of 150 V, process duration of 5-10 min, and pulse duration of 100-300 µs were revealed. The wollastonite addition to the electrolyte based on the aqueous solution of phosphoric acid and hydroxyapatite allowed us to form wollastonite-calcium phosphate coatings on the titanium surface by the microarc oxidation method with enhanced strength properties and an increased ability to osseointegration.

Apparatus and process for the electrolytic reduction of uranium and plutonium oxides

DOEpatents

Poa, David S.; Burris, Leslie; Steunenberg, Robert K.; Tomczuk, Zygmunt

1991-01-01

An apparatus and process for reducing uranium and/or plutonium oxides to produce a solid, high-purity metal. The apparatus is an electrolyte cell consisting of a first container, and a smaller second container within the first container. An electrolyte fills both containers, the level of the electrolyte in the first container being above the top of the second container so that the electrolyte can be circulated between the containers. The anode is positioned in the first container while the cathode is located in the second container. Means are provided for passing an inert gas into the electrolyte near the lower end of the anode to sparge the electrolyte and to remove gases which form on the anode during the reduction operation. Means are also provided for mixing and stirring the electrolyte in the first container to solubilize the metal oxide in the electrolyte and to transport the electrolyte containing dissolved oxide into contact with the cathode in the second container. The cell is operated at a temperature below the melting temperature of the metal product so that the metal forms as a solid on the cathode.

Modifications in structure and interaction of nanoparticle-protein-surfactant complexes in electrolyte solution

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Kumar, S.; Aswal, V. K.; Schweins, R.

2016-05-01

SANS experiments of three-component system of anionic silica nanoparticles, anionic BSA protein and anionic SDS surfactants have been carried out without and with electrolyte in aqueous solution. In both the cases, the interaction of surfactant with protein results in formation of bead-necklace structure of protein-surfactant complexes in solution. These protein-surfactant complexes interact very differently with nanoparticles in absence and presence of electrolyte. In absence of electrolyte, nanoparticles remain in dispersed phase in solution, whereas with the addition of electrolyte the nanoparticles fractal aggregates are formed. SANS describes the phase behavior to be governed by competition of electrostatic and depletion interactions among the components solution.

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.

Study report on modification of the long term circulatory model for the simulation of bed rest

NASA Technical Reports Server (NTRS)

Leonard, J. I.; Grounds, D. J.

1977-01-01

Modifications were made of the circulatory, fluid, and electrolyte control model which was based on the model of Guyton. The modifications included separate leg compartments and the addition of gravity dependency. It was found that these modifications allowed for more accurate bed rest simulation by simulating changes in the orthostatic gradient and simulating the response to the fluid shifts associated with bed rest.

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

NASA Astrophysics Data System (ADS)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li-air battery. Towards this end, using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of properties, we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA +, O2 reduction is a highly reversible one-electron process involving the O2/O2- couple in all of the electrolytes examined with little effect on the nature of the solvent. On the other hand, in Li+-containing electrolytes relevant to the Li-air battery, O2 reduction proceeds in a stepwise fashion to form O2-, O22- and O2- as products. These reactions in presence of Li+ are irreversible or quasi-reversible electrochemical processes and the solvents have significant influence on the kinetics, and reversibility or lack thereof, of the different reduction products. Reversible reduction of O2 to long-lived superoxide in a Li+-conducting electrolyte in DMSO has been shown for the first time here. Chapter 5 is the culmination of the thesis where the practical application of the work is demonstrated. We designed electrolytes that facilitate Li-Air rechargeability, by applying the knowledge gained from chapters 2-4. A rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF6 in tetraethylene glycol dimethyl ether, CH3O(CH2CH 2O)4CH3 was designed, built and its performance studied. It was shown that the cell yields high capacity and can be recharged in spite the absence of catalyst in the carbon cathode. The application of X-ray diffraction to identify these products formed in a porous carbon electrode is shown here for the first time. The rechargeability of the cell was investigated by repeated charge/discharge cycling of the cell, and the factors limiting the cycle life of the cell were studied using AC impedance spectra of the cells as a function of cycle number. In conclusion, the work carried out in this research has shown that the O2 electrochemistry in organic electrolytes is substantially different from that in aqueous electrolytes. Our work has uncovered the key roles the ion conducting salts and the organic solvents play in determining the nature of the reduction products and their reversibility. The results presented here for the first time provide a rational approach to the design and selection of organic electrolyte solutions for use in the rechargeable Li-air battery. (Abstract shortened by UMI.)

Direct electrochemical reduction of metal-oxides

DOEpatents

Redey, Laszlo I.; Gourishankar, Karthick

2003-01-01

A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

Stability of yttria-stabilized zirconia during pyroprocessing tests

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Lee, Jeong; Lee, Sung-Jai; Kim, Sung-Wook; Jeon, Sang-Chae; Cho, Soo Haeng; Oh, Seung Chul; Jeon, Min Ku; Lee, Sang Kwon; Kang, Hyun Woo; Hur, Jin-Mok

2016-07-01

In this study, the feasibility of yttria-stabilized zirconia (YSZ) was investigated for use as a ceramic material, which can be commonly used for both electrolytic reduction and electrorefining. First, the stability of YSZ in salts for electrolytic reduction and electrorefining was examined. Then, its stability was demonstrated by a series of pyroprocessing tests, such as electrolytic reduction, LiCl distillation, electrorefining, and LiClsbnd KCl distillation, using a single stainless steel wire mesh basket containing fuel and YSZ. A single basket was used by its transportation from one test to subsequent tests without the requirements for unloading.

The pH Response and Sensing Mechanism of n-Type ZnO/Electrolyte Interfaces

PubMed Central

Al-Hilli, Safaa; Willander, Magnus

2009-01-01

Ever since the discovery of the pH-sensing properties of ZnO crystals, researchers have been exploring their potential in electrochemical applications. The recent expansion and availability of chemical modification methods has made it possible to generate a new class of electrochemically active ZnO nanorods. This reduction in size of ZnO (to a nanocrystalline form) using new growth techniques is essentially an example of the nanotechnology fabrication principle. The availability of these ZnO nanorods opens up an entire new and exciting research direction in the field of electrochemical sensing. This review covers the latest advances and mechanism of pH-sensing using ZnO nanorods, with an emphasis on the nano-interface mechanism. We discuss methods for calculating the effect of surface states on pH-sensing at a ZnO/electrolyte interface. All of these current research topics aim to explain the mechanism of pH-sensing using a ZnO bulk- or nano-scale single crystal. An important goal of these investigations is the translation of these nanotechnology-modified nanorods into potential novel applications. PMID:22423211

The pH Response and Sensing Mechanism of n-Type ZnO/Electrolyte Interfaces.

PubMed

Al-Hilli, Safaa; Willander, Magnus

2009-01-01

Ever since the discovery of the pH-sensing properties of ZnO crystals, researchers have been exploring their potential in electrochemical applications. The recent expansion and availability of chemical modification methods has made it possible to generate a new class of electrochemically active ZnO nanorods. This reduction in size of ZnO (to a nanocrystalline form) using new growth techniques is essentially an example of the nanotechnology fabrication principle. The availability of these ZnO nanorods opens up an entire new and exciting research direction in the field of electrochemical sensing. This review covers the latest advances and mechanism of pH-sensing using ZnO nanorods, with an emphasis on the nano-interface mechanism. We discuss methods for calculating the effect of surface states on pH-sensing at a ZnO/electrolyte interface. All of these current research topics aim to explain the mechanism of pH-sensing using a ZnO bulk- or nano-scale single crystal. An important goal of these investigations is the translation of these nanotechnology-modified nanorods into potential novel applications.

Enhanced stability of solid oxide fuel cells by employing a modified cathode-interlayer interface with a dense La0.6Sr0.4Co0.2Fe0.8O3-δ thin film

NASA Astrophysics Data System (ADS)

De Vero, Jeffrey C.; Develos-Bagarinao, Katherine; Kishimoto, Haruo; Ishiyama, Tomohiro; Yamaji, Katsuhiko; Horita, Teruhisa; Yokokawa, Harumi

2018-02-01

In La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode/Gd-doped ceria (GDC)/yttria-stabilized zirconia (YSZ)-electrolyte based solid oxide fuel cells (SOFCs), one of the key issues affecting performance and long-term stability is the apparent deactivation of LSCF cathode by the presence of secondary phases such as SrZrO3 at the interfaces. Herein, we report that by modifying the cathode-interlayer interface with a dense LSCF thin film, the severe cation interdiffusion is suppressed especially the fast gas or surface diffusion of Sr into adjacent GDC-interlayer/YSZ-electrolyte resulting in the significant reduction of SrZrO3 formation at the interfaces improving cell stability. In order to understand the present results, the interface chemistry is carefully considered and discussed. The results show that modification of cathode-interlayer interfaces is an important strategy for improving the lifetime of SOFCs.

Lithium-sulfur batteries based on nitrogen-doped carbon and an ionic-liquid electrolyte.

PubMed

Sun, Xiao-Guang; Wang, Xiqing; Mayes, Richard T; Dai, Sheng

2012-10-01

Nitrogen-doped mesoporous carbon (NC) and sulfur were used to prepare an NC/S composite cathode, which was evaluated in an ionic-liquid electrolyte of 0.5 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in methylpropylpyrrolidinium bis(trifluoromethane sulfonyl)imide ([MPPY][TFSI]) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cycle testing. To facilitate the comparison, a C/S composite based on activated carbon (AC) without nitrogen doping was also fabricated under the same conditions. Compared with the AC/S composite, the NC/S composite showed enhanced activity toward sulfur reduction, as evidenced by the lower onset sulfur reduction potential, higher redox current density in the CV test, and faster charge-transfer kinetics, as indicated by EIS measurements. At room temperature under a current density of 84 mA g(-1) (C/20), the battery based on the NC/S composite exhibited a higher discharge potential and an initial capacity of 1420 mAh g(-1), whereas the battery based on the AC/S composite showed a lower discharge potential and an initial capacity of 1120 mAh g(-1). Both batteries showed similar capacity fading with cycling due to the intrinsic polysulfide solubility and the polysulfide shuttle mechanism; capacity fading can be improved by further cathode modification. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microfluidic platform for studying the electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Whipple, Devin Talmage

Diminishing supplies of conventional energy sources and growing concern over greenhouse gas emissions present significant challenges to supplying the world's rapidly increasing demand for energy. The electrochemical reduction of carbon dioxide has the potential to address many of these issues by providing a means of storing electricity in chemical form. Storing electrical energy as chemicals is beneficial for leveling the output of clean, but intermittent renewable energy sources such as wind and solar. Electrical energy stored as chemicals can also be used as carbon neutral fuels for portable applications allowing petroleum derived fuels in the transportation sector to be replaced by more environmentally friendly energy sources. However, to be a viable technology, the electrochemical reduction of carbon dioxide needs to have both high current densities and energetic efficiencies (Chapter 1). Although many researchers have studied the electrochemical reduction of CO2 including parameters such as catalysts, electrolytes and temperature, further investigation is needed to improve the understanding of this process and optimize the performance (Chapter 2). This dissertation reports the development and validation of a microfluidic reactor for the electrochemical reduction of CO2 (Chapter 3). The design uses a flowing liquid electrolyte instead of the typical polymer electrolyte membrane. In addition to other benefits, this flowing electrolyte gives the reactor great flexibility, allowing independent analysis of each electrode and the testing of a wide variety of conditions. In this work, the microfluidic reactor has been used in the following areas: • Comparison of different metal catalysts for the reduction of CO2 to formic acid and carbon monoxide (Chapter 4). • Investigation of the effects of the electrolyte pH on the reduction of CO2 to formic acid and carbon monoxide (Chapter 5). • Study of amine based electrolytes for lowering the overpotentials for CO2 reduction and suppressing undesirable hydrogen evolution (Chapter 6). • Investigation of the effects of reaction temperature on the Faradaic efficiency and current density for CO2 reduction on several catalysts (Chapter 7). These studies demonstrate the utility of this flexible reactor design and provide increased understanding of the electrochemical reduction of CO2 and the critical parameters for optimization of this process.

Artificial Solid Electrolyte Interphase-Protected LixSi Nanoparticles: An Efficient and Stable Prelithiation Reagent for Lithium-Ion Batteries.

PubMed

Zhao, Jie; Lu, Zhenda; Wang, Haotian; Liu, Wei; Lee, Hyun-Wook; Yan, Kai; Zhuo, Denys; Lin, Dingchang; Liu, Nian; Cui, Yi

2015-07-08

Prelithiation is an important strategy to compensate for lithium loss in lithium-ion batteries, particularly during the formation of the solid electrolyte interphase (SEI) from reduced electrolytes in the first charging cycle. We recently demonstrated that LixSi nanoparticles (NPs) synthesized by thermal alloying can serve as a high-capacity prelithiation reagent, although their chemical stability in the battery processing environment remained to be improved. Here we successfully developed a surface modification method to enhance the stability of LixSi NPs by exploiting the reduction of 1-fluorodecane on the LixSi surface to form a continuous and dense coating through a reaction process similar to SEI formation. The coating, consisting of LiF and lithium alkyl carbonate with long hydrophobic carbon chains, serves as an effective passivation layer in the ambient environment. Remarkably, artificial-SEI-protected LixSi NPs show a high prelithiation capacity of 2100 mA h g(-1) with negligible capacity decay in dry air after 5 days and maintain a high capacity of 1600 mA h g(-1) in humid air (∼10% relative humidity). Silicon, tin, and graphite were successfully prelithiated with these NPs to eliminate the irreversible first-cycle capacity loss. The use of prelithiation reagents offers a new approach to realize next-generation high-energy-density lithium-ion batteries.

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

DOE PAGES

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

2015-12-11

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

Antimicrobial effects of electrolytic products of sodium chloride--comparative evaluation with sodium hypochlorite solution and efficacy in handwashing.

PubMed

Hitomi, S; Baba, S; Yano, H; Morisawa, Y; Kimura, S

1998-11-01

We examined the in vitro bactericidal effects and efficacy on handwashing of water containing electrolytic products of sodium chloride (electrolytic water). The electrolytic water, whose pH and concentration of free residual chlorine were 6.7-6.9 and 20-22 ppm, respectively, showed equal reduction of both Staphylococcus aureus and Escherichia coli to dilution of commercially available sodium hypochlorite containing 60 ppm of free residual chlorine. This bactericidal effect was calculated to be due to hypochlorous acid, based on the pH and the amount of chlorine in solution. Handwashing with the electrolytic water reduced the numbers of S. aureus on hands by 1/10(2), while running water and 0.2% benzalkonium chloride with 80% ethanol gave a 1/10 and 1/10(5) reduction, respectively. We conclude that electrolytic water might be applicable for handwashing in place of running water.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

DOEpatents

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Bath for electrolytic reduction of alumina and method therefor

DOEpatents

Brown, Craig W.; Brooks, Richard J.; Frizzle, Patrick B.; Juric, Drago D.

2002-11-26

An electrolytic bath for use during the electrolytic reduction of alumina to aluminum. The bath comprises a molten electrolyte having the following ingredients: (a) AlF.sub.3 and at least one salt selected from the group consisting of NaF, KF, and LiF; and (b) about 0.004 wt. % to about 0.2 wt. %, based on total weight of the molten electrolyte, of at least one transition metal or at least one compound of the metal or both. The compound may be, for example, a fluoride, oxide, or carbonate. The metal can be nickel, iron, copper, cobalt, or molybdenum. The bath can be employed in a combination that includes a vessel for containing the bath and at least one non-consumable anode and at least one dimensionally stable cathode in the bath. Employing the bath of the present invention during electrolytic reduction of alumina to aluminum can improve the wetting of aluminum on a cathode by reducing or eliminating the formation of non-metallic deposits on the cathode. Removing sulfur from the bath can also minimize cathode deposits. Aluminum formed on the cathode can be removed directly from the cathode.

Formation of a Spinel Coating on AZ31 Magnesium Alloy by Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Sieber, Maximilian; Simchen, Frank; Scharf, Ingolf; Lampke, Thomas

2016-03-01

Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values.

Molten carbonate fuel cell reduction of nickel deposits

DOEpatents

Smith, James L.; Zwick, Stanley A.

1987-01-01

A molten carbonate fuel cell with anode and cathode electrodes and an eleolyte formed with two tile sections, one of the tile sections being adjacent the anode and limiting leakage of fuel gas into the electrolyte with the second tile section being adjacent the cathode and having pores sized to permit the presence of oxygen gas in the electrolyte thereby limiting the formation of metal deposits caused by the reduction of metal compositions migrating into the electrolyte from the cathode.

Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

PubMed

Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

2016-01-11

The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixed ion/electron-conductive protective soft nanomatter-based conformal surface modification of lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Park, Jang-Hoon; Kim, Ju-Myung; Lee, Chang Kee; Lee, Sang-Young

2014-10-01

Understanding and control of interfacial phenomena between electrode material and liquid electrolytes are of major scientific importance for boosting development of high-performance lithium ion batteries with reliable electrochemical/safety attributes. Here, as an innovative surface engineering approach to address the interfacial issues, a new concept of mixed ion/electron-conductive soft nanomatter-based conformal surface modification of the cathode material is presented. The soft nanomatter is comprised of an electron conductive carbonaceous (C) substance embedded in an ion conductive polyimide (PI) nanothin compliant film. In addition to its structural uniqueness, the newly proposed surface modification benefits from a simple fabrication process. The PI/carbon soft nanomatter is directly synthesized on LiCoO2 surface via one-pot thermal treatment of polyamic acid (=PI precursor) and sucrose (=carbon source) mixture, where the LiCoO2 powders are chosen as a model system to explore the feasibility of this surface engineering strategy. The resulting PI/carbon coating layer facilitates electronic conduction and also suppresses unwanted side reactions arising from the cathode material-liquid electrolyte interface. These synergistic coating effects of the multifunctional PI/carbon soft nanomatter significantly improve high-voltage cell performance and also mitigate interfacial exothermic reaction between cathode material and liquid electrolyte.

Apparatus and method for the electrolytic production of metals

DOEpatents

Sadoway, Donald R.

1991-01-01

Improved electrolytic cells and methods for producing metals by electrolytic reduction of a compound dissolved in a molten electrolyte are disclosed. In the improved cells and methods, a protective surface layer is formed upon at least one electrode in the electrolytic reduction cell and, optionally, upon the lining of the cell. This protective surface layer comprises a material that, at the operating conditions of the cell: (a) is not substantially reduced by the metal product; (b) is not substantially reactive with the cell electrolyte to form materials that are reactive with the metal product; and, (c) has an electrochemical potential that is more electronegative than that of the compound undergoing electrolysis to produce the metal product of the cell. The protective surface layer can be formed upon an electrode metal layer comprising a material, the oxide of which also satisfies the protective layer selection criteria. The protective layer material can also be used on the surface of a cell lining.

Milk and blood biomarkers associated to the clinical efficacy of a probiotic for the treatment of infectious mastitis.

PubMed

Espinosa-Martos, I; Jiménez, E; de Andrés, J; Rodríguez-Alcalá, L M; Tavárez, S; Manzano, S; Fernández, L; Alonso, E; Fontecha, J; Rodríguez, J M

2016-06-01

Previous studies have shown the efficacy of oral administration of selected lactobacilli strains to treat mastitis. The objective of this study was to find microbiological, biochemical and/or immunological biomarkers of the probiotic effect. Women with (n=23) and without (n=8) symptoms of mastitis received three daily doses (10(9) cfu) of Lactobacillus salivarius PS2 for 21 days. Samples of milk, blood and urine were collected before and after the probiotic intervention, and screened for a wide spectrum of microbiological, biochemical and immunological parameters. In the mastitis group, L. salivarius PS2 intake led to a reduction in milk bacterial counts, milk and blood leukocyte counts and interleukin (IL)-8 level in milk, an increase in those of immunoglobulin (Ig)E, IgG3, epidermal growth factor and IL-7, a modification of the milk electrolyte profile, and a reduction of some oxidative stress biomarkers. Such biomarkers will be useful in future clinical studies involving a larger cohort.

Alternative Anodes for the Electrolytic Reduction of Uranium Dioxide

NASA Astrophysics Data System (ADS)

Merwin, Augustus

Reprocessing of spent nuclear fuel is an essential step in closing the nuclear fuel cycle. In order to consume current stockpiles, ceramic uranium dioxide spent nuclear fuel will be subjected to an electrolytic reduction process. The current reduction process employs a platinum anode and a stainless steel alloy 316 cathode in a molten salt bath consisting of LiCl-2wt% Li 2O and occurs at 700°C. A major shortcoming of the existing process is the degradation of the platinum anode under the severely oxidizing conditions encountered during electrolytic reduction. This work investigates alternative anode materials for the electrolytic reduction of uranium oxide. The high temperature and extreme oxidizing conditions encountered in these studies necessitated a unique set of design constraints on the system. Thus, a customized experimental apparatus was designed and constructed. The electrochemical experiments were performed in an electrochemical reactor placed inside a furnace. This entire setup was housed inside a glove box, in order to maintain an inert atmosphere. This study investigates alternative anode materials through accelerated corrosion testing. Surface morphology was studied using scanning electron microscopy. Surface chemistry was characterized using energy dispersive spectroscopy and Raman spectroscopy. Electrochemical behavior of candidate materials was evaluated using potentiodynamic polarization characteristics. After narrowing the number of candidate electrode materials, ferrous stainless steel alloy 316, nickel based Inconel 718 and elemental tungsten were chosen for further investigation. Of these materials only tungsten was found to be sufficiently stable at the anodic potential required for electrolysis of uranium dioxide in molten salt. The tungsten anode and stainless steel alloy 316 cathode electrode system was studied at the required reduction potential for UO2 with varying lithium oxide concentrations. Electrochemical impedance spectroscopy showed mixed (kinetic and diffusion) control and an overall low impedance due to extreme corrosion. It was observed that tungsten is sufficiently stable in LiCl - 2wt% Li 2O at 700°C at the required anodic potential for the reduction of uranium oxide. This study identifies tungsten to be a superior anode material to platinum for the electrolytic reduction of uranium oxide, both in terms of superior corrosion behavior and reduced cost, and thus recommends that tungsten be further investigated as an alternative anode for the electrolytic reduction of uranium dioxide.

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

NASA Astrophysics Data System (ADS)

Meng, Xiangbo

2015-01-01

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

Copper retention, calcium release and ultrastructural evidence indicate specific Cuprolinic Blue uptake and peculiar modifications in mineralizing aortic valves.

PubMed

Ortolani, F; Tubaro, F; Petrelli, L; Gandaglia, A; Spina, M; Marchini, M

2002-01-01

Previously, reactions with copper phthalocyanines at 0.05 M critical electrolyte concentration were found to cause demineralization in calcifying porcine aortic valves after subdermal implantation in rat, as well as simultaneous visualization of peculiar phthalocyanine-positive layers around cells and cell-derived matrix vesicles. In the present investigation, an appraisal was made of the mechanism and specificity of reactions with Cuprolinic Blue by comparing quantitatively calcium release and copper retention by calcified aortic valves reacted with this phthalocyanine under different critical electrolyte concentration conditions, and the corresponding ultrastructural patterns. It was found that (i) decalcifying properties are inversely proportional to salt molarity; (ii) reactivity to Cuprolinic Blue is critical electrolyte concentration-dependent, since the greatest copper retention occurred in 0.05 M critical electrolyte concentration Cuprolinic Blue-reacted samples, the only ones that also exhibited phthalocyanine-positive layers; (iii) the appearance of phthalocyanine-positive layers depends on Cuprolinic Blue uptake, revealing pericellular clustering of calcium-binding, anionic molecules; and (iv) minor Cuprolinic Blue uptake occurs by residual proteoglycans which still remain in the extracellular matrix after 6-week-long subdermal implantation. The present results indicate that this method is appropriate for the study of mineralized tissues and illustrate peculiar tissue modifications occurring at least in the experimental conditions used here.

Is electrolyte transfer across the urothelium important?: ICI-RS 2015.

PubMed

McCloskey, Karen D; Vahabi, Bahareh; Fry, Christopher H

2017-04-01

This article summarizes discussion at the International Consultation on Incontinence Research Society (ICI-RS) 2015 meeting of urine modification in the urinary tract by the urothelium. It considers the literature and proposes pertinent questions that need to be addressed to understand this phenomenon within a physiological context. Following the ICI-RS meeting, publications in PubMed relating to urine modification in the renal pelvis, ureter, and bladder were reviewed. Historically, the urothelium has been simply considered as a passive, impermeable barrier, preventing contact between urine and the underlying cells. In addition to the ability of the umbrella cells to modify the surface area of the urothelium during bladder filling, the urothelium may also be involved in modifying urine composition. Several lines of evidence support the hypothesis that electrolytes and water can be reabsorbed by the urothelium and that this may have physiological relevance. Firstly, urothelial cells express several types of aquaporins and ion channels; the membrane expression of which is modulated by the extracellular concentration of ions including Na + . Secondly, studies of urine composition in the renal pelvis and bladder demonstrate urine modification, indicating that water and/or electrolyte transport has occurred. Thirdly, hibernating mammals, with urothelial and bladder wall histology similar to non-hibernating mammals are known to produce and reabsorb urine daily, during long periods of hibernation. The phenomenon of urine modification by the urothelium may be physiologically important during normal bladder filling. Research should be focused on investigating how this may change in conditions of urinary dysfunction. © 2017 Wiley Periodicals, Inc.

Modular anode assemblies and methods of using the same for electrochemical reduction

DOEpatents

Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L

2015-02-17

Modular anode assemblies are used in electrolytic oxide reduction systems for scalable reduced metal production via electrolysis. Assemblies include a channel frame connected to several anode rods extending into an electrolyte. An electrical system powers the rods while being insulated from the channel frame. A cooling system removes heat from anode rods and the electrical system. An anode guard attaches to the channel frame to prevent accidental electrocution or damage during handling or repositioning. Each anode rod may be divided into upper and lower sections to permit easy repair and swapping out of lower sections. The modular assemblies may have standardized components to permit placement at multiple points within a reducing system. Example methods may operate an electrolytic oxide reduction system by positioning the modular anode assemblies in the reduction system and applying electrical power to the plurality of anode assemblies.

Electrochemistry-Assisted Top-Down Characterization of Disulfide-Containing Proteins

PubMed Central

Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D.; Chen, Hao

2013-01-01

Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then online ionized into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs. 73 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs. 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research. PMID:22448817

Electrochemistry-assisted top-down characterization of disulfide-containing proteins.

PubMed

Zhang, Yun; Cui, Weidong; Zhang, Hao; Dewald, Howard D; Chen, Hao

2012-04-17

Covalent disulfide bond linkage in a protein represents an important challenge for mass spectrometry (MS)-based top-down protein structure analysis as it reduces the backbone cleavage efficiency for MS/MS dissociation. This study presents a strategy for solving this critical issue via integrating electrochemistry (EC) online with a top-down MS approach. In this approach, proteins undergo electrolytic reduction in an electrochemical cell to break disulfide bonds and then undergo online ionization into gaseous ions for analysis by electron-capture dissociation (ECD) and collision-induced dissociation (CID). The electrochemical reduction of proteins allows one to remove disulfide bond constraints and also leads to increased charge numbers of the resulting protein ions. As a result, sequence coverage was significantly enhanced, as exemplified by β-lactoglobulin A (24 vs 75 backbone cleavages before and after electrolytic reduction, respectively) and lysozyme (5 vs 66 backbone cleavages before and after electrolytic reduction, respectively). This methodology is fast and does not need chemical reductants, which would have an important impact in high-throughput proteomics research.

Electrolytic Reduction of Titania Slag in Molten Calcium Chloride Bath

NASA Astrophysics Data System (ADS)

Mohanty, Jayashree

2012-05-01

Ferro-titanium is prepared by direct electrolytic reduction of titania-rich slag obtained from plasma smelting of ilmenite in molten CaCl2. The product after electro-reduction is characterized by x-ray diffraction, scanning electron microscopy, and electron probe microanalysis. The electrolysis is carried out at a cell voltage of 3.0 V, taking graphite as the electrolysis cell as well as the anode, and a titania-rich slag piece wrapped by a nichrome wire is used as the cathode.

Applications of laser-induced breakdown spectroscopy in the aluminum electrolysis industry

NASA Astrophysics Data System (ADS)

Sun, Lanxiang; Yu, Haibin; Cong, Zhibo; Lu, Hui; Cao, Bin; Zeng, Peng; Dong, Wei; Li, Yang

2018-04-01

The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and corrosive conditions. Monitoring the molten aluminum and electrolyte components is very important for controlling the chemical reaction process. Due to the lack of fast methods to monitor the components, controlling aluminum reduction cells is difficult. In this work, laser-induced breakdown spectroscopy (LIBS) was applied to aluminum electrolysis. A new method for calculating the molecular ratio, which is an important control parameter that represents the acidity of the electrolyte, was proposed. Experiments were first performed on solid electrolyte samples to test the performance of the proposed method. Using this method, the average relative standard deviation (RSD) of the molecular ratio measurement was 0.39%, and the average root mean square error (RMSE) was 0.0236. These results prove that LIBS can accurately measure the molecular ratio. Then, in situ measurements of the molten aluminum and electrolyte were performed in industrial aluminum induction cells using the developed LIBS equipment. The spectra of the molten electrolyte were successfully obtained and were consistent with the spectra of the solid electrolyte.

Topology-based description of the NCA cathode configurational space and an approach of its effective reduction

NASA Astrophysics Data System (ADS)

Zolotarev, Pavel; Eremin, Roman

2018-04-01

Modification of existing solid electrolyte and cathode materialsis a topic of interest for theoreticians and experimentalists. In particular, itrequires elucidation of the influence of dopants on the characteristics of thestudying materials. For the reason of high complexity of theconfigurational space of doped/deintercalated systems, application of thecomputer modeling approaches is hindered, despite significant advances ofcomputational facilities in last decades. In this study, we propose a scheme,which allows to reduce a set of structures of a modeled configurationalspace for the subsequent study by means of the time-consuming quantumchemistry methods. Application of the proposed approach is exemplifiedthrough the study of the configurational space of the commercialLiNi0.8Co0.15Al0.05O2 (NCA) cathode material approximant.

Anode film formation and control

DOEpatents

Koski, Oscar; Marschman, Steven C.

1990-01-01

A protective film is created about the anode within a cryolite-based electrolyte during electrolytic production of aluminum from alumina. The film function to minimize corrosion of the anode by the cryolitic electrolyte and thereby extend the life of the anode. Various operating parameters of the electrolytic process are controlled to maintain the protective film about the anode in a protective state throughout the electrolytic reduction of alumina. Such parameters include electrolyte temperature, electrolyte ratio, current density, and Al.sub.2 O.sub.3 concentration. An apparatus is also disclosed to enable identification of the onset of anode corrosion due to disruption of the film to provide real time information regarding the state of the film.

Anode film formation and control

DOEpatents

Koski, O.; Marschman, S.C.

1990-05-01

A protective film is created about the anode within a cryolite-based electrolyte during electrolytic production of aluminum from alumina. The film functions to minimize corrosion of the anode by the cryolitic electrolyte and thereby extend the life of the anode. Various operating parameters of the electrolytic process are controlled to maintain the protective film about the anode in a protective state throughout the electrolytic reduction of alumina. Such parameters include electrolyte temperature, electrolyte ratio, current density, and Al[sub 2]O[sub 3] concentration. An apparatus is also disclosed to enable identification of the onset of anode corrosion due to disruption of the film to provide real time information regarding the state of the film. 3 figs.

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

PubMed

Azaceta, Eneko; Lutz, Lukas; Grimaud, Alexis; Vicent-Luna, Jose Manuel; Hamad, Said; Yate, Luis; Cabañero, German; Grande, Hans-Jurgen; Anta, Juan A; Tarascon, Jean-Marie; Tena-Zaera, Ramon

2017-04-10

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (M n+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate M n+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of M n+ on oxygen reduction. A case study on the Na-O 2 system is described in detail. Among other things, the Na + concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives.

PubMed

Kalhoff, Julian; Eshetu, Gebrekidan Gebresilassie; Bresser, Dominic; Passerini, Stefano

2015-07-08

Lithium-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mechanical, thermal, or electrical abuse conditions. These safety issues are intrinsically related to their superior energy density, combined with the (present) utilization of highly volatile and flammable organic-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of organic carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather "facile" electrolyte modifications by (partially) replacing the organic solvent or lithium salt and/or the addition of functional electrolyte additives, conceptually new electrolyte systems, including ionic liquids, solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mechanical, thermal, physicochemical, and electrochemical performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Practical high temperature (80 °C) storage study of industrially manufactured Li-ion batteries with varying electrolytes

NASA Astrophysics Data System (ADS)

Genieser, R.; Loveridge, M.; Bhagat, R.

2018-05-01

A previous study is focused on high temperature cycling of industrially manufactured Li-ion pouch cells (NMC-111/Graphite) with different electrolytes at 80 °C [JPS 373 (2018) 172-183]. Within this article the same test set-up is used, with cells stored for 30 days at different open circuit potentials and various electrolytes instead of electrochemical cycling. The most pronounced cell degradation (capacity fade and resistance increase) happens at high potentials. However appropriate electrolyte formulations are able to suppress ageing conditions by forming passivating surface films on both electrodes. Compared with electrochemical cycling at 80 °C, cells with enhanced electrolytes only show a slight resistance increase during storage and the capacity fade is much lower. Additionally it is shown for the first time, that the resistance is decreasing and capacity is regained once these cells are cycled again at room temperature. This is not the case for electrolytes without additives or just vinylene carbonate (VC) as an additive. It is further shown that the resistance increase of cells with the other electrolytes is accompanied by a reduction of the cell volume during further cycling. This behaviour is likely related to the reduction of CO2 at the anode to form additional SEI layer components.

Durable rechargeable zinc-air batteries with neutral electrolyte and manganese oxide catalyst

NASA Astrophysics Data System (ADS)

Sumboja, Afriyanti; Ge, Xiaoming; Zheng, Guangyuan; Goh, F. W. Thomas; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2016-11-01

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm-2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.

Reoxidation of uranium metal immersed in a Li2O-LiCl molten salt after electrolytic reduction of uranium oxide

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Jeon, Min Ku; Lee, Jeong; Kim, Sung-Wook; Lee, Sang Kwon; Lee, Sung-Jai; Heo, Dong Hyun; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok

2017-03-01

We present our findings that uranium (U) metal prepared by using the electrolytic reduction process for U oxide (UO2) in a Li2O-LiCl salt can be reoxidized into UO2 through the reaction between the U metal and Li2O in LiCl. Two salt types were used for immersion of the U metal: one was the salt used for electrolytic reduction, and the other was applied to the unused LiCl salts with various concentrations of Li2O and Li metal. Our results revealed that the degree of reoxidation increases with the increasing Li2O concentration in LiCl and that the presence of the Li metal in LiCl suppresses the reoxidation of the U metal.

Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

PubMed

Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

2018-04-04

Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

Surface Modification of Titanium Using Anodization to Enhance Antimicrobial Properties and Osseointegration

NASA Astrophysics Data System (ADS)

Jain, Sakshi

Titanium and its alloys are frequently used in dental and orthopedic implants because they have good mechanical strength, chemical stability and biocompatibility. These properties can be further improved by surface treatments such as anodization that are able to grow thicker and produce crystalline oxide layers with controlled morphological and physico-chemical properties. Both anatase (A) and rutile (R) crystalline phases of titanium oxide have been shown to promote bioactivity and antimicrobial effects. In a previous study in our laboratories, four electrolyte mixtures were optimized to produce anodized layers on commercially pure titanium consisting of specific anatase and rutile oxide ratios at an endpoint forming voltage of 180 V. In the present study, changes that occurred in the anodized layers with increasing forming voltage including crystallinity, thickness, surface morphology, surface roughness, surface chemistry, fractal dimension, shear strength, and corrosion resistance were determined for each of these electrolytes. The results showed the crystallinity, thickness, surface pore sizes, and surface roughness increased with increasing forming voltage. Incorporation of phosphorus into the anodized layers was shown in phosphoric acid containing electrolytes at higher forming voltages. Decreases in corrosion resistance were also shown at higher forming voltages in each electrolyte due to increased pore interconnectivity within the anodized layers. In addition, the apatite inducing ability of anodized layers in SBF was examined for selected forming voltages in each electrolyte. Anodization in phosphoric acid containing electrolytes was shown to be more favorable for apatite formation. The streptococcal and MRSA bacterial attachment before and after UV treatments was determined for selected forming voltages in each electrolyte. Additionally, the killing efficacy after 10-minute pre-irradiation with UVA or UVC treatments was determined. UVA treatments showed trends of at least a 20% reduction in bacterial attachment regardless of the crystallinity within the oxide for S. sanguinis. The anodized layer with an approximately equal distribution of anatase and rutile phases showed bacterial killing efficacy over 50% for S. sanguinis and over 80% for MRSA after UVA or UVC treatments. Finally, two forming voltage sample groups in two of the electrolytes were examined for MC3T3E-1 cell attachment, proliferation, and differentiation. Total intracellular protein content, alkaline phosphatase (ALP) activity, osteocalcin (OCN) activity, and cellular mineralization were investigated for different time periods up to 21 days. All sample groups showed suitable cellular proliferation, differentiation, and maturation but those anodized in the phosphoric acid containing electrolyte showed delayed proliferation and early differentiation and maturation. Also, anodized samples containing at least 50% anatase were shown to produce higher osteoblast mineralization compared to majority rutile phase anodized layers.

On-line pH modification of carbonate eluents using an electrolytic potassium hydroxide generator for ion chromatography.

PubMed

Novic, Milko; Liu, Yan; Avdalovic, Nebojsa; Pihlar, Boris

2002-05-31

Classical gradient elution, based on the application of a gradient pump used for mixing two or more prepared eluent components in pre-determined concentrations, was replaced by a chromatography system equipped with an isocratic pump and an electrolytic KOH generator. The isocratic pump delivered a constant concentration eluent composed of pure hydrogencarbonate solution. Carbonate ions, the main component of carbonate/hydrogencarbonate-based eluents, were formed by titration of hydrogencarbonate with KOH formed on-line in the electrolytic KOH generator. By changing the concentration of electrolytically-generated KOH, the eluent composition could be changed from pure hydrogencarbonate to a carbonate/hydrogencarbonate buffer, and finally to a carbonate/hydroxide-based eluent. The described system was tested to achieve pH-based changes of retention behavior of phosphate under constant inflow eluent composition conditions.

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

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

1998-01-01

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

Autogenous electrolyte, non-pyrolytically produced solid capacitor structure

DOEpatents

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

1998-03-17

A solid electrolytic capacitor is described having a solid electrolyte comprising manganese dioxide dispersed in an aromatic polyamide capable of further cure to form polyimide linkages, the solid electrolyte being disposed between a first electrode made of valve metal covered by an anodic oxide film and a second electrode opposite the first electrode. The electrolyte autogenously produces water, oxygen, and hydroxyl groups which act as healing substances and is not itself produced pyrolytically. Reduction of the manganese dioxide and the water molecules released by formation of imide linkages result in substantially improved self-healing of anodic dielectric layer defects. 2 figs.

Composition and particle size of electrolytic copper powders prepared in water-containing dimethyl sulfoxide electrolytes

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul'; Abzhalov, B. S.; Mamyrbekova, Aizhan

2017-07-01

The possibility of the electroprecipitation of copper powder via the cathodic reduction of an electrolyte solution containing copper(II) nitrate trihydrate and dimethyl sulfoxide (DMSO) is shown. The effect electrolysis conditions (current density, concentration and temperature of electrolyte) have on the dimensional characteristics of copper powder is studied. The size and shape of the particles of the powders were determined by means of electron microscopy; the qualitative composition of the powders, with X-ray diffraction.

InGaN/GaN quantum dots as optical probes for the electric field at the GaN/electrolyte interface

NASA Astrophysics Data System (ADS)

Teubert, J.; Koslowski, S.; Lippert, S.; Schäfer, M.; Wallys, J.; Dimitrakopulos, G.; Kehagias, Th.; Komninou, Ph.; Das, A.; Monroy, E.; Eickhoff, M.

2013-08-01

We investigated the electric-field dependence of the photoluminescence-emission properties of InGaN/GaN quantum dot multilayers in contact with an electrolyte. Controlled variations of the surface potential were achieved by the application of external electric fields using the electrolytic Schottky contact and by variation of the solution's pH value. Prior to characterization, a selective electrochemical passivation process was required to suppress leakage currents. The quantum dot luminescence is strongly affected by surface potential variations, i.e., it increases exponentially with cathodic bias and acidic pH values. The results cannot be explained by a modification of intra-dot polarization induced electric fields via the quantum confined Stark effect but are attributed to the suppression/enhancement of non-radiative recombination processes, i.e., mainly hole transfer into the electrolyte. The results establish a link between the photoluminescence intensity and the magnitude of electric fields at the semiconductor/electrolyte interface.

Surface and capillary forces encountered by zinc sulfide microspheres in aqueous electrolyte.

PubMed

Gillies, Graeme; Kappl, Michael; Butt, Hans-Jürgen

2005-06-21

The colloid probe technique was used to investigate the interactions between individual zinc sulfide (ZnS) microspheres and an air bubble in electrolyte solution. Incorporation of zinc ions into the electrolyte solution overcomes the disproportionate zinc ion dissolution and mimics high-volume-fraction conditions common in flotation. Determined interaction forces revealed a distinct lack of long-ranged hydrophobic forces, indicated by the presence of a DLVO repulsion prior to particle engulfment. Single microsphere contact angles were determined from particle-bubble interactions. Contact angles increased with decreasing radii and with surface oxidation. Surface modification by the absorption of copper and subsequently potassium O-ethyldithiocarbonate (KED) reduced repulsive forces and strongly increased contact angles.

High power bipolar battery/cells with enhanced overcharge tolerance

DOEpatents

Kaun, T.D.

1998-04-07

A cell or battery of cells having improved overcharge tolerance and increased power capability, and methods for the construction of such cells or batteries, via electrolyte modification, are described. 5 figs.

Modeling Joule Heating Effect on Lunar O2 Generation via Electrolytic Reduction.

NASA Technical Reports Server (NTRS)

Dominquez, Jesus; Poizeau, Sophie; Sibille, Laurent

2009-01-01

Kennedy Space Center is leading research work on lunar O2 generation via electrolytic reduction of regolith; the metal oxide present in the regolith is dissociated in oxygen anions and metal cations leading to the generation of gaseous oxygen at the anode and liquid metal at the cathode. Electrical resistance of molten regolith is high, leading to heating of the melt when electrical current is applied between the electrodes (Joule heating). The authors have developed a 3D model using a rigorous approach for two coupled physics (thermal and electrical potential) to not only study the effect of Joule heating on temperature distribution throughout the molten regolith but also to evaluate and optimize the design of the electrolytic cells. This paper presents the results of the thermal analysis performed on the model and used to validate the design of the electrolytic cell.

Development status of a preprototype water electrolysis subsystem

NASA Technical Reports Server (NTRS)

Martin, R. B.; Erickson, A. C.

1981-01-01

A preprototype water electrolysis subsystem was designed and fabricated for NASA's advanced regenerative life support program. A solid polymer is used for the cell electrolyte. The electrolysis module has 12 cells that can generate 5.5 kg/day of oxygen for the metabolic requirements of three crewmembers, for cabin leakage, and for the oxygen and hydrogen required for carbon dioxide collection and reduction processes. The subsystem can be operated at a pressure between 276 and 2760 kN/sq m and in a continuous constant-current, cyclic, or standby mode. A microprocessor is used to aid in operating the subsystem. Sensors and controls provide fault detection and automatic shutdown. The results of development, demonstration, and parametric testing are presented. Modifications to enhance operation in an integrated and manned test are described. Prospective improvements for the electrolysis subsystem are discussed.

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

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

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE PAGES

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.; ...

2016-12-12

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Tunable Molecular-Scale Materials for Catalyzing the Low-Overpotential Electrochemical Conversion of CO2.

PubMed

Rosen, Brian A; Hod, Idan

2018-04-25

Electrochemical CO 2 reduction provides a clean and viable alternative for mitigating the environmental aspects of global greenhouse gas emissions. To date, the simultaneous goals of CO 2 reduction at high selectivity and activity have yet to be achieved. Here, the importance of engineering both sides of the electrode-electrolyte interface as a rational strategy for achieving this milestone is highlighted. An emphasis is placed on researchers contributing to the design of solid electrodes based on metal-organic frameworks (MOFs) and electrolytes based on room-temperature ionic liquids (RTILs). Future research geared toward optimizing the electrode-electrolyte interface for efficient and selective CO 2 reduction can be achieved by understanding the structure of newly designed RTILs at the electrified interface, as well as structure-activity relationships in highly tunable MOF platforms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pyroprocessing of Oxidized Sodium-Bonded Fast Reactor Fuel -- an Experimental Study of Treatment Options for Degraded EBR-II Fuel

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

S. D. Herrmann; L. A. Wurth; N. J. Gese

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electrometallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li2O at 650 °C with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide. The experimentalmore » study illustrated how zirconium oxide and sodium oxide present different challenges to a lithium-based electrolytic reduction system for conversion of select metal oxides to metal.« less

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-01-23

A method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-02-13

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Cosolvent electrolytes for electrochemical devices

DOEpatents

Wessells, Colin Deane; Firouzi, Ali; Motallebi, Shahrokh; Strohband, Sven

2018-05-15

A system and method for stabilizing electrodes against dissolution and/or hydrolysis including use of cosolvents in liquid electrolyte batteries for three purposes: the extension of the calendar and cycle life time of electrodes that are partially soluble in liquid electrolytes, the purpose of limiting the rate of electrolysis of water into hydrogen and oxygen as a side reaction during battery operation, and for the purpose of cost reduction.

Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.; ...

2016-12-01

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less

Understanding and controlling the rest potential of carbon nanotube-based supercapacitors for energy density enhancement

NASA Astrophysics Data System (ADS)

Yoo, Young-Eun; Park, Jinwoo; Kim, Woong

2018-03-01

We present a novel method for enhancing the energy density of an electrical double layer capacitor (EDLC). Surface modification of single-walled carbon nanotube (SWNT) electrodes significantly affects the rest potential (E0) of EDLCs; acid treatment and polyethyleneimine (PEI) coating of SWNTs shift E0 toward more positive and more negative values, respectively. Adjusting E0 towards the center of the electrolyte stability window can increase the cell voltage and hence the energy density. PEI coating on SWNTs increases the cell voltage from 0.8 V to 1.7 V in tetrabutylammonium perchlorate (TBAP)/tetrahydrofuran (THF) electrolyte, and from 2.5 V to 3.1 V in tetraethylammonium tetrafluoroborate (TEABF4)/3-cyanopropionic acid methyl ester (CPAME), respectively. Moreover, PEI-SWNT EDLCs exhibit excellent cycling stability (92% of capacitance retention over 10000 cycles). We attribute the shift in E0 to a change in the Fermi level of SWNTs owing to the surface charge modification. Injection of electrical charge into PEI-SWNTs consistently yielded similar trends and thus validated our hypothesis. Our results may help to push various electrolytes that have been overlooked so far to new frontiers for obtaining high energy-density supercapacitors.

Synthesis and Characterization of Cellulose-Based Hydrogels to Be Used as Gel Electrolytes

PubMed Central

Navarra, Maria Assunta; Dal Bosco, Chiara; Serra Moreno, Judith; Vitucci, Francesco Maria; Paolone, Annalisa; Panero, Stefania

2015-01-01

Cellulose-based hydrogels, obtained by tuned, low-cost synthetic routes, are proposed as convenient gel electrolyte membranes. Hydrogels have been prepared from different types of cellulose by optimized solubilization and crosslinking steps. The obtained gel membranes have been characterized by infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, and mechanical tests in order to investigate the crosslinking occurrence and modifications of cellulose resulting from the synthetic process, morphology of the hydrogels, their thermal stability, and viscoelastic-extensional properties, respectively. Hydrogels liquid uptake capability and ionic conductivity, derived from absorption of aqueous electrolytic solutions, have been evaluated, to assess the successful applicability of the proposed membranes as gel electrolytes for electrochemical devices. To this purpose, the redox behavior of electroactive species entrapped into the hydrogels has been investigated by cyclic voltammetry tests, revealing very high reversibility and ion diffusivity. PMID:26633528

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

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

Small, Leo J.; Pratt, Harry; Staiger, Chad

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Specific detection of membrane-toxic substances with a conductivity assay.

PubMed

Eich, J; Dürholt, H; Steger-Hartmann, T; Wagner, E

2000-03-01

A conductivity assay that represents a new biotest able to detect the effects of membrane-toxic compounds, e.g., detergents, organic solvents, and radical formers, on various organisms was previously described and developed. The conductivity assay measures ion leakage from cells, tissues, or whole plant and animal organisms whose membrane systems have been damaged by membrane-toxic compounds. In this study the specificity of the conductivity assay for membrane-toxic compounds was tested by comparing the electrolyte efflux from Elodea canadensis leaves during incubation with a well-known detergent (benzalkonium chloride) using different plant physiological and biochemical techniques (photochemical efficiency, plasmolysis capacity, NBT reduction, and electron microscopy of membranes of E. canadensis leaves). The comparison of the different methods proved that the electrolyte loss during benzalkonium chloride incubation determined in the conductivity assay is due to membrane impairment. The observed electrolyte loss correlated with a reduction of photochemical efficiency and a decrease in both plasmolysis and NBT reduction capacity. Furthermore, a disintegration of the plasmalemma could be seen in the electron micrographs. These results indicate that the measured electrolyte loss in the conductivity assay is a specific effect of membrane-toxic compounds. Copyright 2000 Academic Press.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Curvature in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Li, Wenxia; Hasinska, Kathy; Seabaugh, Matt; Swartz, Scott; Lannutti, John

At this point in history, curvature is inherent to the laminated components that comprise solid oxide fuel cells (SOFCs). Surprisingly, however, this fact has never been previously quantified in the literature. In addition, potential curvature changes associated with NiO reduction and re-oxidation during operation have not been investigated. In this report, an optical profilometer was employed to non-destructively quantify the surface curvature or cracking behavior observed on a large scale in industrially manufactured cells. This provides insights into the challenges that the component materials face as well as additional appreciation for why, in spite of a concerted effort to commercialize SOFC power generation, all currently manufactured SOFC stacks fail. Our results demonstrate that cracked electrolyte areas (caused by differential sintering) are flatter than uncracked regions. The height of the electrolyte surface ranged from 86 to 289 μm above the baseline following sintering. Reduction typically results in increases in curvature of up to 214 μm. Initial crack density appears to affect curvature evolution during reduction; the higher the crack density, the smaller the curvature increase following reduction at 600 °C. In general, however, we observed that the electrolyte layer is remarkably resistant to further cracking during these typographic changes. Following oxidation at 750 °C, large changes in curvature (up to 280 μm) are noted that appear to be related to the strength of the bond between the electrolyte and the underlying anode.

Characterizing the surface charge of synthetic nanomembranes by the streaming potential method

PubMed Central

Datta, Subhra; Conlisk, A. T.; Kanani, Dharmesh M.; Zydney, Andrew L.; Fissell, William H.; Roy, Shuvo

2010-01-01

The inference of the surface charge of polyethylene glycol (PEG)-coated and uncoated silicon membranes with nanoscale pore sizes from streaming potential measurements in the presence of finite electric double layer (EDL) effects is studied theoretically and experimentally. The developed theoretical model for inferring the pore wall surface charge density from streaming potential measurements is applicable to arbitrary pore cross-sectional shapes and accounts for the effect of finite salt concentration on the ionic mobilities and the thickness of the deposited layer of PEG. Theoretical interpretation of the streaming potential data collected from silicon membranes having nanoscale pore sizes, with/without pore wall surface modification with PEG, indicates that finite electric double layer (EDL) effects in the pore-confined electrolyte significantly affect the interpretation of the membrane charge and that surface modification with PEG leads to a reduction in the pore wall surface charge density. The theoretical model is also used to study the relative significance of the following uniquely nanoscale factors affecting the interpretation of streaming potential in moderate to strongly charged pores: altered net charge convection by applied pressure differentials, surface-charge effects on ionic conduction, and electroosmotic convection of charges. PMID:20462592

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Nanopipette delivery: influence of surface charge.

PubMed

Shi, Wenqing; Sa, Niya; Thakar, Rahul; Baker, Lane A

2015-07-21

In this report, transport through a nanopipette is studied and the interplay between current rectification and ion delivery for small pipettes is examined. First, surface charge dependence of concentration polarization effects in a quartz nanopipette was investigated. Electrical characterization was performed through current-potential (I-V) measurements. In addition, fluorescein (an anionic fluorescent probe) was utilized to optically map ion enrichment and ion depletion in the nanopipette tip. Bare nanopipettes and polyethylenimine (PEI)-modified nanopipettes were examined. Results confirm that concentration polarization is a surface charge dependent phenomenon and delivery can be controlled through modification of surface charge. The relationship between concentration polarization effects and voltage-driven delivery of charged electroactive species was investigated with a carbon ring/nanopore electrode fabricated from pyrolyzed parylene C (PPC). Factors such as surface charge polarity of the nanopipette, electrolyte pH, and electrolyte concentration were investigated. Results indicate that with modification of surface charge, additional control over delivery of charged species can be achieved.

Preparation of superhydrophobic titanium surfaces via electrochemical etching and fluorosilane modification

NASA Astrophysics Data System (ADS)

Lu, Yao; Xu, Wenji; Song, Jinlong; Liu, Xin; Xing, Yingjie; Sun, Jing

2012-12-01

The preparation of superhydrophobic surfaces on hydrophilic metal substrates depends on both surface microstructures and low surface energy modification. In this study, a simple and inexpensive electrochemical method for preparing robust superhydrophobic titanium surfaces is reported. The neutral sodium chloride solution is used as electrolyte. Fluoroalkylsilane (FAS) was used to reduce the surface energy of the electrochemically etched surface. Scanning electron microscopy (SEM) images, energy-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) spectra, and contact angle measurement are performed to characterize the morphological features, chemical composition, and wettability of the titanium surfaces. Stability and friction tests indicate that the prepared titanium surfaces are robust. The analysis of electrolyte, reaction process, and products demonstrates that the electrochemical processing is very inexpensive and environment-friendly. This method is believed to be easily adaptable for use in large-scale industry productions to promote the application of superhydrophobic titanium surfaces in aviation, aerospace, shipbuilding, and the military industry.

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

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

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

DOUBLE-BAKED, SELF-CHANNELLING ELECTRODE

DOEpatents

Piper, R.D.; Leifield, R.F.

1963-03-12

A method is given for making an electrode for use in the electrolytic reduction of uranium oxides to uranium metal in a fused salt electrolyte. Uranlum oxide such as UO/sub 2/ is mixed with somewhat less than the stoichiometric amount of carbon needed for the reduction, and the mixture is baked and crushed to make a nonspherical material. The latter is then mixed with a carbon binder sufficient to satisfy stoichiometry, pressed into a shape such as a cylinder, and baked. (AEC)

Complete reduction of high-density UO2 to metallic U in molten Li2O-LiCl

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Lee, Jeong

2017-10-01

The large size and high density of spent fuel pellets make it difficult to use the pellets directly in electrolytic reduction (also called as oxide reduction, OR) for pyroprocessing owing to the slow diffusion of molten Li2O-LiCl salt electrolyte into the pellets. In this study, we investigated complete OR of high-density UO2 to metallic U without any remaining UO2. Only partial reductions near the surface of high-density UO2 pellets were observed under operation conditions employing fast electrolysis rate that allowed previously complete reduction of low-density UO2 pellets. Complete reduction of high-density UO2 pellets was observed at fast electrolysis rate when the pellet size was reduced. The complete reduction of high-density UO2 pellets without size reduction was achieved at slow electrolysis rate, which allowed sufficient chemical reduction of UO2 with the lithium metal generated by the cathode reaction.

The Electrolyte Factor in O2 Reduction Electrocatalysis

DTIC Science & Technology

1993-04-23

molecule thick and does not seem to interfere with 02 and water/proton transport at this interface. This layer resembles a self-ordered Langmuir - Blodgett ... liquid electrolyte from within the polymer is in contact with the catalyst and completes the ionic circuit between the ionic conducting polymer and the...the free energy of adsorption of H2 0 and ionic components because of the lower effective dielectric constant in the electrolyte phase immediately

Solvent decompositions and physical properties of decomposition compounds in Li-ion battery electrolytes studied by DFT calculations and molecular dynamics simulations.

PubMed

Tasaki, Ken

2005-02-24

The density functional theory (DFT) calculations have been performed for the reduction decompositions of solvents widely used in Li-ion secondary battery electrolytes, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonates (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC), including a typical electrolyte additive, vinylene carbonate (VC), at the level of B3LYP/6-311+G(2d,p), both in the gas phase and solution using the polarizable conductor calculation model. In the gas phase, the first electron reduction for the cyclic carbonates and for the linear carbonates is found to be exothermic and endothermic, respectively, while the second electron reduction is endothermic for all the compounds examined. On the contrary, in solution both first and second electron reductions are exothermic for all the compounds. Among the solvents and the additive examined, the likelihood of undergoing the first electron reduction in solution was found in the order of EC > PC > VC > DMC > EMC > DEC with EC being the most likely reduced. VC, on the other hand, is most likely to undergo the second electron reduction among the compounds, in the order of VC > EC > PC. Based on the results, the experimentally demonstrated effectiveness of VC as an excellent electrolyte additive was discussed. The bulk thermodynamic properties of two dilithium alkylene glycol dicarbonates, dilithium ethylene glycol dicarbonate (Li-EDC) and dilithium 1,2-propylene glycol dicarbonate (Li-PDC), as the major component of solid-electrolyte interface (SEI) films were also examined through molecular dynamics (MD) simulations in order to understand the stability of the SEI film. It was found that film produced from a decomposition of EC, modeled by Li-EDC, has a higher density, more cohesive energy, and less solubility to the solvent than the film produced from decomposition of PC, Li-PDC. Further, MD simulations of the interface between the decomposition compound and graphite suggested that Li-EDC has more favorable interactions with the graphite surface than Li-PDC. The difference in the SEI film stability and the behavior of Li-ion battery cycling among the solvents were discussed in terms of the molecular structures.

The lithium storage performance of electrolytic-carbon from CO2

NASA Astrophysics Data System (ADS)

Tang, Juanjuan; Deng, Bowen; Xu, Fei; Xiao, Wei; Wang, Dihua

2017-02-01

Sustainable and affordable energy resources are urgently demanded to mitigate environmental issues. Herein, carbon materials, prepared by electrochemical reduction of greenhouse gas, CO2, in Li-Na-K carbonate molten salts (electrolytic-carbon), are tested as negative electrode materials for Li-ion batteries. Owing to the small particle size and suitable surface area, the electrolytic-carbon exhibits a high reversible capacity of 798 mAh g-1 (more than two times of graphites' theoretical capacity) at 50 mA g-1 and 266 mAh g-1 with a stable cyclability over 500 cycles at a current density up to 500 mA g-1, as well as remarkable rate performance. Furthermore, a comprehensively study was conducted to investigate the effects of electrolysis temperature and cell voltage on the electrochemical performance of the electrolytic-carbon. These results demonstrate a promising strategy to develop renewable high-performance carbon negative electrode materials for Li-ion batteries by molten salt capture and electrochemical reduction of CO2.

Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes

DOE PAGES

Baskin, Artem; Prendergast, David

2016-02-05

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Methods and electrolytes for electrodeposition of smooth films

DOEpatents

Zhang, Jiguang; Xu, Wu; Graff, Gordon L; Chen, Xilin; Ding, Fei; Shao, Yuyan

2015-03-17

Electrodeposition involving an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and/or film surface. For electrodeposition of a first conductive material (C1) on a substrate from one or more reactants in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second conductive material (C2), wherein cations of C2 have an effective electrochemical reduction potential in the solution lower than that of the reactants.

Highly uniform and monodisperse carbon nanospheres enriched with cobalt-nitrogen active sites as a potential oxygen reduction electrocatalyst

NASA Astrophysics Data System (ADS)

Wan, Xing; Wang, Hongjuan; Yu, Hao; Peng, Feng

2017-04-01

Uniform cobalt and nitrogen co-doped carbon nanospheres (CoN-CNS) with high specific surface area (865 m2 g-1) have been prepared by a simple but efficient method. The prepared CoN-CNS catalyst exhibits outstanding catalytic performance for the oxygen reduction reaction (ORR) in both alkaline and acidic electrolytes. In alkaline electrolyte, the prepared CoN-CNS has more positive half-wave potential and larger kinetic current density than commercial Pt/C. In acidic electrolyte, CoN-CNS also shows good ORR activity with high electron transfer number, its onset and half-wave potentials are all close to those of commercial carbon supported platinum catalyst (Pt/C). CoN-CNS catalyst shows more superior stability and higher methanol-tolerance than commercial Pt/C both in alkaline and in acidic electrolytes. The potassium thiocyanate-poisoning test further confirms that the cobalt-nitrogen active sites exist in CoN-CNS, which are dominating to endow high ORR catalytic activity in acidic electrolyte. This study develops a new method to prepare non-precious metal catalyst with excellent ORR performances for direct methanol fuel cells.

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-01

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

DOEpatents

Bailey, James L.; Barnes, Laurel A.; Wiedmeyer, Stanley G.; Williamson, Mark A.; Willit, James L.

2014-07-08

An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies and an anode shroud for each of the anode assemblies. The anode shroud may be used to dilute, cool, and/or remove off-gas from the electrolytic oxide reduction system. The anode shroud may include a body portion having a tapered upper section that includes an apex. The body portion may have an inner wall that defines an off-gas collection cavity. A chimney structure may extend from the apex of the upper section and be connected to the off-gas collection cavity of the body portion. The chimney structure may include an inner tube within an outer tube. Accordingly, a sweep gas/cooling gas may be supplied down the annular space between the inner and outer tubes, while the off-gas may be removed through an exit path defined by the inner tube.

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes.

PubMed

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-21

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

Fluid-electrolyte shifts and maximal oxygen uptake in man at simulated altitude /2,287 m/

NASA Technical Reports Server (NTRS)

Greenleaf, J. E.; Bernauer, E. M.; Adams, W. C.; Juhos, L.

1978-01-01

Experiments were conducted on six trained distance runners (21-23 yr) subjected to an eight-day dietary control at sea level, followed by an eight-day stay in an altitude chamber (2287-m altitude) and a four-day recovery at sea level. Fluid and electrolyte shifts during exercise at altitude were evaluated to gain insight into the mechanism of reduction in working capacity. The results are discussed in terms of resting fluid volumes and blood constituents, maximal exercise variables, and maximal exercise fluid-electrolyte shifts. Since there are no significant changes in fluid balance or resting plasma volume (PV) at altitude, it is concluded that neither these nor the excessive PV shifts with exercise contribute to the reduction in maximal oxygen uptake at altitude. During altitude exposure the percent loss in PV is found to follow the percent reduction in maximal oxygen uptake; however, on the first day of recovery the percent change in PV remains depressed while maximal oxygen uptake returns to control levels.

High Rate Oxygen Reduction in Non-aqueous Electrolytes with the Addition of Perfluorinated Additives

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

Wang, Y.; Yang, X.; Zheng, D.

2011-08-04

The discharge rate capability of Li-air batteries is substantially increased by using perfluorinated compounds as oxygen carriers. The solubility of oxygen in a non-aqueous electrolyte can be significantly increased by the introduction of such compounds, which leads to the increase in the diffusion-limited current of oxygen reduction on the gas diffusion electrode in a Li-air battery. The perfluorinated compound is found to be stable within the electrochemical window of the electrolyte. A powder microelectrode and a rotating disk electrode were used to study the gas diffusion-limited current together with a rotating disk electrode. A 5 mA cm{sup -2} discharge ratemore » is demonstrated in a lab Li-O{sub 2} cell.« less

Richland five-year O2 R and D Program. Integrated site operation

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

Not Available

1966-07-11

The technical feasibility of using an electrolytic reduction process to reduce metal scrap and oxide to usable uranium metal is being studied. The incentives for using electrolytic reduction at Richland may be summarized as follows: (1) reduce the unit and total costs of producing plutonium; (2) increase the flexibility of the Richland reactors for producing isotopes, particularly U-236; and (3) simplify the present fuel cycle complex. The scope of the mission is limited to the evaluation of hollow extruded I and E cores, the evaluation of electro-reduced uranium, an investigation of the solution rate of UO{sub 2} in the electrolyte,more » and small-scale irradiations of UO{sub 2} fuels in the N and K Reactors. Progress during FY 1966 is summarized.« less

Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

PubMed

Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

2016-03-01

Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

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

Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon

Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which aremore » anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.« less

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

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less

A novel carbon electrode material for highly improved EDLC performance.

PubMed

Fang, Baizeng; Binder, Leo

2006-04-20

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.

Development of Lithium Dimethyl Phosphate as an Electrolyte Additive for Lithium Ion Batteries

DOE PAGES

Milien, Mickdy S.; Tottempudi, Usha; Son, Miyoung; ...

2016-04-27

The novel electrolyte additive lithium dimethyl phosphate (LiDMP) has been synthesized and characterized. Incorporation of LiDMP (0.1% wt) into LiPF 6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC) (3:7 wt) results in improved rate performance and reduced impedance for graphite / LiNi 1/3Mn 1/3Co 1/3O 2 cells. Ex-situ surface analysis of the electrodes suggests that incorporation of LiDMP results in a modification of the solid electrolyte interphase (SEI) on the anode. A decrease in the concentration of lithium alkyl carbonates and an increase in the concentration of lithium fluoro phosphates are observed. The change in the anode SEImore » structure is responsible for the increased rate performance and decreased cell impedance.« less

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.

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.

Blood volume regulating hormones, fluid and electrolyte modifications during 21 and 198-day space flights (Altair-MIR 1993)

NASA Astrophysics Data System (ADS)

Vorobiev, D.; Maillet, A.; Fortrat, J. O.; Pastushkova, L.; Allevard, A. M.; Sigaudo, D.; Cartier, R.; Patricot, M.; Andre-Deshays, C.; Kotovskaya, A.; Grigoriev, A.; Gharib, C.; Gauquelin, G.

During the Altair MIR' 93 mission we studied several parameters involved in blood volume regulation. The experiment was done on two cosmonauts before (B-60, B-30), during (D6, D12, D18 for French and D7, D12, D17 for Russian) and after the flight (R+1, R+3 and R+7). Space flight durations were different for two cosmonauts: for the Russian the flight duration was 198 days and for the French 21 days. On board the MIR station only urinary (volume and electrolytes, atrial natriuretic peptide (ANP), cyclic guanosine monophosphate (cGMP) and catecholamines) and salivary (cGMP and cortisol) samples were collected, centrifuged and stored in freezer. Lithium was used as a tracer to know exactly the 24 h urine output (CNES urine collection Kit). Before and after flight, blood was drawn with an epicite needle and vacutainer system for hormonal assays (renin, antidiuretic hormone, cGMP, ANP and aldosterone) in two positions: after 30 min rest in upright seated position and after 90 min of supine position. Salivary samples were collected simultaneously. During flight a decrease of diuresis and ANP and an increase of osmolality were found. No modifications of hematocrit, but an increase of salivary cGMP and cortisol were also observed. The decrease of urinary ANP is in favor of hypovolemia as described in previous flights. The postflight examinations revealed changes in fluid-electrolyte metabolism which indicate a hypohydration status and a stimulation of hormonal system responsible for water and electrolyte retention in order to readapt to the normal gravity.

Functional interface of polymer modified graphite anode

NASA Astrophysics Data System (ADS)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

Electrochemical performance and thermal stability analysis of LiNixCoyMnzO2 cathode based on a composite safety electrolyte.

PubMed

Jiang, Lihua; Wang, Qingsong; Sun, Jinhua

2018-06-05

LiNi x Co y Mn z O 2 (NCM) cathode material with high energy density is one of the best choices for power batteries. But the safety issue also becomes more prominent with higher nickel content. The improvement of thermal stability by material modification is often complex and limited. In this study, a composite safety electrolyte additive consisting of perfluoro-2-methyl-3-pentanone, N, N-Dimethylacetamide (and fluorocarbon surfactant is proved to be effective and simple in improving the thermal stability of NCM materials. Electrochemical compatibility of composite safety electrolyte with various NCM materials is investigated. Uniform interface film, lower impedance and polarization for NCM (622) cycled in composite safety electrolyte are proved to be the main reasons to ensure good cycle performance. Homemade pouch cells (NCM (622)/C) are used to verify the effectiveness for practical application, accelerating rate calorimeter and nail penetration test shows a slower temperature rise and delay of thermal runaway. For heating experiment, no fire appears for pouch cell with composite safety electrolyte. Thus, this composite safety electrolyte is effective to improve the safety of lithium ion batteries with NCM materials.(. Copyright © 2018 Elsevier B.V. All rights reserved.

Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte.

PubMed

Garner, Logan E; Steirer, K Xerxes; Young, James L; Anderson, Nicholas C; Miller, Elisa M; Tinkham, Jonathan S; Deutsch, Todd G; Sellinger, Alan; Turner, John A; Neale, Nathan R

2017-02-22

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2 ) illumination resulting from the covalently bound surface dipole. Though X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aluminum reference electrode

DOEpatents

Sadoway, Donald R.

1988-01-01

A stable reference electrode for use in monitoring and controlling the process of electrolytic reduction of a metal. In the case of Hall cell reduction of aluminum, the reference electrode comprises a pool of molten aluminum and a solution of molten cryolite, Na.sub.3 AlF.sub.6, wherein the electrical connection to the molten aluminum does not contact the highly corrosive molten salt solution. This is accomplished by altering the density of either the aluminum (decreasing the density) or the electrolyte (increasing the density) so that the aluminum floats on top of the molten salt solution.

Electrolytic oxide reduction system

DOEpatents

Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L; Berger, John F

2015-04-28

An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies, a plurality of cathode assemblies, and a lift system configured to engage the anode and cathode assemblies. The cathode assemblies may be alternately arranged with the anode assemblies such that each cathode assembly is flanked by two anode assemblies. The lift system may be configured to selectively engage the anode and cathode assemblies so as to allow the simultaneous lifting of any combination of the anode and cathode assemblies (whether adjacent or non-adjacent).

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

DOE PAGES

Mani, Tomoyasu; Grills, David C.; Miller, John R.

2015-01-02

A recently-developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ν(C≡N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion-pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion-pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion-pairing. As a result, this new method has the potential to probe the geometry of ion-pairing and allows the reduction potentials of moleculesmore » to be determined in the absence of electrolyte in an environment of low dielectric constant.« less

One-step large-scale synthesis of micrometer-sized silver nanosheets by a template-free electrochemical method

NASA Astrophysics Data System (ADS)

Park, Sun Hwa; Son, Jin Gyeong; Lee, Tae Geol; Park, Hyun Min; Song, Jae Yong

2013-05-01

We have synthesized micrometer-sized Ag nanosheets via a facile, one-step, template-free electrochemical deposition in an ultra-dilute silver nitrate aqueous electrolyte. The nanosheet growth was revealed to occur in three stages: (1) formation of polygonal Ag nuclei on a substrate, (2) growth of {112}-faceted nanowire from the nuclei, and (3) anisotropic growth of (111)-planar nanosheets, approximately 20 to 50 nm in thickness and 10 μm in width, in the <112>-direction. The vertical growth of the facet nanowire was induced by the strong interface anisotropy between the deposit and electrolyte due to the ultra-dilute concentration of electrolyte and high reduction potential. The thickness of Ag nanosheets was controllable by the adjustment of the reduction/oxidation potential and frequency of the reverse-pulse potentiodynamic mode.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

New Insights into the Electroreduction of Ethylene Sulfite as Electrolyte Additive for Facilitating Solid Electrolyte Interphase of Lithium Ion Battery

PubMed Central

Sun, Youmin; Wang, Yixuan

2017-01-01

To help understand the solid electrolyte interphase (SEI) formation facilitated by electrolyte additives of lithium-ion batteries (LIB) the supermolecular clusters [(ES)Li+(PC)m](PC)n (m=1–2; n=0, 6, and 9) were used to investigate the electroreductive decompositions of the electrolyte additive, ethylene sulfite (ES), as well as the solvent, propylene carbonate (PC) with density functional theory. The results show that ES can be reduced prior to PC, resulting in a reduction precursor that will then undergo a ring opening decomposition to yield a radical anion. A new concerted pathway (path B) was located for the ring opening of the reduced ES, which has much lower energy barrier than the previously reported stepwise pathway (path A). The transition state for the ring opening of PC induced by the reduced ES (path C, indirect path) is closer to that of path A than path B in energy. The direct ring opening of the reduced PC (path D) has lower energy barrier than those of paths A, B and C, yet it is less favorable than the latter paths in terms of thermodynamics (vertical electron affinity or the reduction potential dissociation energy). The overall rate constant including the initial reduction and the subsequent ring opening for path B is the largest among the four paths, followed by paths A>C>D, which further signifies the importance of the concerted new path in facilitating the SEI. The hybrid models, the supermolecular cluster augmented by polarized continuum model, PCM-[(ES)Li+(PC)2](PC)n (n=0,6, and 9), were used to further estimate the reduction potential by taking into account both explicit and implicit solvent effects. The second solvation shell of Li+ in [(ES)Li+(PC)2](PC)n (n=6, and 9) partially compensates the overestimation of solvent effects arising from the PCM model for the naked (ES)Li+(PC)2, and the theoretical reduction potential with PCM-[(ES)Li+(PC)2](PC)6 (1.90–1.93V) agrees very well with the experimental one (1.8–2.0V). PMID:28220165

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

PubMed

Sun, Youmin; Wang, Yixuan

2017-03-01

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

Electrolytic production of high purity aluminum using inert anodes

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Jr., Douglas A.

2001-01-01

A method of producing commercial purity aluminum in an electrolytic reduction cell comprising inert anodes is disclosed. The method produces aluminum having acceptable levels of Fe, Cu and Ni impurities. The inert anodes used in the process preferably comprise a cermet material comprising ceramic oxide phase portions and metal phase portions.

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

PubMed

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

2016-10-12

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

Surface degradation of Li1-xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations

NASA Astrophysics Data System (ADS)

Sallis, S.; Pereira, N.; Mukherjee, P.; Quackenbush, N. F.; Faenza, N.; Schlueter, C.; Lee, T.-L.; Yang, W. L.; Cosandey, F.; Amatucci, G. G.; Piper, L. F. J.

2016-06-01

The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1-xNi0.8Co0.15Al0.05O2 binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li+ extraction is driving the rise in impedance.

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

PubMed

Xiao, Wei; Wang, Dihua

2014-05-21

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

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

DOE PAGES

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra; ...

2017-07-24

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

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

Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra

The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably formore » HCOO –, C 2H 4, and C 2H 5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO 2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. As a result, the observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.« less

Additive effect on reductive decomposition and binding of carbonate-based solvent toward solid electrolyte interphase formation in lithium-ion battery.

PubMed

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

2013-08-14

The solid-electrolyte interphase (SEI) formed through the reductive decomposition of solvent molecules plays a crucial role in the stability and capability of a lithium-ion battery (LIB). Here we investigated the effects of adding vinylene carbonate (VC) to ethylene carbonate (EC) solvent, a typical electrolyte in LIBs, on the reductive decomposition. We focused on both thermodynamics and kinetics of the possible processes and used density functional theory-based molecular dynamics with explicit solvent and Blue-moon ensemble technique for the free energy change. We considered Li(+) in only EC solvent (EC system) and in EC solvent with a VC additive (EC/VC system) to elucidate the additive effects. In addition to clarifying the equilibrium properties, we evaluated the free energy changes along several EC or VC decomposition pathways under one-electron (1e) reduction condition. Two-electron (2e) reduction and attacks of anion radicals to intact molecules were also examined. The present results completely reproduce the gaseous products observed in the experiments. We also found a new mechanism involving the VC additive: the VC additive preferentially reacts with the EC anion radical to suppress the 2e reduction of EC and enhance the initial SEI formation, contrary to the conventional scenario in which VC additive is sacrificially reduced and its radical oligomerization becomes the source of SEI. Because our mechanism needs only 1e reduction, the irreversible capacity at the SEI formation will decrease, which is also consistent with the experimental observations. These results reveal the primary role of VC additive in the EC solvent.

Low temperature aluminum reduction cell using hollow cathode

DOEpatents

Brown, Craig W.; Frizzle, Patrick B.

2002-08-20

A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte. A plurality of non-consumable anodes are disposed substantially vertically in the electrolyte along with a plurality of monolithic hollow cathodes. Each cathode has a top and bottom and the cathodes are disposed vertically in the electrolyte and the anodes and the cathodes are arranged in alternating relationship. Each of the cathodes is comprised of a first side facing a first opposing anode and a second side facing a second opposing anode. The first and second sides are joined by ends to form a reservoir in the hollow cathode for collecting aluminum therein deposited at the cathode.

Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

NASA Astrophysics Data System (ADS)

Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

2017-02-01

The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

High-Energy-Density Electrolytic Capacitors

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S.; Lewis, Carol R.

1993-01-01

Reductions in weight and volume make new application possible. Supercapacitors and improved ultracapacitors advanced electrolytic capacitors developed for use as electric-load-leveling devices in such applications as electric vehicle propulsion systems, portable power tools, and low-voltage pulsed power supplies. One primary advantage: offer power densities much higher than storage batteries. Capacitors used in pulse mode, with short charge and discharge times. Derived from commercially available ultracapacitors. Made of lightweight materials; incorporate electrode/electrolyte material systems capable of operation at voltages higher than previous electrode/electrolyte systems. By use of innovative designs and manufacturing processes, made in wide range of rated capacitances and in rated operating potentials ranging from few to several hundred volts.

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

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

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li–S Battery

DOE PAGES

See, Kimberly A.; Wu, Heng -Liang; Lau, Kah Chun; ...

2016-11-16

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can bemore » introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2-LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2-LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. Furthermore, the electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.« less

Effect of Hydrofluoroether Cosolvent Addition on Li Solvation in Acetonitrile-Based Solvate Electrolytes and Its Influence on S Reduction in a Li-S Battery.

PubMed

See, Kimberly A; Wu, Heng-Liang; Lau, Kah Chun; Shin, Minjeong; Cheng, Lei; Balasubramanian, Mahalingam; Gallagher, Kevin G; Curtiss, Larry A; Gewirth, Andrew A

2016-12-21

Li-S batteries are a promising next-generation battery technology. Due to the formation of soluble polysulfides during cell operation, the electrolyte composition of the cell plays an active role in directing the formation and speciation of the soluble lithium polysulfides. Recently, new classes of electrolytes termed "solvates" that contain stoichiometric quantities of salt and solvent and form a liquid at room temperature have been explored due to their sparingly solvating properties with respect to polysulfides. The viscosity of the solvate electrolytes is understandably high limiting their viability; however, hydrofluoroether cosolvents, thought to be inert to the solvate structure itself, can be introduced to reduce viscosity and enhance diffusion. Nazar and co-workers previously reported that addition of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) to the LiTFSI in acetonitrile solvate, (MeCN) 2 -LiTFSI, results in enhanced capacity retention compared to the neat solvate. Here, we evaluate the effect of TTE addition on both the electrochemical behavior of the Li-S cell and the solvation structure of the (MeCN) 2 -LiTFSI electrolyte. Contrary to previous suggestions, Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that TTE coordinates to Li + at the expense of MeCN coordination, thereby producing a higher content of free MeCN, a good polysulfide solvent, in the electrolyte. The electrolytes containing a higher free MeCN content facilitate faster polysulfide formation kinetics during the electrochemical reduction of S in a Li-S cell likely as a result of the solvation power of the free MeCN.

Formulations for Stronger Solid Oxide Fuel-Cell Electrolytes

NASA Technical Reports Server (NTRS)

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

2004-01-01

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

78 FR 24673 - Airworthiness Directives; The Boeing Company Airplanes

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-26

... involving lithium ion battery failures that resulted in release of flammable electrolytes, heat damage, and... prompted by recent incidents involving lithium ion battery failures that resulted in release of flammable... modification of the battery system, or other actions. That AD resulted from recent incidents involving lithium...

Adsorption of Uranyl Ions at the Nano-hydroxyapatite and Its Modification

NASA Astrophysics Data System (ADS)

Skwarek, Ewa; Gładysz-Płaska, Agnieszka; Bolbukh, Yuliia

2017-04-01

Nano-hydroxyapatite and its modification, hydroxyapatite with the excess of phosphorus (P-HAP) and hydroxyapatite with the carbon ions built into the structure (C-HAP), were prepared by the wet method. They were studied by means of XRD, accelerated surface area and porosimetry (ASAP), and SEM. The size of crystallites computed using the Scherrer method was nano-hydroxyapatite (HAP) = 20 nm; P-HAP—impossible to determine; C-HAP = 22 nm; nano-HAP/U(VI) = 13.7 nm; P-HAP/U(VI)—impossible to determine, C-HAP/U(VI) = 11 nm. There were determined basic parameters characterizing the double electrical layer at the nano-HAP/electrolyte and P-HAP/electrolyte, C-HAP/electrolyte inter faces: density of the surface charge and zeta potential. The adsorption properties of nano-HAP sorbent in relation to U(VI) ions were studied by the batch technique. The adsorption processes were rapid in the first 60 min and reached the equilibrium within approximately 120 min (for P-HAP) and 300 min (for C-HAP and nano-HAP). The adsorption process fitted well with the pseudo-second-order kinetics. The Freundlich, Langmuir-Freundlich, and Dubinin-Radushkevich models of isotherms were examined for their ability to the equilibrium sorption data. The maximum adsorption capabilities ( q m ) were 7.75 g/g for P-HAP, 1.77 g/g for C-HAP, and 0.8 g/g for HAP at 293 K.

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

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

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan

2015-11-10

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

Aluminum reference electrode

DOEpatents

Sadoway, D.R.

1988-08-16

A stable reference electrode is described for use in monitoring and controlling the process of electrolytic reduction of a metal. In the case of Hall cell reduction of aluminum, the reference electrode comprises a pool of molten aluminum and a solution of molten cryolite, Na[sub 3]AlF[sub 6], wherein the electrical connection to the molten aluminum does not contact the highly corrosive molten salt solution. This is accomplished by altering the density of either the aluminum (decreasing the density) or the electrolyte (increasing the density) so that the aluminum floats on top of the molten salt solution. 1 fig.

Electrochemical performance evaluations and safety investigations of pentafluoro(phenoxy)cyclotriphosphazene as a flame retardant electrolyte additive for application in lithium ion battery systems using a newly designed apparatus for improved self-extinguishing time measurements

NASA Astrophysics Data System (ADS)

Dagger, Tim; Lürenbaum, Constantin; Schappacher, Falko M.; Winter, Martin

2017-02-01

A modified self-extinguishing time (SET) device which enhances the reproducibility of the results is presented. Pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is investigated as flame retardant electrolyte additive for lithium ion batteries (LIBs) in terms of thermal stability and electrochemical performance. SET measurements and adiabatic reaction calorimetry are applied to determine the flammability and the reactivity of a standard LIB electrolyte containing 5% FPPN. The results reveal that the additive-containing electrolyte is nonflammable for 10 s whereas the commercially available reference electrolyte inflames instantaneously after 1 s of ignition. The onset temperature of the safety enhanced electrolyte is delayed by ≈ 21 °C. Compatibility tests in half cells show that the electrolyte is reductively stable while the cyclic voltammogram indicates oxidative decomposition during the first cycle. Cycling experiments in full cells show improved cycling performance and rate capability, which can be attributed to cathode passivation during the first cycle. Post-mortem analysis of the electrolyte by gas chromatography-mass spectrometry confirms the presence of the additive in high amounts after 501 cycles which ensures enhanced safety of the electrolyte. The investigations present FPPN as stable electrolyte additive that improves the intrinsic safety of the electrolyte and its cycling performance at the same time.

Process for electrochemically gasifying coal using electromagnetism

DOEpatents

Botts, Thomas E.; Powell, James R.

1987-01-01

A process for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution.

Liquid-Feed Methanol Fuel Cell With Membrane Electrolyte

NASA Technical Reports Server (NTRS)

Surampudi, Subbarao; Narayanan, S. R.; Halpert, Gerald; Frank, Harvey; Vamos, Eugene

1995-01-01

Fuel cell generates electricity from direct liquid feed stream of methanol/water solution circulated in contact with anode, plus direct gaseous feed stream of air or oxygen in contact with cathode. Advantages include relative simplicity and elimination of corrosive electrolytic solutions. Offers potential for reductions in size, weight, and complexity, and for increases in safety of fuel-cell systems.

Electrolytic production of high purity aluminum using ceramic inert anodes

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.; DiMilia, Robert A.; Dynys, Joseph M.; Phelps, Frankie E.; LaCamera, Alfred F.

2002-01-01

A method of producing commercial purity aluminum in an electrolytic reduction cell comprising ceramic inert anodes is disclosed. The method produces aluminum having acceptable levels of Fe, Cu and Ni impurities. The ceramic inert anodes used in the process may comprise oxides containing Fe and Ni, as well as other oxides, metals and/or dopants.

A long life 4 V class lithium-ion polymer battery with liquid-free polymer electrolyte

NASA Astrophysics Data System (ADS)

Kobayashi, Yo; Shono, Kumi; Kobayashi, Takeshi; Ohno, Yasutaka; Tabuchi, Masato; Oka, Yoshihiro; Nakamura, Tatsuya; Miyashiro, Hajime

2017-02-01

Ether-based solid polymer electrolyte (SPE) is one of the most well-known lithium ion conductors. Unlike the other inorganic electrolytes, SPE exhibits advantages of flexibility and large-area production, enabling low cost production of large size batteries. However, because the ether group is oxidized at 4 V versus Li/Li+ cathode, and due to its high irreversibility with the carbon anode, ether-based SPE was believed to be inapplicable to 4 V class lithium-ion batteries with carbon anode. Here we report a remarkably stable SPE in combination with a 4 V class cathode and carbon anode achieved by the proper design at the interface. The introduced boron-based lithium salt prohibits further oxidation of SPE at the cathode interface. The surface modification of graphite by the annealing of polyvinyl chloride mostly prohibits the continuous consumption of lithium at the graphite anode. Using above interface design, we achieved 60% capacity retention after 5400 cycles. The proposed battery provides a possible approach for realizing flammable electrolyte-free lithium-ion batteries, which achieve innovative safety improvements of large format battery systems for stationary use.

Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Gao, Han

Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms. The optimized polymer electrolyte demonstrated even higher proton conductivity than pure HPAs and the enabled electrochemical capacitors have demonstrated an exceptionally high rate capability of 50 Vs-1 in cyclic voltammograms and a 10 ms time constant in impedance analyses.

Oxygen solubility and transport in Li–air battery electrolytes: Establishing criteria and strategies for electrolyte design

DOE PAGES

Gittleson, Forrest S.; Jones, Reese E.; Ward, Donald K.; ...

2017-02-15

Li–air or Li–oxygen batteries promise significantly higher energies than existing commercial battery technologies, yet their development has been hindered by a lack of suitable electrolytes. In this article, we evaluate the physical properties of varied electrolyte compositions to form generalized criteria for electrolyte design. We show that oxygen transport through non-aqueous electrolytes has a critical impact on the discharge rate and capacity of Li–air batteries. Through experiments and molecular dynamics simulations, we highlight that the choice of salt species and concentration have an outsized influence on oxygen solubility, while solvent choice is the major influence on oxygen diffusivity. The stabilitymore » of superoxide reaction intermediates, key to the oxygen reduction mechanism, is also affected by variations in salt concentration and the choice of solvent. The importance of reactant transport is confirmed through Li–air cell discharge, which demonstrates good agreement between the observed and calculated mass transport-limited currents. Furthermore, these results showcase the impact of electrolyte composition on transport in metal–air batteries and provide guiding principles and simulation-based tools for future electrolyte design.« less

Thermally stable electrolytes for rechargeable lithium batteries, phase 2

NASA Technical Reports Server (NTRS)

Dominey, L. A.; Goldman, J. L.; Koch, V. R.

1989-01-01

During the second year of research under NASA SBIR Contract NAS7-967, Covalent Associates and NASA contract monitors at the Jet Propulsion Laboratory agreed to perform an evaluation of the three best electrolytes developed during Phase 2. Due to the extensive period of time required to collect meaningful cycling data, we realized the study would extend well beyond the original formal end of the Phase 2 program (August 31, 1988). The substitution of this effort in lieu of an earlier proposed 20-cell final deliverable is formally documented in Modification No. 1 of Contract NAS7-967 as task 7. This Addendum contains the results of the cycling studies performed at Covalent Associates. In addition, sealed ampoules of each of these three electrolytes were delivered to the Jet Propulsion Laboratory Electrochemical Power Group. Their concurrent evaluation in a different test vehicle has also been recently concluded and their results are also summarized herein.

Tetraarylborate polymer networks as single-ion conducting solid electrolytes

DOE PAGES

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

2015-06-23

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

Thermally stable electrolytes for rechargeable lithium batteries, phase 2

NASA Astrophysics Data System (ADS)

Dominey, L. A.; Goldman, J. L.; Koch, V. R.

1989-09-01

During the second year of research under NASA SBIR Contract NAS7-967, Covalent Associates and NASA contract monitors at the Jet Propulsion Laboratory agreed to perform an evaluation of the three best electrolytes developed during Phase 2. Due to the extensive period of time required to collect meaningful cycling data, we realized the study would extend well beyond the original formal end of the Phase 2 program (August 31, 1988). The substitution of this effort in lieu of an earlier proposed 20-cell final deliverable is formally documented in Modification No. 1 of Contract NAS7-967 as task 7. This Addendum contains the results of the cycling studies performed at Covalent Associates. In addition, sealed ampoules of each of these three electrolytes were delivered to the Jet Propulsion Laboratory Electrochemical Power Group. Their concurrent evaluation in a different test vehicle has also been recently concluded and their results are also summarized herein.

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, James A.; Hayden, H. Wayne

1995-01-01

An apparatus and method for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode.

Electrochemical method of producing eutectic uranium alloy and apparatus

DOEpatents

Horton, J.A.; Hayden, H.W.

1995-01-10

An apparatus and method are disclosed for continuous production of liquid uranium alloys through the electrolytic reduction of uranium chlorides. The apparatus includes an electrochemical cell formed from an anode shaped to form an electrolyte reservoir, a cathode comprising a metal, such as iron, capable of forming a eutectic uranium alloy having a melting point less than the melting point of pure uranium, and molten electrolyte in the reservoir comprising a chlorine or fluorine containing salt and uranium chloride. The method of the invention produces an eutectic uranium alloy by creating an electrolyte reservoir defined by a container comprising an anode, placing an electrolyte in the reservoir, the electrolyte comprising a chlorine or fluorine containing salt and uranium chloride in molten form, positioning a cathode in the reservoir where the cathode comprises a metal capable of forming an uranium alloy having a melting point less than the melting point of pure uranium, and applying a current between the cathode and the anode. 2 figures.

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

DOE PAGES

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

2015-08-03

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

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Aulich, Ted R.; Olson, Edwin S.; Jiang, Junhua

2013-03-19

The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be solid.

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Effects of electrolytes on redox potentials through ion pairing

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

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode-Electrolyte Interface in Lithium-Ion Batteries.

PubMed

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

2017-12-27

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in lithium-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a "corrosion inhibitor film" that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot be mitigated. Effect of two exemplary electrolyte additives, lithium difluoro(oxalato)borate (LiDFOB) and 3-hexylthiophene (3HT), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next-generation high-energy-density lithium-ion chemistries.

Effects of electrolytes on redox potentials through ion pairing

DOE PAGES

Bird, Matthew J.; Iyoda, Tomokazu; Bonura, Nicholas; ...

2017-09-21

Here, reduction potentials have been determined for two molecules, benzophenone (BzPh) and perylene (Per), effectively in the complete absence of electrolyte as well as in the presence of three different supporting electrolytes in the moderately polar solvent THF. A description of how this can be so, and qualifications, are described in the discussion section. The primary tool in this work, pulse radiolysis, measures electron transfer (ET) equilibria in solution to obtain differences in redox potentials. Voltammetry measures redox potentials by establishing ET equilibria at electrodes, but electrolytes are needed for current flow. Results here show that without electrolyte the redoxmore » potentials were 100–451 mV more negative than those with 100 mM electrolyte. These changes depended both on the molecule and the electrolyte. In THF the dominant contributor to stabilization of radical anions by electrolyte was ion pairing. An equation was derived to give changes in redox potentials when electrolyte is added in terms of ion pair dissociation constants and activity coefficients. Definite values were determined for energetics, ΔG d°, of ion pairing. Values of ΔG d° for pairs with TBA + give some doubt that it is a “weakly-coordinating cation.” Computations with DFT methods were moderately successful at describing the ion paring energies.« less

Edge-selenated graphene nanoplatelets as durable metal-free catalysts for iodine reduction reaction in dye-sensitized solar cells

PubMed Central

Ju, Myung Jong; Jeon, In-Yup; Kim, Hong Mo; Choi, Ji Il; Jung, Sun-Min; Seo, Jeong-Min; Choi, In Taek; Kang, Sung Ho; Kim, Han Seul; Noh, Min Jong; Lee, Jae-Joon; Jeong, Hu Young; Kim, Hwan Kyu; Kim, Yong-Hoon; Baek, Jong-Beom

2016-01-01

Metal-free carbon-based electrocatalysts for dye-sensitized solar cells (DSSCs) are sufficiently active in Co(II)/Co(III) electrolytes but are not satisfactory in the most commonly used iodide/triiodide (I−/I3−) electrolytes. Thus, developing active and stable metal-free electrocatalysts in both electrolytes is one of the most important issues in DSSC research. We report the synthesis of edge-selenated graphene nanoplatelets (SeGnPs) prepared by a simple mechanochemical reaction between graphite and selenium (Se) powders, and their application to the counter electrode (CE) for DSSCs in both I−/I3− and Co(II)/Co(III) electrolytes. The edge-selective doping and the preservation of the pristine graphene basal plane in the SeGnPs were confirmed by various analytical techniques, including atomic-resolution transmission electron microscopy. Tested as the DSSC CE in both Co(bpy)32+/3+ (bpy = 2,2′-bipyridine) and I−/I3− electrolytes, the SeGnP-CEs exhibited outstanding electrocatalytic performance with ultimately high stability. The SeGnP-CE–based DSSCs displayed a higher photovoltaic performance than did the Pt-CE–based DSSCs in both SM315 sensitizer with Co(bpy)32+/3+ and N719 sensitizer with I−/I3− electrolytes. Furthermore, the I3− reduction mechanism, which has not been fully understood in carbon-based CE materials to date, was clarified by an electrochemical kinetics study combined with density functional theory and nonequilibrium Green’s function calculations. PMID:27386557

Hydroelectrolytic and hormonal modifications related to prolonged bedrest in antiorthostatic position

NASA Astrophysics Data System (ADS)

Güell, A.; Dupui, Ph.; Fanjaud, G.; Bes, A.; Moatti, J. P.; Gharrib, Cl.

The effects of prolonged bedrest in antiorthostatic position (-4° head down) on electrolyte balance were studied in 4 young volunteers. An increase was noted in sodium excretion during the first 4 days. Plasma renin activity and plasma aldosterone varied in parallel manner during the same period. Potassium balance and creatinine clearance were not significantly modified. In light of these data we feel that prolonged bedrest in antiorthostatic position constitutes an effective way to simulate on earth metabolic and hormonal modifications occurring in man under weightlessness conditions.

A view on thermodynamics of concentrated electrolytes: Modification necessity for electrostatic contribution of osmotic coefficient

NASA Astrophysics Data System (ADS)

Sahu, Jyoti; Juvekar, Vinay A.

2018-05-01

Prediction of the osmotic coefficient of concentrated electrolytes is needed in a wide variety of industrial applications. There is a need to correctly segregate the electrostatic contribution to osmotic coefficient from nonelectrostatic contribution. This is achieved in a rational way in this work. Using the Robinson-Stokes-Glueckauf hydrated ion model to predict non-electrostatic contribution to the osmotic coefficient, it is shown that hydration number should be independent of concentration so that the observed linear dependence of osmotic coefficient on electrolyte concentration in high concentration range could be predicted. The hydration number of several electrolytes (LiCl, NaCl, KCl, MgCl2, and MgSO4) has been estimated by this method. The hydration number predicted by this model shows correct dependence on temperature. It is also shown that the electrostatic contribution to osmotic coefficient is underpredicted by the Debye-Hückel theory at concentration beyond 0.1 m. The Debye-Hückel theory is modified by introducing a concentration dependent hydrated ionic size. Using the present analysis, it is possible to correctly estimate the electrostatic contribution to the osmotic coefficient, beyond the range of validation of the D-H theory. This would allow development of a more fundamental model for electrostatic interaction at high electrolyte concentrations.

Reduced temperature aluminum production in an electrolytic cell having an inert anode

DOEpatents

Dawless, Robert K.; Ray, Siba P.; Hosler, Robert B.; Kozarek, Robert L.; LaCamera, Alfred F.

2000-01-01

Aluminum is produced by electrolytic reduction of alumina in a cell having a cathode, an inert anode and a molten salt bath containing metal fluorides and alumina. The inert anode preferably contains copper, silver and oxides of iron and nickel. Reducing the molten salt bath temperature to about 900-950.degree. C. lowers corrosion on the inert anode constituents.

Diffusion welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon

DOEpatents

Byrne, Stephen C.; Vasudevan, Asuri K.

1984-01-01

A nonconsumable electrode assembly suitable for use in the production of metal by electrolytic reduction of a metal compound dissolved in a molten salt, the assembly comprising a metal conductor diffusion welded to a portion of a ceramic electrode body having a level of free metal or metal alloy sufficient to effect a metal bond.

Interlocking wettable ceramic tiles

DOEpatents

Tabereaux, Jr., Alton T.; Fredrickson, Guy L.; Groat, Eric; Mroz, Thomas; Ulicny, Alan; Walker, Mark F.

2005-03-08

An electrolytic cell for the reduction of aluminum having a layer of interlocking cathode tiles positioned on a cathode block. Each tile includes a main body and a vertical restraining member to prevent movement of the tiles away from the cathode block during operation of the cell. The anode of the electrolytic cell may be positioned about 1 inch from the interlocking cathode tiles.

CO2 decomposition using electrochemical process in molten salts

NASA Astrophysics Data System (ADS)

Otake, Koya; Kinoshita, Hiroshi; Kikuchi, Tatsuya; Suzuki, Ryosuke O.

2012-08-01

The electrochemical decomposition of CO2 gas to carbon and oxygen gas in LiCl-Li2O and CaCl2-CaO molten salts was studied. This process consists of electrochemical reduction of Li2O and CaO, as well as the thermal reduction of CO2 gas by the respective metallic Li and Ca. Two kinds of ZrO2 solid electrolytes were tested as an oxygen ion conductor, and the electrolytes removed oxygen ions from the molten salts to the outside of the reactor. After electrolysis in both salts, the aggregations of nanometer-scale amorphous carbon and rod-like graphite crystals were observed by transmission electron microscopy. When 9.7 %CO2-Ar mixed gas was blown into LiCl-Li2O and CaCl2-CaO molten salts, the current efficiency was evaluated to be 89.7 % and 78.5 %, respectively, by the exhaust gas analysis and the supplied charge. When a solid electrolyte with higher ionic conductivity was used, the current and carbon production became larger. It was found that the rate determining step is the diffusion of oxygen ions into the ZrO2 solid electrolyte.

Chemically rechargeable battery

NASA Technical Reports Server (NTRS)

Graf, James E. (Inventor); Rowlette, John J. (Inventor)

1984-01-01

Batteries (50) containing oxidized, discharged metal electrodes such as an iron-air battery are charged by removing and storing electrolyte in a reservoir (98), pumping fluid reductant such as formalin (aqueous formaldehyde) from a storage tank (106) into the battery in contact with the surfaces of the electrodes. After sufficient iron hydroxide has been reduced to iron, the spent reductant is drained, the electrodes rinsed with water from rinse tank (102) and then the electrolyte in the reservoir (106) is returned to the battery. The battery can be slowly electrically charged when in overnight storage but can be quickly charged in about 10 minutes by the chemical procedure of the invention.

Hydrothermal Synthesis of Platinum-Group-Metal-Free Catalysts: Structural Elucidation and Oxygen Reduction Catalysis

DOE PAGES

Gokhale, Rohan; Tsui, Lok-Kun; Roach, Kristin; ...

2017-12-07

In this paper, a hydrothermal approach to generate a platinum-group-metal-free (PGM-free) Fe-N-C catalyst for the oxygen reduction reaction (ORR) is introduced. The process involves partial carbonization by hydrothermal means followed by thermal treatment to obtain the final catalysts. Detailed X-ray scattering analysis of the glucose-imidazole catalysts (termed as GLU-IMID-C catalysts), obtained for the first time with the use of CarbonXS GUI program, reveals the presence of face-centered cubic (FCC) iron nanoparticles embedded in partially graphitic carbon in all catalyst variations. We also report the physical characterization of these catalysts by using X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area analysis, and transmissionmore » electron microscopy. The electrocatalytic behavior of the catalysts towards oxygen reduction is studied separately in acidic and alkaline electrolytes by rotating ring disk electrode measurements. The catalysts exhibit high ORR activity in acidic (0.5 M H 2SO 4) and alkaline (0.1 M KOH) electrolytes. Lastly, a precursor structure-performance relationship of these catalysts and their performance trends in both electrolytes has been discussed in this work.« less

Hydrothermal Synthesis of Platinum-Group-Metal-Free Catalysts: Structural Elucidation and Oxygen Reduction Catalysis

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

Gokhale, Rohan; Tsui, Lok-Kun; Roach, Kristin

In this paper, a hydrothermal approach to generate a platinum-group-metal-free (PGM-free) Fe-N-C catalyst for the oxygen reduction reaction (ORR) is introduced. The process involves partial carbonization by hydrothermal means followed by thermal treatment to obtain the final catalysts. Detailed X-ray scattering analysis of the glucose-imidazole catalysts (termed as GLU-IMID-C catalysts), obtained for the first time with the use of CarbonXS GUI program, reveals the presence of face-centered cubic (FCC) iron nanoparticles embedded in partially graphitic carbon in all catalyst variations. We also report the physical characterization of these catalysts by using X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area analysis, and transmissionmore » electron microscopy. The electrocatalytic behavior of the catalysts towards oxygen reduction is studied separately in acidic and alkaline electrolytes by rotating ring disk electrode measurements. The catalysts exhibit high ORR activity in acidic (0.5 M H 2SO 4) and alkaline (0.1 M KOH) electrolytes. Lastly, a precursor structure-performance relationship of these catalysts and their performance trends in both electrolytes has been discussed in this work.« less

Process for electrochemically gasifying coal

DOEpatents

Botts, T.E.; Powell, J.R.

1985-10-25

A process is claimed for electrochemically gasifying coal by establishing a flowing stream of coal particulate slurry, electrolyte and electrode members through a transverse magnetic field that has sufficient strength to polarize the electrode members, thereby causing them to operate in combination with the electrolyte to electrochemically reduce the coal particulate in the slurry. Such electrochemical reduction of the coal produces hydrogen and carbon dioxide at opposite ends of the polarized electrode members. Gas collection means are operated in conjunction with the process to collect the evolved gases as they rise from the slurry and electrolyte solution. 7 figs.

High Performance of Supercapacitor from PEDOT:PSS Electrode and Redox Iodide Ion Electrolyte

PubMed Central

Gao, Xing; Zu, Lei; Cai, Xiaomin; Li, Ce; Lian, Huiqin; Liu, Yang; Wang, Xiaodong; Cui, Xiuguo

2018-01-01

Insufficient energy density and poor cyclic stability is still challenge for conductive polymer-based supercapacitor. Herein, high performance electrochemical system has been assembled by combining poly (3,4-ethylenedioxythiophene) (PEDOT):poly (styrene sulfonate) (PSS) redox electrode and potassium iodide redox electrolyte, which provide the maximum specific capacity of 51.3 mAh/g and the retention of specific capacity of 87.6% after 3000 cycles due to the synergic effect through a simultaneous redox reaction both in electrode and electrolyte, as well as the catalytic activity for reduction of triiodide of the PEDOT:PSS. PMID:29772662

Hormonal regulation of fluid and electrolyte metabolism during periods of headward fluid shifts

NASA Technical Reports Server (NTRS)

Keil, Lanny C.; Severs, W. B.; Thrasher, T.; Ramsay, D. J.

1991-01-01

In the broadest sense, this project evaluates how spaceflight induced shifts of blood and interstitial fluids into the thorax affect regulation by the central nervous system (CNS) of fluid-electrolyte hormone secretion. Specifically, it focuses on the role of hormones related to salt/water balance and their potential function in the control of intracranial pressure and cerebrospinal fluid (CSF) composition. Fluid-electrolyte status during spaceflight gradually equilibrates, with a reduction in all body fluid compartments. Related to this is the cardiovascular deconditioning of spaceflight which is manifested upon return to earth as orthostatic intolerance.

Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure.

PubMed

Borodin, Oleg; Ren, Xiaoming; Vatamanu, Jenel; von Wald Cresce, Arthur; Knap, Jaroslaw; Xu, Kang

2017-12-19

Electroactive interfaces distinguish electrochemistry from chemistry and enable electrochemical energy devices like batteries, fuel cells, and electric double layer capacitors. In batteries, electrolytes should be either thermodynamically stable at the electrode interfaces or kinetically stable by forming an electronically insulating but ionically conducting interphase. In addition to a traditional optimization of electrolytes by adding cosolvents and sacrificial additives to preferentially reduce or oxidize at the electrode surfaces, knowledge of the local electrolyte composition and structure within the double layer as a function of voltage constitutes the basis of manipulating an interphase and expanding the operating windows of electrochemical devices. In this work, we focus on how the molecular-scale insight into the solvent and ion partitioning in the electrolyte double layer as a function of applied potential could predict changes in electrolyte stability and its initial oxidation and reduction reactions. In molecular dynamics (MD) simulations, highly concentrated lithium aqueous and nonaqueous electrolytes were found to exclude the solvent molecules from directly interacting with the positive electrode surface, which provides an additional mechanism for extending the electrolyte oxidation stability in addition to the well-established simple elimination of "free" solvent at high salt concentrations. We demonstrate that depending on their chemical structures, the anions could be designed to preferentially adsorb or desorb from the positive electrode with increasing electrode potential. This provides additional leverage to dictate the order of anion oxidation and to effectively select a sacrificial anion for decomposition. The opposite electrosorption behaviors of bis(trifluoromethane)sulfonimide (TFSI) and trifluoromethanesulfonate (OTF) as predicted by MD simulation in highly concentrated aqueous electrolytes were confirmed by surface enhanced infrared spectroscopy. The proton transfer (H-transfer) reactions between solvent molecules on the cathode surface coupled with solvent oxidation were found to be ubiquitous for common Li-ion electrolyte components and dependent on the local molecular environment. Quantum chemistry (QC) calculations on the representative clusters showed that the majority of solvents such as carbonates, phosphates, sulfones, and ethers have significantly lower oxidation potential when oxidation is coupled with H-transfer, while without H-transfer their oxidation potentials reside well beyond battery operating potentials. Thus, screening of the solvent oxidation limits without considering H-transfer reactions is unlikely to be relevant, except for solvents containing unsaturated functionalities (such as C═C) that oxidize without H-transfer. On the anode, the F-transfer reaction and LiF formation during anion and fluorinated solvent reduction could be enhanced or diminished depending on salt and solvent partitioning in the double layer, again giving an additional tool to manipulate the order of reductive decompositions and interphase chemistry. Combined with experimental efforts, modeling results highlight the promise of interphasial compositional control by either bringing the desired components closer to the electrode surface to facilitate redox reaction or expelling them so that they are kinetically shielded from the potential of the electrode.

Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

DOE PAGES

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai; ...

2016-08-22

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

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.

Ionic Liquid Hybrid Electrolytes for Lithium-Ion Batteries: A Key Role of the Separator-Electrolyte Interface in Battery Electrochemistry.

PubMed

Huie, Matthew M; DiLeo, Roberta A; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2015-06-10

Batteries are multicomponent systems where the theoretical voltage and stoichiometric electron transfer are defined by the electrochemically active anode and cathode materials. While the electrolyte may not be considered in stoichiometric electron-transfer calculations, it can be a critical factor determining the deliverable energy content of a battery, depending also on the use conditions. The development of ionic liquid (IL)-based electrolytes has been a research area of recent reports by other researchers, due, in part, to opportunities for an expanded high-voltage operating window and improved safety through the reduction of flammable solvent content. The study reported here encompasses a systematic investigation of the physical properties of IL-based hybrid electrolytes including quantitative characterization of the electrolyte-separator interface via contact-angle measurements. An inverse trend in the conductivity and wetting properties was observed for a series of IL-based electrolyte candidates. Test-cell measurements were undertaken to evaluate the electrolyte performance in the presence of functioning anode and cathode materials, where several promising IL-based hybrid electrolytes with performance comparable to that of conventional carbonate electrolytes were identified. The study revealed that the contact angle influenced the performance more significantly than the conductivity because the cells containing IL-tetrafluoroborate-based electrolytes with higher conductivity but poorer wetting showed significantly decreased performance relative to the cells containing IL-bis(trifluoromethanesulfonyl)imide electrolytes with lower conductivity but improved wetting properties. This work contributes to the development of new IL battery-based electrolyte systems with the potential to improve the deliverable energy content as well as safety of lithium-ion battery systems.

Small-Angle Neutron Scattering Study of Interplay of Attractive and Repulsive Interactions in Nanoparticle-Polymer System.

PubMed

Kumar, Sugam; Aswal, Vinod K; Kohlbrecher, Joachim

2016-02-16

The phase behavior of nanoparticle (silica)-polymer (polyethylene glycol) system without and with an electrolyte (NaCl) has been studied. It is observed that nanoparticle-polymer system behaves very differently in the presence of electrolyte. In the absence of electrolyte, the nanoparticle-polymer system remains in one-phase even at very high polymer concentrations. On the other hand, a re-entrant phase behavior is found in the presence of electrolyte, where one-phase (individual) system undergoes two-phase (nanoparticle aggregation) and then back to one-phase with increasing polymer concentration. The regime of two-phase system has been tuned by varying the electrolyte concentration. The polymer concentration range over which the two-phase system exists is significantly enhanced with the increase in the electrolyte concentration. These systems have been characterized by small-angle neutron scattering (SANS) experiments of contrast-marching the polymer to the solvent. The data are modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The phase behavior of nanoparticle-polymer system is explained by interplay of attractive (polymer-induced attractive depletion between nanoparticles) and repulsive (nanoparticle-nanoparticle electrostatic repulsion and polymer-polymer repulsion) interactions present in the system. In the absence of electrolyte, the strong electrostatic repulsion between nanoparticles dominates over the polymer-induced depletion attraction and the nanoparticle system remains in one-phase. With addition of electrolyte, depletion attraction overcomes electrostatic repulsion at some polymer concentration, resulting into nanoparticle aggregation and two-phase system. Further addition of polymer increases the polymer-polymer repulsion which eventually reduces the strength of depletion and hence re-entrant phase behavior. The effects of varying electrolyte concentration on the phase behavior of nanoparticle-polymer system are understood in terms of modifications in nanoparticle-nanoparticle and polymer-polymer interactions. The nanoparticle aggregates in two-phase systems are found to have surface fractal morphology.

Improving the Durability of Methanol Oxidation Reaction Electro-Catalysts Through the Modification of Carbon Architectures

DTIC Science & Technology

2014-01-01

zeolite template was used in conjunction with liquid cyanamide to form a carbon nitride structure with a better 2D mesoporous hexagonal framework, resulting...the core. Both hybrid inorganic–organic polymer networks and 139 zeolitic inorganic–organic polymer electrolyte materials were used to impregnate an

Surface modification by electrolytic plasma processing for high Nb-TiAl alloys

NASA Astrophysics Data System (ADS)

Gui, Wanyuan; Hao, Guojian; Liang, Yongfeng; Li, Feng; Liu, Xiao; Lin, Junpin

2016-12-01

Metal surface modification by electrolytic plasma processing (EPP) is an innovative treatment widely commonly applied to material processing and pretreatment process of coating and galvanization. EPP involves complex processes and a great deal of parameters, such as preset voltage, current, solution temperature and processing time. Several characterization methods are presented in this paper for evaluating the micro-structure surfaces of Ti45Al8Nb alloys: SEM, EDS, XRD and 3D topography. The results showed that the oxide scale and other contaminants on the surface of Ti45Al8Nb alloys can be effectively removed via EPP. The typical micro-crater structure of the surface of Ti45Al8Nb alloys were observed by 3D topography after EPP to find that the mean diameter of the surface structure and roughness value can be effectively controlled by altering the processing parameters. The mechanical properties of the surface according to nanomechanical probe testing exhibited slight decrease in microhardness and elastic modulus after EPP, but a dramatic increase in surface roughness, which is beneficial for further processing or coating.

Chemical characterization of solid polymer electrolyte membrane surfaces in LiFePO4 half-cells

NASA Astrophysics Data System (ADS)

Kyu, Thein; He, Ruixuan; Peng, Fang; Dunn, William E.; Kyu's Group Team, Dr.

High temperature (60 °C) capacity retention of succinonitrile plasticized solid polymer electrolyte membrane (PEM) in a LiFePO4 half-cell was investigated with or without lithium bis(oxalato)borate (LiBOB) modification. Various symmetric cells and half-cells were studied under different thermal and electrochemical conditions. At room temperature cycling, the unmodified PEM in the half-cell appeared stable up to 50 cycles tested. Upon cycling at 60 °C, the capacity decays rapidly and concurrently the cell resistance increased. The chemical compositions of the solid PEM surfaces on both cathode and anode sides were analyzed. New IR bands (including those belonged to amide) were discerned on the unmodified PEM surface of the Li electrode side at 60 °C suggestive of side reaction, but no new bands develop during room temperature cycling. To our astonishment, the side reaction was effectively suppressed upon LiBOB addition (0.4 wt%) into the PEM, contributing to increased high temperature capacity retention at 60°C. Plausible mechanisms of capacity fading and improved cycling performance due to LiBOB modification are discussed.

Surface Texture-Induced Enhancement of Optical and Photoelectrochemical Activity of Cu2ZnSnS4 Photocathodes

NASA Astrophysics Data System (ADS)

Sarswat, Prashant K.; Deka, Nipon; Jagan Mohan Rao, S.; Free, Michael L.; Kumar, Gagan

2017-08-01

The objective of this work is to understand and improve the photocatalytic activity of Cu2ZnSnS4 (CZTS) through postgrowth modification techniques to create surface textures. This objective can be achieved using a combination of solvents, etching agents, and anodization techniques. One of the most effective surface treatments for enhancing the surface properties of photovoltaic materials is formation of nanoscale flakes, although other surface modifications were also evaluated. The superior performance of textured films can be attributed to enhanced surface area of absorber material exposed to electrolyte, ZnS deficiency, and high catalytic activity due to reduced charge-transfer resistance. Fine-tuning of ion flux and electrolyte stoichiometry can be used to create a controlled growth algorithm for CZTS thin films. The resulting information can be utilized to optimize film properties. The utility of nanostructured or engineered surfaces was evaluated using photoelectrochemical measurements. Finite-difference time-domain (FDTD)-assisted simulations were conducted for selected texturing, revealing enhanced surface area of absorbing medium that ultimately resulted in greater power loss of light in the medium.

Nonconsumable electrode assembly and use thereof for the electrolytic production of metals and silicon

DOEpatents

Byrne, Stephen C.; Ray, Siba P.

1984-01-01

A nonconsumable electrode assembly suitable for use in the production of metal by electrolytic reduction of a metal compound dissolved in a molten salt, the assembly comprising a metal conductor attached to a ceramic electrode body by a metal bond on a portion of the body having a level of free metal or metal alloy sufficient to effect a metal bond.

Effects of preparation relief and flow channels on seating full coverage castings during cementation.

PubMed

Webb, E L; Murray, H V; Holland, G A; Taylor, D F

1983-06-01

Machined steel dies were used to study the effects of three die modifications on seating full coverage castings during cementation. The die modifications consisted of occlusal channels, occlusal surface relief, and axial channels. Fourteen specimens having one or more forms of die modification were compared with two control specimens having no die modifications. Statistical analysis of the data revealed that the addition of four axial channels to the simulated preparation on the steel die produced a significant reduction in the mean marginal discrepancy during cementation. Occlusal modifications alone failed to produce significant reductions in marginal discrepancies when compared with the control specimens. Occlusal modifications in conjunction with axial channels failed to produce further significant reductions in marginal discrepancies when compared with those reductions observed in specimens having only axial channels.

Adsorption of Uranyl Ions at the Nano-hydroxyapatite and Its Modification.

PubMed

Skwarek, Ewa; Gładysz-Płaska, Agnieszka; Bolbukh, Yuliia

2017-12-01

Nano-hydroxyapatite and its modification, hydroxyapatite with the excess of phosphorus (P-HAP) and hydroxyapatite with the carbon ions built into the structure (C-HAP), were prepared by the wet method. They were studied by means of XRD, accelerated surface area and porosimetry (ASAP), and SEM. The size of crystallites computed using the Scherrer method was nano-hydroxyapatite (HAP) = 20 nm; P-HAP-impossible to determine; C-HAP = 22 nm; nano-HAP/U(VI) = 13.7 nm; P-HAP/U(VI)-impossible to determine, C-HAP/U(VI) = 11 nm. There were determined basic parameters characterizing the double electrical layer at the nano-HAP/electrolyte and P-HAP/electrolyte, C-HAP/electrolyte inter faces: density of the surface charge and zeta potential. The adsorption properties of nano-HAP sorbent in relation to U(VI) ions were studied by the batch technique. The adsorption processes were rapid in the first 60 min and reached the equilibrium within approximately 120 min (for P-HAP) and 300 min (for C-HAP and nano-HAP). The adsorption process fitted well with the pseudo-second-order kinetics. The Freundlich, Langmuir-Freundlich, and Dubinin-Radushkevich models of isotherms were examined for their ability to the equilibrium sorption data. The maximum adsorption capabilities (q m ) were 7.75 g/g for P-HAP, 1.77 g/g for C-HAP, and 0.8 g/g for HAP at 293 K.

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

PubMed

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

2018-05-07

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

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

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

Gao, Han; Maglia, Filippo; Lamp, Peter

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generatedmore » from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.« less

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

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

Leaching of manganese from electrolytic manganese residue by electro-reduction.

PubMed

Shu, Jiancheng; Liu, Renlong; Liu, Zuohua; Chen, Hongliang; Tao, Changyuan

2017-08-01

In this study, an improved process for leaching manganese from electrolytic manganese residue (EMR) by electro-reduction was developed. The mechanisms of the electro-reduction leaching were investigated through X-ray diffraction, scanning electron microscopy, X-ray fluorescence, and Brunauer Emmett Teller. The results show that the electric field could change the surface charge distribution of EMR particles, and the high-valent manganese can be reduced by electric field. The leaching efficient of manganese reached 84.1% under the optimal leaching condition: 9.2 wt% H 2 SO 4 , current density of 25 mA/cm 2 , solid-to-liquid ratio of 1:5, and leaching time for 1 h. It is 37.9% higher than that attained without an electric field. Meanwhile, the manganese content in EMR decreased from 2.57% to 0.48%.

The healing effect of electrolytic-reduction ion water on burn wounds.

PubMed

Okajima, Masahiro; Shimokawa, Ken-ichi; Ishii, Fumiyoshi

2010-02-01

We prepared a lotion using electrolytic-reduction ion water (ERI), and evaluated the healing effects of this lotion (ERI lotion) on burn wounds. Third degree burn wounds were induced in the mouse dorsal skin, and ERI lotion or physiological salt (PS) lotion was applied to the wounds from immediately after injury [ERI (+) group and ERI (-) group as a control group, respectively]. The burn wound area was measured, and its serial changes were evaluated. In addition, histological examination of the burn wound site (on day 3) was performed. Comparison of the ERI (+) and (-) groups showed a significant reduction in the burn wound area in the former. Histological examination confirmed many interstitial spaces, blood vessels, and lymphatic vessels in the subcutaneous tissue in the ERI (-) compared with the ERI (+) group. These results suggest the promotion of burn wound healing by ERI lotion.

Electrochemical reduction of (U-40Pu-5Np)O 2 in molten LiCl electrolyte

NASA Astrophysics Data System (ADS)

Iizuka, Masatoshi; Sakamura, Yoshiharu; Inoue, Tadashi

2006-12-01

The electrochemical reduction of neptunium-containing MOX ((U-40Pu-5Np)O 2) was performed in molten lithium chloride melt at 923 K to investigate fundamental behavior of the transuranium elements and applicability of the method to reduction process for these materials. The Np-MOX was electrochemically reduced at the potential lower than -0.6 V vs. Bi-35 mol% Li reference electrode. The reduced metal grains in the surface region of the sample cohered with each other and made the layer of relatively high density, although it did not prevent the reduction of the sample toward the center. Complete reduction of the Np-MOX was shown by the weight change measurement through the electrochemical reduction and also by SEM-EDX observation. The chemical composition of the reduction products was homogeneous and agreed to that of the initial Np-MOX, which indicates that the reduction was completed and not selective among the actinides. The concentrations of the actinide elements, especially plutonium and americium in the electrolyte, increased with the progress of the tests, although their absolute values were very small. It is quite likely that plutonium and americium dissolve into the melt in the same manner as the lanthanide elements in the lithium reduction process.

Electron-beam-induced topographical, chemical, and structural patterning of amorphous titanium oxide films.

PubMed

Kern, P; Müller, Y; Patscheider, J; Michler, J

2006-11-30

Electrolytically deposited amorphous TiO2 films on steel are remarkably sensitive to electron beam (e-beam) irradiation at moderate energies at 20 keV, resulting in controlled local oxide reduction and crystallization, opening the possibility for local topographical, chemical, and structural modifications within a biocompatible, amorphous, and semiconducting matrix. The sensitivity is shown to vary significantly with the annealing temperature of as-deposited films. Well-defined irradiation conditions in terms of probe current IP (5 microA) and beam size were achieved with an electron probe microanalyzer. As shown by atomic force and optical microscopy, micro-Raman spectroscopy, wavelength-dispersive X-ray (WDX), and Auger analyses, e-beam exposure below 1 Acm-2 immediately leads to electron-stimulated oxygen desorption, resulting in a well-defined volume loss primarily limited to the irradiated zone under the electron probe and in a blue color shift in this zone because of the presence of Ti2O3. Irradiation at 5 Acm(-2) (IP = 5 microA) results in local crystallization into anatase phase within 1 s of exposure and in reduction to TiO after an extended exposure of 60 s. Further reduction to the metallic state could be observed after 60 s of exposure at approximately 160 Acm(-2). The local reduction could be qualitatively sensed with WDX analysis and Auger line scans. An estimation of the film temperature in the beam center indicates that crystallization occurs at less than 150 degrees C, well below the atmospheric crystallization temperature of the present films. The high e-beam sensitivity in combination with the well-defined volume loss from oxygen desorption allows for precise electron lithographic topographical patterning of the present oxides. Irradiation effects leading to the observed reduction and crystallization phenomena under moderate electron energies are discussed.

Plasma Electrolytic Oxidation Coatings on Pure Ti Substrate: Effects of Na3PO4 Concentration on Morphology and Corrosion Behavior of Coatings in Ringer's Physiological Solution

NASA Astrophysics Data System (ADS)

Roknian, Masoud; Fattah-alhosseini, Arash; Gashti, Seyed Omid

2018-03-01

Plasma electrolytic oxidation has been used as a relatively new method for applying ceramic coatings having different features. In the present study, commercially pure titanium is used as substrate, and effects of trisodium phosphate electrolyte concentration on the microstructure, as well as corrosion behavior of the coating in Ringer's physiological solution are investigated. The morphology and phase compositions of coatings were analyzed by using scanning electron microscopy (SEM) and x-ray diffraction patterns. The study on the corrosion behavior of samples in a Ringer's physiological solution was carried out using open-circuit potential potentiodynamic polarization and electrochemical impedance spectroscopy. The results of electrochemical analysis proved that higher concentration of phosphate electrolyte leads to increase in the corrosion resistance of applied coatings. Accordingly, obtained results revealed that the optimum electrolyte concentration for the best corrosion behavior was 20 g L-1. Furthermore, SEM images and reduction in the dielectric breakdown potential indicated that increase in the electrolyte concentration leads to morphological improvement and smoothening of the surface.

Simple battery armor to protect against gastrointestinal injury from accidental ingestion

PubMed Central

Laulicht, Bryan; Deshpande, Vikram; Langer, Robert; Karp, Jeffrey M.

2014-01-01

Inadvertent battery ingestion in children and the associated morbidity and mortality results in thousands of emergency room visits every year. Given the risk for serious electrochemical burns within hours of ingestion, the current standard of care for the treatment of batteries in the esophagus is emergent endoscopic removal. Safety standards now regulate locked battery compartments in toys, which have resulted in a modest reduction in inadvertent battery ingestion; specifically, 3,461 ingestions were reported in 2009, and 3,366 in 2013. Aside from legislation, minimal technological development has taken place at the level of the battery to limit injury. We have constructed a waterproof, pressure-sensitive coating, harnessing a commercially available quantum tunneling composite. Quantum tunneling composite coated (QTCC) batteries are nonconductive in the low-pressure gastrointestinal environment yet conduct within the higher pressure of standard battery housings. Importantly, this coating technology enables most battery-operated equipment to be powered without modification. If these new batteries are swallowed, they limit the external electrolytic currents responsible for tissue injury. We demonstrate in a large-animal model a significant decrease in tissue injury with QTCC batteries compared with uncoated control batteries. In summary, here we describe a facile approach to increasing the safety of batteries by minimizing the risk for electrochemical burn if the batteries are inadvertently ingested, without the need for modification of most battery-powered devices. PMID:25368176

Simple battery armor to protect against gastrointestinal injury from accidental ingestion.

PubMed

Laulicht, Bryan; Traverso, Giovanni; Deshpande, Vikram; Langer, Robert; Karp, Jeffrey M

2014-11-18

Inadvertent battery ingestion in children and the associated morbidity and mortality results in thousands of emergency room visits every year. Given the risk for serious electrochemical burns within hours of ingestion, the current standard of care for the treatment of batteries in the esophagus is emergent endoscopic removal. Safety standards now regulate locked battery compartments in toys, which have resulted in a modest reduction in inadvertent battery ingestion; specifically, 3,461 ingestions were reported in 2009, and 3,366 in 2013. Aside from legislation, minimal technological development has taken place at the level of the battery to limit injury. We have constructed a waterproof, pressure-sensitive coating, harnessing a commercially available quantum tunneling composite. Quantum tunneling composite coated (QTCC) batteries are nonconductive in the low-pressure gastrointestinal environment yet conduct within the higher pressure of standard battery housings. Importantly, this coating technology enables most battery-operated equipment to be powered without modification. If these new batteries are swallowed, they limit the external electrolytic currents responsible for tissue injury. We demonstrate in a large-animal model a significant decrease in tissue injury with QTCC batteries compared with uncoated control batteries. In summary, here we describe a facile approach to increasing the safety of batteries by minimizing the risk for electrochemical burn if the batteries are inadvertently ingested, without the need for modification of most battery-powered devices.

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

DOE PAGES

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

2015-10-08

Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2B 12H 12, which contains large, icosahedral, divalent B 12H 12 2– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2B 12H 12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11H 12 and NaCB 11H 12 salts, which contain icosahedral, monovalent CB 11H 12–more » anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm –1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.« less

New electrolytes for aluminum production: Ionic liquids

NASA Astrophysics Data System (ADS)

Zhang, Mingming; Kamavarum, Venkat; Reddy, Ramana G.

2003-11-01

In this article, the reduction, refining/recycling, and electroplating of aluminum from room-temperature molten salts are reviewed. In addition, the characteristics of several non-conventional organic solvents, electrolytes, and molten salts are evaluated, and the applicability of these melts for production of aluminum is discussed with special attention to ionic liquids. Also reviewed are electrochemical processes and conditions for electrodeposition of aluminum using ionic liquids at near room temperatures.

Fundamental Investigations of Durability at a Polymer Electrolyte-Electrode Interface

DTIC Science & Technology

2008-04-01

before before σ -σ σ after before before σ -σ σ Cleavage of the side chain ether linkage (Fig. 3), which intrudes into the hydrophilic ionic cluster...directly correlated to peroxide yields measured Figure 3: ATR-FTIR Spectrum of Nafion ®112 (H-form) indicating absorption bands obtained using...electrocatalyst-based fuel cell electrode (referred as sacrificial electrode) directly into the liquid electrolyte, in which oxygen reduction was

A temperature-controlled photoelectrochemical cell for quantitative product analysis.

PubMed

Corson, Elizabeth R; Creel, Erin B; Kim, Youngsang; Urban, Jeffrey J; Kostecki, Robert; McCloskey, Bryan D

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO 2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

A temperature-controlled photoelectrochemical cell for quantitative product analysis

NASA Astrophysics Data System (ADS)

Corson, Elizabeth R.; Creel, Erin B.; Kim, Youngsang; Urban, Jeffrey J.; Kostecki, Robert; McCloskey, Bryan D.

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

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

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

Insights into the use of polyethylene oxide in energy storage/conversion devices: a critical review

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2017-11-01

In this review, the latest updates in poly (ethylene oxide) based electrolytes are summarized. The ultimate goal of researchers globally is towards the development of free-standing solid polymeric separators for energy storage devices. This single free-standing solid polymeric separator may replace the liquid and separator (organic/inorganic) used in existing efficient/smart energy technology. As an example, polyethylene oxide (PEO) consists of an electron donor-rich group which provides coordinating sites to the cation for migration. Owing to this exclusive structure, PEO exhibits some remarkable properties, such as a low glass transition temperature, excellent flexibility, and the ability to make complexation with various metal salts which are unattainable by another polymer host. Hence, the PEO is an emerging candidate that has been most examined or is currently under consideration for application in energy storage devices. This review article first provides a detailed study of the PEO properties, characteristics of the constituents of the polymer electrolyte, and suitable approaches for the modification of polymer electrolytes. Then, the synthesization and characterizations techniques are outlined. The structures, characteristics, and performance during charge-discharge of four types of electrolyte/separators (liquid, plasticized, and dispersed and intercalated electrolyte) are highlighted. The suitable ion transport mechanism proposed by researchers in different renowned groups have been discussed for the better understanding of the ion dynamics in such systems.

Pulsating electrolyte flow in a full vanadium redox battery

NASA Astrophysics Data System (ADS)

Ling, C. Y.; Cao, H.; Chng, M. L.; Han, M.; Birgersson, E.

2015-10-01

Proper management of electrolyte flow in a vanadium redox battery (VRB) is crucial to achieve high overall system efficiency. On one hand, constant flow reduces concentration polarization and by extension, energy efficiency; on the other hand, it results in higher auxiliary pumping costs, which can consume around 10% of the discharge power. This work seeks to reduce the pumping cost by adopting a novel pulsing electrolyte flow strategy while retaining high energy efficiency. The results indicate that adopting a short flow period, followed by a long flow termination period, results in high energy efficiencies of 80.5% with a pumping cost reduction of over 50%.

Determination of the Cryolite Ratio of KF-NaF-AlF3 Electrolyte by Conductivity Method

NASA Astrophysics Data System (ADS)

Yan, Hengwei; Yang, Jianhong; Liu, Zhanwei; Wang, Chengzhi; Ma, Wenhui

2018-05-01

The cryolite ratio (CR) is an important parameter for the electrolyte in aluminum reduction cells. The measurement method for the CR of the KF-NaF-AlF3 system acid (CR < 3) electrolyte by means of electrical conductivity was initially developed, and the formula for calculating the CR was deduced. This method has the advantages of simple operation and high precision. In addition, the relative standard deviations (RSD) of the measurement are < 1.2 pct, and the analysis error of the NaF or KF content has little effect on the determination of the CR.

The EChemPen: A Guiding Hand to Learn Electrochemical Surface Modifications

ERIC Educational Resources Information Center

Valetaud, Mathieu; Loget, Gabriel; Roche, Je´rome; Hu¨sken, Nina; Fattah, Zahra; Badets, Vasilica; Fontaine, Olivier; Zigah, Dodzi

2015-01-01

The Electrochemical Pen (EChemPen) was developed as an attractive tool for learning electrochemistry. The fabrication, principle, and operation of the EChemPen are simple and can be easily performed by students in practical classes. It is based on a regular fountain pen principle, where the electrolytic solution is dispensed at a tip to locally…

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

Towards the next generation of solid oxide fuel cells operating below 600 °c with chemically stable proton-conducting electrolytes.

PubMed

Fabbri, Emiliana; Bi, Lei; Pergolesi, Daniele; Traversa, Enrico

2012-01-10

The need for reducing the solid oxide fuel cell (SOFC) operating temperature below 600 °C is imposed by cost reduction, which is essential for widespread SOFC use, but might also disclose new applications. To this aim, high-temperature proton-conducting (HTPC) oxides have gained widespread interest as electrolyte materials alternative to oxygen-ion conductors. This Progress Report describes recent developments in electrolyte, anode, and cathode materials for protonic SOFCs, addressing the issue of chemical stability, processability, and good power performance below 600 °C. Different fabrication methods are reported for anode-supported SOFCs, obtained using state-of-the-art, chemically stable proton-conducting electrolyte films. Recent findings show significant improvements in the power density output of cells based on doped barium zirconate electrolytes, pointing out towards the feasibility of the next generation of protonic SOFCs, including a good potential for the development of miniaturized SOFCs as portable power supplies. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite polymer electrolytes based on MG49 and carboxymethyl cellulose from kenaf

NASA Astrophysics Data System (ADS)

Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan

2013-11-01

The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF3SO3 were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2-10 wt%) via solution-casting method. The conductivity was increased with carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10-7 Scm-1 upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.

Sulfonated polystyrene and its characterization as a material of electrolyte polymer

NASA Astrophysics Data System (ADS)

Ngadiwiyana; Ismiyarto; Gunawan; Purbowatiningrum, RS; Prasetya, N. B. A.; Kusworo, T. D.; Susanto, H.

2018-05-01

The research of polystyrene modification from Styrofoam waste and its application as a main material of electrolyte polymer had been done. The sulfonation reaction of polystyrene was conducted using sulfuric acid as sufonation agent and the reactions were done with variation times of 1, 2, 3, 4 and 5 h. The characterization of the sulfonated products covered analysis of functional groups using FT-IR spectrophotometer, sulfonation degree, measurements of ion exchange capacity, conductivity and swelling degree. The sulfonated polystyrene product was white solid as confirmed by the spectra of FT-IR with the presence of wide band absorption of O=S=O at the wavenumber of 1080-1411 cm-1 as indication. The research showed the best sulfonated polystyrene prepared in 4 h as a material of electrolyte polymer, since it had the highest degree of sulfonation, ion exchange capacity, conductivity and swelling degree with the values were 28.52 %, 1.550 meg/g, 15,924.10-6 Ω-1cm-1 and 332.4 %, respectively.

The effects of cations and anions on hydrogen chemisorption at Pt

NASA Technical Reports Server (NTRS)

Huang, J. C.; Ogrady, W. E.; Yeager, E.

1977-01-01

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

High performance, flexible, poly(3,4-ethylenedioxythiophene) supercapacitors achieved by doping redox mediators in organogel electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Huanhuan; Li, Jinyu; Gu, Cheng; Yao, Mingming; Yang, Bing; Lu, Ping; Ma, Yuguang

2016-11-01

The relatively low energy density is now a central issue hindering the development of supercapacitors as energy storage devices. Various approaches are thus developed to enhance the energy density, mainly centering on the fabrication of electrode materials or optimization of cell configurations. Compared with these approaches, modifications in electrolytes are much simple and versatile. Herein, we integrate the wide voltages endowed by organic electrolytes and the additional capacitances brought by redox mediators, to fabricate high energy density supercapacitors. On the basis of this idea, supercapacitors with poly(3,4-ethylenedioxythiophene) (PEDOT) as electrode material exhibit extended operating voltage of 1.5 V, extraordinary capacitance of 363 F g-1 and high energy density of 27.4 Wh kg-1. The redox mediators reported here, ferrocene and 4-oxo-2,2,6,6-tetramethylpiperidinooxy, are the first time being applied in supercapacitors, especially in the gel state. While providing additional faradaic capacitances, they also exhibit synergistic interaction with PEDOT and improve the cycling stability of supercapacitors.

New Perspective in the Formulation and Characterization of Didodecyldimethylammonium Bromide (DMAB) Stabilized Poly(Lactic-co-Glycolic Acid) (PLGA) Nanoparticles

PubMed Central

Gossmann, Rebecca; Langer, Klaus; Mulac, Dennis

2015-01-01

Over the last few decades the establishment of nanoparticles as suitable drug carriers with the transport of drugs across biological barriers such as the gastrointestinal barrier moved into the focus of many research groups. Besides drug transport such carrier systems are well suited for the protection of drugs against enzymatic and chemical degradation. The preparation of biocompatible and biodegradable nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) is intensively described in literature, while especially nanoparticles with cationic properties show a promising increased cellular uptake. This is due to the electrostatic interaction between the cationic surface and the negatively charged lipid membrane of the cells. Even though several studies achieved the successful preparation of nanoparticles stabilized with the cationic surfactants such as didodecyldimethylammonium bromide (DMAB), in most cases insufficient attention was paid to a precise analytical characterization of the nanoparticle system. The aim of the present work was to overcome this deficit by presenting a new perspective in the formulation and characterization of DMAB-stabilized PLGA nanoparticles. Therefore these nanoparticles were carefully examined with regard to particle diameter, zeta potential, the effect of variation in stabilizer concentration, residual DMAB content, and electrolyte stability. Without any steric stabilization, the DMAB-modified nanoparticles were sensitive to typical electrolyte concentrations of biological environments due to compression of the electrical double layer in conjunction with a decrease in zeta potential. To handle this problem, the present study proposed two modifications to enable electrolyte stability. Both polyvinyl alcohol (PVA) and polyethylene glycol (PEG) modified DMAB-PLGA-nanoparticles were stable during electrolyte addition. Furthermore, in contrast to unmodified DMAB-PLGA-nanoparticles and free DMAB, such modifications led to a lower cytotoxic activity against Caco-2 cells. In conclusion this study offers a closer and critical point of view on preparation, in vitro and analytical evaluation of DMAB-stabilized PLGA nanoparticles for the physiological use. PMID:26147338

New Perspective in the Formulation and Characterization of Didodecyldimethylammonium Bromide (DMAB) Stabilized Poly(Lactic-co-Glycolic Acid) (PLGA) Nanoparticles.

PubMed

Gossmann, Rebecca; Langer, Klaus; Mulac, Dennis

2015-01-01

Over the last few decades the establishment of nanoparticles as suitable drug carriers with the transport of drugs across biological barriers such as the gastrointestinal barrier moved into the focus of many research groups. Besides drug transport such carrier systems are well suited for the protection of drugs against enzymatic and chemical degradation. The preparation of biocompatible and biodegradable nanoparticles based on poly(lactic-co-glycolic acid) (PLGA) is intensively described in literature, while especially nanoparticles with cationic properties show a promising increased cellular uptake. This is due to the electrostatic interaction between the cationic surface and the negatively charged lipid membrane of the cells. Even though several studies achieved the successful preparation of nanoparticles stabilized with the cationic surfactants such as didodecyldimethylammonium bromide (DMAB), in most cases insufficient attention was paid to a precise analytical characterization of the nanoparticle system. The aim of the present work was to overcome this deficit by presenting a new perspective in the formulation and characterization of DMAB-stabilized PLGA nanoparticles. Therefore these nanoparticles were carefully examined with regard to particle diameter, zeta potential, the effect of variation in stabilizer concentration, residual DMAB content, and electrolyte stability. Without any steric stabilization, the DMAB-modified nanoparticles were sensitive to typical electrolyte concentrations of biological environments due to compression of the electrical double layer in conjunction with a decrease in zeta potential. To handle this problem, the present study proposed two modifications to enable electrolyte stability. Both polyvinyl alcohol (PVA) and polyethylene glycol (PEG) modified DMAB-PLGA-nanoparticles were stable during electrolyte addition. Furthermore, in contrast to unmodified DMAB-PLGA-nanoparticles and free DMAB, such modifications led to a lower cytotoxic activity against Caco-2 cells. In conclusion this study offers a closer and critical point of view on preparation, in vitro and analytical evaluation of DMAB-stabilized PLGA nanoparticles for the physiological use.

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.

Reduction of capacity decay in vanadium flow batteries by an electrolyte-reflow method

NASA Astrophysics Data System (ADS)

Wang, Ke; Liu, Le; Xi, Jingyu; Wu, Zenghua; Qiu, Xinping

2017-01-01

Electrolyte imbalance is a major issue with Vanadium flow batteries (VFBs) as it has a significant impact on electrolyte utilization and cycle life over extended charge-discharge cycling. This work seeks to reduce capacity decay and prolong cycle life of VFBs by adopting a novel electrolyte-reflow method. Different current density and various start-up time of the method are investigated in the charge-discharge tests. The results show that the capacity decay rate is reduced markedly and the cycle life is prolonged substantially by this method. In addition, the coulomb efficiency, voltage efficiency and energy efficiency remain stable during the whole cycle life test, which indicates this method has little impact on the long lifetime performance of the VFBs. The method is low-cost, simple, effective, and can be applied in industrial VFB productions.

High capacity of lithium-sulfur batteries at low electrolyte/sulfur ratio enabled by an organosulfide containing electrolyte

DOE PAGES

Chen, Shuru; Gao, Yue; Yu, Zhaoxin; ...

2016-11-30

We present that lithium-sulfur (Li-S) battery is a promising energy storage technology to replace lithium ion batteries for higher energy density and lower cost. Dissolution of lithium polysulfide intermediates in conventional Li-S electrolytes is known as one of the key technical barriers to the development of Li-S, because it promotes redistribution and irreversible deposition of Li 2S, and also forces large amounts of electrolyte to be used, shortening cycling life and driving down cell energy density. Recently, dimethyl disulfide as a functional co-solvent has been demonstrated to show an alternate electrochemical reaction pathway for sulfur cathodes by the formation ofmore » dimethyl polysulfides and lithium organosulfides as intermediates and reduction products. In this work, comprehensive studies show that this new pathway not only provides high capacity but also enables excellent capacity retention through a built-in automatic discharge shutoff mechanism by tuning carbon/sulfur ratio in sulfur cathodes to reduce unfavorable Li 2S formation. Furthermore, this new electrolyte system is also found to enable high capacity of high-sulfur-loading cathodes with low electrolyte/sulfur (E/S) ratios, such as a stable specific capacity of around 1000 mAh g -1 using a low electrolyte amount (i.e, E/S ratio of 5 mL g -1) and highsulfur-loading (4 mg cm -2) cathodes. This electrolyte system almost doubles the capacity obtained with conventional electrolytes under the same harsh conditions. In conclusion, these results highlight the practical potential of this electrolyte system to enable high-energy-density Li-S batteries.« less

High capacity of lithium-sulfur batteries at low electrolyte/sulfur ratio enabled by an organosulfide containing electrolyte

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

Chen, Shuru; Gao, Yue; Yu, Zhaoxin

We present that lithium-sulfur (Li-S) battery is a promising energy storage technology to replace lithium ion batteries for higher energy density and lower cost. Dissolution of lithium polysulfide intermediates in conventional Li-S electrolytes is known as one of the key technical barriers to the development of Li-S, because it promotes redistribution and irreversible deposition of Li 2S, and also forces large amounts of electrolyte to be used, shortening cycling life and driving down cell energy density. Recently, dimethyl disulfide as a functional co-solvent has been demonstrated to show an alternate electrochemical reaction pathway for sulfur cathodes by the formation ofmore » dimethyl polysulfides and lithium organosulfides as intermediates and reduction products. In this work, comprehensive studies show that this new pathway not only provides high capacity but also enables excellent capacity retention through a built-in automatic discharge shutoff mechanism by tuning carbon/sulfur ratio in sulfur cathodes to reduce unfavorable Li 2S formation. Furthermore, this new electrolyte system is also found to enable high capacity of high-sulfur-loading cathodes with low electrolyte/sulfur (E/S) ratios, such as a stable specific capacity of around 1000 mAh g -1 using a low electrolyte amount (i.e, E/S ratio of 5 mL g -1) and highsulfur-loading (4 mg cm -2) cathodes. This electrolyte system almost doubles the capacity obtained with conventional electrolytes under the same harsh conditions. In conclusion, these results highlight the practical potential of this electrolyte system to enable high-energy-density Li-S batteries.« less

40 CFR 424.67 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... control technology. 424.67 Section 424.67 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS FERROALLOY MANUFACTURING POINT SOURCE CATEGORY Electrolytic... reduction attainable by the application of the best conventional pollutant control technology. Except as...

Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

PubMed Central

Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

2015-01-01

A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells. PMID:26100367

Carbothermic Reduction of Nickeliferous Laterite Ores for Nickel Pig Iron Production in China: A Review

NASA Astrophysics Data System (ADS)

Rao, Mingjun; Li, Guanghui; Jiang, Tao; Luo, Jun; Zhang, Yuanbo; Fan, Xiaohui

2013-11-01

Both the consumption and production of crude stainless steel in China rank first in the world. In 2011, the nickel production in China amounted to 446 kilotons, with the proportion of electrolytic nickel and nickel pig iron (NPI) registering 41.5% and 56.5%, respectively. NPI is a low-cost feedstock for stainless steel production when used as a substitute for electrolytic nickel. The existing commercial NPI production processes such as blast furnace smelting, rotary kiln-electric furnace smelting, and Krupp-Renn (Nipon Yakin Oheyama) processes are discussed. As low-temperature (below 1300°C) reduction of nickeliferous laterite ores followed by magnetic separation could provide an alternative avenue without smelting at high temperature (~1500°C) for producing ferronickel with low cost, the fundamentals and recent developments of the low-temperature reduction of nickeliferous laterite ores are reviewed.

Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

NASA Astrophysics Data System (ADS)

Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

2015-06-01

A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells.

A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte

DOE PAGES

Ma, Yulin; Zhou, Yan; Du, Chunyu; ...

2017-02-15

Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li 1.16Ni 0.2Co 0.1Mn 0.54O 2. Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency aremore » significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.« less

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.

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.

Gamma ray degradation of electrolytes containing alkylcarbonate solvents and a lithium salt

NASA Astrophysics Data System (ADS)

Caillon-Caravanier, Magaly; Jones, Jennifer; Anouti, Mérièm; Montigny, Frédéric; Willmann, Patrick; David, Jean-Pierre; Soonckindt, Sabine; Lemordant, Daniel

Lithium-ion batteries for space applications, such as satellites, are subjected to cosmic radiations, in particular, γ-irradiation. In this study, the effects of this radiation on electrolytes and their components used in the lithium-ion batteries are investigated. The conductivity and viscosity of the samples have been measured before and after the irradiation. The modifications are evaluated by spectral analyses such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H and 13C NMR), solid phase microextraction-gas chromatography (SPME-GC) and gas chromatography-mass spectroscopy (GC-MS). The experimental results show that only the samples containing vinylene carbonate and/or the lithium salt LiPF 6 are degraded by γ-radiation.

Gas Hydrate Stability at Low Temperatures and High Pressures with Applications to Mars and Europa

NASA Technical Reports Server (NTRS)

Marion, G. M.; Kargel, J. S.; Catling, D. C.

2004-01-01

Gas hydrates are implicated in the geochemical evolution of both Mars and Europa [1- 3]. Most models developed for gas hydrate chemistry are based on the statistical thermodynamic model of van der Waals and Platteeuw [4] with subsequent modifications [5-8]. None of these models are, however, state-of-the-art with respect to gas hydrate/electrolyte interactions, which is particularly important for planetary applications where solution chemistry may be very different from terrestrial seawater. The objectives of this work were to add gas (carbon dioxide and methane) hydrate chemistries into an electrolyte model parameterized for low temperatures and high pressures (the FREZCHEM model) and use the model to examine controls on gas hydrate chemistries for Mars and Europa.

Public perceptions of hurricane modification.

PubMed

Klima, Kelly; Bruine de Bruin, Wändi; Morgan, M Granger; Grossmann, Iris

2012-07-01

If hurricane modification were to become a feasible strategy for potentially reducing hurricane damages, it would likely generate public discourse about whether to support its implementation. To facilitate an informed and constructive discourse, policymakers need to understand how people perceive hurricane modification. Here, we examine Florida residents' perceptions of hurricane modification techniques that aim to alter path and wind speed. Following the mental models approach, we conducted a survey study about public perceptions of hurricane modification that was guided by formative interviews on the topic. We report a set of four primary findings. First, hurricane modification was perceived as a relatively ineffective strategy for damage reduction, compared to other strategies for damage reduction. Second, hurricane modification was expected to lead to changes in projected hurricane path, but not necessarily to the successful reduction of projected hurricane strength. Third, more anger was evoked when a hurricane was described as having changed from the initially forecasted path or strength after an attempted modification. Fourth, unlike what we expected, participants who more strongly agreed with statements that recognized the uncertainty inherent in forecasts reported more rather than less anger at scientists across hurricane modification scenarios. If the efficacy of intensity-reduction techniques can be increased, people may be willing to support hurricane modification. However, such an effort would need to be combined with open and honest communications to members of the general public. © 2011 Society for Risk Analysis.

Superior Performance of a Lithium-Sulfur Battery Enabled by a Dimethyl Trisulfide Containing Electrolyte

DOE PAGES

Chen, Shuru; Wang, Daiwei; Zhao, Yuming; ...

2018-04-26

The lithium-sulfur (Li-S) battery offers a high theoretical energy density of ≈2600 Wh/kg -1 and low cost, positioning it as a promising candidate for next-generation battery technology. However, problems including disastrous Li polysulfides dissolution and irreversible Li 2S deposition have severely retarded the development of Li-S batteries. To solve these issues, we recently reported a functional dimethyl disulfide (DMDS)-containing electrolyte that promoted an alternate electrochemical reaction pathway for sulfur cathodes by a formation of dimethyl polysulfides and Li organosulfides as intermediates and reduction products, leading to significantly boosted Li-S cell capacity with improved cycling reversibility and stability. Here in thismore » work, dimethyl trisulfide (DMTS), a primary discharge-charge intermediate in the DMDS-containing electrolyte, which is also a commercially available reagent, was further investigated as a co-solvent in functional electrolytes for Li-S batteries. Due to the higher theoretical capacity of DMTS and its better reactivity with Li 2S than DMDS, a 25 vol% DMTS-containing electrolyte enables Li-S batteries with even higher cell capacity and improved cycling performance than using previous optimal 50 vol% DMDS-containing electrolyte.« less

Superior Performance of a Lithium-Sulfur Battery Enabled by a Dimethyl Trisulfide Containing Electrolyte

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

Chen, Shuru; Wang, Daiwei; Zhao, Yuming

The lithium-sulfur (Li-S) battery offers a high theoretical energy density of ≈2600 Wh/kg -1 and low cost, positioning it as a promising candidate for next-generation battery technology. However, problems including disastrous Li polysulfides dissolution and irreversible Li 2S deposition have severely retarded the development of Li-S batteries. To solve these issues, we recently reported a functional dimethyl disulfide (DMDS)-containing electrolyte that promoted an alternate electrochemical reaction pathway for sulfur cathodes by a formation of dimethyl polysulfides and Li organosulfides as intermediates and reduction products, leading to significantly boosted Li-S cell capacity with improved cycling reversibility and stability. Here in thismore » work, dimethyl trisulfide (DMTS), a primary discharge-charge intermediate in the DMDS-containing electrolyte, which is also a commercially available reagent, was further investigated as a co-solvent in functional electrolytes for Li-S batteries. Due to the higher theoretical capacity of DMTS and its better reactivity with Li 2S than DMDS, a 25 vol% DMTS-containing electrolyte enables Li-S batteries with even higher cell capacity and improved cycling performance than using previous optimal 50 vol% DMDS-containing electrolyte.« less

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.

Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

PubMed

Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

2015-12-25

We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance.

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

PubMed

Yim, Taeeun; Han, Young-Kyu

2017-09-27

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

Extraction of manganese from electrolytic manganese residue by bioleaching.

PubMed

Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

2011-01-01

Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. Copyright © 2010 Elsevier Ltd. All rights reserved.

Non-electrolytic synthesis of copper oxide/carbon nanocomposite by surface plasma in super-dehydrated ethanol

NASA Astrophysics Data System (ADS)

Kozak, Dmytro S.; Sergiienko, Ruslan A.; Shibata, Etsuro; Iizuka, Atsushi; Nakamura, Takashi

2016-02-01

Electrolytic processes are widely used to synthesize different nanomaterials and it does not depend on what kind of the method has been applied (wet-chemistry, sonochemistry, plasma chemistry, electrolysis and so on). Generally, the reactions in the electrolyte are considered to be reduction/oxidation (REDOX) reactions between chemical reagents or the deposition of matter on the electrodes, in line with Faraday’s law. Due to the presence of electroconductive additives in any electrolyte, the polarization effect of polar molecules conducting an electrical current disappears, when external high-strength electric field is induced. Because initially of the charge transfer always belongs of electroconductive additive and it does not depend on applied voltage. The polarization of ethanol molecules has been applied to conduct an electric current by surface plasma interaction for the synthesis of a copper oxide/carbon nanocomposite material.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

DOEpatents

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

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

Baskin, Artem; Prendergast, David

In this paper, we reveal the general mechanisms of partial reduction of multivalent complex cations in conditions specific for the bulk solvent and in the vicinity of the electrified metal electrode surface and disclose the factors affecting the reductive stability of electrolytes for multivalent electrochemistry. Using a combination of ab initio techniques, we clarify the relation between the reductive stability of contact-ion pairs comprising a multivalent cation and a complex anion, their solvation structures, solvent dynamics, and the electrode overpotential. We found that for ion pairs with multiple configurations of the complex anion and the Mg cation whose available orbitalsmore » are partially delocalized over the molecular complex and have antibonding character, the primary factor of the reductive stability is the shape factor of the solvation sphere of the metal cation center and the degree of the convexity of a polyhedron formed by the metal cation and its coordinating atoms. We focused specifically on the details of Mg (II) bis(trifluoromethanesulfonyl)imide in diethylene glycol dimethyl ether (Mg(TFSI) 2)/diglyme) and its singly charged ion pair, MgTFSI +. In particular, we found that both stable (MgTFSI) + and (MgTFSI) 0 ion pairs have the same TFSI configuration but drastically different solvation structures in the bulk solution. This implies that the MgTFSI/dyglyme reductive stability is ultimately determined by the relative time scale of the solvent dynamics and electron transfer at the Mg–anode interface. In the vicinity of the anode surface, steric factors and hindered solvent dynamics may increase the reductive stability of (MgTFSI) + ion pairs at lower overpotential by reducing the metal cation coordination, in stark contrast to the reduction at high overpotential accompanied by TFSI decomposition. By examining other solute/solvent combinations, we conclude that the electrolytes with highly coordinated Mg cation centers are more prone to reductive instability due to the chemical decomposition of the anion or solvent molecules. Finally, the obtained findings disclose critical factors for stable electrolyte design and show the role of interfacial phenomena in reduction of multivalent ions.« less

Surface modifications of photoanodes in dye sensitized solar cells: enhanced light harvesting and reduced recombination

NASA Astrophysics Data System (ADS)

Saxena, Vibha; Aswal, D. K.

2015-06-01

In a quest to harvest solar power, dye-sensitized solar cells (DSSCs) have potential for low-cost eco-friendly photovoltaic devices. The major processes which govern the efficiency of a DSSC are photoelectron generation, injection of photo-generated electrons to the conduction band (CB) of the mesoporous nanocrystalline semiconductor (nc-SC); transport of CB electrons through nc-SC and subsequent collection of CB electrons at the counter electrode (CE) through the external circuit; and dye regeneration by redox couple or hole transport layer (HTL). Most of these processes occur at various interfaces of the photoanode. In addition, recombination losses of photo-generated electrons with either dye or redox molecules take place at the interfaces. Therefore, one of the key requirements for high efficiency is to improve light harvesting of the photoanode and to reduce the recombination losses at various interfaces. In this direction, surface modification of the photoanode is the simplest method among the various other approaches available in the literature. In this review, we present a comprehensive discussion on surface modification of the photoanode, which has been adopted in the literature for not only enhancing light harvesting but also reducing recombination. Various approaches towards surface modification of the photoanode discussed are (i) fluorine-doped tin oxide (FTO)/nc-SC interface modified via a compact layer of semiconductor material which blocks exposed sites of FTO to electrolyte (or HTL), (ii) nc-SC/dye interface modification either through acid treatment resulting in enhanced dye loading due to a positively charged surface or by depositing insulating/semiconducting blocking layer on the nc-SC surface, which acts as a tunneling barrier for recombination, (iii) nc-SC/dye interface modified by employing co-adsorbents which helps in reducing the dye aggregation and thereby recombination, and (iv) dye/electrolyte (or dye/HTL) interface modification using additives which provides surface passivation as well as positive movement of the nc-SC Fermi level owing to negative charge at the surface and hence improves light harvesting and reduced recombination. Finally, we discuss the advantages and disadvantages of various approaches towards high-efficiency DSSCs.

Friction welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon

DOEpatents

Byrne, Stephen C.; Ray, Siba P.; Rapp, Robert A.

1984-01-01

A nonconsumable electrode assembly suitable for use in the production of metal by electrolytic reduction of a metal compound dissolved in a molten salt, the assembly comprising a metal conductor and a ceramic electrode body connected by a friction weld between a portion of the body having a level of free metal or metal alloy sufficient to effect such a friction weld and a portion of the metal conductor.

Colloidal Stability in Asymmetric Electrolytes: Modifications of the Schulze-Hardy Rule.

PubMed

Trefalt, Gregor; Szilagyi, Istvan; Téllez, Gabriel; Borkovec, Michal

2017-02-21

The Schulze-Hardy rule suggests a strong dependence of the critical coagulation concentration (CCC) on the ionic valence. This rule is addressed theoretically and confronted with recent experimental results. The commonly presented derivation of this rule assumes symmetric electrolytes and highly charged particles. Both assumptions are incorrect. Symmetric electrolytes containing multivalent ions are hardly soluble, and experiments are normally carried out with the well-soluble salts of asymmetric electrolytes containing monovalent and multivalent ions. In this situation, however, the behavior is completely different whether the multivalent ions represent the counterions or co-ions. When these ions represent the counterions, meaning that the multivalent ions have the opposite sign than the charge of the particle, they adsorb strongly to the particles. Thereby, they progressively reduce the magnitude of the surface charge with increasing valence. In fact, this dependence of the charge density on the counterion valence is mainly responsible for the decrease of the CCC with the valence. In the co-ion case, where the multivalent ions have the same sign as the charge of the particle, the multivalent ions are repelled from the particles, and the surfaces remain highly charged. In this case, the inverse Schulze-Hardy rule normally applies, whereby the CCC varies inversely proportional to the co-ion valence.

Investigation of a novel ternary electrolyte based on dimethyl sulfite and lithium difluoromono(oxalato)borate for lithium ion batteries

NASA Astrophysics Data System (ADS)

Chen, Renjie; Zhu, Lu; Wu, Feng; Li, Li; Zhang, Rong; Chen, Shi

2014-01-01

Lithium difluoromono(oxalato)borate (LiODFB) has been used as a novel lithium salt for battery in recent studies. In this study, a series of novel electrolytes has been prepared by adding 30 vol% dimethyl sulfite (DMS) or dimethyl carbonate (DMC) as co-solvent into an ethylene carbonate (EC)/ethyl methyl carbonate (EMC) + LiX mixture, in which the LiX could be LiClO4, LiODFB, LiBOB, LiTFSI, or LiCF3SO3. These ternary electrolytes have been investigated for use in lithium ion batteries. FT-IR spectroscopy analysis shows that characteristic functional groups (-CO3, -SO3) undergo red-shift or blue-shift with the addition of different lithium salts. The LiODFB-EC/EMC/DMS electrolyte exhibits high ionic conductivity, which is mainly because of the low melting point of DMS, and LiODFB possessing high solubility. The Li/MCMB cells containing this novel electrolyte exhibit high capacities, good cycling performance, and excellent rate performance. These performances are probably because both LiODFB and DMS can assist in the formation of SEI films by reductive decomposition. Additionally, the discharge capacity of Li/LiCoO2 half cell containing LiODFB-EC/EMC/DMS electrolyte is 130.9 mAh g-1 after 50 cycles, and it is very comparable with the standard-commercial electrolyte. The results show that this study produces a promising electrolyte candidate for lithium ion batteries.

Density Functional Theory Research into the Reduction Mechanism for the Solvent/Additive in a Sodium-Ion Battery.

PubMed

Liu, Qi; Mu, Daobin; Wu, Borong; Wang, Lei; Gai, Liang; Wu, Feng

2017-02-22

The solid-electrolyte interface (SEI) film in a sodium-ion battery is closely related to capacity fading and cycling stability of the battery. However, there are few studies on the SEI film of sodium-ion batteries and the mechanism of SEI film formation is unclear. The mechanism for the reduction of ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), ethylene sulfite (ES), 1,3-propylene sulfite (PS), and fluorinated ethylene carbonate (FEC) is studied by DFT. The reaction activation energies, Gibbs free energies, enthalpies, and structures of the transition states are calculated. It is indicated that VC, ES, and PS additives in the electrolyte are all easier to form organic components in the anode SEI film by one-electron reduction. The priority of one-electron reduction to produce organic SEI components is in the order of VC>PC>EC; two-electron reduction to produce the inorganic Na 2 CO 3 component is different and follows the order of EC>PC>VC. Two-electron reduction for sulfites ES and PS to form inorganic Na 2 SO 3 is harder than that of carbonate ester reduction. It is also suggested that the one- and two-electron reductive decomposition pathway for FEC is more feasible to produce inorganic NaF components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

48 CFR 52.215-11 - Price Reduction for Defective Certified Cost or Pricing Data-Modifications.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 48 Federal Acquisition Regulations System 2 2011-10-01 2011-10-01 false Price Reduction for... CONTRACT CLAUSES Text of Provisions and Clauses 52.215-11 Price Reduction for Defective Certified Cost or Pricing Data—Modifications. As prescribed in 15.408(c), insert the following clause: Price Reduction for...

In-situ chemical reduction produced graphene paper for flexible supercapacitors with impressive capacitive performance

NASA Astrophysics Data System (ADS)

Ye, Xingke; Zhu, Yucan; Tang, Zhonghua; Wan, Zhongquan; Jia, Chunyang

2017-08-01

For practical applications of graphene-based materials in flexible supercapacitors, a technological breakthrough is currently required to fabricate high-performance graphene paper by a facile method. Herein, highly conductive (∼6900 S m-1) graphene paper with loose multilayered structure is produced by a high-efficiency in-situ chemical reduction process, which assembles graphite oxide suspensions into film and simultaneously conducts chemical reduction. Graphene papers with different parameters (including different types and doses of reductants, different thicknesses and areas of films) are successfully fabricated through this in-situ chemical reduction method. Meanwhile, the influences of the graphene papers with different parameters upon the supercapacitor performance are systematically investigated. Flexible supercapacitor based on the graphene paper exhibits high areal capacitance (152.4 mF cm-2 at current density of 2.0 mA cm-2 in aqueous electrolyte), and excellent rate performance (88.7% retention at 8.0 mA cm-2). Furthermore, bracelet-shaped all-solid supercapacitor with fascinating cycling stability (96.6% retention after 10 000 cycles) and electrochemical stability (an almost negligible capacity loss under different bending states and 99.6% retention after 4000 bending cycles) is established by employing the graphene paper electrode material and polymer electrolyte.

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

Electrochemical process for the preparation of nitrogen fertilizers

DOEpatents

Aulich, Ted R [Grand Forks, ND; Olson, Edwin S [Grand Forks, ND; Jiang, Junhua [Grand Forks, ND

2012-04-10

The present invention provides methods and apparatus for the preparation of nitrogen fertilizers including ammonium nitrate, urea, urea-ammonium nitrate, and/or ammonia, at low temperature and pressure, preferably at ambient temperature and pressure, utilizing a source of carbon, a source of nitrogen, and/or a source of hydrogen or hydrogen equivalent. Implementing an electrolyte serving as ionic charge carrier, (1) ammonium nitrate is produced via the reduction of a nitrogen source at the cathode and the oxidation of a nitrogen source at the anode; (2) urea or its isomers are produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source; (3) ammonia is produced via the reduction of nitrogen source at the cathode and the oxidation of a hydrogen source or a hydrogen equivalent such as carbon monoxide or a mixture of carbon monoxide and hydrogen at the anode; and (4) urea-ammonium nitrate is produced via the simultaneous cathodic reduction of a carbon source and a nitrogen source, and anodic oxidation of a nitrogen source. The electrolyte can be aqueous, non-aqueous, or solid.

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.

Preparation of Ferrotitanium Alloys by Electrolysis-Assisted Calciothermic Reduction of Ilmenite in Equimolar CaCl2-NaCl Electrolyte: Effect of Calcium Oxide

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Zhang, Yingjie; Hua, Yixin; Xu, Cunying; Dong, Peng; Zhang, Qibo; Wang, Ding

2018-04-01

The effect of CaO content on the preparation of ferrotitanium alloys from ilmenite with the method of the electrolysis-assisted calciothermic reduction has been investigated by use of ilmenite powders as raw materials that positions them next to the cathodic molybdenum plate, equimolar CaCl2-NaCl molten salt with 2-7 mol.% CaO as electrolyte and graphite as anode at 700°C with cell voltage of 2.8 V under argon atmosphere. It is demonstrated that increasing the reactant CaO content is beneficial to the calciothermic reduction of ilmenite and the intermediate CaTiO3. Experimental results also show that after 14 h of calciothermic reduction process, the products are ferrotitanium alloys and the specific energy consumption is only about 10.21 kWh kg-1 when adding 5 mol.% CaO into equimolar CaCl2-NaCl molten salt and approximately 14.40 kWh kg-1 when CaO content is increased to 7 mol.%.

Nanostructuring-induced modification of optical properties of p-GaAs (1 0 0)

NASA Astrophysics Data System (ADS)

Naddaf, M.; Saloum, S.

2009-10-01

A pulsed anodic etching method has been utilized for nanostructuring of p-type GaAs (1 0 0) surface, using HCl-based solution as electrolyte. The resulting porous GaAs layer is characterized by atomic force microscopy (AFM), room temperature photoluminescence (PL), Raman spectroscopy and optical reflectance measurements. AFM imaging reveals that the porous GaAs layer is consisted of a pillar-like of few nm in width distributed between more-reduced size nanostructures. In addition to the “infrared” PL band of un-etched GaAs, a strong “green” PL band is observed in the etched sample. The broad visible PL band of a high-energy (3.82 eV) excitation is found to compose of two PL band attributed to excitons confinement in two different sizes distribution of GaAs nanocrystals. The quantum confinement effects in GaAs nanocrystallites is also evidenced from Raman spectroscopy through the pronounced appearance of the transverse optical (TO) phonon line in the spectra of the porous sample. Porosity-induced a significant reduction of the specular reflection, in the spectral range (400-800 nm), is also demonstrated.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

NASA Astrophysics Data System (ADS)

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production

PubMed Central

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-01-01

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production. PMID:27431993

Engineering MoSx/Ti/InP Hybrid Photocathode for Improved Solar Hydrogen Production.

PubMed

Li, Qiang; Zheng, Maojun; Zhong, Miao; Ma, Liguo; Wang, Faze; Ma, Li; Shen, Wenzhong

2016-07-19

Due to its direct band gap of ~1.35 eV, appropriate energy band-edge positions, and low surface-recombination velocity, p-type InP has attracted considerable attention as a promising photocathode material for solar hydrogen generation. However, challenges remain with p-type InP for achieving high and stable photoelectrochemical (PEC) performances. Here, we demonstrate that surface modifications of InP photocathodes with Ti thin layers and amorphous MoSx nanoparticles can remarkably improve their PEC performances. A high photocurrent density with an improved PEC onset potential is obtained. Electrochemical impedance analyses reveal that the largely improved PEC performance of MoSx/Ti/InP is attributed to the reduced charge-transfer resistance and the increased band bending at the MoSx/Ti/InP/electrolyte interface. In addition, the MoSx/Ti/InP photocathodes function stably for PEC water reduction under continuous light illumination over 2 h. Our study demonstrates an effective approach to develop high-PEC-performance InP photocathodes towards stable solar hydrogen production.

Novel ternary molten salt electrolytes for intermediate-temperature sodium/nickel chloride batteries

NASA Astrophysics Data System (ADS)

Li, Guosheng; Lu, Xiaochuan; Coyle, Christopher A.; Kim, Jin Y.; Lemmon, John P.; Sprenkle, Vincent L.; Yang, Zhenguo

2012-12-01

The sodium-nickel chloride (ZEBRA) battery is operated at relatively high temperature (250-350 °C) to achieve adequate electrochemical performance. Reducing the operating temperature in the range of 150200 °C can not only lead to enhanced cycle life by suppressing temperature-related degradations, but also allow the use of lower cost materials for construction. To achieve adequate electrochemical performance at lower operating temperatures, reduction in ohmic losses is required, including the reduced ohmic resistance of β″-alumina solid electrolyte (BASE) and the incorporation of low melting point secondary electrolytes. In present work, planar-type Na/NiCl2 cells with a thin BASE (600 μm) and low melting point secondary electrolyte were evaluated at reduced temperatures. Molten salts used as secondary electrolytes were fabricated by the partial replacement of NaCl in the standard secondary electrolyte (NaAlCl4) with other lower melting point alkali metal salts such as NaBr, LiCl, and LiBr. Electrochemical characterization of these ternary molten salts demonstrated improved ionic conductivity and sufficient electrochemical window at reduced temperatures. Furthermore, Na/NiCl2 cells with 50 mol% NaBr-containing secondary electrolyte exhibited reduced polarizations at 175 °C compared to the cell with the standard NaAlCl4 catholyte. The cells also exhibited stable cycling performance even at 150 °C.

Physiological and performance effects of carbohydrate gels consumed prior to the extra-time period of prolonged simulated soccer match-play.

PubMed

Harper, Liam D; Briggs, Marc A; McNamee, Ged; West, Daniel J; Kilduff, Liam P; Stevenson, Emma; Russell, Mark

2016-06-01

The physiological and performance effects of carbohydrate-electrolyte gels consumed before the 30min extra-time period of prolonged soccer-specific exercise were investigated. Randomised, double-blind, crossover. Eight English Premier League academy soccer players performed 120min of soccer-specific exercise on two occasions while consuming fluid-electrolyte beverages before exercise, at half-time and 90min. Carbohydrate-electrolyte (0.7±0.1gkg(-1) BM) or energy-free placebo gels were consumed ∼5min before extra-time. Blood samples were taken before exercise, at half-time and every 15min during exercise. Physical (15-m and 30-m sprint speed, 30-m sprint maintenance and countermovement jump height) and technical (soccer dribbling) performance was assessed throughout each trial. Carbohydrate-electrolyte gels improved dribbling precision (+29±20%) and raised blood glucose concentrations by 0.7±0.8mmoll(-1) during extra-time (both p<0.01). Supplementation did not affect sprint velocities (15m and 30m), 30-m sprint maintenance or dribbling speed as reductions compared to 0-15min values occurred at 105-120min irrespective of trial (all p<0.05). Plasma osmolality and blood sodium concentrations increased post-exercise vs. the opening 15min (p<0.05) but no effect of supplementation existed. Selected markers of physical performance (jump height, 30-m sprint velocity and 30-m repeated sprint maintenance) also reduced by >3% during half-time (all p<0.05). Carbohydrate-electrolyte gel ingestion raised blood glucose concentrations and improved dribbling performance during the extra-time period of simulated soccer match-play. Supplementation did not attenuate reductions in physical performance and hydration status that occurred during extra-time. Copyright © 2015 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Improved electrochemical and thermal properties of nickel rich LiNi0.6Co0.2Mn0.2O2 cathode materials by SiO2 coating

NASA Astrophysics Data System (ADS)

Cho, Woosuk; Kim, Sang-Min; Song, Jun Ho; Yim, Taeeun; Woo, Sang-Gil; Lee, Ko-Woon; Kim, Jeom-Soo; Kim, Young-Jun

2015-05-01

A surface coating of SiO2 is applied to a Ni rich LiNi0.6Co0.2Mn0.2O2 cathode material in a bid to improve its electrochemical and thermal properties. A uniform coating is achieved through a wet process using nano-sized SiO2 powder, and though the coated electrode is found to exhibit a reduced rate capability, its cycle performance at a high temperature of 60 °C is greatly enhanced. The effect of this SiO2 coating is further investigated by electrochemical impedance spectroscopy, which confirms that it suppresses the growth of interfacial impedance during progressive cycles. The SiO2 coating also demonstrates good HF scavenging ability, producing a subsequent reduction in the degradation of the active core material. The thermal properties of LiNi0.6Co0.2Mn0.2O2 are also improved by the SiO2 coating due to a reduction in the direct contact between the electrode and electrolyte. On the basis of these results, SiO2 coating is considered a viable surface modification method for improving the electrochemical and thermal properties of LiNi0.6Co0.2Mn0.2O2.

X-Ray Absorption Spectroscopy of Electrochemically Generated Species

DTIC Science & Technology

1993-02-01

that is a modification of our previously reported design (17) with reticulated vitreous carbon (RVC) as the working electrode. A peristaltic pump...and a flowing analyte stream. A packed carbon -bed bulk electrolysis cell generates the desired metal oxidation state. Completa oxidation and...packed carbon -bed bulk electrolysis cell generates the desired metal oxidation state. The system consists of a closed loop of electrolyte solution

Fluid/electrolyte and endocrine changes in space flight

NASA Technical Reports Server (NTRS)

Huntoon, Carolyn Leach

1989-01-01

The primary effects of space flight that influence the endocrine system and fluid and electrolyte regulation are the reduction of hydrostatic gradients, reduction in use and gravitational loading of bone and muscle, and stress. Each of these sets into motion a series of responses that culminates in alteration of some homeostatic set points for the environment of space. Set point alterations are believed to include decreases in venous pressure; red blood cell mass; total body water; plasma volume; and serum sodium, chloride, potassium, and osmolality. Serum calcium and phosphate increase. Hormones such as erythropoietin, atrial natriuretic peptide, aldosterone, cortisol, antidiuretic hormone, and growth hormone are involved in the dynamic processes that bring about the new set points. The inappropriateness of microgravity set points for 1-G conditions contributes to astronaut postflight responses.

[Advances in microbial genome reduction and modification].

PubMed

Wang, Jianli; Wang, Xiaoyuan

2013-08-01

Microbial genome reduction and modification are important strategies for constructing cellular chassis used for synthetic biology. This article summarized the essential genes and the methods to identify them in microorganisms, compared various strategies for microbial genome reduction, and analyzed the characteristics of some microorganisms with the minimized genome. This review shows the important role of genome reduction in constructing cellular chassis.

Atomistic Structure and Dynamics of the Solvation Shell Formed by Organic Carbonates around Lithium Ions via Infrared Spectroscopies

NASA Astrophysics Data System (ADS)

Kuroda, Daniel; Fufler, Kristen

Lithium-ion batteries have become ubiquitous to the portable energy storage industry, but efficiency issues still remain. Currently, most technological and scientific efforts are focused on the electrodes with little attention on the electrolyte. For example, simple fundamental questions about the lithium ion solvation shell composition in commercially used electrolytes have not been answered. Using a combination of linear and non-linear IR spectroscopies and theoretical calculations, we have carried out a thorough investigation of the solvation structure and dynamics of the lithium ion in various linear and cyclic carbonates at common battery electrolyte concentrations. Our studies show that carbonates coordinate the lithium ion tetrahedrally. They also reveal that linear and cyclic carbonates have contrasting dynamics in which cyclic carbonates present the most ordered structure. Finally, our experiments demonstrate that simple structural modifications in the linear carbonates impact significantly the microscopic interactions of the system. The stark differences in the solvation structure and dynamics among different carbonates reveal previously unknown details about the molecular level picture of these systems.

Identifying compatibility of lithium salts with LiFePO4 cathode using a symmetric cell

NASA Astrophysics Data System (ADS)

Tong, Bo; Wang, Jiawei; Liu, Zhenjie; Ma, Lipo; Zhou, Zhibin; Peng, Zhangquan

2018-04-01

The electrochemical performance of lithium-ion batteries is dominated by the interphase electrochemistry between the electrolyte and electrode materials. A multitude of efforts have been dedicated to the solid electrolyte interphase (SEI) formed on the anode. However, the interphase on the cathode, namely the cathode electrolyte interphase (CEI), is left aside, partially due to the fact that it is hard to single out the CEI considering the complicated anode-cathode inter-talk. Herein, a partially delithiated lithium iron phosphate (Li0.25FePO4) electrode is used as the anode. Owing to a high voltage plateau (≈3.45 V vs. Li/Li+), negligible reduction reactions of electrolyte occur on the L0.25FePO4 anode. Therefore, the CEI can be investigated exclusively. Using a LiFePO4|Li0.25FePO4 symmetric cell configuration, we scrutinize the compatibility of the electrolytes containing a wide spectrum of lithium salts, Li[(FSO2)(Cm F2m+1SO2)N] (m = 0, 1, 2, 4), with the LiFePO4, in both cycling and calendar tests. It is found that the Li[(FSO2)(n-C4F9SO2)N] (LiFNFSI)-based electrolyte exhibits the highest compatibility with LiFePO4.

Preparation of Ferrotitanium from Ilmenite by Electrolysis-Assisted Calciothermic Reduction in CaCl2-NaCl Molten Salt

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Hua, Yixin; Xu, Cunying; Li, Jian; Li, Yan; Gong, Kai; Ru, Juanjian; Xiong, Li

2016-02-01

Electrolysis-assisted calciothermic reduction method is proposed and successfully used to prepare ferrotitanium alloy from ilmenite by using equal-molar CaCl2-NaCl molten salt as electrolyte, molybdenum rod as cathode, and graphite as anode at 973 K with cell voltages of 3.2-4.4 V under inert atmosphere. Thermodynamics analysis of the process is presented, and the products obtained are examined with x-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. It is demonstrated that the calciothermic reduction of ilmenite is a stepwise process since intermediate CaTiO3 is observed in the products partially reduced. In the calciothermic reduction process, the reduction of FeTiO3 first gives rise to the formation of Fe and CaTiO3, which as intermediates will further react with calcium metal to form ferrotitanium alloys. This is in good agreement with the prediction of thermodynamics. Experimental results also show that increasing cell voltage can accelerate the formation of calcium metal through electrolysis of CaO and CaCl2 and, hence, promote the calciothermic reduction of ilmenite. As the electrolytic zone and reduction zone are combined in the same bath, the theoretical energy requirement for the production of FeTi in the calciothermic process is lower than that in the aluminothermic process.

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

PubMed

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

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

PubMed

Nohira, Toshiyuki; Yasuda, Kouji; Ito, Yasuhiko

2003-06-01

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

Oxygen reduction reaction catalyzed by nickel complexes based on thiophosphorylated calix[4]resorcinols and immobilized in the membrane electrode assembly of fuel cells.

PubMed

Kadirov, M K; Knyazeva, I R; Nizameev, I R; Safiullin, R A; Matveeva, V I; Kholin, K V; Khrizanforova, V V; Ismaev, T I; Burilov, A R; Budnikova, Yu H; Sinyashin, O G

2016-10-18

The catalytic activity of the nickel complexes of thiophosphorylated calix[4]resorcinols for oxygen reduction in a polymer electrolyte membrane fuel cell (PEMFC) has been studied. The conformation of the macrocyclic ligand determines the morphology and catalytic properties of the resulting organometallic species.

Reaction mechanisms for the limited reversibility of Li-O 2 chemistry in organic carbonate electrolytes

NASA Astrophysics Data System (ADS)

Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Ji-Guang

The Li-O 2 chemistry in nonaqueous liquid carbonate electrolytes and the underlying reason for its limited reversibility was systematically investigated. X-ray diffraction data showed that regardless of discharge depth lithium alkylcarbonates (lithium propylenedicarbonate (LPDC), or lithium ethylenedicarbonate (LEDC), with other related derivatives) and lithium carbonate (Li 2CO 3) are constantly the main discharge products, while lithium peroxide (Li 2O 2) or lithium oxide (Li 2O) is hardly detected. These lithium alkylcarbonates are generated from the reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. More significantly, in situ gas chromatography/mass spectroscopy analysis revealed that Li 2CO 3 and Li 2O cannot be oxidized even when charged to 4.6 V vs. Li/Li +, while LPDC, LEDC and Li 2O 2 are readily oxidized, with CO 2 and CO released from LPDC and LEDC and O 2 evolved from Li 2O 2. Therefore, the apparent reversibility of Li-O 2 chemistry in an organic carbonate-based electrolyte is actually an unsustainable process that consists of (1) the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharging and (2) the subsequent oxidation of these same alkylcarbonates during charging. Therefore, a stable electrolyte that does not lead to an irreversible by-product formation during discharging and charging is necessary for truly rechargeable Li-O 2 batteries.

Annealing Would Improve beta" - Alumina Solid Electrolyte

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

PubMed Central

Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

2015-01-01

The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells.

PubMed

Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

2015-02-01

The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells.

Formation of TiO2 nanostructure by plasma electrolytic oxidation for Cr(VI) reduction

NASA Astrophysics Data System (ADS)

Torres, D. A.; Gordillo-Delgado, F.; Plazas-Saldaña, J.

2017-01-01

Plasma electrolytic oxidation (PEO) is an environmentally friendly technique that allows the growth of ceramic coatings without organic solvents and non-toxic residues. This method was applied to ASME SB-265 titanium (Ti) plates (2×2×0.1cm) using voltage pulses from a switching power supply (340V) for 10 minutes at frequency of 1000Hz changing duty cycle at 10, 60 and 90% and the electrolytes were Na3PO4 and NaOH. The treated sheets surfaces were analysed by X-ray diffraction and scanning electron microscopy. According to the diffractograms, the duty cycle increase produces amorphous TiO2 coating on Ti sheets and the thickness increases. After sintering at 900°C during 1 hour, the 10% duty cycle generated a combination of anatase and rutile phases at the sample surface with weight percentages of 13.3 and 86.6% and particle sizes of 32.461±0.009nm and 141.14±0.03 nm, respectively. With this sample, the total reduction of hexavalent chromium was reached at 50 minutes for 1ppm solution. This photocatalytic activity was measured following the colorimetric method ASTM-3500-Cr B.

Sieving of electrolytes at capillary wall of cat skeletal muscle by osmotic water flow.

PubMed

Watson, P D

1993-12-01

To test the hypothesis that a significant proportion of transcapillary water flow occurs through solute-restricting channels, we investigated the effects of transcapillary water movement on plasma electrolytes in isolated perfused cat skeletal muscle. The lower hindlimbs of anesthetized cats were perfused with a plasma-albumin solution and were weighed to determine transcapillary water movement. Osmolality was increased 60-70 mosmol/kgH2O with sucrose, creating water fluxes of 8-10 ml.min-1.100 g-1, and the changes in the venous concentrations of sodium, potassium, and chloride were determined. The ion concentrations were all reduced by 6-7% with no significant difference between them. The amount of reduction was quantitatively explained by the flow of ion-free water from the interstitial space into plasma and the diffusion of electrolyte in the same direction. These findings support the hypothesis that important water-only transcapillary channels exist in mammalian skeletal muscle. The observations may also explain some of the electrolyte changes seen in intense exercise.

Releasing metal catalysts via phase transition: (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 as a redox stable anode material for solid oxide fuel cells.

PubMed

Xiao, Guoliang; Wang, Siwei; Lin, Ye; Zhang, Yanxiang; An, Ke; Chen, Fanglin

2014-11-26

Donor-doped perovskite-type SrTiO3 experiences stoichiometric changes at high temperatures in different Po2 involving the formation of Sr or Ti-rich impurities. NiO is incorporated into the stoichiometric strontium titanate, SrTi0.8Nb0.2O3-δ (STN), to form an A-site deficient perovskite material, (NiO)0.05-(SrTi0.8Nb0.2O3)0.95 (Ni-STN), for balancing the phase transition. Metallic Ni nanoparticles can be released upon reduction instead of forming undesired secondary phases. This material design introduces a simple catalytic modification method with good compositional control of the ceramic backbones, by which transport property and durability of solid oxide fuel cell anodes are largely determined. Using Ni-STN as anodes for solid oxide fuel cells, enhanced catalytic activity and remarkable stability in redox cycling have been achieved. Electrolyte-supported cells with the cell configuration of Ni-STN-SDC anode, La0.8Sr0.2Ga0.87Mg0.13O3 (LSGM) electrolyte, and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode produce peak power densities of 612, 794, and 922 mW cm(-2) at 800, 850, and 900 °C, respectively, using H2 as the fuel and air as the oxidant. Minor degradation in fuel cell performance resulted from redox cycling can be recovered upon operating the fuel cells in H2. Such property makes Ni-STN a promising regenerative anode candidate for solid oxide fuel cells.

Double-plasma enhanced carbon shield for spatial/interfacial controlled electrodes in lithium ion batteries via micro-sized silicon from wafer waste

NASA Astrophysics Data System (ADS)

Chen, Bing-Hong; Chuang, Shang-I.; Duh, Jenq-Gong

2016-11-01

Using spatial and interfacial control, the micro-sized silicon waste from wafer slurry could greatly increase its retention potential as a green resource for silicon-based anode in lithium ion batteries. Through step by step spatial and interfacial control for electrode, the cyclability of recycled waste gains potential performance from its original poor retention property. In the stages of spatial control, the electrode stabilizers of active, inactive and conductive additives were mixed into slurries for maintaining architecture and conductivity of electrode. In addition, a fusion electrode modification of interfacial control combines electrolyte additive, technique of double-plasma enhanced carbon shield (D-PECS) to convert the chemical bond states and to alter the formation of solid electrolyte interphases (SEIs) in the first cycle. The depth profiles of chemical composition from external into internal electrode illustrate that the fusion electrode modification not only forms a boundary to balance the interface between internal and external electrodes but also stabilizes the SEIs formation and soothe the expansion of micro-sized electrode. Through these effect approaches, the performance of micro-sized Si waste electrode can be boosted from its serious capacity degradation to potential retention (200 cycles, 1100 mAh/g) and better meet the requirements for facile and cost-effective in industrial production.

Combinations of laxatives and green banana biomass on the treatment of functional constipation in children and adolescents: a randomized study.

PubMed

Cassettari, Vanessa Mello Granado; Machado, Nilton Carlos; Lourenção, Pedro Luiz Toledo de Arruda; Carvalho, Marry Assis; Ortolan, Erika Veruska Paiva

2018-01-05

Evaluate the effect of combinations of green banana biomass and laxatives in children and adolescents with chronic constipation. This was a randomized study of 80 children and adolescents with functional constipation according to the Rome IV Criteria, who were divided into five groups: (1) green banana biomass alone; (2) green banana biomass plus PEG 3350 with electrolytes; (3) green banana biomass plus sodium picosulfate; (4) PEG 3350 with electrolytes alone; and (5) sodium picosulfate alone. Primary outcome measure was the reduction of the proportion of patients with Bristol Stool Form Scale ratings 1 or 2. Secondary outcome measures were: increase of the proportion of >3 bowel movements/week and reduction of the proportion of fecal incontinence, straining on defecation, painful defecation, blood in stool, abdominal pain, and decreased laxative doses. On consumption of green banana biomass alone, a statistically significant reduction was observed in the proportion of children with Bristol Stool Form Scale rating 1 or 2, straining on defecation, painful defecation, and abdominal pain. Conversely, no reduction was observed in fecal incontinence episodes/week, blood in stool, and no increase was observed in the proportion of children with >3 bowel movements/week. The percentage of children who required decreased laxative dose was high when green banana biomass was associated with sodium picosulfate (87%), and PEG 3350 with electrolytes (63%). Green banana biomass alone and associated with laxatives was well tolerated, and no adverse effects were reported. Green banana biomass is advantageous as an adjunct therapy on functional constipation, mainly for reducing doses of laxatives. Copyright © 2017 Sociedade Brasileira de Pediatria. Published by Elsevier Editora Ltda. All rights reserved.

Effects of anodic oxidation and hydrothermal treatment on surface characteristics and biocompatibility of Ti-30Nb-1Fe-1Hf alloy

NASA Astrophysics Data System (ADS)

Ou, Shih-Fu; Chou, Hsin-Hua; Lin, Chao-Sung; Shih, Ching-Jui; Wang, Kuang-Kuo; Pan, Yung-Ning

2012-06-01

Anodic oxidation followed by hydrothermal treatment has been widely applied for surface modification of titanium alloys to precipitate a crystalline hydroxyapatite (HA) layer in order to achieve improved osteoconduction. A majority of the studies in the literature imposed relatively high powers to enhance Ca and P in the anodic oxide film (AOF). However, high powers have been found to cause deterioration of the adhesive strength in one of the author's previous study. In this study, a new electrolyte comprising calcium acetate monohydrate (CA), β-glycerophosphate disodium pentahydrate (β-GP) and HA powder was developed, and the Ti-30Nb-1Fe-1Hf alloy was anodized in this HA-containing electrolyte to a relatively low voltage. Results show that the AOF anodized in the HA-containing electrolyte exhibits a better HA forming ability during hydrothermal treatment, attributing to the presence of HA powder in the electrolyte that effectively enhances both the Ca content and Ca/P ratio in the AOF. On the other hand, the adhesive strength was little affected due to the decrease in size of the craters residing in the AOF. With respect to the biological responses, not much difference in biocompatibility of the treated and untreated Ti-Nb surfaces was obtained. However, the anodized and hydrothermally treated surface promotes the attachment of cells.

Improvements to Zirconia Thick-Film Oxygen Sensors

NASA Astrophysics Data System (ADS)

Maskell, William C.; Brett, Daniel J. L.; Brandon, Nigel P.

2013-06-01

Thick-film zirconia gas sensors are normally screen-printed onto a planar substrate. A sandwich of electrode-electrolyte-electrode is fired at a temperature sufficient to instigate sintering of the zirconia electrolyte. The resulting porous zirconia film acts as both the electrolyte and as the diffusion barrier through which oxygen diffuses. The high sintering temperature results in de-activation of the electrodes so that sensors must be operated at around 800 °C for measurements in the percentage range of oxygen concentration. This work shows that the use of cobalt oxide as a sintering aid allows reduction of the sensor operating temperature by 100-200 °C with clear benefits. Furthermore, an interesting and new technique is presented for the investigation of the influence of dopants and of the through-porosity of ionically-conducting materials.

Automatic electrochemical ambient air monitor for chloride and chlorine

DOEpatents

Mueller, Theodore R.

1976-07-13

An electrochemical monitoring system has been provided for determining chloride and chlorine in air at levels of from about 10-1000 parts per billion. The chloride is determined by oxidation to chlorine followed by reduction to chloride in a closed system. Chlorine is determined by direct reduction at a platinum electrode in 6 M H.sub.2 SO.sub.4 electrolyte. A fully automated system is utilized to (1) acquire and store a value corresponding to electrolyte-containing impurities, (2) subtract this value from that obtained in the presence of air, (3) generate coulometrically a standard sample of chlorine mixed with air sample, and determine it as chlorine and/or chloride, and (4) calculate, display, and store for permanent record the ratio of the signal obtained from the air sample and that obtained with the standard.

Platinum nanoparticles on carbon-nanotube support prepared by room-temperature reduction with H2 in ethylene glycol/water mixed solvent as catalysts for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Zheng, Yuying; Dou, Zhengjie; Fang, Yanxiong; Li, Muwu; Wu, Xin; Zeng, Jianhuang; Hou, Zhaohui; Liao, Shijun

2016-02-01

Polyol approach is commonly used in synthesizing Pt nanoparticles in polymer electrolyte membrane fuel cells. However, the application of this process consumes a great deal of time and energy, as the reduction of precursors requires elevated temperatures and several hours. Moreover, the ethylene glycol and its oxidizing products bound to Pt are difficult to remove. In this work, we utilize the advantages of ethylene glycol and prepare Pt nanoparticles through a room-temperature hydrogen gas reduction in an ethylene glycol/water mixed solvent, which is followed by subsequent harvesting by carbon nanotubes as electrocatalysts. This method is simple, facile, and time-efficient, as the entire room-temperature reduction process is completed in a few minutes. As the solvent changes from water to an ethylene glycol/water mix, the size of Pt nanoparticles varies from 10 to 3 nm and their shape transitions from polyhedral to spherical. Pt nanoparticles prepared in a 1:1 volume ratio mixture of ethylene glycol/water are uniformly dispersed with an average size of ∼3 nm. The optimized carbon nanotube-supported Pt electrocatalyst exhibits excellent methanol oxidation and oxygen reduction activities. This work demonstrates the potential use of mixed solvents as an approach in materials synthesis.

Feasibility tests of nickel as a containment material of molten Li2O-LiCl salt containing Li metal at 650 °C during electrolytic reduction

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Lee, Jeong

2017-11-01

In this study, we investigated the feasibility of nickel (Ni) as a material to contain molten Li2O-LiCl salt containing lithium (Li) metal at 650 °C as an electrolyte during the electrolytic reduction process of pyroprocessing (also known as oxide reduction, OR). First, the behaviors of Ni in four different LiCl salts (0.1 wt% Li-LiCl, 1 and 8 wt% Li2O-LiCl, and 8 wt% Li2O-0.1 wt% Li-LiCl) in an argon atmosphere were examined through immersion tests. Then, Ni was used as a vessel material for five consecutive OR runs of simulated oxide fuel using 1.0 wt% Li2O-LiCl salt. The tested Ni was analyzed by microbalance, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. Concentrations of Ni in the salt were measured using inductively coupled plasma atomic emission spectroscopy. No corrosion product of Ni, except Cr2Ni3, was observed on the Ni used for both the salt-immersion tests and the OR runs because the Ni was not exposed to oxygen gas. However, leaching of Ni in the OR salt containing excessive Li metal was observed. Therefore, Ni can be used as the salt containment material in the OR process when excessive Li metal and oxygen gas in the salt are maintained at low levels.

Molten salt applications in materials processing

NASA Astrophysics Data System (ADS)

Mishra, Brajendra; Olson, David L.

2005-02-01

The science of molten salt electrochemistry for electrowinning of reactive metals, such as calcium, and its in situ application in pyro-reduction has been described. Calcium electrowinning has been performed in a 5 10 wt% calcium oxide calcium chloride molten salt by the electrolytic dissociation of calcium oxide. This electrolysis requires the use of a porous ceramic sheath around the anode to keep the cathodically deposited calcium and the anodic gases separate. Stainless steel cathode and graphite anode have been used in the temperature range of 850 950 °C. This salt mixture is produced as a result of the direct oxide reduction (DOR) of reactive metal oxides by calcium in a calcium chloride bath. The primary purpose of this process is to recover the expensive calcium reductant and to recycle calcium chloride. Experimental data have been included to justify the suitability as well as limitations of the electrowinning process. Transport of oxygen ions through the sheath is found to be the rate controlling step. Under the constraints of the reactor design, a calcium recovery rate of approx. 150 g/h was achieved. Feasibility of a process to produce metals by pyrometallurgical reduction, using the calcium reductant produced electrolytically within the same reactor, has been shown in a hybrid process. Several processes are currently under investigation to use this electrowon calcium for in situ reduction of metal oxides.

Aluminum reduction cell electrode

DOEpatents

Goodnow, Warren H.; Payne, John R.

1982-01-01

The invention is directed to cathode modules comprised of refractory hard metal materials, such as TiB.sub.2, for an electrolytic cell for the reduction of alumina wherein the modules may be installed and replaced during operation of the cell and wherein the structure of the cathode modules is such that the refractory hard metal materials are not subjected to externally applied forces or rigid constraints.

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1989-01-01

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation. Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium).

Evolution of thermal stress and failure probability during reduction and re-oxidation of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Wang, Yu; Jiang, Wenchun; Luo, Yun; Zhang, Yucai; Tu, Shan-Tung

2017-12-01

The reduction and re-oxidation of anode have significant effects on the integrity of the solid oxide fuel cell (SOFC) sealed by the glass-ceramic (GC). The mechanical failure is mainly controlled by the stress distribution. Therefore, a three dimensional model of SOFC is established to investigate the stress evolution during the reduction and re-oxidation by finite element method (FEM) in this paper, and the failure probability is calculated using the Weibull method. The results demonstrate that the reduction of anode can decrease the thermal stresses and reduce the failure probability due to the volumetric contraction and porosity increasing. The re-oxidation can result in a remarkable increase of the thermal stresses, and the failure probabilities of anode, cathode, electrolyte and GC all increase to 1, which is mainly due to the large linear strain rather than the porosity decreasing. The cathode and electrolyte fail as soon as the linear strains are about 0.03% and 0.07%. Therefore, the re-oxidation should be controlled to ensure the integrity, and a lower re-oxidation temperature can decrease the stress and failure probability.

A p-nitroaniline redox-active solid-state electrolyte for battery-like electrochemical capacitive energy storage combined with an asymmetric supercapacitor based on metal oxide functionalized β-polytype porous silicon carbide electrodes.

PubMed

Kim, Myeongjin; Yoo, Jeeyoung; Kim, Jooheon

2017-05-23

A unique redox active flexible solid-state asymmetric supercapacitor with ultra-high capacitance and energy density was fabricated using a composite comprising MgCo 2 O 4 nanoneedles and micro and mesoporous silicon carbide flakes (SiCF) (SiCF/MgCo 2 O 4 ) as the positive electrode material. Due to the synergistic effect of the two materials, this hybrid electrode has a high specific capacitance of 516.7 F g -1 at a scan rate of 5 mV s -1 in a 1 M KOH aqueous electrolyte. To obtain a reasonable matching of positive and negative electrode pairs, a composite of Fe 3 O 4 nanoparticles and SiCF (SiCF/Fe 3 O 4 ) was synthesized for use as a negative electrode material, which shows a high capacitance of 423.2 F g -1 at a scan rate of 5 mV s -1 . Therefore, by pairing the SiCF/MgCo 2 O 4 positive electrode and the SiCF/Fe 3 O 4 negative electrode with a redox active quasi-solid-state PVA-KOH-p-nitroaniline (PVA-KOH-PNA) gel electrolyte, a novel solid-state asymmetric supercapacitor device was assembled. Because of the synergistic effect between the highly porous SiCF and the vigorous redox-reaction of metal oxides, the hybrid nanostructure electrodes exhibited outstanding charge storage and transport. In addition, the redox active PVA-KOH-PNA electrolyte adds additional pseudocapacitance, which arises from the nitro-reduction and oxidation and reduction process of the reduction product of p-phenylenediamine, resulting in an enhancement of the capacitance (a specific capacitance of 161.77 F g -1 at a scan rate of 5 mV s -1 ) and energy density (maximum energy density of 72.79 Wh kg -1 at a power density of 727.96 W kg -1 ).

Effects of temperature and gas-liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts.

PubMed

Lobaccaro, Peter; Singh, Meenesh R; Clark, Ezra Lee; Kwon, Youngkook; Bell, Alexis T; Ager, Joel W

2016-09-29

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. We show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena taking place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of <10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. We show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2 .

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts

DOE PAGES

Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee; ...

2016-09-06

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. Here we show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena takingmore » place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of < 10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. Finally, we show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2.« less

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts

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

Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. Here we show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena takingmore » place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of < 10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. Finally, we show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2.« less

Novel Organic Field Effect Transistors via Nano-Modification

DTIC Science & Technology

2005-07-01

mobility by using two kinds of nano-scale films. One is to apply the photoalignment method on a nano-scale film to control the orientation of pentacene ...scale film (polymer electrolyte) to control moving of ions in/out an active semiconducor, pentacene or conducting polymer, for improving carrier...mobility. In this project, pentacene or a series of conducting polymers, such as the derivatives of PANI and P3HT will be patterned and manufactured in

Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

NASA Astrophysics Data System (ADS)

Lian, Cheng; Liu, Honglai; Henderson, Douglas; Wu, Jianzhong

2016-10-01

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this study, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance-voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitors containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors. The authors are saddened by the passing of George Stell but are pleased to contribute this article in his memory. Some years ago, DH gave a talk at a Gordon Conference that contained an approximation that George had demonstrated previously to be in error in one of his publications. Rather than making this point loudly in the discussion, George politely, quietly, and privately pointed this out later. In 2002, DH shared a room with George at a conference in China. This is remembered fondly.

Electrodeposition of platinum on highly oriented pyrolytic graphite. Part I: electrochemical characterization.

PubMed

Lu, Guojin; Zangari, Giovanni

2005-04-28

The electrochemical deposition of Pt on highly oriented pyrolytic graphite (HOPG) from H2PtCl6 solutions was investigated by cyclic voltammetry and chronoamperometry. The effects of deposition overpotential, H2PtCl6 concentration, supporting electrolyte, and anion additions on the deposition process were evaluated. Addition of chloride inhibits Pt deposition due to adsorption on the substrate and blocking of reduction sites, while SO4(2-) and ClO4- slightly promote Pt reduction. By comparing potentiostatic current-time transients with the Scharifker-Hills model, a transition from progressive to instantaneous nucleation was observed when increasing the deposition overpotential. Following addition of chloride anions the fit of experimental transients with the instantaneous nucleation mode improves, while the addition of SO4(2-) induces only small changes. Chloride anions strongly inhibit the reduction process, which is shifted in the cathodic direction. The above results indicate that the most appropriate conditions for growing Pt nanoparticles on HOPG with narrow size distribution are to use an H2PtCl6 solution with HCl as supporting electrolyte and to apply a high cathodic overpotential.

Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

DOE PAGES

Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.; ...

2016-03-18

Graphitic materials are very essential in energy conversion and storage because of their excellent chemical and electrical properties. The strategy for obtaining functional graphitic materials involves graphite oxidation and subsequent dissolution in aqueous media, forming graphene-oxide nanosheets (GNs). Restacked GNs contain substantial intercalated water that can react with heteroatom dopants or the graphene lattice during reduction. We demonstrate that removal of intercalated water using simple solvent treatments causes significant structural reorganization, substantially affecting the oxygen reduction reaction (ORR) activity and stability of nitrogen-doped graphitic systems. Amid contrasting reports describing the ORR activity of GN-based catalysts in alkaline electrolytes, we demonstratemore » superior activity in an acidic electrolyte with an onset potential of ~0.9 V, a half-wave potential (E ½) of 0.71 V, and a selectivity for four-electron reduction of >95%. Finally and further, durability testing showed E ½ retention >95% in N 2- and O 2-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.« less

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

PubMed

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

Aluminum reduction cell electrode

DOEpatents

Goodnow, W.H.; Payne, J.R.

1982-09-14

The invention is directed to cathode modules comprised of refractory hard metal materials, such as TiB[sub 2], for an electrolytic cell for the reduction of alumina wherein the modules may be installed and replaced during operation of the cell and wherein the structure of the cathode modules is such that the refractory hard metal materials are not subjected to externally applied forces or rigid constraints. 9 figs.

For cermet inert anode containing oxide and metal phases useful for the electrolytic production of metals

DOEpatents

Ray, Siba P.; Liu, Xinghua; Weirauch, Douglas A.

2002-01-01

A cermet inert anode for the electrolytic production of metals such as aluminum is disclosed. The inert anode comprises a ceramic phase including an oxide of Ni, Fe and M, where M is at least one metal selected from Zn, Co, Al, Li, Cu, Ti, V, Cr, Zr, Nb, Ta, W, Mo, Hf and rare earths, preferably Zn and/or Co. Preferred ceramic compositions comprise Fe.sub.2 O.sub.3, NiO and ZnO or CoO. The cermet inert anode also comprises a metal phase such as Cu, Ag, Pd, Pt, Au, Rh, Ru, Ir and/or Os. A preferred metal phase comprises Cu and Ag. The cermet inert anodes may be used in electrolytic reduction cells for the production of commercial purity aluminum as well as other metals.

Simulation of synaptic short-term plasticity using Ba(CF3SO3)2-doped polyethylene oxide electrolyte film.

PubMed

Chang, C T; Zeng, F; Li, X J; Dong, W S; Lu, S H; Gao, S; Pan, F

2016-01-07

The simulation of synaptic plasticity using new materials is critical in the study of brain-inspired computing. Devices composed of Ba(CF3SO3)2-doped polyethylene oxide (PEO) electrolyte film were fabricated and with pulse responses found to resemble the synaptic short-term plasticity (STP) of both short-term depression (STD) and short-term facilitation (STF) synapses. The values of the charge and discharge peaks of the pulse responses did not vary with input number when the pulse frequency was sufficiently low(~1 Hz). However, when the frequency was increased, the charge and discharge peaks decreased and increased, respectively, in gradual trends and approached stable values with respect to the input number. These stable values varied with the input frequency, which resulted in the depressed and potentiated weight modifications of the charge and discharge peaks, respectively. These electrical properties simulated the high and low band-pass filtering effects of STD and STF, respectively. The simulations were consistent with biological results and the corresponding biological parameters were successfully extracted. The study verified the feasibility of using organic electrolytes to mimic STP.

Pd surface functionalization of 3D electroformed Ni and Ni-Mo alloy metallic nanofoams for hydrogen production

NASA Astrophysics Data System (ADS)

Petica, A.; Brincoveanu, O.; Golgovici, F.; Manea, A. C.; Enachescu, M.; Anicai, L.

2018-03-01

The paper presents some experimental results regarding the functionalization of 3D electroformed Ni and Ni-Mo alloy nanofoams with Pd nanoclusters, as potential cathodic materials suitable for HER during seawater electrolysis. The electrodeposition from aqueous electrolytes containing NiCl2 and NH4Cl has been applied to prepare the 3D Ni nanofoams. Ni-Mo alloys have been electrodeposited involving aqueous ammonium citrate type electrolytes. Pd surface functionalization has been performed using both electroless and electrochemical procedures. Pd content varied in the range of 0.5 – 8 wt.%, depending on the applied procedure and the operation conditions. The use of a porous structure associated with alloying element (i.e. Mo) and Pd surface functionalization facilitated enhanced performances from HER view point in seawater electrolyte (lower Tafel slopes). The determined Tafel slope values ranged from 123 to 105 mV.dec-1, suggesting the Volmer step as rate determining step. The improvement of the HER catalytic activity may be ascribed to a synergistic effect between the high real active area of the 3D electroformed metallic substrate, Ni alloying with a left transition metal and surface modification using Pd noble metal.

Simulation of synaptic short-term plasticity using Ba(CF3SO3)2-doped polyethylene oxide electrolyte film

PubMed Central

Chang, C. T.; Zeng, F.; Li, X. J.; Dong, W. S.; Lu, S. H.; Gao, S.; Pan, F.

2016-01-01

The simulation of synaptic plasticity using new materials is critical in the study of brain-inspired computing. Devices composed of Ba(CF3SO3)2-doped polyethylene oxide (PEO) electrolyte film were fabricated and with pulse responses found to resemble the synaptic short-term plasticity (STP) of both short-term depression (STD) and short-term facilitation (STF) synapses. The values of the charge and discharge peaks of the pulse responses did not vary with input number when the pulse frequency was sufficiently low(~1 Hz). However, when the frequency was increased, the charge and discharge peaks decreased and increased, respectively, in gradual trends and approached stable values with respect to the input number. These stable values varied with the input frequency, which resulted in the depressed and potentiated weight modifications of the charge and discharge peaks, respectively. These electrical properties simulated the high and low band-pass filtering effects of STD and STF, respectively. The simulations were consistent with biological results and the corresponding biological parameters were successfully extracted. The study verified the feasibility of using organic electrolytes to mimic STP. PMID:26739613

Simulation of synaptic short-term plasticity using Ba(CF3SO3)2-doped polyethylene oxide electrolyte film

NASA Astrophysics Data System (ADS)

Chang, C. T.; Zeng, F.; Li, X. J.; Dong, W. S.; Lu, S. H.; Gao, S.; Pan, F.

2016-01-01

The simulation of synaptic plasticity using new materials is critical in the study of brain-inspired computing. Devices composed of Ba(CF3SO3)2-doped polyethylene oxide (PEO) electrolyte film were fabricated and with pulse responses found to resemble the synaptic short-term plasticity (STP) of both short-term depression (STD) and short-term facilitation (STF) synapses. The values of the charge and discharge peaks of the pulse responses did not vary with input number when the pulse frequency was sufficiently low(~1 Hz). However, when the frequency was increased, the charge and discharge peaks decreased and increased, respectively, in gradual trends and approached stable values with respect to the input number. These stable values varied with the input frequency, which resulted in the depressed and potentiated weight modifications of the charge and discharge peaks, respectively. These electrical properties simulated the high and low band-pass filtering effects of STD and STF, respectively. The simulations were consistent with biological results and the corresponding biological parameters were successfully extracted. The study verified the feasibility of using organic electrolytes to mimic STP.

FTIR spectra of plasticized grafted natural rubber-LiCF3SO3 electrolytes.

PubMed

Kumutha, K; Alias, Y

2006-05-15

Chemical modification of natural rubber (NR) has frequently been attempted to improve the performance in specific application. 30% poly(methyl metacrylate) (PMMA) grafted into NR (MG30) has been explored as a potential candidate for polymer electrolytes. The complexation effect of salt and plasticizer in polymer host electrolytes had been investigated using FTIR. The carbonyl stretch of MG30 locates at 1729 cm-1, with the addition of lithium trimethanesulfonate (LiCF3SO3) salt, new band evolves at lower frequency region at 1643-1645 cm-1. The nondegenerate vibrational mode of nus(SO3) of salted electrolytes appearing at 1031-1034 cm-1 comes from 'free' trimethanesulfonate anions and the 1040-1046 cm-1 absorption from the monodentate ion paired with triflates. These indicate MG30-salt interaction. When MG30 and ethylene carbonate (EC) formed film, the CH3 asymmetric bend of MG30 appearing at 1447cm-1 is shifted to 1449 cm-1 in the EC-polymer complex. The CO stretching at 1729 cm-1 also shifted to 1728 cm-1. Hence, the EC-MG30 system is complexed to each other. EC-LiCF3SO3 interactions are indicated by the shifting of CO bending band of EC from 718 cm-1 being shifted to 720 cm-1 in the complex. In Li+-EC interaction where the ring breathing region at 897 cm-1 in EC has shifted to 899 cm-1 in EC-salt spectrum. The band appearing at 1643-1645 cm-1 due to the coordination of Li+<--O-C is still under observation and new peaks at 1779 and 1809 cm-1 are responsible to the carbonyl stretches of EC in plasticized salt-polymer electrolytes.

Anode-cathode power distribution systems and methods of using the same for electrochemical reduction

DOEpatents

Koehl, Eugene R; Barnes, Laurel A; Wiedmeyer, Stanley G; Williamson, Mark A; Willit, James L

2014-01-28

Power distribution systems are useable in electrolytic reduction systems and include several cathode and anode assembly electrical contacts that permit flexible modular assembly numbers and placement in standardized connection configurations. Electrical contacts may be arranged at any position where assembly contact is desired. Electrical power may be provided via power cables attached to seating assemblies of the electrical contacts. Cathode and anode assembly electrical contacts may provide electrical power at any desired levels. Pairs of anode and cathode assembly electrical contacts may provide equal and opposite electrical power; different cathode assembly electrical contacts may provide different levels of electrical power to a same or different modular cathode assembly. Electrical systems may be used with an electrolyte container into which the modular cathode and anode assemblies extend and are supported above, with the modular cathode and anode assemblies mechanically and electrically connecting to the respective contacts in power distribution systems.

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

PubMed

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

2016-03-28

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

Controlled electro-implementation of fluoride in titanium implant surfaces enhances cortical bone formation and mineralization.

PubMed

Taxt-Lamolle, Sébastien F; Rubert, Marina; Haugen, Håvard J; Lyngstadaas, Ståle Petter; Ellingsen, Jan Eirik; Monjo, Marta

2010-03-01

Previous studies have shown that bone-to-implant attachment of titanium implants to cortical bone is improved when the surface is modified with hydrofluoric acid. The aim of this study was to investigate if biological factors are involved in the improved retention of these implants. Fluoride was implemented in implant surfaces by cathodic reduction with increasing concentrations of HF in the electrolyte. The modified implants were placed in the cortical bone in the tibias of New Zealand white rabbits. After 4 weeks of healing, wound fluid collected from the implant site showed lower lactate dehydrogenase activity and less bleeding in fluoride-modified implants compared to control. A significant increase in gene expression levels of osteocalcin and tartrate-resistant acid phosphatase (TRAP) was found in the cortical bone attached to Ti implants modified with 0.001 and 0.01 vol.% HF, while Ti implants modified with 0.1% HF showed only induced TRAP mRNA levels. These results were supported by the performed micro-CT analyses. The volumetric bone mineral density of the cortical bone hosting Ti implants modified with 0.001% and 0.01% HF was higher both in the newly woven bone (<100 microm from the interface) and in the older Haversian bone (>100 microm). In conclusion, the modulation of these biological factors by surface modification of titanium implants with low concentrations of HF using cathodic reduction may explain their improved osseointegration properties. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Hurdles to organic quinone flow cells. Electrode passivation by quinone reduction in acetonitrile Li electrolytes

NASA Astrophysics Data System (ADS)

Rueda-García, D.; Dubal, D. P.; Huguenin, F.; Gómez-Romero, P.

2017-05-01

The uses of quinones in Redox Flow Batteries (RFBs) has been mainly circumscribed to aqueous solutions (of derivatives with polar groups) despite a larger solubility and wider electrochemical window provided by organic media. The redox mechanism of quinones in protic media is simpler and better known than in aprotic media, where radical species are involved. This paper reports the behaviour of methyl-p-benzoquinone (MBQ) under electrochemical reduction conditions in a LiClO4sbnd CH3CN electrolyte and various working electrodes. We detected the reversible generation of a bright green coating on the working electrode and the subsequent formation of a polymer (the nature of which depends on the presence or absence of oxygen). These coatings prevent the regular redox process of methyl-p-benzoquinone from taking place on the surface of the electrode and is generated regardless of the electrode material used or the presence of O2 in solution. In addition to MBQ, the green passivating layer was also found for less sterically hindered quinones such as p-benzoquinone or 1,4-naphthoquinone, but not for anthraquinone. We have also shown the central role of Li+ in the formation of this green layer. This work provides important guidelines for the final use of quinones in RFBs with organic electrolytes.

Betavoltaic Enhancement Using Defect-Engineered TiO2 Nanotube Arrays through Electrochemical Reduction in Organic Electrolytes.

PubMed

Ma, Yang; Wang, Na; Chen, Jiang; Chen, Changsong; San, Haisheng; Chen, Jige; Cheng, Zhengdong

2018-06-19

Utilizing high-energy beta particles emitted from radioisotopes for long-lifetime betavoltaic cells is a great challenge due to low energy conversion efficiency. Here, we report a betavoltaic cell fabricated using TiO 2 nanotube arrays (TNTAs) electrochemically reduced in ethylene glycol electrolyte (EGECR-TNTAs) for the enhancement of the betavoltaic effect. The electrochemical reduction of TNTAs using high cathodic bias in organic electrolytes is indeed a facile and effective strategy to induce in situ self-doping of oxygen vacancy (OV) and Ti 3+ defects. The black EGECR-TNTAs are highly stable with a significantly narrower band gap and higher electrical conductivity as well as UV-vis-NIR light absorption. A 20 mCi of 63 Ni betavoltaic cell based on the reduced TNTAs exhibits a maximum ECE of 3.79% with open-circuit voltage of 1.04 V, short-circuit current density of 117.5 nA cm -2 , and a maximum power density of 39.2 nW cm -2 . The betavoltaic enhancement can be attributed to the enhanced charge carrier transport and separation as well as multiple exciton generation of electron-hole pairs due the generation of OV and Ti 3+ interstitial bands below the conductive band of TiO 2.

The role of electrolyte and polyelectrolyte on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, at the air-water interface.

PubMed

Zhang, X L; Taylor, D J F; Thomas, R K; Penfold, J

2011-04-15

The role of the polyelectrolyte, poly(ethyleneimine), PEI, and the electrolytes NaCl and CaCl(2), on the adsorption of the anionic surfactant, sodium dodecylbenzenesulfonate, LAS, at the air-water interface have been investigated by neutron reflectivity and surface tension. The surface tension data for the PEI/LAS mixtures are substantially affected by pH and the addition of electrolyte, and are consistent with a strong adsorption of surface polymer/surfactant complexes down to relatively low surfactant concentrations. The effects are most pronounced at high pH, and this is confirmed by the adsorption data obtained directly from neutron reflectivity. However, the effects of the addition of PEI and electrolyte on the LAS adsorption are not as pronounced as previously reported for PEI/SDS mixtures. This is attributed primarily to the steric hindrance of the LAS phenyl group resulting in a reduction in the ion-dipole attraction between the LAS sulfonate and amine groups that dominates the interaction at high pH. Copyright © 2011 Elsevier Inc. All rights reserved.

The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

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

Xiang, Hongfa; Mei, Donghai; Yan, Pengfei

2015-09-10

Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes thatmore » of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.« less

Electrochemical reduction of UO2 in LiCl-Li2O molten salt using porous and nonporous anode shrouds

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun; Park, Wooshin; Im, Hun Suk; Hong, Sun-Seok; Hur, Jin-Mok

2014-01-01

Electrochemical reductions of uranium oxide in a molten LiCl-Li2O electrolyte were carried out using porous and nonporous anode shrouds. The study focused on the effect of the type of anode shroud on the current density by running experiments with six anode shrouds. Dense ceramics, MgO, and MgO (3 wt%) stabilized ZrO2 (ZrO2-MgO) were used as nonporous shrouds. STS 20, 100, and 300 meshes and ZrO2-MgO coated STS 40 mesh were used as porous shrouds. The current densities (0.34-0.40 A cm-2) of the electrolysis runs using the nonporous anode shrouds were much lower than those (0.76-0.79 A cm-2) of the runs using the porous shrouds. The ZrO2-MgO shroud (600-700 MPa at 25 °C) showed better bending strength than that of MgO (170 MPa at 25 °C). The high current densities achieved in the electrolysis runs using the porous anode shrouds were attributed to the transport of O2- ions through the pores in meshes of the shroud wall. ZrO2-MgO coating on STS mesh was chemically unstable in a molten LiCl-Li2O electrolyte containing Li metal. The electrochemical reduction runs using STS 20, 100, and 300 meshes showed similar current densities in spite of their different opening sizes. The STS mesh shrouds which were immersed in a LiCl-Li2O electrolyte were stable without any damage or corrosion.

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

PubMed

Mao, Xuhui; Yuan, Songhu; Fallahpour, Noushin; Ciblak, Ali; Howard, Joniqua; Padilla, Ingrid; Loch-Caruso, Rita; Alshawabkeh, Akram N

2012-11-06

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

PubMed

Delaporte, Nicolas; Perea, Alexis; Lebègue, Estelle; Ladouceur, Sébastien; Zaghib, Karim; Bélanger, Daniel

2015-08-26

The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C.

Light-Induced Surface Reactions at the Bismuth Vanadate/Potassium Phosphate Interface.

PubMed

Favaro, Marco; Abdi, Fatwa F; Lamers, Marlene; Crumlin, Ethan J; Liu, Zhi; van de Krol, Roel; Starr, David E

2018-01-18

Bismuth vanadate has recently drawn significant research attention as a light-absorbing photoanode due to its performance for photoelectrochemical water splitting. In this study, we use in situ ambient pressure X-ray photoelectron spectroscopy with "tender" X-rays (4.0 keV) to investigate a polycrystalline bismuth vanadate (BiVO 4 ) electrode in contact with an aqueous potassium phosphate (KPi) solution at open circuit potential under both dark and light conditions. This is facilitated by the creation of a 25 to 30 nm thick electrolyte layer using the "dip-and-pull" method. We observe that under illumination bismuth phosphate forms on the BiVO 4 surface leading to an increase of the surface negative charge. The bismuth phosphate layer may act to passivate surface states observed in photoelectrochemical measurements. The repulsive interaction between the negatively charged surface under illumination and the phosphate ions in solution causes a shift in the distribution of ions in the thin aqueous electrolyte film, which is observed as an increase in their photoelectron signals. Interestingly, we find that such changes at the BiVO 4 /KPi electrolyte interface are reversible upon returning to dark conditions. By measuring the oxygen 1s photoelectron peak intensities from the phosphate ions and liquid water as a function of time under dark and light conditions, we determine the time scales for the forward and reverse reactions. Our results provide direct evidence for light-induced chemical modification of the BiVO 4 /KPi electrolyte interface.

Polyethylene glycol without electrolytes for children with constipation and encopresis.

PubMed

Loening-Baucke, Vera

2002-04-01

Children with functional constipation and encopresis benefit from behavior modification and from long-term laxative medication. Polyethylene glycol without electrolytes has become the first option for many pediatric gastroenterologists. Twenty-eight children treated with polyethylene glycol without electrolytes were compared with 21 children treated with milk of magnesia to evaluate the efficiency, acceptability, side effects, and treatment dosage of polyethylene glycol in long-term treatment of functional constipation and encopresis. Children were rated as "doing well," "improved," or "not doing well," depending on resolution of constipation and encopresis. At the 1-, 3-, 6-, and 12-month follow-ups, bowel movement frequency increased and soiling frequency decreased significantly in both groups. At the 1-month follow-up, children on polyethylene glycol were soiling more frequently (P < 0.01) and fewer were improved (P < 0.01). At the 3- and 6-month follow-ups, both groups had similarly improved. At the 12-month visit, 61% of children on polyethylene glycol and 67% of children on milk of magnesia were doing well. Children on polyethylene glycol soiled more frequently (P < 0.01). None refused polyethylene glycol, but 33% refused to take milk of magnesia. The mean initial treatment dosage of polyethylene glycol was 0.6 +/- 0.2 g/kg daily. Polyethylene glycol had no taste, and no loss of efficacy occurred. Polyethylene glycol did not cause clinically significant side effects. Polyethylene glycol without electrolytes is an alternative for long-term management of children with constipation and encopresis.

Electroactive ionic liquids based on 2,5-ditert-butyl-1,4-dimethoxybenzene and triflimide anion as redox shuttle for Li4Ti5O12/LiFePO4 lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gélinas, Bruno; Bibienne, Thomas; Dollé, Mickael; Rochefort, Dominic

2017-12-01

In order to increase the solubility and oxidation potential of redox shuttles, electroactive ionic liquids (RILs) based on the modification of 1,4-dimethoxybenzene with triflimide anions were synthesized. We developed two synthetic routes to obtain these RILs in which the triflimide was either linked on the benzene ring or as a ether on 2,5-ditert-butyl-1,4-dimethoxybenzene (DDB). These RILs all have melting points below 100 °C, but above room temperature. The structural impact of electroactive anion was evaluated in this study by determining the redox potential and electrochemical stability. The electrochemical properties of these RILs were investigated by cyclic voltammetry and the diffusion coefficients were measured by double potential step chronoamperometry. The viscosity and ionic conductivity measurements of redox-active electrolyte were obtained at different temperatures and the RIL additives are shown to have a low impact on these electrolyte properties at concentrations up to 0.3 M. The charge-overcharge-discharge cycles of Li/LiFePO4 half-cells and Li4Ti5O12/LiFePO4 full cells with a 100% overcharge are presented using redox-active electrolyte (0.3 M concentration level) at 0.1 C rate. This study highlights the potential of electroactive ionic liquids as highly soluble and stable functional additives in Li-ion battery electrolytes.

Evaluation of the prototype dual-axis wall attitude measurement sensor

NASA Technical Reports Server (NTRS)

Wong, Douglas T.

1994-01-01

A prototype dual-axis electrolytic tilt sensor package for angular position measurements was built and evaluated in a laboratory environment. The objective was to investigate the use of this package for making wind tunnel wall attitude measurements for the National Transonic Facility (NTF) at NASA Langley Research Center (LaRC). The instrumentation may replace an existing, more costly, and less rugged servo accelerometer package (angle-of-attack package) currently in use. The dual-axis electrolytic tilt sensor package contains two commercial electrolytic tilt sensors thermally insulated with NTF foam, all housed within a stainless steel package. The package is actively heated and maintained at 160 F using foil heating elements. The laboratory evaluation consisted of a series of tests to characterize the linearity, repeatability, cross-axis interaction, lead wire effect, step response, thermal time constant, and rectification errors. Tests revealed that the total RMS errors for the x-axis sensor is 0.084 degree, and 0.182 degree for the y-axis sensor. The RMS errors are greater than the 0.01 degree specification required for NTF wall attitude measurements. It is therefore not a viable replacement for the angle-of-attack package in the NTF application. However, with some physical modifications, it can be used as an inexpensive 5-degree range dual-axis inclinometer with overall accuracy approaching 0.01 degree under less harsh environments. Also, the data obtained from the tests can be valuable for wind tunnel applications of most types of electrolytic tilt sensors.

The Effect of Silane Addition on Chitosan-Fly Ash/CTAB as Electrolyte Membrane

NASA Astrophysics Data System (ADS)

Kusumastuti, E.; Isnaeni, D.; Sulistyaningsih, T.; Mahatmanti, F. W.; Jumaeri; Atmaja, L.; Widiastuti, N.

2017-02-01

Electrolyte membrane is an important component in fuel cell system, because it may influence fuel cell performance. Many efforts have been done to produce electrolyte membrane to replace comercial membrane. In this research, electrolyte membrane is composed of chitosan as an organic matrix and fly ash modified with CTAB and silane as inorganic filler. Fly ash is modified using silane as coupling agent to improve interfacial morphology between organic matrix and inorganic filler. This research aims to determine the best membrane performance based on its characteristics such as water uptake, mechanical properties, proton conductivity, and methanol permeability. The steps that have been done include silica preparation from fly ash, modification of silica surface with CTAB, silica coupling process with silane, synthesis of membranes with inversion phase method, and membrane characterization. The result shows that membrane C-FA/CTAB-Silane 10% (w/w) has the best performance with proton conductivity 8.00 x 10-4 S.cm-1, methanol permeability 3.37 x 10-7 cm.s-1, and selectivity 2.12 x 103 S.s.cm-3. The result of FTIR analysis on membrane C-FA/CTAB-Silane 10% shows that there is only physical interaction occured between chitosan, fly ash and silane, because there is no peak differences significantly at wave number 1000-1250 cm-1, while morphology analysis on membrane with Scanning Electron Microscopy (SEM) shows good dispersion and there is no agglomeration on chitosan matrix.

Enzyme-modified electrolyte-gated organic field-effect transistors

NASA Astrophysics Data System (ADS)

Buth, Felix; Donner, Andreas; Stutzmann, Martin; Garrido, Jose A.

2012-10-01

Organic solution-gated field-effect transistors (SGFETs) can be operated at low voltages in aqueous environments, paving the way to the use of organic semiconductors in bio-sensing applications. However, it has been shown that these devices exhibit only a rather weak sensitivity to standard electrolyte parameters such as pH and ionic strength. In order to increase the sensitivity and to add specificity towards a given analyte, the covalent attachment of functional groups and enzymes to the device surface would be desirable. In this contribution we demonstrate that enzyme modified organic SGFETs can be used for the in-situ detection of penicillin in the low μM regime. In a first step, silane molecules with amine terminal groups are grafted to α-sexithiophene-based thin film transistors. Surface characterization techniques like X-ray photoemission confirm the modification of the surface with these functional groups, which are stable in standard aqueous electrolytes. We show that the presence of surface-bound amphoteric groups (e.g. amino or carboxylic moieties) increases the pH-sensitivity of the organic SGFETs. In addition, these groups serve as anchoring sites for the attachment of the enzyme penicillinase. The resulting enzyme-FETs are used for the detection of penicillin, enabling the study of the influence of the buffer strength and the pH of the electrolyte on the enzyme kinetics. The functionalization of the organic FETs shown here can be extended to a large variety of enzymes, allowing the specific detection of different chemical and biochemical analytes.

Lithium secondary batteries: Role of polymer cathode morphology

NASA Astrophysics Data System (ADS)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

Novel Organic-Inorganic Hybrid Electrolyte to Enable LiFePO4 Quasi-Solid-State Li-Ion Batteries Performed Highly around Room Temperature.

PubMed

Tan, Rui; Gao, Rongtan; Zhao, Yan; Zhang, Mingjian; Xu, Junyi; Yang, Jinlong; Pan, Feng

2016-11-16

A novel type of organic-inorganic hybrid polymer electrolytes with high electrochemical performances around room temperature is formed by hybrid of nanofillers, Y-type oligomer, polyoxyethylene and Li-salt (PBA-Li), of which the T g and T m are significantly lowered by blended heterogeneous polyethers and embedded nanofillers with benefit of the dipole modification to achieve the high Li-ion migration due to more free-volume space. The quasi-solid-state Li-ion batteries based on the LiFePO 4 /15PBA-Li/Li-metal cells present remarkable reversible capacities (133 and 165 mAh g -1 @0.2 C at 30 and 45 °C, respectively), good rate ability and stable cycle performance (141.9 mAh g -1 @0.2 C at 30 °C after 150 cycles).

Molten salt bath circulation design for an electrolytic cell

DOEpatents

Dawless, Robert K.; LaCamera, Alfred F.; Troup, R. Lee; Ray, Siba P.; Hosler, Robert B.

1999-01-01

An electrolytic cell for reduction of a metal oxide to a metal and oxygen has an inert anode and an upwardly angled roof covering the inert mode. The angled roof diverts oxygen bubbles into an upcomer channel, thereby agitating a molten salt bath in the upcomer channel and improving dissolution of a metal oxide in the molten salt bath. The molten salt bath has a lower velocity adjacent the inert anode in order to minimize corrosion by substances in the bath. A particularly preferred cell produces aluminum by electrolysis of alumina in a molten salt bath containing aluminum fluoride and sodium fluoride.

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.

The electrocatalytic reduction of nitrate in water on Pd/Sn-modified activated carbon fiber electrode.

PubMed

Wang, Ying; Qu, Jiuhui; Wu, Rongcheng; Lei, Pengju

2006-03-01

The Pd/Sn-modified activated carbon fiber (ACF) electrodes were successfully prepared by the impregnation of Pd2+ and Sn2+ ions onto ACF, and their electrocatalytic reduction capacity for nitrate ions in water was evaluated in a batch experiment. The electrode was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and temperature programmed reduction (TPR). The capacity for nitrate reduction depending on Sn content on the electrode and the pH of electrolyte was discussed at length. The results showed that at an applied current density of 1.11 mA cm(-2), nitrate ions in water (solution volume: 400 mL) were reduced from 110 to 3.4 mg L(-1) after 240 min with consecutive change of intermediate nitrite. Ammonium ions and nitrogen were formed as the main final products. The amount of other possible gaseous products (including NO and N2O) was trace. With the increase of Sn content on the Pd/Sn-modified ACF electrode, the activity for nitrate reduction went up to reach a maximum (at Pd/Sn = 4) and then decreased, while the selectivity to N2 was depressed. Higher pH value of electrolyte exhibited more suppression effect on the reduction of nitrite than that of nitrate. However, no significant influence on the final ammonia formation was observed. Additionally, Cu ion in water was found to cover the active sites of the electrode to make the electrode deactivated.

A method for making an alkaline battery electrode plate

NASA Technical Reports Server (NTRS)

Chida, K.; Ezaki, T.

1983-01-01

A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

Fabrication and Performance of Zirconia Electrolysis Cells for Cabon Dioxide Reduction for Mars In Situ Resource Utilization Applications

NASA Technical Reports Server (NTRS)

Minh, N. Q.; Chung, B. W.; Doshi, R.; Lear, G. R.; Montgomery, K.; Ong, E. T.

1999-01-01

Use of the Martian atmosphere (95% CO2) to produce oxygen (for propellant and life support) can significantly lower the required launch mass and dramatically reduce the total cost for Mars missions. Zirconia electrolysis cells are one of the technologies being considered for oxygen generation from carbon dioxide in Mars In Situ Resource Utilization (ISRU) production plants. The attractive features of the zirconia cell for this application include simple operation and lightweight, low volume system. A zirconia electrolysis cell is an all-solid state device, based on oxygen-ion conducting zirconia electrolytes, that electrochemically reduces carbon dioxide to oxygen and carbon monoxide. The cell consists of two porous electrodes (the anode and cathode) separated by a dense zirconia electrolyte. Typical zirconia cells contain an electrolyte layer which is 200 to 400 micrometer thick. The electrical conductivity requirement for the electrolyte necessitates an operating temperature of 9000 to 10000C. Recently, the fabrication of zirconia cells by the tape calendering has been evaluated. This fabrication process provides a simple means of making cells having very thin electrolytes (5 to 30 micrometers). Thin zirconia electrolytes reduce cell ohmic losses, permitting efficient operation at lower temperatures (8000C or below). Thus, tape-calendered cells provides not only the potential of low temperature operation but also the flexibility in operating temperatures. This paper describes the fabrication of zirconia cells by the tape calendering method and discusses the performance results obtained to date.

Reviving lithium cobalt oxide-based lithium secondary batteries-toward a higher energy density.

PubMed

Wang, Longlong; Chen, Bingbing; Ma, Jun; Cui, Guanglei; Chen, Liquan

2018-06-29

By breaking through the energy density limits step-by-step, the use of lithium cobalt oxide-based Li-ion batteries (LCO-based LIBs) has led to the unprecedented success of consumer electronics over the past 27 years. Recently, strong demands for the quick renewal of the properties of electronic products every so often have resulted in smarter, larger screened, more lightweight devices with longer standby times that have pushed the energy density of LCO-based LIBs nearly to their limit. As a result, with the aim of achieving a higher energy density and lifting the upper cut-off voltage of LCO above 4.45 V (vs. Li/Li+), the development of LCO-based all-solid-state lithium batteries (ASSLBs) with a Li metal anode and LCO-based full cells with high-performance anodes have become urgent scientific and technological requirements. This review summarizes the key challenges of synthesizing LCO-based LBs with a higher energy density from the perspectives of structure and interface stability, and gives an account of effective modification strategies in view of the electrodes, liquid electrolytes, binders, separators, solid electrolytes and LCO-based full cells. The improvement mechanisms of these modification strategies and the controversy over them are also analyzed critically. Moreover, some perspectives regarding the remaining challenges for LCO-based LBs towards a higher energy density and possible future research focuses are also presented.

Phase composition and fine structure of 0.18C-1Cr-3Ni-1Mo-Fe steel after plasma-electrolytic treatment

NASA Astrophysics Data System (ADS)

Popova, Natalya; Bayatanova, Lyayla; Nikonenko, Elena; Skakov, Mazhyn; Kozlov, Eduard

2017-01-01

The paper presents the transmission electron microscopy (TEM) investigation of 0.18C-1Cr-3Mn-1Mo- Fe steel specimens to study phase transitions and modification of fine structure after plasma-electrolytic treatment (carbonitriding at 850°C during 5 min). TEM investigations involve two points: on the specimen surface and at ˜40 µm distance from it. The experiments show that the structure in the original state is a mixture consisting of ferrite and perlite grains. Carbonitriding results in a considerable modification of the quality and quantity of steel structure. Thus, on the surface, α-phase is represented by lamellar martensite, while at ˜40 µm depth - by massive and lamellar martensite tempered at low and high temperatures. Moreover, on the subsurface of the martensite plates' boundaries retained austenite layers are observed, while inside plates the particles of alloyed cementite, carbonitrides of M23(C,N)6, M2C0.61N0.39, M6,2C3,5N0,3, M(C,N)2, Cr12Fe32Mo7Ni7 types, and β-graphite are present. In the specimen at the depth of ˜40 µm, retained austenite layers are observed on the boundaries of martensite laths and plates, while inside plates only the particles of alloyed cementite and M23(C,N)6 carbonitride are formed.

Understanding ionic conductivity trends in polyborane solid electrolytes from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Varley, Joel; Kweon, Kyoung; Mehta, Prateek; Shea, Patrick; Heo, Tae Wook; Stavila, Vitalie; Udovic, Terrence; Wood, Brandon

Polyborane salts based on B12H122- , B10H102- , and their carboborane counterparts CB11H12- and CB9H10- demonstrate extraordinary Li and Na superionic conductivity that make them attractive as electrolytes in all-solid-state batteries. Their rich chemical and structural diversity creates a versatile design space that could be used to optimize materials with even higher conductivity at lower temperatures; however, many mechanistic details remain enigmatic, including reasons why certain modifications lead to improved performance. Here, we use extensive ab initio molecular dynamics simulations to broadly explore the dependence of ionic conductivity on cation/anion pair combinations for Li and Na polyborane salts. Further simulations based on Li2B12H12 as a model system are used to probe the additional influence of local perturbations, including modifications to chemistry, stoichiometry, and composition. Carbon doping, anion alloying, and cation off-stoichiometry are found to be favorable because they introduce intrinsic disorder, which facilitates local deviations from the expected cation population. Anion reorientations are also discovered to be critical for conduction, with benefits associated with lattice expansion traceable to the facilitation of anion rotation at larger volumes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Plasma Electrolytic Oxidation of Titanium Implant Surfaces: Microgroove-Structures Improve Cellular Adhesion and Viability.

PubMed

Hartjen, Philip; Hoffmann, Alexia; Henningsen, Anders; Barbeck, Mike; Kopp, Alexander; Kluwe, Lan; Precht, Clarissa; Quatela, Olivia; Gaudin, Robert; Heiland, Max; Friedrich, Reinhard E; Knipfer, Christian; Grubeanu, Daniel; Smeets, Ralf; Jung, Ole

2018-01-01

Plasma electrolytic oxidation (PEO) is an established electrochemical treatment technique that can be used for surface modifications of metal implants. In this study we to treated titanium implants with PEO, to examine the resulting microstructure and to characterize adhesion and viability of cells on the treated surfaces. Our aim was to identify an optimal surface-modification for titanium implants in order to improve soft-tissue integration. Three surface-variants were generated on titanium alloy Ti6Al4V by PEO-treatment. The elemental composition and the microstructures of the surfaces were characterized using energy dispersive X-ray spectroscopy, scanning electron microscopy and profilometry. In vitro cytocompatibility of the surfaces was assessed by seeding L929 fibroblasts onto them and measuring the adhesion, viability and cytotoxicity of cells by means of live/dead staining, XTT assay and LDH assay. Electron microscopy and profilometry revealed that the PEO-surface variants differed largely in microstructure/topography, porosity and roughness from the untreated control material as well as from one another. Roughness was generally increased after PEO-treatment. In vitro, PEO-treatment led to improved cellular adhesion and viability of cells accompanied by decreased cytotoxicity. PEO-treatment provides a promising strategy to improve the integration of titanium implants with surrounding tissues. Copyright© 2018, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

Grain boundary modification to suppress lithium penetration through garnet-type solid electrolyte

NASA Astrophysics Data System (ADS)

Hongahally Basappa, Rajendra; Ito, Tomoko; Morimura, Takao; Bekarevich, Raman; Mitsuishi, Kazutaka; Yamada, Hirotoshi

2017-09-01

Garnet-type solid electrolytes are one of key materials to enable practical usage of lithium metal anode for high-energy-density batteries. However, it suffers from lithium growth in pellets on charging, which causes short circuit. In this study, grain boundaries of Li6.5La3Zr1.5Ta0.5O12 (LLZT) pellets are modified with Li2CO3 and LiOH to investigate the influence of the microstructure of grain boundaries on lithium growth and to study the mechanism of the lithium growth. In spite of similar properties (relative density of ca. 96% and total ionic conductivity of 7 × 10-4 S cm-1 at 25 °C), the obtained pellets exhibit different tolerance on the short circuit. The LLZT pellets prepared from LiOH-modified LLZT powders exhibit rather high critical current density of 0.6 mA cm-2, at which short circuit occurs. On the other hand, the LLZT pellets without grain boundary modification short-circuited at 0.15 mA cm-2. Microstructural analyses by means of SEM, STEM and EIS suggest that lithium grows through interconnected open voids, and reveal that surface layers such as Li2CO3 and LiOH are not only plug voids but also facilitate the sintering of LLZT to suppress the lithium growth. The results indicate a strategy towards short-circuit-free lithium metal batteries.

Electrochemical Interfaces and Electrode Processes.

DTIC Science & Technology

1984-08-15

reduction of 02 on such surfaces has been of special interest. Some of these complexes such as the iron tetrasulfonated phthalocyanines (TSPc) have high...high area carbon electrodes in porous carbon electrolyte structures (14,22,27). We have been successful in examining the Fe phthalocyanine and Co...Zagal, B. Z. Nikolic and R. R. Adzic, 1 May 1979. 50. A Mechanistic Study of 02 Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite

Membraneless laminar flow cell for electrocatalytic CO2 reduction with liquid product separation

NASA Astrophysics Data System (ADS)

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; Ager, Joel W.

2017-04-01

The production of liquid fuel products via electrochemical reduction of CO2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O2) from reaching the cathode. Ion-conducting membranes have been applied in CO2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flow cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.

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

DOE PAGES

Li, Yunsong; Leung, Kevin; Qi, Yue

2016-09-30

A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li + ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li + + e → Li 0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphasemore » (SEI)”, as “the most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li + ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li + and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li + transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

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

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

Li, Yunsong; Leung, Kevin; Qi, Yue

A nanometer thick passivation layer will spontaneously form on Li-metal in battery applications due to electrolyte reduction reactions. This passivation layer in rechargeable batteries must have “selective” transport properties: blocking electrons from attacking the electrolytes, while allowing Li + ion to pass through so the electrochemical reactions can continue. The classical description of the electrochemical reaction, Li + + e → Li 0, occurring at the Li-metal|electrolyte interface is now complicated by the passivation layer and will reply on the coupling of electronic and ionic degrees of freedom in the layer. We consider the passivation layer, called “solid electrolyte interphasemore » (SEI)”, as “the most important but the least understood in rechargeable Li-ion batteries,” partly due to the lack of understanding of its structure–property relationship. In predictive modeling, starting from the ab initio level, we find that it is an important tool to understand the nanoscale processes and materials properties governing the interfacial charge transfer reaction at the Li-metal|SEI|electrolyte interface. Here, we demonstrate pristine Li-metal surfaces indeed dissolve in organic carbonate electrolytes without the SEI layer. Based on joint modeling and experimental results, we point out that the well-known two-layer structure of SEI also exhibits two different Li + ion transport mechanisms. The SEI has a porous (organic) outer layer permeable to both Li + and anions (dissolved in electrolyte), and a dense (inorganic) inner layer facilitate only Li + transport. This two-layer/two-mechanism diffusion model suggests only the dense inorganic layer is effective at protecting Li-metal in electrolytes. This model suggests a strategy to deconvolute the structure–property relationships of the SEI by analyzing an idealized SEI composed of major components, such as Li 2CO 3, LiF, Li 2O, and their mixtures. After sorting out the Li+ ion diffusion carriers and their diffusion pathways, we design methods to accelerate the Li + ion conductivity by doping and by using heterogonous structure designs. We will predict the electron tunneling barriers and connect them with measurable first cycle irreversible capacity loss. We note that the SEI not only affects Li + and e – transport, but it can also impose a potential drop near the Li-metal|SEI interface. Our challenge is to fully describe the electrochemical reactions at the Li -metal|SEI|electrolyte interface. This will be the subject of ongoing efforts.« less

Behavior Modification in Coaching.

ERIC Educational Resources Information Center

Lynch, Annette Rutt; Stillman, Stephen M.

1979-01-01

An example of behavior modification used in athletic coaching is presented. The case study involves a member of a women's basketball team and details the use of behavior modification for both weight reduction and skill improvement. (JMF)

Chloride supporting electrolytes for all-vanadium redox flow batteries.

PubMed

Kim, Soowhan; Vijayakumar, M; Wang, Wei; Zhang, Jianlu; Chen, Baowei; Nie, Zimin; Chen, Feng; Hu, Jianzhi; Li, Liyu; Yang, Zhenguo

2011-10-28

This paper examines vanadium chloride solutions as electrolytes for an all-vanadium redox flow battery. The chloride solutions were capable of dissolving more than 2.3 M vanadium at varied valence states and remained stable at 0-50 °C. The improved stability appeared due to the formation of a vanadium dinuclear [V(2)O(3)·4H(2)O](4+) or a dinuclear-chloro complex [V(2)O(3)Cl·3H(2)O](3+) in the solutions over a wide temperature range. The all-vanadium redox flow batteries with the chloride electrolytes demonstrated excellent reversibility and fairly high efficiencies. Only negligible, if any, gas evolution was observed. The improved energy capacity and good performance, along with the ease in heat management, would lead to substantial reduction in capital cost and life-cycle cost, making the vanadium chloride redox flow battery a promising candidate for stationary applications. This journal is © the Owner Societies 2011

Electro-catalytic oxidation device for removing carbon from a fuel reformate

DOEpatents

Liu, Di-Jia [Naperville, IL

2010-02-23

An electro-catalytic oxidation device (ECOD) for the removal of contaminates, preferably carbonaceous materials, from an influent comprising an ECOD anode, an ECOD cathode, and an ECOD electrolyte. The ECOD anode is at a temperature whereby the contaminate collects on the surface of the ECOD anode as a buildup. The ECOD anode is electrically connected to the ECOD cathode, which consumes the buildup producing electricity and carbon dioxide. The ECOD anode is porous and chemically active to the electro-catalytic oxidation of the contaminate. The ECOD cathode is exposed to oxygen, and made of a material which promotes the electro-chemical reduction of oxygen to oxidized ions. The ECOD electrolyte is non-permeable to gas, electrically insulating and a conductor to oxidized. The ECOD anode is connected to the fuel reformer and the fuel cell. The ECOD electrolyte is between and in ionic contact with the ECOD anode and the ECOD cathode.

Magsonic™ Carbothermal Technology Compared with the Electrolytic and Pidgeon Processes

NASA Astrophysics Data System (ADS)

Prentice, Leon H.; Haque, Nawshad

A broad technology comparison of carbothermal magnesium production with present technologies has not been previously presented. In this paper a comparative analysis of CSIRO's MagSonic™ process is made with the electrolytic and Pidgeon processes. The comparison covers energy intensity (GJ/tonne Mg), labor intensity (person-hours/tonne Mg), capital intensity (USD/tonne annual Mg installed capacity), and Global Warming Potential (GWP, tonnes CO2-equivalent/tonne Mg). Carbothermal technology is advantageous on all measures except capital intensity (where it is roughly twice the capital cost of a similarly-sized Pidgeon plant). Carbothermal and electrolytic production can have comparatively low environmental impacts, with typical emissions one-sixth those of the Pidgeon process. Despite recent progress, the Pidgeon process depends upon abundant energy and labor combined with few environmental constraints. Pressure is expected to increase on environmental constraints and labor and energy costs over the coming decade. Carbothermal reduction technology appears to be competitive for future production.

The nature of interfacial instabilities in liquid metal batteries in a vertical magnetic field

NASA Astrophysics Data System (ADS)

Molokov, S.

2018-02-01

The nature of instabilities in liquid metal batteries in the presence of a vertical magnetic field has been studied. The battery consists of two liquid metal layers, connected to the collectors, and a layer with an electrolyte inbetween. The closed geometry in the horizontal plane has been replaced by a half-plane to get a better insight into the problem. As in aluminium reduction cells the instability is generated at the electrically insulating sidewall of the battery. A travelling-wave solution has been obtained, which shows that there are two modes of the instability, fast and slow. Either of these modes may be most unstable depending on the values of various parameters, the most important of which are the well-known parameter of the instability, β, and the density of the electrolyte. For the intermediate range of the electrolyte density the medium-size batteries may be expected to be stable.

Heat Acclimation and Water-Immersion Deconditioning: Fluid Electrolyte Shifts with Tilting

NASA Technical Reports Server (NTRS)

Conertino, V. A.; Shvartz, E.; Haines, R. F.; Bhattacharya, A.; Superinde, S. J.; Keil, L. C.; Greenlean, J. E.

1977-01-01

One of the major problems encountered by astronauts exposed to space flight is a reduction of orthostatic tolerance on return to earth. Many studies have been performed in an attempt to define the physiologic mechanism of orthostatic intolerance and to develop some remedial treatment. Exercise training does not appear to enhance orthostatic tolerance . In contrast, heat acclimation (i.e., exercise training in the heat) has been reported to enhance orthostatic tolerance. Since plasma volume increases with both exercise training and heat acclimation, it is not clear what role fluid and electrolytes play in determining tolerance to hydrostatic pressure. The purpose of this study was to compare the effects of exercise training in a cool environment and heat acclimation on resting plasma volume (PV) and the ensuing fluid and electrolyte shifts which occur during head-up tilting before and after water immersion deconditioning.

Glass cylindrical filter for electrolysis cell

NASA Astrophysics Data System (ADS)

Abe, Shinichi; Akiyama, Fuminori

1992-09-01

Some electrolysis requires separation of electrolytic solution by a filter between two electrodes in order to prevent products from reacting secondarily at another electrode. These filters are usually made of a glass filter or ion exchanger membrane, and they are fixed at the electrolysis cell or cover one electrode. This report presents a detachable glass cylindrical filter for electrolytic reaction. The glass cylindrical filter was made from glass filter powder placed in a mold and heated at 800 C for 18 minutes. Using this filter, electrolytic reduction of carbon dioxide was performed in 0 C hot water with benzoin. This reaction produces aqueous oil from carbon dioxide and water. The products were compared with and without the filter and, although the yield did not differ between the two reaction systems, products without the filter contained highly polymerized oil compared to those with the filter. This suggests that the aqueous oil was produced at the cathode and polymerized at the anode.

Lignin Modification for Biopolymer/Conjugated Polymer Hybrids as Renewable Energy Storage Materials.

PubMed

Nilsson, Ting Yang; Wagner, Michal; Inganäs, Olle

2015-12-07

Lignin derivatives, which arise as waste products from the pulp and paper industry and are mainly used for heating, can be used as charge storage materials. The charge storage function is a result of the quinone groups formed in the lignin derivative. Herein, we modified lignins to enhance the density of such quinone groups by covalently linking monolignols and quinones through phenolation. The extra guaiacyl, syringyl, and hydroquinone groups introduced by phenolation of kraft lignin derivatives were monitored by (31) P nuclear magnetic resonance and size exclusion chromatography. Electropolymerization in ethylene glycol/tetraethylammonium tosylate electrolyte was used to synthesize the kraft lignin/polypyrrole hybrid films. These modifications changed the phenolic content of the kraft lignin with attachment of hydroquinone units yielding the highest specific capacity (around 70 mA h g(-1) ). The modification of softwood and hardwood lignin derivatives yielded 50 % and 23 % higher charge capacity than the original lignin, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of electrochemically deposited apatite using supercritical water.

PubMed

Ban, S; Hasegawa, J

2001-12-01

Supercritical water was used as a modification method of electrochemically deposited apatite on pure titanium. The apatites were coated on a commercially pure titanium plate using a hydrothermal-electrochemical method. A constant direct current at 12.5 mA/cm2 was loaded for 1 hr at 25, 60, 100, 150 and 200 degrees C in an electrolyte containing calcium and phosphate ions. The deposited apatite on the titanium substrate was stored in supercritical water at 450 degrees C under 45 MPa for 8 hr. With this treatment, the crystallinity of the apatites increased, sharp edges of the deposited apatites were rounded off, and the bonding strength of the titanium substrate to the deposited apatites significantly increased. On the other hand, weight loss in 0.01 N HCl decreased and the weight gain rate in a simulated body fluid also decreased with this treatment. It is suggested that the modification using supercritical water improved the mechanical strength of the deposited apatite, but worsened its bioactivity.

40 CFR 421.52 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... CATEGORY Primary Electrolytic Copper Refining Subcategory § 421.52 Effluent limitations guidelines...,000 lb of product) Total suspended solids 0.100 0.050 Copper 0.0017 0.0008 Cadmium 0.00006 0.00003...

40 CFR 421.52 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... CATEGORY Primary Electrolytic Copper Refining Subcategory § 421.52 Effluent limitations guidelines...,000 lb of product) Total suspended solids 0.100 0.050 Copper 0.0017 0.0008 Cadmium 0.00006 0.00003...

Ultramicroelectrode Studies of Self-Terminated Nickel Electrodeposition and Nickel Hydroxide Formation upon Water Reduction.

PubMed

Ritzert, Nicole L; Moffat, Thomas P

2016-12-08

The interaction between electrodeposition of Ni and electrolyte breakdown, namely the hydrogen evolution reaction (HER) via H 3 O + and H 2 O reduction, was investigated under well-defined mass transport conditions using ultramicroelectrodes (UME's) coupled with optical imaging, generation/collection scanning electrochemical microscopy (G/C-SECM), and preliminary microscale pH measurements. For 5 mmol/L NiCl 2 + 0.1 mol/L NaCl, pH 3.0, electrolytes, the voltammetric current at modest overpotentials, i.e. , between -0.6 V and -1.4 V vs. Ag/AgCl, was distributed between metal deposition and H 3 O + reduction, with both reactions reaching mass transport limited current values. At more negative potentials, an unusual sharp current spike appeared upon the onset of H 2 O reduction that was accompanied by a transient increase in H 2 production. The peak potential of the current spike was a function of both [Ni(H 2 O) 6 ] 2+ (aq) concentration and pH. The sharp rise in current was ascribed to the onset of autocatalytic H 2 O reduction, where electrochemically generated OH - species induce heterogeneous nucleation of Ni(OH) 2(ads) islands, the perimeter of which is reportedly active for H 2 O reduction. As the layer coalesces, further metal deposition is quenched while H 2 O reduction continues albeit at a decreased rate as fewer of the most reactive sites, e.g. , Ni/Ni(OH) 2 island edges, are available. At potentials below -1.5 V vs. Ag/AgCl, H 2 O reduction is accelerated, leading to homogeneous precipitation of bulk Ni(OH) 2 · x H 2 O within the nearly hemispherical diffusion layer of the UME.

A comparative study of quasi-solid nanoclay gel electrolyte and liquid electrolyte dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Main, Laura

Dye sensitized solar cells (DSSCs) are currently being explored as a cheaper alternative to the more common silicon (Si) solar cell technology. In addition to the cost advantages, DSSCs show good performance in low light conditions and are not sensitive to varying angles of incident light like traditional Si cells. One of the major challenges facing DSSCs is loss of the liquid electrolyte, through evaporation or leakage, which lowers stability and leads to increased degradation. Current research with solid-state and quasi-solid DSSCs has shown success regarding a reduction of electrolyte loss, but at a cost of lower conversion efficiency output. The research work presented in this paper focuses on the effects of using nanoclay material as a gelator in the electrolyte of the DSSC. The data showed that the quasi-solid cells are more stable than their liquid electrolyte counterparts, and achieved equal or better I-V characteristics. The quasi-solid cells were fabricated with a gel electrolyte that was prepared by adding 7 wt% of Nanoclay, Nanomer® (1.31PS, montmorillonite clay surface modified with 15-35% octadecylamine and 0.5-5 wt% aminopropyltriethoxysilane, Aldrich) to the iodide/triiodide liquid electrolyte, (Iodolyte AN-50, Solaronix). Various gel concentrations were tested in order to find the optimal ratio of nanoclay to liquid. The gel electrolyte made with 7 wt% nanoclay was more viscous, but still thin enough to allow injection with a standard syringe. Batches of cells were fabricated with both liquid and gel electrolyte and were evaluated at STC conditions (25°C, 100 mW/cm2) over time. The gel cells achieved efficiencies as high as 9.18% compared to the 9.65% achieved by the liquid cells. After 10 days, the liquid cell decreased to 1.75%, less than 20% of its maximum efficiency. By contrast, the gel cell's efficiency increased for two weeks, and did not decrease to 20% of maximum efficiency until 45 days. After several measurements, the liquid cells showed visible signs of leakage through the sealant, whereas the gel cells did not. This resistance to leakage likely contributed to the improved performance of the quasi-solid cells over time, and is a significant advantage over liquid electrolyte DSSCs.

Surface modification by carbon ion implantation for the application of ni-based amorphous alloys as bipolar plate in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Kim, Min-Uk; Kim, Do-Hyang; Han, Seung-hee; Fleury, Eric; Seok, Hyun-Kwang; Cha, Pil-Ryung; Kim, Yu-Chan

2011-04-01

Ni-based amorphous alloys with surface modification by carbon ion implantation are proposed as an alternative bipolar plate material for polymer electrolyte membrane fuel cells (PEMFCs). Both Ni60Nb20Ti10Zr10 alloys with and without carbon ion implantation have corrosion resistance as good as graphite as well as much lower contact resistance than 316L stainless steel in the PEMFC environment. The formation of conductive surface carbide due to carbon ion implantation results in a decrease in the contact resistance to a level comparable to that of graphite. This combination of excellent properties indicates that carbon ion implanted Ni-based amorphous alloys can be potential candidate materials for bipolar plates in PEMFCs.

Overhead Projector Demonstrations.

ERIC Educational Resources Information Center

Kolb, Doris, Ed.

1988-01-01

Provides two demonstrations: (1) electrolyte migration of ions using colored ions which cross a strip of gelatin allowing for noticeable migration; and (2) photochemical reduction of Fe+3 by the citrate ion. Points out both reactions can be done in a Petri dish using common lab materials. (MVL)

Au nanorice assemble electrolytically into mesostars.

PubMed

Bardhan, Rizia; Neumann, Oara; Mirin, Nikolay; Wang, Hui; Halas, Naomi J

2009-02-24

Star-shaped mesotructures are formed when an aqueous suspension of Au nanorice particles, which consist of prolate hematite cores and a thin Au shell, is subjected to an electric current. The nanorice particles assemble to form hyperbranched micrometer-scale mesostars. To our knowledge, this is the first reported observation of nanoparticle assembly into larger ordered structures under the influence of an electrochemical process (H(2)O electrolysis). The assembly is accompanied by significant modifications in the morphology, dimensions, chemical composition, crystallographic structure, and optical properties of the constituent nanoparticles.

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

2014-10-30

The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes

PubMed Central

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

2017-01-01

Lithium metal is strongly regarded as a promising electrode material in next-generation rechargeable batteries due to its extremely high theoretical specific capacity and lowest reduction potential. However, the safety issue and short lifespan induced by uncontrolled dendrite growth have hindered the practical applications of lithium metal anodes. Hence, we propose a flexible anion-immobilized ceramic–polymer composite electrolyte to inhibit lithium dendrites and construct safe batteries. Anions in the composite electrolyte are tethered by a polymer matrix and ceramic fillers, inducing a uniform distribution of space charges and lithium ions that contributes to a dendrite-free lithium deposition. The dissociation of anions and lithium ions also helps to reduce the polymer crystallinity, rendering stable and fast transportation of lithium ions. Ceramic fillers in the electrolyte extend the electrochemically stable window to as wide as 5.5 V and provide a barrier to short circuiting for realizing safe batteries at elevated temperature. The anion-immobilized electrolyte can be applied in all–solid-state batteries and exhibits a small polarization of 15 mV. Cooperated with LiFePO4 and LiNi0.5Co0.2Mn0.3O2 cathodes, the all–solid-state lithium metal batteries render excellent specific capacities of above 150 mAh⋅g−1 and well withstand mechanical bending. These results reveal a promising opportunity for safe and flexible next-generation lithium metal batteries. PMID:28973945

Enhanced electrochemical performance of in situ reduced graphene oxide-polyaniline nanotubes hybrid nanocomposites using redox-additive aqueous electrolyte

NASA Astrophysics Data System (ADS)

Devi, Madhabi; Kumar, A.

2018-02-01

Reduced graphene oxide (RGO)-polyaniline nanotubes (PAniNTs) nanocomposites have been synthesized by in situ reduction of GO. The morphology and structure of the nanocomposites are characterized by HRTEM, XRD and micro-Raman spectroscopy. The electrical and electrochemical performances of the nanocomposites are investigated for different RGO concentrations by conductivity measurements, cyclic voltammetry, charge-discharge and electrochemical impedance spectroscopy. Highest gravimetric specific capacitance of 448.71 F g-1 is obtained for 40 wt.% of RGO-PAniNTs nanocomposite as compared to 194.92 F g-1 for pure PAniNTs in 1 M KCl electrolyte. To further improve the electrochemical performance of the nanocomposite electrode, KI is used as redox-additive with 1 M KCl electrolyte. Highest gravimetric specific capacitance of 876.43 F g-1 and an improved cyclic stability of 91% as compared to 79% without KI after 5000 cycles is achieved for an optimized 0.1 M KI concentration. This is attributed to the presence of different ionic species of I- ions that give rise to a number of possible redox reactions improving the pseudocapacitance of the electrode. This improved capacitive performance is compared with that of catechol redox-additive in 1 M KCl electrolyte, and that of KI and catechol redox-additives added to 1 M H2SO4 electrolyte.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

Direct printing and reduction of graphite oxide for flexible supercapacitors

NASA Astrophysics Data System (ADS)

Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

2014-08-01

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm3 in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

Influence of supporting electrolyte in electricity generation and degradation of organic pollutants in photocatalytic fuel cell.

PubMed

Khalik, Wan Fadhilah; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Voon, Chun-Hong; Yusuf, Sara Yasina; Yusoff, Nik Athirah; Lee, Sin-Li

2016-08-01

This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.

Durability of the Li 1+xTi 2–xAl x(PO 4) 3 Solid Electrolyte in Lithium–Sulfur Batteries

DOE PAGES

Wang, Shaofei; Ding, Yu; Zhou, Guangmin; ...

2016-10-31

Adoption of cells with a solid-state electrolyte is a promising solution for eliminating the polysulfide shuttle problem in Li-S batteries. Among the various known lithium-ion conducting solid electrolytes, the sodium superionic conductor (NASICON)-type Li 1+xTi 2-xAl x(PO 4) 3 offers the advantage of good stability under ambient conditions and in contact with air. Accordingly, we present here a comprehensive assessment of the durability of Li 1+xTi 2-xAl x(PO 4) 3 in contact with polysulfide solution and in Li-S cells. Because of its high reduction potential (2.5 V vs Li/Li +), Li 1+xTi 2-xAl x(PO 4) 3 gets lithiated in contactmore » with lithium polysulfide solution and Li 2CO 3 is formed on the particle surface, blocking the interfacial lithium-ion transport between the liquid and solid-state electrolytes. After the lithium insertion into the NASICON framework, the crystal expands in an anisotropic way, weakening the crystal bonds, causing fissures and resultant cracks in the ceramic, corroding the grain boundaries by polysulfide solution, and leaving unfavorable pores. The assembly of pores creates a gateway for polysulfide diffusion from the cathode side to the anode side, causing an abrupt decline in cell performance. Therefore, the solid-state electrolytes need to have good chemical compatibility with both the electrode and electrolyte, long-term stability under harsh chemical environment, and highly stable grain boundaries.« less

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

DOE PAGES

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

2016-04-09

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

Molten salt bath circulation design for an electrolytic cell

DOEpatents

Dawless, R.K.; LaCamera, A.F.; Troup, R.L.; Ray, S.P.; Hosler, R.B.

1999-08-17

An electrolytic cell for reduction of a metal oxide to a metal and oxygen has an inert anode and an upwardly angled roof covering the inert mode. The angled roof diverts oxygen bubbles into an upcomer channel, thereby agitating a molten salt bath in the upcomer channel and improving dissolution of a metal oxide in the molten salt bath. The molten salt bath has a lower velocity adjacent the inert anode in order to minimize corrosion by substances in the bath. A particularly preferred cell produces aluminum by electrolysis of alumina in a molten salt bath containing aluminum fluoride and sodium fluoride. 4 figs.

Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics

DOE PAGES

Pant, Lalit M.; Weber, Adam Z.

2017-04-14

A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.

Assessment of the electrochemical effects of pulsed electric fields in a biological cell suspension.

PubMed

Chafai, Djamel Eddine; Mehle, Andraž; Tilmatine, Amar; Maouche, Bachir; Miklavčič, Damijan

2015-12-01

Electroporation of cells is successfully used in biology, biotechnology and medicine. Practical problems still arise in the electroporation of cells in suspension. For example, the determination of cell electroporation is still a demanding and time-consuming task. Electric pulses also cause contamination of the solution by the metal released from the electrodes and create local enhancements of the electric field, leading to the occurrence of electrochemical reactions at the electrode/electrolyte interface. In our study, we investigated the possibility of assessing modifications to the cell environment caused by pulsed electric fields using electrochemical impedance spectroscopy. We designed an experimental protocol to elucidate the mechanism by which a pulsed electric field affects the electrode state in relation to different electrolyte conductivities at the interface. The results show that a pulsed electric field affects electrodes and its degree depends on the electrolyte conductivity. Evolution of the electrochemical reaction rate depends on the initial free charges and those generated by the pulsed electric field. In the presence of biological cells, the initial free charges in the medium are reduced. The electrical current path at low frequency is longer, i.e., conductivity is decreased, even in the presence of increased permeability of the cell membrane created by the pulsed electric field. Copyright © 2015 Elsevier B.V. All rights reserved.

Optimal condition for fabricating superhydrophobic Aluminum surfaces with controlled anodizing processes

NASA Astrophysics Data System (ADS)

Saffari, Hamid; Sohrabi, Beheshteh; Noori, Mohammad Reza; Bahrami, Hamid Reza Talesh

2018-03-01

A single step anodizing process is used to produce micro-nano structures on Aluminum (1050) substrates with sulfuric acid as electrolyte. Therefore, surface energy of the anodized layer is reduced using stearic acid modification. Undoubtedly, effects of different parameters including anodizing time, electrical current, and type and concentration of electrolyte on the final contact angle are systemically studied and optimized. Results show that anodizing current of 0.41 A, electrolyte (sulfuric acid) concentration of 15 wt.% and anodizing time of 90 min are optimal conditions which give contact angle as high as 159.2° and sliding angle lower than 5°. Moreover, the study reveals that adding oxalic acid to the sulfuric acid cannot enhance superhydrophobicity of the samples. Also, scanning electron microscopy images of samples show that irregular (bird's nest) structures present on the surface instead of high-ordered honeycomb structures expecting from normal anodizing process. Additionally, X-ray diffraction analysis of the samples shows that only amorphous structures present on the surface. The Brunauer-Emmett-Teller (BET) specific surface area of the anodized layer is 2.55 m2 g-1 in optimal condition. Ultimately, the surface keeps its hydrophobicity in air and deionized water (DIW) after one week and 12 weeks, respectively.

Effect of cations in the background electrolyte on the adsorption kinetics of copper and cadmium and the isoelectric point of imogolite.

PubMed

Arancibia-Miranda, Nicolás; Silva-Yumi, Jorge; Escudey, Mauricio

2015-12-15

Modification of surface charge and changes in the isoelectric point (IEP) of synthetic imogolite were studied for various cations in the background electrolyte (K(+), NH4(+), Mg(2+), and Ca(2+)). From the electrophoretic mobility data, it was established that the K(+) (KCl) concentration does not affect the IEP of imogolite; therefore, KCl is a suitable background electrolyte. In terms of the magnitude of changes in the IEP and surface charge, the cations may be ranked in the following order: Mg(2+)≈Ca(2+)>NH4(+)>K(+). Four different kinetic models were used to evaluate the influence of Mg(2+), Ca(2+), NH4(+), and K(+) on the adsorption of Cd and Cu on synthetic imogolite. When adsorption occurs in the presence of cations with the exception of K(+), the kinetics of the process is well described by the pseudo-first order model. On the other hand, when adsorption is conducted in the presence of K(+), the adsorption kinetics is well described by the pseudo-second order, Elovich, and Weber-Morris models. From the surface charge measurements, the affinity between imogolite and the cations and their effect on the adsorption of trace elements, namely Cu and Cd, were established. Copyright © 2015 Elsevier B.V. All rights reserved.

Surface Modification of the LiFePO4 Cathode for the Aqueous Rechargeable Lithium Ion Battery.

PubMed

Tron, Artur; Jo, Yong Nam; Oh, Si Hyoung; Park, Yeong Don; Mun, Junyoung

2017-04-12

The LiFePO 4 surface is coated with AlF 3 via a simple chemical precipitation for aqueous rechargeable lithium ion batteries (ARLBs). During electrochemical cycling, the unfavorable side reactions between LiFePO 4 and the aqueous electrolyte (1 M Li 2 SO 4 in water) leave a highly resistant passivation film, which causes a deterioration in the electrochemical performance. The coated LiFePO 4 by 1 wt % AlF 3 has a high discharge capacity of 132 mAh g -1 and a highly improved cycle life, which shows 93% capacity retention even after 100 cycles, whereas the pristine LiFePO 4 has a specific capacity of 123 mAh g -1 and a poor capacity retention of 82%. The surface analysis results, which include X-ray photoelectron spectroscopy and transmission electron microscopy results, show that the AlF 3 coating material is highly effective for reducing the detrimental surface passivation by relieving the electrochemical side reactions of the fragile aqueous electrolyte. The AlF 3 coating material has good compatibility with the LiFePO 4 cathode material, which mitigates the surface diffusion obstacles, reduces the charge-transfer resistances and improves the electrochemical performance and surface stability of the LiFePO 4 material in aqueous electrolyte solutions.

[Adverse effects of drugs in intensive care units: analysis of the administration of electrolyte solutions and antibiotics].

PubMed

Manenti, S; Chaves, A B; Leopoldino, R S; Padilha, K G

1998-12-01

The aims of this study were: 1) to verify the incidence of adverse occurrences (AOs) with medication related to the time of electrolyte solutions infusion and the frequency of doses of antibiotics prescribed and administered to the patients; 2) to characterize the nature of those occurrences. The study was developed in two ICUs of a general hospital of São Paulo City. The population was composed by 51 patients that were in the ICUs in August of 1996. Sixty percent of the patients were older than 60 years, 58.8% were women, 49.1% remained in ICU from 1 to 4 days and 41.2% went to the Intermediate Care Units after ICU. Regarding the incidence of AOs related to the time of administration of the electrolyte solutions and the frequency of doses of antibiotics the non execution of the patient's medical prescriptions was verified in 76.3% and 38.8% respectively. The largest frequency of irregularities with the electrolyte solutions (60.2%) was the infusion faster than the prescribed time followed by the reduction of the number of doses of antibiotics administered. Taking these into consideration we have to invest in preventive measures to reduce those occurrences.

Critical evaluation of the stability of highly concentrated LiTFSI - Acetonitrile electrolytes vs. graphite, lithium metal and LiFePO4 electrodes

NASA Astrophysics Data System (ADS)

Nilsson, Viktor; Younesi, Reza; Brandell, Daniel; Edström, Kristina; Johansson, Patrik

2018-04-01

Highly concentrated LiTFSI - acetonitrile electrolytes have recently been shown to stabilize graphite electrodes in lithium-ion batteries (LIBs) much better than comparable more dilute systems. Here we revisit this system in order to optimise the salt concentration vs. both graphite and lithium metal electrodes with respect to electrochemical stability. However, we observe an instability regardless of concentration, making lithium metal unsuitable as a counter electrode, and this also affects evaluation of e.g. graphite electrodes. While the highly concentrated electrolytes have much improved electrochemical stabilities, their reductive decomposition below ca. 1.2 V vs. Li+/Li° still makes them less practical vs. graphite electrodes, and the oxidative reaction with Al at ca. 4.1 V vs. Li+/Li° makes them problematic for high voltage LIB cells. The former originates in an insufficiently stable solid electrolyte interphase (SEI) dissolving and continuously reforming - causing self-discharge, as observed by paused galvanostatic cycling, while the latter is likely caused by aluminium current collector corrosion. Yet, we show that medium voltage LiFePO4 positive electrodes can successfully be used as counter and reference electrodes.

Designing solid-liquid interphases for sodium batteries.

PubMed

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin; Gunceler, Deniz; Zachman, Michael J; Tu, Zhengyuan; Shin, Jung Hwan; Nath, Pooja; Agrawal, Akanksha; Kourkoutis, Lena F; Arias, Tomas A; Archer, Lynden A

2017-10-12

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

An All-vanadium Continuous-flow Photoelectrochemical Cell for Extending State-of-charge in Solar Energy Storage.

PubMed

Wei, Zi; Shen, Yi; Liu, Dong; Liu, Fuqiang

2017-04-04

Greater levels of solar energy storage provide an effective solution to the inherent nature of intermittency, and can substantially improve reliability, availability, and quality of the renewable energy source. Here we demonstrated an all-vanadium (all-V) continuous-flow photoelectrochemical storage cell (PESC) to achieve efficient and high-capacity storage of solar energy, through improving both photocurrent and photocharging depth. It was discovered that forced convective flow of electrolytes greatly enhanced the photocurrent by 5 times comparing to that with stagnant electrolytes. Electrochemical impedance spectroscopy (EIS) study revealed a great reduction of charge transfer resistance with forced convective flow of electrolytes as a result of better mass transport at U-turns of the tortuous serpentine flow channel of the cell. Taking advantage of the improved photocurrent and diminished charge transfer resistance, the all-V continuous-flow PESC was capable of producing ~20% gain in state of charge (SOC) under AM1.5 illumination for ca. 1.7 hours without any external bias. This gain of SOC was surprisingly three times more than that with stagnant electrolytes during a 25-hour period of photocharge.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Surface and interface engineering of anatase TiO2 anode for sodium-ion batteries through Al2O3 surface modification and wise electrolyte selection

NASA Astrophysics Data System (ADS)

Li, Tao; Gulzar, Umair; Bai, Xue; Monaco, Simone; Longoni, Gianluca; Prato, Mirko; Marras, Sergio; Dang, Zhiya; Capiglia, Claudio; Proietti Zaccaria, Remo

2018-04-01

In the present study, Al2O3 is utilized for the first time as coating agent on nanostructured anatase TiO2 in order to investigate its effect on sodium-ion batteries performance. Our results show that the Al2O3 coating, introduced by a facile two-step approach, provides beneficial effects to the TiO2-based anodes. However, the coated TiO2 still suffers of capacity fading upon cycling when using 1.0 M of NaClO4 in propylene carbonate (PC) as electrolyte. To address this issue, the influence of different electrolytes (NaClO4 salt in various solvents) is further studied. It is found that the modified TiO2 exhibits significant improvements in cycling performance using binary ethylene carbonate (EC) and PC solvent mixture without the need of the commonly used fluoroethylene carbonate (FEC) additive. Under the best configuration, our battery could deliver a high reversible capacity of 188.1 mAh g-1 at 0.1C after 50 cycles, good rate capability up to 5C, and remarkable long-term cycling stability at 1C rate for 650 cycles. This excellent performance can be ascribed to the synergistic effects of surface and interface engineering enabling the formation of a stable and highly ionic conductive interface layer in EC:PC based electrolyte which combines the native SEI film and an 'artificial' SEI layer of irreversibly formed Na-Al-O.

An Original Behavior Modification Program for Weight Reduction: Minimal Intervention and Permanent Habit Change.

ERIC Educational Resources Information Center

Lublin, Irwin; Kirkish, Patricia

This description of a weight reduction program, based on generalizations derived from eight years of work with overweight persons, discusses the clients' rationalization of overeating behaviors. In this behavior modification program, the client is required to permanently give up one high calorie food and to write down all foods eaten before actual…

Teaching Electrochemistry in the General Chemistry Laboratory through Corrosion Exercises

ERIC Educational Resources Information Center

Sanders, Richard W.; Crettol, Gregory L.; Brown, Joseph D.; Plummer, Patrick T.; Schendorf, Tara M.; Oliphant, Alex; Swithenbank, Susan B.; Ferrante, Robert F.; Gray, Joshua P.

2018-01-01

Electrochemistry is primarily taught in first-year undergraduate courses through batteries; this lab focuses instead on corrosion to apply electrochemical concepts of electrolytes, standard reduction potentials, galvanic cells, and other chemistry concepts including Le Chatelier's Principle and Henry's Law. Students investigate galvanic corrosion…

Activity inhibition and its mitigation in high temperature proton exchange membrane fuel cells: The role of phosphoric acid, ammonium trifluoromethanesulfonate, and polyvinylidene difluoride

NASA Astrophysics Data System (ADS)

Holst-Olesen, Kaspar; Nesselberger, Markus; Perchthaler, Markus; Hacker, Viktor; Arenz, Matthias

2014-12-01

In the presented work we systematically study the influence of phosphoric acid, ammonium trifluoromethanesulfonate (ATFMS), and polyvinylidene difluoride (PVDF) on the oxygen reduction reaction (ORR) activity of carbon supported, Pt based catalysts. The influence of phosphoric acid is investigated in a mixed solution of perchloric acid with small amounts of phosphoric acid added. Thin-film rotating disk electrode (TF-RDE) measurements show that such a mixed electrolyte is advantageous as the oxygen reduction reaction (ORR) is inhibited without influencing the oxygen solubility in the electrolyte. In contrast to previous reports it is seen when investigating additives that ATFMS acts as a catalyst poison; whereas the results provide evidence of a better performance in case of the PVDF incorporated catalysts as compared to reference samples without PVDF. The technological relevance of the PVDF improvements and its stability over prolonged time was validated by membrane electrode assembly (MEA) tests.

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

NASA Astrophysics Data System (ADS)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

Nitrogen-doped three-dimensional graphene-supported platinum catalysts for polymer electrolyte membrane fuel cells application

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Li, Xingxing; Yuan, Wensen; Zhu, Huanhuan; Qin, Yong; Zhang, Shuai; Yuan, Ningyi; Lin, Bencai; Ding, Jianning

Catalysts are a key component of polymer electrolyte membrane fuel cells (PEMFCs). In this work, nitrogen-doped three-dimensional graphene-supported platinum (Pt-3DNG) catalysts are successfully prepared and characterized. SEM and TEM images show the Pt nanoparticles are uniformly dispersed in the sheets of nitrogen-doped 3DNG. Compared with that of the commercial Pt/C catalysts, Pt-3DNG show much better oxygen reduction reaction (ORR) activity and cycling stability, and the reduction in limit current density after 1000 cycles is only about 1.6% for the Pt-3DNG catalysts, whereas 7.2% for the commercial Pt/C catalysts. The single cell using Pt-3DNG catalysts in both the anode and the cathode show a higher peak power density (21.47mW cm-2) than that using commercial Pt/C catalysts (20.17mW cm-2) under the same conditions. These properties make this type of catalyst suitable for the application in PEMFCs.

Lithium Dinitramide as an Additive in Lithium Power Cells

NASA Technical Reports Server (NTRS)

Gorkovenko, Alexander A.

2007-01-01

Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.

Not of African Descent: Dental Modification among Indigenous Caribbean People from Canímar Abajo, Cuba

PubMed Central

Roksandic, Mirjana; Alarie, Kaitlynn; Rodríguez Suárez, Roberto; Huebner, Erwin; Roksandic, Ivan

2016-01-01

Dental modifications in the Caribbean are considered to be an African practice introduced to the Caribbean archipelago by the influx of enslaved Africans during colonial times. Skeletal remains which exhibited dental modifications are by default considered to be Africans, African descendants, or post-contact indigenous people influenced by an African practice. Individual E-105 from the site of Canímar Abajo (Cuba), with a direct 14C AMS date of 990–800 cal BC, provides the first unequivocal evidence of dental modifications in the Antilles prior to contact with Europeans in AD 1492. Central incisors showing evidence of significant crown reduction (loss of crown volume regardless of its etiology) were examined macroscopically and with a scanning electron microscope (SEM) to determine if the observed alterations were due to deliberate modification or other (unintentional) factors considered: postmortem breakage, violent accidental breakage, non-dietary use of teeth, and wear caused by habitual or repeated actions. The pattern of crown reduction is consistent with deliberate dental modification of the type commonly encountered among African and African descendent communities in post-contact Caribbean archaeological assemblages. Six additional individuals show similar pattern of crown reduction of maxillary incisors with no analogous wear in corresponding mandibular dentition. PMID:27071012

Not of African Descent: Dental Modification among Indigenous Caribbean People from Canímar Abajo, Cuba.

PubMed

Roksandic, Mirjana; Alarie, Kaitlynn; Rodríguez Suárez, Roberto; Huebner, Erwin; Roksandic, Ivan

2016-01-01

Dental modifications in the Caribbean are considered to be an African practice introduced to the Caribbean archipelago by the influx of enslaved Africans during colonial times. Skeletal remains which exhibited dental modifications are by default considered to be Africans, African descendants, or post-contact indigenous people influenced by an African practice. Individual E-105 from the site of Canímar Abajo (Cuba), with a direct 14C AMS date of 990-800 cal BC, provides the first unequivocal evidence of dental modifications in the Antilles prior to contact with Europeans in AD 1492. Central incisors showing evidence of significant crown reduction (loss of crown volume regardless of its etiology) were examined macroscopically and with a scanning electron microscope (SEM) to determine if the observed alterations were due to deliberate modification or other (unintentional) factors considered: postmortem breakage, violent accidental breakage, non-dietary use of teeth, and wear caused by habitual or repeated actions. The pattern of crown reduction is consistent with deliberate dental modification of the type commonly encountered among African and African descendent communities in post-contact Caribbean archaeological assemblages. Six additional individuals show similar pattern of crown reduction of maxillary incisors with no analogous wear in corresponding mandibular dentition.

Graphene/graphene-tube nanocomposites templated from cage-containing metal-organic frameworks for oxygen reduction in Li-O₂ batteries.

PubMed

Li, Qing; Xu, Ping; Gao, Wei; Ma, Shuguo; Zhang, Guoqi; Cao, Ruiguo; Cho, Jaephil; Wang, Hsing-Lin; Wu, Gang

2014-03-05

Nitrogen-doped graphene/graphene-tube nanocomposites are prepared by a hightemperature approach using a newly designed cage-containing metal-organic framework (MOF) to template nitrogen/carbon (dicyandiamide) and iron precursors. The resulting N-Fe-MOF catalysts universally exhibit high oxygen-reduction activity in acidic, alkaline, and non-aqueous electrolytes and superior cathode performance in Li-O2 batteries. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

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

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

Membraneless laminar flow cell for electrocatalytic CO 2 reduction with liquid product separation

DOE PAGES

Monroe, Morgan M.; Lobaccaro, Peter; Lum, Yanwei; ...

2017-03-16

The production of liquid fuel products via electrochemical reduction of CO 2 is a potential path to produce sustainable fuels. However, to be practical, a separation strategy is required to isolate the fuel-containing electrolyte produced at the cathode from the anode and also prevent the oxidation products (i.e. O 2) from reaching the cathode. Ion-conducting membranes have been applied in CO 2 reduction reactors to achieve this separation, but they represent an efficiency loss and can be permeable to some product species. An alternative membraneless approach is developed here to maintain product separation through the use of a laminar flowmore » cell. Computational modelling shows that near-unity separation efficiencies are possible at current densities achievable now with metal cathodes via optimization of the spacing between the electrodes and the electrolyte flow rate. Laminar flow reactor prototypes were fabricated with a range of channel widths by 3D printing. CO 2 reduction to formic acid on Sn electrodes was used as the liquid product forming reaction, and the separation efficiency for the dissolved product was evaluated with high performance liquid chromatography. Trends in product separation efficiency with channel width and flow rate were in qualitative agreement with the model, but the separation efficiency was lower, with a maximum value of 90% achieved.« less

A study of microbial profile modification

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

Bae, J.H.; Lee, H.O.

1995-12-31

A microbial profile modification method using spores was investigated. A halotolerant, spore-forming, biopolymer-producing mesophile was used in Berea cores with a specifically formulated nutrient package to reduce the permeability of the rock. The degree of permeability reduction varied widely depending on the stimulation protocols used. The incubation period had a significant impact on permeability reduction, and there appeared to be an optimum incubation time for maximum permeability reduction. The reduction persisted for many PV of brine injection and appeared very stable. For our microbes used in this study, the permeability reduction was about the same when the NaCl concentration wasmore » above 2 wt% in the range from 0 wt% to 10 wt%.« less

40 CFR 424.77 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... control technology. 424.77 Section 424.77 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS FERROALLOY MANUFACTURING POINT SOURCE CATEGORY Electrolytic... attainable by the application of the best conventional pollutant control technology. Except as provided in...

Surface modification and electrochemical properties of activated carbons for supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Yang, Dan; Qiu, Wenmei; Xu, Jingcai; Han, Yanbing; Jin, Hongxiao; Jin, Dingfeng; Peng, Xiaoling; Hong, Bo; Li, Ji; Ge, Hongliang; Wang, Xinqing

2015-12-01

Modifications with different acids (HNO3, H2SO4, HCl and HF, respectively) were introduced to treat the activated carbons (ACs) surface. The microstructures and surface chemical properties were discussed by X-ray diffraction (XRD), thermogravimetric analysis (TGA), ASAP, Raman spectra and Fourier transform infrared (FTIR) spectra. The ACs electrode-based supercapacitors were assembled with 6 mol ṡ L-1 KOH electrolyte. The electrochemical properties were studied by galvanostatic charge-discharge and cyclic voltammetry. The results indicated that although the BET surface area of modified ACs decreased, the functional groups were introduced and the ash contents were reduced on the surface of ACs, receiving larger specific capacitance to initial AC. The specific capacitance of ACs modified with HCl, H2SO4, HF and HNO3 increased by 31.4%, 23%, 21% and 11.6%, respectively.

Improve electrochemical performance of CeO2 surface modification LiNi0.80Co0.15Al0.05O2 cathode material

NASA Astrophysics Data System (ADS)

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

2014-06-01

Lithium ion battery cathode material LiNi0.8Co0.15Al0.05O2 cathode has successfully prepared by co-precipitation. CeO2 surface modification has improved LiNi0.80Co0.15Al0.05O2 electrochemical performance use sol-gel method and subsequent heat treatment at 600 °C for 5 h. Different to other conventional coating material, CeO2 coating layer can not only inhibit the reaction of the electrode and the electrolyte, but also can reduce the impedance of electron transfer due to its high conductivity, and inhibit the production of Ni2+ because of its high oxidation. The surface-modified and pristine LiNi0.80Co0.15Al0.05O2 powders are characterized by XRD, SEM, TEM, XPS, CV and DSC. When CeO2 coating is 0.02% (mole ratio), contrast to pristine NCA, the CeO2-coated NCA cathode exhibits no decrease in its initial specific capacity of 184 mAh g -1 (at 0.2 C) and excellent capacity retention (86% of its initial capacity at 1 C) between 2.75 and 4.3 V after 100 cycles. The results indicate that the CeO2 surface treatment should be an effective way to improve cycle properties due to CeO2 inhibit the electrodes and the electrolyte side effects.

Interphase evolution at two promising electrode materials for Li-ion batteries: LiFePO4 and LiNi1/2 Mn1/2O2.

PubMed

Dupré, Nicolas; Cuisinier, Marine; Martin, Jean-Frederic; Guyomard, Dominique

2014-07-21

The present review reports the characterization and control of interfacial processes occurring on olivine LiFePO(4) and layered LiNi(1/2) Mn(1/2)O(2), standing here as model compounds, during storage and electrochemical cycling. The formation and evolution of the interphase created by decomposition of the electrolyte is investigated by using spectroscopic tools such as magic-angle-spinning nuclear magnetic resonance ((7)Li,(19)F and (31)P) and electron energy loss spectroscopy, in parallel to X-ray photoelectron spectroscopy, to quantitatively describe the interphase and unravel its architecture. The influence of the pristine surface chemistry of the active material is carefully examined. The importance of the chemical history of the surface of the electrode material before any electrochemical cycling and the strong correlation between interface phenomena, the formation/evolution of an interphase, and the electrochemical behavior appear clearly from the use of these combined characterization probes. This approach allows identifying interface aging and failure mechanisms. Different types of surface modifications are then investigated, such as intrinsic modifications upon aging in air or methods based on the use of additives in the electrolyte or carbon coatings on the surface of the active materials. In each case, the species detected on the surface of the materials during storage and cycling are correlated with the electrochemical performance of the modified positive electrodes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

PubMed

Cirtiu, Ciprian Mihai; Hassani, Hicham Oudghiri; Bouchard, Nicolas-Alexandre; Rowntree, Paul A; Ménard, Hugues

2006-07-04

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.

Understanding performance limitation and suppression of leakage current or self-discharge in electrochemical capacitors: a review.

PubMed

Ike, Innocent S; Sigalas, Iakovos; Iyuke, Sunny

2016-01-14

Self-discharge is known to have considerable adverse effects on the performance and application of electrochemical capacitors (ECs). Thus, obtaining an understanding of EC self-discharge mechanism(s) and subsequent derivation and solution of EC models, subject to a particular mechanism or combination of mechanisms during charging, discharging and storage of the device, is the only way to solve problems associated with EC self-discharge. In this review, we summarize recent progress with respect to EC self-discharge by considering the two basic types, electric double-layer capacitors (EDLC) and pseudocapacitors, and their hybrids with their respective charge storage mechanisms, distinguishable self-discharge mechanisms, charge redistribution and charge/energy loss during self-discharge. It was clearly observed that most of the voltage reduction is not purely due to the self-discharge effect but is basically due to redistribution of charge carriers deep inside pores and can therefore be retrieved from a capacitor during long-time discharging. Tuning the self-discharge rate is therefore feasible for single-walled carbon nanotube (SWNT) ECs and can be achieved by simply adjusting the surface chemistry of the nanotubes. The effects of surface chemistry modification on EC self-discharge are very important in studying and suppressing the self-discharge process and will benefit potential applications of ECs with respect to energy retention. Self-discharge can be averted by the use of redox couples that are transformed to insoluble species via electrolysis and adsorbed onto the activated carbon electrode in redox-couple EDLCs, thus transforming the EDLC electrolyte into a material that can store charge. Self-discharge in ECs can also be successfully suppressed by utilizing an ion-interchange layer (ion-exchange membrane), separator or CuSO4 mobile electrolyte that can be converted into an insoluble species by electrolysis during the charge/discharge process. This will help in producing a modern-day blueprint for ECs with high capacitance and improved energy sustainability.

The impact of metformin, oral contraceptives, and lifestyle modification on polycystic ovary syndrome in obese adolescent women in two randomized, placebo-controlled clinical trials.

PubMed

Hoeger, Kathleen; Davidson, Kristen; Kochman, Lynda; Cherry, Tracy; Kopin, Laurie; Guzick, David S

2008-11-01

Polycystic ovary syndrome (PCOS) presents in adolescence, and obesity is a common finding. The benefits and risks of alternate approaches to the management of PCOS in obese adolescent women are not clear. We investigated the effects of metformin, oral contraceptives (OCs), and/or lifestyle modification in obese adolescent women with PCOS. Two small, randomized, placebo-controlled clinical trials were performed. A total of 79 obese adolescent women with PCOS participated. In the single treatment trial, subjects were randomized to metformin, placebo, a lifestyle modification program, or OC. In the combined treatment trial, all subjects received lifestyle modification and OC and were randomized to metformin or placebo. Serum concentrations of androgens and lipids were measured. Lifestyle modification alone resulted in a 59% reduction in free androgen index with a 122% increase in SHBG. OC resulted in a significant decrease in total testosterone (44%) and free androgen index (86%) but also resulted in an increase in C-reactive protein (39.7%) and cholesterol (14%). The combination of lifestyle modification, OC, and metformin resulted in a 55% decrease in total testosterone, as compared to 33% with combined treatment and placebo, a 4% reduction in waist circumference, and a significant increase in HDL (46%). In these preliminary trials, both lifestyle modification and OCs significantly reduce androgens and increase SHBG in obese adolescents with PCOS. Metformin, in combination with lifestyle modification and OC, reduces central adiposity, reduces total testosterone, and increases HDL, but does not enhance overall weight reduction.

Framework 'interstitial' oxygen in La(10)(GeO(4))(5-)(GeO(5))O(2) apatite electrolyte.

PubMed

Pramana, Stevin S; Klooster, Wim T; White, T J

2007-08-01

Oxygen conduction at low temperatures in apatites make these materials potentially useful as electrolytes in solid-oxide fuel cells, but our understanding of the defect structures enabling ion migration is incomplete. While conduction along [001] channels is dominant, considerable inter-tunnel mobility has been recognized. Using neutron powder diffraction of stoichiometric 'La(10)(GeO(4))(6)O(3)', it has been shown that this compound is more correctly described as an La(10)(GeO(4))(5-)(GeO(5))O(2) apatite, in which high concentrations of interstitial oxygen reside within the channel walls. It is suggested that these framework interstitial O atoms provide a reservoir of ions that can migrate into the conducting channels of apatite, via a mechanism of inter-tunnel oxygen diffusion that transiently converts GeO(4) tetrahedra to GeO(5) distorted trigonal bipyramids. This structural modification is consistent with known crystal chemistry and may occur generally in oxide apatites.

Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability.

PubMed

Shin, Dong Won; Guiver, Michael D; Lee, Young Moo

2017-03-22

A fundamental understanding of polymer microstructure is important in order to design novel polymer electrolyte membranes (PEMs) with excellent electrochemical performance and stabilities. Hydrocarbon-based polymers have distinct microstructure according to their chemical structure. The ionic clusters and/or channels play a critical role in PEMs, affecting ion conductivity and water transport, especially at medium temperature and low relative humidity (RH). In addition, physical properties such as water uptake and dimensional swelling behavior depend strongly on polymer morphology. Over the past few decades, much research has focused on the synthetic development and microstructural characterization of hydrocarbon-based PEM materials. Furthermore, blends, composites, pressing, shear field, electrical field, surface modification, and cross-linking have also been shown to be effective approaches to obtain/maintain well-defined PEM microstructure. This review summarizes recent work on developments in advanced PEMs with various chemical structures and architecture and the resulting polymer microstructures and morphologies that arise for potential application in fuel cell, lithium ion battery, redox flow battery, actuators, and electrodialysis.

Design of new triphenylamine-sensitized solar cells: a theoretical approach.

PubMed

Preat, Julien; Jacquemin, Denis; Perpète, Eric A

2010-07-15

This work reports a theoretical study of the photovoltaic properties of a series of original conjugated metal-free organic dyes containing the triphenylamine (TPA) moiety. These compounds have recently been develop for dye sensitized solar cells (DSSCs). Our (TD)DFT-based procedure made it possible to get insights into the geometrical and electronic structures of the dyes and to unravel the structural modifications optimizing the properties of TPA-based DSSCs. In particular, we aimed at improving the electron injection process as well as the light harvesting efficiency of the dyes. On the other hand, molecular dynamic (MD) investigations of the kinetics of the regeneration step have been performed for both "classical" (CHCl(3)/I(3)(-)/I(-)/Li(+)) and iodide imidazolium-based solvent-free electrolytes (DMII(+)/I(-)). The MD simulations helped to understand the regeneration mechanism for the solvent-free electrolyte: it combines the DMII(+)/DMII(0) couple to the I(3)(-)/I(-) redox system which acts as a "mediator".

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

Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan

The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF{sub 3}SO{sub 3} were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2–10 wt%) via solution-casting method. The conductivity was increased withmore » carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10{sup −7} Scm{sup −1} upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.« less

Understanding self-photorechargeability of WO(3) for H(2) generation without light illumination.

PubMed

Ng, Charlene; Iwase, Akihide; Ng, Yun Hau; Amal, Rose

2013-02-01

This work presents insight into the self-photorechargeability of WO(3), whereby the intercalation of positive alkali cations is accompanied by the simultaneous storage of photo-excited electrons. The cyclic voltammetry studies verify the photo-assisted intercalation and de-intercalation of Na(+) and K(+) from the flower structured WO(3). A storage capacity of up to 0.722 C cm(-2) can be achieved in a saturated (0.68 M) K(2)SO(4) electrolyte solution. However, the best photo recharge-discharge stability of the electrode are observed at a lower (0.1 M) cation concentration. At high electrolyte concentrations, the intercalated cations are firmly trapped, as indicated by the structural modifications observed in Raman analysis, resulting in much less photocharging and discharging abilities in subsequent cycles. The study also shows that the stored electrons can be successfully used to generate H(2) with 100 % faradaic efficiency in the absence of light. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

1997-12-01

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

Enhanced photoelectrochemical performance of inorganic-organic hybrid consisting of BiVO4 and PEDOT:PSS

NASA Astrophysics Data System (ADS)

Trzciński, K.; Szkoda, M.; Siuzdak, K.; Sawczak, M.; Lisowska-Oleksiak, A.

2016-12-01

The PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)) was electrodeposited on a thin layer of bismuth vanadate (BiVO4) prepared using the pulsed laser deposition technique onto FTO. The inorganic-organic junction was characterized by Raman spectroscopy, UV-vis spectroscopy and scanning electron microscopy. Chronoamperometry curves, recorded under simulated solar light illumination, were performed to determine generated photocurrent during water and hydroquinone oxidation at the electrode surface. Experiments were performed for three types of electrode materials: (i) FTO/BiVO4, (ii) FTO/PEDOT:PSS and (iii) FTO/BiVO4/PEDOT:PSS in aqueous electrolyte. Almost 5 times higher photocurrent in electrolyte containing hole scavenger was generated after modification of BiVO4 photoanode with electrodeposited polymer. It is noteworthy that anodic photocurrent was stable even after 4 h of illumination. Cyclic voltammetry curves of FTO/BiVO4/PEDOT:PSS recorded before and after experiments performed under electrode illumination indicated that the organic part in tested junction is photo-corrosion resistant.

Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems

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

Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.

In recent years room temperature Li+ ion conductors have been intensively revisited in order to develop safe lithium ion (Li-ion) batteries and beyond that can be deployed in the electrical vehicles. Through careful modification on materials synthesis, promising solid Li+ conductors with high ionic conductivity, competitve with liquid electrolytes, have been demonstrated. However, the integration of those highly conductive solid electrolytes into the whole system is still very challenging mainly due to the high impedance existing in the different interfaces throughout the entire battery structure. Herein , this review paper focuses on the overview of the interfacial behaviors between Li+more » conductors and cathode/anode materials. The origin, evolution and potential solutions to reuce these interfacial impedances are reviewed for various battery systems spanning from Li-ion, lithium sulfur (Li-S), lithium oxygen (Li-O2) batteries to lithium metal protection. The predicted gravimetric and volumetric energy densities at different scenarios are also discussed along with the prospectives for further development of solid state batteries.« less

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Experimental Study of Hydroxy Gas (HHO) Production with Variation in Current, Voltage and Electrolyte Concentration

NASA Astrophysics Data System (ADS)

Alam, Noor; Pandey, K. M.

2017-08-01

In this paper, work has been carried out experimentally for the investigation of the effects of variation incurrent, voltage, temperature, chemical concentration and reaction time on the amount of hydroxy gas produced. Further effects on the overall electrolysis efficiency of advance alkaline water is also studied. The hydroxy gas (HHO) has been produced experimentally by the electrolysis of alkaline water with parallel plate electrode of 316L-grade stainless steel. The electrode has been selected on the basis of corrosion resistance and inertness with respect to electrolyte (KOH). The process used for the production of HHO is conventional as compared to the other production processes because of reduced energy consumption, less maintenance and low setup cost. From the experimental results, it has been observed that with increase in voltage, temperature and electrolyte concentration of alkaline solution, the production of hydroxy gas has increased about 30 to 40% with reduction in electrical energy consumption.

Metabolic complications associated with use of diuretics.

PubMed

Palmer, Biff F

2011-11-01

Diuretics are commonly used therapeutic agents that act to inhibit sodium transport systems along the length of the renal tubule. The most effective diuretics are inhibitors of sodium chloride transport in the thick ascending limb of Henle. Loop diuretics mobilize large amounts of sodium chloride and water and produce a copious diuresis with a sharp reduction of extracellular fluid volume. As the site of action of diuretics moves downstream (thiazide and potassium-sparing diuretics), their effectiveness declines because the transport systems they inhibit have low transport capacity. Depending on the site of action diuretics can influence the renal handling of electrolyte-free water, calcium, potassium, protons, sodium bicarbonate, and uric acid. As a result, electrolyte and acid-base disorders commonly accompany diuretic use. Glucose and lipid abnormalities also can occur, particularly with the use of thiazide diuretics. This review focuses on the biochemical complications associated with the use of diuretics. The development of these complications can be minimized with careful monitoring, dosage adjustment, and replacement of electrolyte losses. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis, characterization and application of doped electrolytic manganese dioxides

NASA Astrophysics Data System (ADS)

Jantscher, Wolfgang; Binder, Leo; Fiedler, Dirk A.; Andreaus, Reinhard; Kordesch, Karl

Electrolytic manganese dioxides (EMDs) were prepared on the 100 g scale by anodic deposition from acidic aqueous solutions of manganese sulfate. In situ doping with titanium ions was achieved by addition of tetra- n-butoxytitanium to the electrolytic bath. Samples were also doped ex situ by washing the products with aqueous barium hydroxide solution. The EMDs were characterized by electron microscopy studies and BET surface area determinations. Cyclic abrasive stripping voltammetry was successfully applied to evaluate the rechargeability of the newly synthesized undoped and doped EMDs in 9 M KOH. Relative discharge capacities at different depths of discharge (DOD) with respect to the first one-electron reduction of γ-MnO 2 are compared for different EMDs. At about 30% DOD, resulting relative discharge capacities show essentially the same trend as those measured in AA cells from about 10 to 20 discharge/charge cycles onwards. Accordingly, titanium-doped EMD was shown to exhibit superior charge retention and rechargeability when compared to the titanium-free samples.

First-Principles Modeling of Mn(II) Migration above and Dissolution from Li x Mn 2 O 4 (001) Surfaces

DOE PAGES

Leung, Kevin

2016-12-10

The density functional theory and ab initio molecular dynamics simulations are applied to investigate the migration of Mn(II) ions to above-surface sites on spinel Li xMn 2O 4 (001) surfaces, the subsequent Mn dissolution into the organic liquid electrolyte, and the detrimental effects on graphite anode solid electrolyte interphase (SEI) passivating films after Mn(II) ions diffuse through the separator. The dissolution mechanism proves complex; the much-quoted Hunter disproportionation of Mn(III) to form Mn(II) is far from sufficient. Key steps that facilitate Mn(II) loss include concerted liquid/solid-state motions; proton-induced weakening of Mn–O bonds forming mobile OH – surface groups; and chemicalmore » reactions of adsorbed decomposed organic fragments. Mn(II) lodged between the inorganic Li 2CO 3 and organic lithium ethylene dicarbonate (LEDC) anode SEI components facilitate electrochemical reduction and decomposition of LEDC. Our findings help inform future design of protective coatings, electrolytes, additives, and interfaces.« less

Lithium ethylene dicarbonate identified as the primary product of chemical and electrochemical reduction of EC in 1.2 M LiPF6/EC:EMC electrolyte.

PubMed

Zhuang, Guorong V; Xu, Kang; Yang, Hui; Jow, T Richard; Ross, Philip N

2005-09-22

Lithium ethylene dicarbonate ((CH2OCO2Li)2) was chemically synthesized and its Fourier transform infrared (FTIR) spectrum was obtained and compared with that of surface films formed on Ni after cyclic voltammetry (CV) in 1.2 M lithium hexafluorophosphate (LiPF6)/ethylene carbonate (EC):ethyl methyl carbonate (EMC) (3:7, w/w) electrolyte and on metallic lithium cleaved in-situ in the same electrolyte. By comparison of IR experimental spectra with that of the synthesized compound, we established that the title compound is the predominant surface species in both instances. Detailed analysis of the IR spectrum utilizing quantum chemical (Hartree-Fock) calculations indicates that intermolecular association through O...Li...O interactions is very important in this compound. It is likely that the title compound in the passivation layer has a highly associated structure, but the exact intermolecular conformation could not be established on the basis of analysis of the IR spectrum.

BF 3-promoted electrochemical properties of quinoxaline in propylene carbonate

DOE PAGES

Carino, Emily V.; Diesendruck, Charles E.; Moore, Jeffrey S.; ...

2015-02-04

Electrochemical and density functional studies demonstrate that coordination of electrolyte constituents to quinoxalines modulates their electrochemical properties. Quinoxalines are shown to be electrochemically inactive in most electrolytes in propylene carbonate, yet the predicted reduction potential is shown to match computational estimates in acetonitrile. We find that in the presence of LiBF 4 and trace water, an adduct is formed between quinoxaline and the Lewis acid BF3, which then displays electrochemical activity at 1–1.5 V higher than prior observations of quinoxaline electrochemistry in non-aqueous media. Direct synthesis and testing of a bis-BF 3 quinoxaline complex further validates the assignment of themore » electrochemically active species, presenting up to a ~26-fold improvement in charging capacity, demonstrating the advantages of this adduct over unmodified quinoxaline in LiBF 4-based electrolyte. The use of Lewis acids to effectively “turn on” the electrochemical activity of organic molecules may lead to the development of new active material classes for energy storage applications.« less

Acetazolamide in the treatment of metabolic alkalosis in critically ill patients.

PubMed

Marik, P E; Kussman, B D; Lipman, J; Kraus, P

1991-09-01

Metabolic alkalosis is a common acid-base disturbance in critically ill patients. In many patients correction of fluid and electrolyte status does not fully correct the metabolic derangement. In this study we examined the effect of 500 mg of intravenous acetazolamide, after correcting for fluid and electrolyte abnormalities, on the acid-base status of 30 ventilated patients. In all patients studied there was a fall of total serum bicarbonate; the mean reduction at 24 hours was 6.4 mmol/L, with a normalization of the base excess and pH. The onset of action was rapid (within 2 hours), and the maximal effect occurred at a mean of 15.5 hours, although there was wide variation. The effect of acetazolamide was still apparent at 48 hours. No adverse effects were noted. We conclude that in patients with metabolic alkalosis, once fluid and electrolyte abnormalities have been corrected, acetazolamide is an effective and safe form of therapy with a quick onset and long duration of action.

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

PubMed Central

Zhao, Yunlong; Xu, Lin; Mai, Liqiang; Han, Chunhua; An, Qinyou; Xu, Xu; Liu, Xue; Zhang, Qingjie

2012-01-01

Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire. PMID:23150570

Photodissociable dimer reduction products of 2-thiopyrimidine derivatives.

PubMed Central

Wrona, M; Giziewicz, J; Shugar, D

1975-01-01

Both 4,6-dimethyl-2-thipyrimidine and its 1-methyl derivative undergo polarographic reduction in aqueous medium, via a 1e/1H+ reduction to a free radical which rapidly dimerizes to products isolates and identified as 4,4'-bis-(4,6-dimethyl-3,4-dihydropyrimidin-2-thione) and the corresponding 1-methyl dimer. The dimers may be oxidized electrolytically to regenerate the parent monomers. Both dimers also undergo photodissociation to quantitatively regenerate the parent monomers, in high quantum yield, 0.23 and 0.35 M/Einstein. The correlation between electrochemical and photochemical reductions of 2-thiopyrimidines are discussed, as well as the significance of the dimer photodissociation reactions in relation to nucleic acid photochemistry. PMID:28516

Direct printing and reduction of graphite oxide for flexible supercapacitors

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

Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo

2014-08-04

We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart powermore » applications.« less

Electrolytic exfoliation of graphite in water with multifunctional electrolytes: en route towards high quality, oxide-free graphene flakes.

PubMed

Munuera, J M; Paredes, J I; Villar-Rodil, S; Ayán-Varela, M; Martínez-Alonso, A; Tascón, J M D

2016-02-07

Electrolytic--usually referred to as electrochemical--exfoliation of graphite in water under anodic potential holds enormous promise as a simple, green and high-yield method for the mass production of graphene, but currently suffers from several drawbacks that hinder its widespread adoption, one of the most critical being the oxidation and subsequent structural degradation of the carbon lattice that is usually associated with such a production process. To overcome this and other limitations, we introduce and implement the concept of multifunctional electrolytes. The latter are amphiphilic anions (mostly polyaromatic hydrocarbons appended with sulfonate groups) that play different relevant roles as (1) an intercalating electrolyte to trigger exfoliation of graphite into graphene flakes, (2) a dispersant to afford stable aqueous colloidal suspensions of the flakes suitable for further use, (3) a sacrificial agent to prevent graphene oxidation during exfoliation and (4) a linker to promote nanoparticle anchoring on the graphene flakes, yielding functional hybrids. The implementation of this strategy with some selected amphiphiles even furnishes anodically exfoliated graphenes of a quality similar to that of flakes produced by direct, ultrasound- or shear-induced exfoliation of graphite in the liquid phase (i.e., almost oxide- and defect-free). These high quality materials were used for the preparation of catalytically efficient graphene-Pt nanoparticle hybrids, as demonstrated by model reactions (reduction of nitroarenes). The multifunctional performance of these electrolytes is also discussed and rationalized, and a mechanistic picture of their oxidation-preventing ability is proposed. Overall, the present results open the prospect of anodic exfoliation as a competitive method for the production of very high quality graphene flakes.

Lunar Metal Oxide Electrolysis with Oxygen and Photovoltaic Array Production Applications

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Ethridge, E.; Hudson, S.; Sen, S.

2006-01-01

This paper presents the results of a Marshall Space Flight Center funded effort to conduct an experimental demonstration of the processing of simulated lunar resources by the molten oxide electrolysis (MOE) process to produce oxygen and metal from lunar resources to support human exploration of space. Oxygen extracted from lunar materials can be used for life support and propellant, and silicon and metallic elements produced can be used for in situ fabrication of thin-film solar cells for power production. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis, MOE, is chosen for extraction, since the electron is the most practical reducing agent. MOE was also chosen for following reasons. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. In the experiments reported here, melts containing iron oxide were electrolyzed in a low temperature supporting oxide electrolyte (developed by D. Sadoway, MIT). The production of oxygen and reduced iron were observed. Electrolysis was also performed on the supporting electrolyte with JSC-1 Lunar Simulant. The cell current for the supporting electrolyte alone is negligible while the current for the electrolyte with JSC-1 shows significant current and a peak at about -0.6 V indicating reductive reaction in the simulant.

Highly conducting leakage-free electrolyte for SrCoOx-based non-volatile memory device

NASA Astrophysics Data System (ADS)

Katase, Takayoshi; Suzuki, Yuki; Ohta, Hiromichi

2017-10-01

The electrochemical switching of SrCoOx-based non-volatile memory with a thin-film-transistor structure was examined by using liquid-leakage-free electrolytes with different conductivities (σ) as the gate insulator. We first examined leakage-free water, which is incorporated in the amorphous (a-) 12CaO.7Al2O3 film with a nanoporous structure (Calcium Aluminate with Nanopore), but the electrochemical oxidation/reduction of the SrCoOx layer required the application of a high gate voltage (Vg) up to 20 V for a very long current-flowing-time (t) ˜40 min, primarily due to the low σ [2.0 × 10-8 S cm-1 at room temperature (RT)] of leakage-free water. We then controlled the σ of the leakage-free electrolyte, infiltrated in the a-NaxTaO3 film with a nanopillar array structure, from 8.0 × 10-8 S cm-1 to 2.5 × 10-6 S cm-1 at RT by changing the x = 0.01-1.0. As the result, the t, required for the metallization of the SrCoOx layer under small Vg = -3 V, becomes two orders of magnitude shorter with increase of the σ of the a-NaxTaO3 leakage-free electrolyte. These results indicate that the ion migration in the leakage-free electrolyte is the rate-determining step for the electrochemical switching, compared to the other electrochemical process, and the high σ of the leakage-free electrolyte is the key factor for the development of the non-volatile SrCoOx-based electro-magnetic phase switching device.

Reduction of aircraft gas turbine engine pollutant emissions

NASA Technical Reports Server (NTRS)

Diehl, L. A.

1978-01-01

To accomplish simultaneous reduction of unburned hydrocarbons, carbon monoxide, and oxides of nitrogen, required major modifications to the combustor. The modification most commonly used was a staged combustion technique. While these designs are more complicated than production combustors, no insurmountable operational difficulties were encountered in either high pressure rig or engine tests which could not be resolved with additional normal development. The emission reduction results indicate that reductions in unburned hydrocarbons were sufficient to satisfy both near and far-termed EPA requirements. Although substantial reductions were observed, the success in achieving the CO and NOx standards was mixed and depended heavily on the engine/engine cycle on which it was employed. Technology for near term CO reduction was satisfactory or marginally satisfactory. Considerable doubt exists if this technology will satisfy all far-term requirements.

Effect of surface modification on carbon nanotubes (CNTs) catalyzed nitrobenzene reduction by sulfide.

PubMed

Liu, Qi; Zhao, Han-Qing; Li, Lei; He, Pan-Pan; Wang, Yi-Xuan; Yang, Hou-Yun; Hu, Zhen-Hu; Mu, Yang

2018-06-04

Carbon nanotubes (CNTs) could be directly used as metal-free catalysts for the reduction of nitroaromatics by sulfide in water, but their catalytic ability need a further improvement. This study evaluated the feasibility of surface modification through thermal and radiation pretreatments to enhance catalytic activity of CNTs on nitrobenzene reduction by sulfide. The results show that thermal treatment could effectively improve the catalytic behaviors of CNTs for the reduction of nitrobenzene by sulfide, where the optimum annealing temperature was 400 °C. However, plasma radiation pretreatment didn't result in an obvious improvement of the CNTs catalytic activity. Moreover, the possible reasons have been explored and discussed in the study. Additionally, the impacts of various operational parameters on nitrobenzene reduction catalyzed by the CNTs after an optimized surface modification were also evaluated. It was found that the rate of nitrobenzene removal by sulfide was positively correlated with CNTs doses in a range of 0.3-300 mg L -1 ; the optimum pH was around 8.0; higher temperature and sulfide concentration facilitated the reaction; and the presence of humic acid exhibited a negative effect on nitrobenzene reduction. Copyright © 2018 Elsevier B.V. All rights reserved.

Operando Raman Micro Spectroscopy of Polymer Electrolyte Fuel Cells

DTIC Science & Technology

2016-01-16

understanding of the processes such as oxygen reduc- tion reaction (ORR), carbon corrosion, and catalysis process of ORR in PEMFCs catalyzed by Pt or...Journal of Membrane Science, 392, 88 (2012). 46. F. Jaouen, F. Charreteur, and J. P. Dodelet, “Fe-based catalysts for oxygen reduction in PEMFCs

Porous carbon nanotube/graphene composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Jing; Tang, Jie; Yuan, Jinshi; Zhang, Kun; Yu, Xiaoliang; Sun, Yige; Zhang, Han; Qin, Lu-Chang

2018-02-01

Carbon nanotubes (CNTs) are an effective spacer to prevent the re-stacking of graphene layers. However, the aggregation of CNTs always reduces the specific surface area of resulting CNT/graphene composites. Meanwhile, different pores always have different contributions to the specific capacitance. In this study, CNT/graphene composites with different porous structures are synthesized by co-reduction of oxidized CNTs and graphene oxide with different mixing ratios. With an optimized CNT content of 20%, the CNT/graphene composite shows 206 F g-1 in 1-ethyl-3-methylimidazolium tetrafluoroborate electrolyte. It is found that pores larger than twice the size of electrolyte ions can make greater contributions to the specific capacitance.

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.; Burrows, B.

1972-01-01

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Cost analysis of oxygen recovery systems

NASA Technical Reports Server (NTRS)

Yakut, M. M.

1973-01-01

Report is made of the cost analysis of four leading oxygen recovery subsystems which include two carbon dioxide reduction subsystems and two water electrolysis subsystems, namely, the solid polymer electrolyte and the circulating KOH electrolyte. The four oxygen recovery systems were quantitatively evaluated. System characteristics, including process flows, performance, and physical characteristics were also analyzed. Additionally, the status of development of each of the systems considered and the required advance technology efforts required to bring conceptual and/or pre-prototype hardware to an operational prototype status were defined. Intimate knowledge of the operations, development status, and capabilities of the systems to meet space mission requirements were found to be essential in establishing the cost estimating relationships for advanced life support systems.

Apparatus for Screening Multiple Oxygen-Reduction Catalysts

NASA Technical Reports Server (NTRS)

Whitacre, Jay; Narayanan, Sekharipuram

2009-01-01

An apparatus that includes an array of multiple electrodes has been invented as a means of simultaneously testing multiple materials for their utility as oxygen-reduction catalysts in fuel cells. The apparatus ensures comparability of test results by exposing all the catalyst-material specimens to the same electrolytic test solution at the same potential. Heretofore, it has been possible to test only one specimen at a time, using a precise rotating disk electrode that provides a controlled flux of solution to the surface of the specimen.

One step electrodeposition of Cu2ZnSnS4 thin films in a novel bath with sulfurization free annealing

NASA Astrophysics Data System (ADS)

Tang, Aiyue; Li, Zhilin; Wang, Feng; Dou, Meiling; Pan, Youya; Guan, Jingyu

2017-04-01

Cu2ZnSnS4 (CZTS) is a quaternary kesterite compound with suitable band gap for thin film solar cells. In most electrodeposition-anneal routes, sulfurization is inevitable because the as-deposited film is lack of S. In this work, a novel green electrolyte was designed for synthesizing CZTS thin films with high S content. In the one-step electrodeposition, K4P2O7 and C7H6O6S were added to form complex with metallic ions in the electrolyte, which could attribute to co-deposition. The as-deposited film obtained high S content satisfying stoichiometry. After a sulfurization free annealing, the continuous and uniform CZTS thin film was obtained, which had pure kesterite structure and a suitable band gap of 1.53 eV. Electrodeposition mechanism investigation revealed that the K4P2O7 prevented the excessive deposition of Cu2+ and Sn2+. The C7H6O6S promoted the reduction of Zn2+. So the additives narrowed the co-deposition potentials of the metallic elements through a synergetic effect. They also promoted the reduction of S2O32- to ensure the co-deposition of the four elements and the stoichiometry. The sulfurization free annealing process can promote the commercialization of CZTS films and the successful design principle of environmental friendly electrolytes could be applied in other electrodeposition systems.

Performance comparison of protonic and sodium phosphomolybdovanadate polyoxoanion catholytes within a chemically regenerative redox cathode polymer electrolyte fuel cell

NASA Astrophysics Data System (ADS)

Ward, David B.; Gunn, Natasha L. O.; Uwigena, Nadine; Davies, Trevor J.

2018-01-01

The direct reduction of oxygen in conventional polymer electrolyte fuel cells (PEFCs) is seen by many researchers as a key challenge in PEFC development. Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells offer an alternative approach via the indirect reduction of oxygen, improving durability and reducing cost. These systems substitute gaseous oxygen for a liquid catalyst that is reduced at the cathode then oxidised in a regeneration vessel via air bubbling. A key component of a CRRC system is the liquid catalyst or catholyte. To date, phosphomolybdovanadium polyoxometalates with empirical formula H3+nPVnMo12-nO40 have shown the most promise for CRRC PEFC systems. In this work, four catholyte formulations are studied and compared against each other. The catholytes vary in vanadium content, pH and counter ion, with empirical formulas H6PV3Mo9O40, H7PV4Mo8O40, Na3H3PV3Mo9O40 and Na4H3PV4Mo8O40. Thermodynamic properties, cell performance and regeneration rates are measured, generating new insights into how formulation chemistry affects the components of a CRRC system. The results include the best CRRC PEFC performance reported to date, with noticeable advantages over conventional PEFCs. The optimum catholyte formulation is then determined via steady state tests, the results of which will guide further optimization of the catholyte formulation.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

DOE PAGES

Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

2016-12-08

Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

Effects of Functional Groups in Redox-Active Organic Molecules: A High-Throughput Screening Approach

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

Pelzer, Kenley M.; Cheng, Lei; Curtiss, Larry A.

Nonaqueous redox flow batteries have attracted recent attention with their potential for high electrochemical storage capacity, with organic electrolytes serving as solvents with a wide electrochemical stability window. Organic molecules can also serve as electroactive species, where molecules with low reduction potentials or high oxidation potentials can provide substantial chemical energy. To identify promising electrolytes in a vast chemical space, high-throughput screening (HTS) of candidate molecules plays an important role, where HTS is used to calculate properties of thousands of molecules and identify a few organic molecules worthy of further attention in battery research. Here, in this work, we presentmore » reduction and oxidation potentials obtained from HTS of 4178 molecules. The molecules are composed of base groups of five- or six-membered rings with one or two functional groups attached, with the set of possible functional groups including both electron-withdrawing and electron-donating groups. In addition to observing the trends in potentials that result from differences in organic base groups and functional groups, we analyze the effects of molecular characteristics such as multiple bonds, Hammett parameters, and functional group position. In conclusion, this work provides useful guidance in determining how the identities of the base groups and functional groups are correlated with desirable reduction and oxidation potentials.« less

Organic Solar Cells Based on Electrodeposited Polyaniline Films

NASA Astrophysics Data System (ADS)

Inoue, Kei; Akiyama, Tsuyoshi; Suzuki, Atsushi; Oku, Takeo

2012-04-01

Polyaniline thin films as hole transporting layers were fabricated on transparent indium-tin-oxide electrodes by electrodeposition of aniline in an aqueous H2SO4 electrolyte solution. Emerald-green polyaniline films were obtained, which showed stable redox waves. A mixed solution of polythiophene and fullerene derivative was spin-coated onto the electrodeposited polyaniline film. After the modification of titanium oxide film on the surface of the polythiophene/fullerene layer, an aluminum electrode was fabricated by vacuum deposition. The obtained solar cells generated stable photocurrent and photovoltage under light illumination.

Electron transporting water-gated thin film transistors

NASA Astrophysics Data System (ADS)

Al Naim, Abdullah; Grell, Martin

2012-10-01

We demonstrate an electron-transporting water-gated thin film transistor, using thermally converted precursor-route zinc-oxide (ZnO) intrinsic semiconductors with hexamethyldisilazene (HMDS) hydrophobic surface modification. Water gated HMDS-ZnO thin film transistors (TFT) display low threshold and high electron mobility. ZnO films constitute an attractive alternative to organic semiconductors for TFT transducers in sensor applications for waterborne analytes. Despite the use of an electrolyte as gate medium, the gate geometry (shape of gate electrode and distance between gate electrode and TFT channel) is relevant for optimum performance of water-gated TFTs.

NuLYTELY (PEG 3350, sodium chloride, sodium bicarbonate and potassium chloride for oral solution).

PubMed

Swartz, M L

1992-02-01

NuLYTELY (PEG 3350, Sodium Chloride, Sodium Bicarbonate, and Potassium Chloride for Oral Solution), a product from Braintree Laboratories, Inc. is a modification of GoLYTELY (PEG 3350 and Electrolytes for Oral Solution) that has been found to have the same therapeutic advantages in terms of safety, efficacy, speed and patient acceptance. This product was developed to improve upon the taste of GoLYTELY. NuLYTELY represents an effective alternative for bowel cleansing prior to colonoscopy that may be more acceptable to some patients.

Application of a diffusion model to measure ion leakage of resurrection plant leaves undergoing desiccation.

PubMed

Mihailova, Gergana; Kocheva, Konstantina; Goltsev, Vasilij; Kalaji, Hazem M; Georgieva, Katya

2018-04-01

Haberlea rhodopensis is a chlorophyll-retaining resurrection plant, which can survive desiccation to air dry state under both low light and sunny environments. Maintaining the integrity of the membrane during dehydration of resurrection plants is extremely important. In the present study, the diffusion model was improved and used for a first time to evaluate the changes in ion leakage through different cellular compartments upon desiccation of H. rhodopensis and to clarify the reasons for significant increase of electrolyte leakage from dry leaves. The applied diffusion approach allowed us to distinguish the performance of plants subjected to dehydration and subsequent rehydration under different light intensities. Well-hydrated (control) shade plants had lower and slower electrolyte leakage compared to control sun plants as revealed by lower values of phase amplitudes, lower rate constants and ion concentration. In well-hydrated and moderately dehydrated plants (50% relative water content, RWC) ion efflux was mainly due to leakage from apoplast. The electrolyte leakage sharply increased in severely desiccated leaves (8% RWC) from both sun and shade plants mainly due to ion efflux from symplast. After 1 day of rehydration the electrolyte leakage was close to control values, indicating fast recovery of plants. We suggest that the enhanced leakage in air-dried leaves should not be considered as damage but rather as a survival mechanism based on a reversible modification in the structure of cell wall, plasma membrane and alterations in vacuolar system of the cells. However, further studies should be conducted to investigate the changes in cell wall/plasma membrane to support this conclusion. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Biomaterials for the Decorporation of Sr-85 in the Rat

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

Levitskaia, Tatiana G.; Creim, Jeffrey A.; Curry, Terry L.

2010-09-01

Although four stable isotopes of strontium occur naturally, strontium-90 is produced by nuclear fission and is present in surface soil around the world as a result of fallout from atmospheric nuclear weapons tests. It can easily transfer to man in the event of a nuclear/radiological emergency or through the plant-animal-human food chain causing long-term exposures. Strontium is chemically and biologically similar to calcium, and is incorporated primarily into bone following internal deposition. Alginic acid (alginate) obtained from seaweed (kelp) extract selectively binds ingested strontium in the GI tract blocking its systemic uptake and reducing distribution to bone in rats, whilemore » other natural polysaccharides including chitosan and hyaluronic acid had little in vivo affinity for strontium. Alginate exhibits the unique ability to discriminate between strontium and calcium and has been previously shown to reduce intestinal absorption and skeletal retention of strontium without changing calcium metabolism. In our studies, the effect of commercially available alginate on strontium intestinal absorption was examined. One problem associated with alginate treatment is its limited solubility and gel formation in water. The aqueous solubility of sodium alginate was improved in a sodium chloride/sodium bicarbonate electrolyte solution containing low molecular weight polyethylene glycol (PEG). Furthermore, oral administration of the combined alginate/electrolyte//PEG solution synergistically accelerated removal of internal strontium in rats when compared to treatment with individual sodium alginate/electrolyte or electrolyte/PEG solutions. Importantly, both alginate and PEG are nontoxic, readily available materials that can be easily administered orally in case of a national emergency when potentially large numbers of the population may require medical treatment for internal depositions. Our results suggest further studies to optimize in vivo decorporation performance of engineered alginate material via modification of its chemical and physicochemical properties is warranted.« less

Contact electrification induced interfacial reactions and direct electrochemical nanoimprint lithography in n-type gallium arsenate wafer.

PubMed

Zhang, Jie; Zhang, Lin; Wang, Wei; Han, Lianhuan; Jia, Jing-Chun; Tian, Zhao-Wu; Tian, Zhong-Qun; Zhan, Dongping

2017-03-01

Although metal assisted chemical etching (MacEtch) has emerged as a versatile micro-nanofabrication method for semiconductors, the chemical mechanism remains ambiguous in terms of both thermodynamics and kinetics. Here we demonstrate an innovative phenomenon, i.e. , the contact electrification between platinum (Pt) and an n-type gallium arsenide (100) wafer (n-GaAs) can induce interfacial redox reactions. Because of their different work functions, when the Pt electrode comes into contact with n-GaAs, electrons will move from n-GaAs to Pt and form a contact electric field at the Pt/n-GaAs junction until their electron Fermi levels ( E F ) become equal. In the presence of an electrolyte, the potential of the Pt/electrolyte interface will shift due to the contact electricity and induce the spontaneous reduction of MnO 4 - anions on the Pt surface. Because the equilibrium of contact electrification is disturbed, electrons will transfer from n-GaAs to Pt through the tunneling effect. Thus, the accumulated positive holes at the n-GaAs/electrolyte interface make n-GaAs dissolve anodically along the Pt/n-GaAs/electrolyte 3-phase interface. Based on this principle, we developed a direct electrochemical nanoimprint lithography method applicable to crystalline semiconductors.

Optimization of electrochemical dechlorination of trichloroethylene in reducing electrolytes

PubMed Central

Mao, Xuhui; Ciblak, Ali; Baek, Kitae; Amiri, Mohammad; Loch-Caruso, Rita; Alshawabkeh, Akram N.

2012-01-01

Electrochemical dechlorination of trichloroethylene (TCE) in aqueous solution is investigated in a closed, liquid-recirculation system. The anodic reaction of cast iron generates ferrous species, creating a chemically reducing electrolyte (negative ORP value). The reduction of TCE on the cathode surface is enhanced under this reducing electrolyte because of the absence of electron competition. In the presence of the iron anode, the performances of different cathodes are compared in a recirculated electrolysis system. The copper foam shows superior capability for dechlorination of aqueous TCE. Electrolysis by cast iron anode and copper foam cathode is further optimized though a multivariable experimental design and analysis. The conductivity of the electrolyte is identified as an important factor for both final elimination efficiency (FEE) of TCE and specific energy consumption. The copper foam electrode exhibits high TCE elimination efficiency in a wide range of initial TCE concentration. Under coulostatic conditions, the optimal conditions to achieve the highest FEE are 9.525 mm thick copper foam electrode, 40 mA current and 0.042 mol L−1 Na2SO4. This novel electrolysis system is proposed to remediate groundwater contaminated by chlorinated organic solvents, or as an improved iron electrocoagulation process capable of treating the wastewater co-contaminated with chlorinated compounds. PMID:22264798

A search map for organic additives and solvents applicable in high-voltage rechargeable batteries.

PubMed

Park, Min Sik; Park, Insun; Kang, Yoon-Sok; Im, Dongmin; Doo, Seok-Gwang

2016-09-29

Chemical databases store information such as molecular formulas, chemical structures, and the physical and chemical properties of compounds. Although the massive databases of organic compounds exist, the search of target materials is constrained by a lack of physical and chemical properties necessary for specific applications. With increasing interest in the development of energy storage systems such as high-voltage rechargeable batteries, it is critical to find new electrolytes efficiently. Here we build a search map to screen organic additives and solvents with novel core and functional groups, and thus establish a database of electrolytes to identify the most promising electrolyte for high-voltage rechargeable batteries. This search map is generated from MAssive Molecular Map BUilder (MAMMBU) by combining a high-throughput quantum chemical simulation with an artificial neural network algorithm. MAMMBU is designed for predicting the oxidation and reduction potentials of organic compounds existing in the massive organic compound database, PubChem. We develop a search map composed of ∼1 000 000 redox potentials and elucidate the quantitative relationship between the redox potentials and functional groups. Finally, we screen a quinoxaline compound for an anode additive and apply it to electrolytes and improve the capacity retention from 64.3% to 80.8% near 200 cycles for a lithium ion battery in experiments.

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

DOE PAGES

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.; ...

2017-05-12

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

Fluorinated End-Groups in Electrolytes Induce Ordered Electrolyte/Anode Interface Even at Open-Circuit Potential as Revealed by Sum Frequency Generation Vibrational Spectroscopy

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

Horowitz, Yonatan; Han, Hui-Ling; Ralston, Walter T.

Fluorine-based additives have a tremendously beneficial effect on the performance of lithium-ion batteries, yet the origin of this phenomenon is unclear. This study shows that the formation of a solid-electrolyte interphase (SEI) on the anode surface in the first five charge/discharge cycles is affected by the stereochemistry of the electrolyte molecules on the anode surface starting at open-circuit potential (OCP). This study shows an anode-specific model system, the reduction of 1,2-diethoxy ethane with lithium bis(trifluoromethane)sulfonimide, as a salt on an amorphous silicon anode, and compares the electrochemical response and SEI formation to its fluorinated version, bis(2,2,2-trifluoroethoxy) ethane (BTFEOE), by summore » frequency generation (SFG) vibrational spectroscopy under reaction conditions. The SFG results suggest that the —CF 3 end-groups of the linear ether BTFEOE change their adsorption orientation on the a-Si surface at OCP, leading to a better protective layer. Finally, supporting evidence from ex situ scanning electron microscopy and X-ray photoelectron spectroscopy depth profiling measurements shows that the fluorinated ether, BTFEOE, yields a smooth SEI on the a-Si surface and enables lithium ions to intercalate deeper into the a-Si bulk.« less

The impact of alkyl sulfate surfactant geometry and electrolyte on the co-adsorption of anionic surfactants with model perfumes at the air-solution interface.

PubMed

Bradbury, Robert; Penfold, Jeffrey; Thomas, Robert K; Tucker, Ian M; Petkov, Jordan T; Jones, Craig

2013-08-01

The impact of surfactant geometry and electrolyte on the co-adsorption of anionic surfactants and model perfumes at the air-solution interface has been studied by neutron reflectivity. The more hydrophobic perfume linalool, competes more favourably for the surface with sodium dodecylsulfate than was previously reported for the anionic surfactant, sodium dodecyl 6-benzenesulfonate. Due to an increase in surface activity of the sodium dodecylsulfate, the addition of electrolyte results in a reduction in the linalool adsorption. Changing the alkyl chain length affects the relative adsorption of linalool and surfactant at the interface. Similar measurements for the different alkyl sulfates and with electrolyte with the more hydrophilic perfume phenyl ethanol, reveal broadly similar trends. Although the relative adsorption of phenyl ethanol with sodium dodecylsulfate is substantially enhanced compared to sodium dodecyl-6-benzenesulfonate the effects are not as significant as was observed with linalool. The variations with alkyl chain geometry show the importance of the hydrophobic interaction between the perfume and surfactant and changes in the packing constraints on the relative adsorption. The results highlight the importance of the specific interaction between the surfactant and perfume, and the surfactant and perfume geometries on the relative adsorption at the interface. Copyright © 2013 Elsevier Inc. All rights reserved.

Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging

PubMed Central

Michalak, Barbara; Sommer, Heino; Mannes, David; Kaestner, Anders; Brezesinski, Torsten; Janek, Jürgen

2015-01-01

Gas generation as a result of electrolyte decomposition is one of the major issues of high-performance rechargeable batteries. Here, we report the direct observation of gassing in operating lithium-ion batteries using neutron imaging. This technique can be used to obtain qualitative as well as quantitative information by applying a new analysis approach. Special emphasis is placed on high voltage LiNi0.5Mn1.5O4/graphite pouch cells. Continuous gassing due to oxidation and reduction of electrolyte solvents is observed. To separate gas evolution reactions occurring on the anode from those associated with the cathode interface and to gain more insight into the gassing behavior of LiNi0.5Mn1.5O4/graphite cells, neutron experiments were also conducted systematically on other cathode/anode combinations, including LiFePO4/graphite, LiNi0.5Mn1.5O4/Li4Ti5O12 and LiFePO4/Li4Ti5O12. In addition, the data were supported by gas pressure measurements. The results suggest that metal dissolution in the electrolyte and decomposition products resulting from the high potentials adversely affect the gas generation, particularly in the first charge cycle (i.e., during graphite solid-electrolyte interface layer formation). PMID:26496823

Tunable transport property of oxygen ion in metal oxide thin film: Impact of electrolyte orientation on conductivity.

PubMed

Arunkumar, P; Ramaseshan, R; Dash, S; Babu, K Suresh

2017-06-14

Quest for efficient ion conducting electrolyte thin film operating at intermediate temperature (~600 °C) holds promise for the real-world utilization of solid oxide fuel cells. Here, we report the correlation between mixed as well as preferentially oriented samarium doped cerium oxide electrolyte films fabricated by varying the substrate temperatures (100, 300 and 500 °C) over anode/ quartz by electron beam physical vapor deposition. Pole figure analysis of films deposited at 300 °C demonstrated a preferential (111) orientation in out-off plane direction, while a mixed orientation was observed at 100 and 500 °C. As per extended structural zone model, the growth mechanism of film differs with surface mobility of adatom. Preferential orientation resulted in higher ionic conductivity than the films with mixed orientation, demonstrating the role of growth on electrochemical properties. The superior ionic conductivity upon preferential orientation arises from the effective reduction of anisotropic nature and grain boundary density in highly oriented thin films in out-of-plane direction, which facilitates the hopping of oxygen ion at a lower activation energy. This unique feature of growing an oriented electrolyte over the anode material opens a new approach to solving the grain boundary limitation and makes it as a promising solution for efficient power generation.

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

Sr- and Nb-co-doped Li7La3Zr2O12 solid electrolyte with Al2O3 addition towards high ionic conductivity

NASA Astrophysics Data System (ADS)

Lin, Changwei; Tang, Yu; Song, Jun; Han, Lei; Yu, Jingbo; Lu, Anxian

2018-06-01

In the present study, series of garnet-type Li6.75+ x La3- x Sr x Zr1.75Nb0.25O12 solid electrolytes [LLSZN with various Sr contents ( x = 0.05-0.25)] have been prepared via conventional solid-state method. The effects of Sr contents on their phase structure and ionic conductivity have been systematically investigated on the combined measurements of X-ray diffraction and scanning electron microscopy and alter current impedance spectroscopy. Our results reveal that a phase transition from tetragonal to cubic structure occurs when both Sr and Nb elements is introduced, and such a cubic structure can be stable over the whole Sr contents variation, which is suggested to provide a beneficial impact on the performance of LLSZN. Accordingly, both relative density and total ionic conductivity exhibit a favorable tendency of increasing first and then decreasing with increased Sr contents, wherein a peak value at 93.46% and 5.09 × 10-4 S cm-1, respectively, can be well achieved. Particularly, the maximum ionic conductivity is almost twice that of the compared sample (2.93 × 10-4 S cm-1), and possess the minimum activation energy 0.30 eV. Such a modification method, featured with higher efficiency and lower cost, is expected to be helpful for the development of solid electrolyte.

Electrochemical and impedance investigation of the effect of lithium malonate on the performance of natural graphite electrodes in lithium-ion batteries

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

Sun, Xiao-Guang; Dai, Sheng

2010-01-01

Lithium malonate (LM) was coated on the surface of a natural graphite (NG) electrode, which was then tested as the negative electrode in the electrolytes of 0.9 M LiPF6/EC-PC-DMC (1/1/3, by weight) and 1.0 M LiBF4/EC-PC-DMC (1/1/3, by weight) under a current density of 0.075 mA cm-2. LM was also used as an additive to the electrolyte of 1.0 M LiPF6/EC-DMC-DEC (1/1/1, by volume) and tested on a bare graphite electrode. It was found that both the surface coating and the additive approach were effective in improving first charge discharge capacity and coulomb efficiency. Electrochemical impedance spectra showed that themore » decreased interfacial impedance was coupled with improved coulomb efficiency of the cells using coated graphite electrodes. Cyclic voltammograms (CVs) on fresh bare and coated natural graphite electrodes confirmed that all the improvement in the half-cell performance was due to the suppression of the solvent decomposition through the surface modification with LM. The CV data also showed that the carbonate electrolyte with LM as the additive was not stable against oxidation, which resulted in lower capacity of the full cell with commercial graphite and LiCoO2 electrodes.« less

Influence of the electrolyte's pH on the properties of electrochemically deposited hydroxyapatite coating on additively manufactured Ti64 alloy.

PubMed

Vladescu, Alina; Vranceanu, Diana M; Kulesza, Slawek; Ivanov, Alexey N; Bramowicz, Mirosław; Fedonnikov, Alexander S; Braic, Mariana; Norkin, Igor A; Koptyug, Andrey; Kurtukova, Maria O; Dinu, Mihaela; Pana, Iulian; Surmeneva, Maria A; Surmenev, Roman A; Cotrut, Cosmin M

2017-12-01

Properties of the hydroxyapatite obtained by electrochemical assisted deposition (ED) are dependent on several factors including deposition temperature, electrolyte pH and concentrations, applied potential. All of these factors directly influence the morphology, stoichiometry, crystallinity, electrochemical behaviour, and particularly the coating thickness. Coating structure together with surface micro- and nano-scale topography significantly influence early stages of the implant bio-integration. The aim of this study is to analyse the effect of pH modification on the morphology, corrosion behaviour and in vitro bioactivity and in vivo biocompatibility of hydroxyapatite prepared by ED on the additively manufactured Ti64 samples. The coatings prepared in the electrolytes with pH = 6 have predominantly needle like morphology with the dimensions in the nanometric scale (~30 nm). Samples coated at pH = 6 demonstrated higher protection efficiency against the corrosive attack as compared to the ones coated at pH = 5 (~93% against 89%). The in vitro bioactivity results indicated that both coatings have a greater capacity of biomineralization, compared to the uncoated Ti64. Somehow, the coating deposited at pH = 6 exhibited good corrosion behaviour and high biomineralization ability. In vivo subcutaneous implantation of the coated samples into the white rats for up to 21 days with following histological studies showed no serious inflammatory process.

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

NASA Technical Reports Server (NTRS)

Mccallister, R. H.; Taylor, L. A.

1973-01-01

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

Nanoprocess and nanoscale surface functionalization on cathode materials for advanced lithium-ion batteries.

PubMed

Alaboina, Pankaj Kumar; Uddin, Md-Jamal; Cho, Sung-Jin

2017-10-26

Nanotechnology-driven development of cathode materials is an essential part to revolutionize the evolution of the next generation lithium ion batteries. With the progress of nanoprocess and nanoscale surface modification investigations on cathode materials in recent years, the advanced battery technology future seems very promising - Thanks to nanotechnology. In this review, an overview of promising nanoscale surface deposition methods and their significance in surface functionalization on cathodes is extensively summarized. Surface modified cathodes are provided with a protective layer to overcome the electrochemical performance limitations related to side reactions with electrolytes, reduce self-discharge reactions, improve thermal and structural stability, and further enhance the overall battery performance. The review addresses the importance of nanoscale surface modification on battery cathodes and concludes with a comparison of the different nanoprocess techniques discussed to provide a direction in the race to build advanced lithium-ion batteries.

Photoelectrochemical characteristics of dye-sensitized solar cells incorporating innovative and inexpensive materials

NASA Astrophysics Data System (ADS)

Harlow, Lisa Jean

The use of energy is going to continue to increase rapidly due to population and economic advances occurring throughout the world. The most widely used energies produce carbon dioxide during their combustion and have finite limits on how much of these resources are available. A strong push to utilizing renewable energy is necessary to keep up with the demand. The only renewable energy that has unlimited supply is solar. Our goal is to find cost-effective alternatives to historically the most extensively used materials in dye-sensitized solar cells. In order to rely on efficiency changes coinciding with the introduction of a new component, a standard baseline of performance is necessary to establish. A reproducible fabrication procedure composed of standard materials was instituted; the efficiency parameters exhibited a less than 10% standard deviation for any set of solar cells. Any modifications to the cell components would be apparent in the change in efficiency. Our cell modifications focused on economical alternatives to the electrolyte, the counter electrode and the chromophore. Solution-based electrolytes were replaced with a non-volatile ionic liquid, 1-methyl-3-propylimidazolium iodide, and then a poly(imidazole-functionalized) silica nanoparticle. Solid-state electrolytes reduce or prevent leakage and could ease manufacturing in large-scale devices. Platinum has been the counter electrode catalyst primarily used with the iodide/triiodide redox couple, but is a rare metal making it rather costly. We reduce platinum loading by introducing a novel counter electrode that employs platinum nanoparticles embedded on a graphene nanoplatelet paper. The highly conductive carbon base also negates the use of the expensive conductive substrate necessary for the platinum catalyst, further reducing cost. We also study the differences in transitioning from ruthenium polypyridyls to iron-based chromophores in dye-sensitized solar cells. Iron introduces low-lying ligand field states which the charge-transfer transitions necessary for electron injection deactivate to. We study a series of molecules that converts from a historically well-known ruthenium dye stepwise to an iron-based chromophore that has exhibited photocurrent previously. Converting to iron proves to be complicated and we aim to continue our investigation in order to gain a better understanding of the complexity.

A taxonomy of apatite frameworks for the crystal chemical design of fuel cell electrolytes

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

Pramana, Stevin S.; Klooster, Wim T.; Institute of Materials Research and Engineering, 3 Research Link, Singapore 117602

2008-08-15

Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Taking the neutral apatite [La{sub 8}Sr{sub 2}][(GeO{sub 4}){sub 6}]O{sub 2} as a prototype electrolyte, this classification scheme correctly predicted that 'excess' oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}, rather than the presumptive tunnel location of [La{sub 9}Sr][(GeO{sub 4}){sub 6}]O{sub 2.5}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytesmore » of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed, with potentially superior low-temperature ion conduction, mediated by the introduction of oxygen to the framework reservoir. - Graphical abstract: Apatite framework taxonomy succinctly rationalises the crystallographic modifications of this structural family as a function of chemical composition. Neutron diffraction identified that the excess oxygen in La{sub 9}SrGe{sub 6}O{sub 26.5} is tenanted in the framework as [La{sub 9}Sr][(GeO{sub 4}){sub 5.5}(GeO{sub 5}){sub 0.5}]O{sub 2}. The implication of this approach is that in addition to the three known apatite genera-A{sub 10}(BO{sub 3}){sub 6}X{sub 2}, A{sub 10}(BO{sub 4}){sub 6}X{sub 2}, A{sub 10}(BO{sub 5}){sub 6}X{sub 2}-hybrid electrolytes of the types A{sub 10}(BO{sub 3}/BO{sub 4}/BO{sub 5}){sub 6}X{sub 2} can be designed.« less

Functionalized graphene hydrogel-based high-performance supercapacitors.

PubMed

Xu, Yuxi; Lin, Zhaoyang; Huang, Xiaoqing; Wang, Yang; Huang, Yu; Duan, Xiangfeng

2013-10-25

Functionalized graphene hydrogels are prepared by a one-step low-temperature reduction process and exhibit ultrahigh specific capacitances and excellent cycling stability in the aqueous electrolyte. Flexible solid-state supercapacitors based on functionalized graphene hydrogels are demonstrated with superior capacitive performances and extraordinary mechanical flexibility. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

40 CFR 421.53 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Electrolytic Copper Refining Subcategory § 421.53 Effluent limitations guidelines representing the degree of... for monthly average mg/kg (pounds per million pounds) of copper cast Arsenic .692 .309 Copper .638... cathode copper production Arsenic .000 .000 Copper .000 .000 Nickel .000 .000 (c) Subpart E—Spent...

40 CFR 421.53 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Electrolytic Copper Refining Subcategory § 421.53 Effluent limitations guidelines representing the degree of... for monthly average mg/kg (pounds per million pounds) of copper cast Arsenic .692 .309 Copper .638... cathode copper production Arsenic .000 .000 Copper .000 .000 Nickel .000 .000 (c) Subpart E—Spent...

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

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

2006-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

21 CFR 862.1655 - Pyruvic acid test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

... treatment of acid-base and electrolyte disturbances or anoxia (the reduction of oxygen in body tissues). (b... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Pyruvic acid test system. 862.1655 Section 862....1655 Pyruvic acid test system. (a) Identification. A pyruvic acid test system is a device intended to...

21 CFR 862.1655 - Pyruvic acid test system.

Code of Federal Regulations, 2013 CFR

2013-04-01

... treatment of acid-base and electrolyte disturbances or anoxia (the reduction of oxygen in body tissues). (b... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Pyruvic acid test system. 862.1655 Section 862....1655 Pyruvic acid test system. (a) Identification. A pyruvic acid test system is a device intended to...

21 CFR 862.1655 - Pyruvic acid test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

... treatment of acid-base and electrolyte disturbances or anoxia (the reduction of oxygen in body tissues). (b... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Pyruvic acid test system. 862.1655 Section 862....1655 Pyruvic acid test system. (a) Identification. A pyruvic acid test system is a device intended to...

21 CFR 862.1655 - Pyruvic acid test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... treatment of acid-base and electrolyte disturbances or anoxia (the reduction of oxygen in body tissues). (b... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Pyruvic acid test system. 862.1655 Section 862....1655 Pyruvic acid test system. (a) Identification. A pyruvic acid test system is a device intended to...

21 CFR 862.1655 - Pyruvic acid test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

... treatment of acid-base and electrolyte disturbances or anoxia (the reduction of oxygen in body tissues). (b... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Pyruvic acid test system. 862.1655 Section 862....1655 Pyruvic acid test system. (a) Identification. A pyruvic acid test system is a device intended to...

Hydrogen generation by electrolysis of aqueous organic solutions

NASA Technical Reports Server (NTRS)

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

2002-01-01

A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

Preparation and physicochemical properties of surfactant-free emulsions using electrolytic-reduction ion water containing lithium magnesium sodium silicate.

PubMed

Okajima, Masahiro; Wada, Yuko; Hosoya, Takashi; Hino, Fumio; Kitahara, Yoshiyasu; Shimokawa, Ken-ichi; Ishii, Fumiyoshi

2013-04-01

Surfactant-free emulsions by adding jojoba oil, squalane, olive oil, or glyceryl trioctanoate (medium chain fatty acid triglycerides, MCT) to electrolytic-reduction ion water containing lithium magnesium sodium silicate (GE-100) were prepared, and their physiochemical properties (thixotropy, zeta potential, and mean particle diameter) were evaluated. At an oil concentration of 10%, the zeta potential was ‒22.3 ‒ ‒26.8 mV, showing no marked differences among the emulsions of various types of oil, but the mean particle diameters in the olive oil emulsion (327 nm) and MCT emulsion (295 nm) were smaller than those in the other oil emulsions (452-471 nm). In addition, measurement of the hysteresis loop area of each type of emulsion revealed extremely high thixotropy of the emulsion containing MCT at a low concentration and the olive emulsion. Based on these results, since surfactants and antiseptic agents markedly damage sensitive skin tissue such as that with atopic dermatitis, surfactant- and antiseptic-free emulsions are expected to be new bases for drugs for external use.

Titanium deposition from ionic liquids - appropriate choice of electrolyte and precursor.

PubMed

Berger, Claudia A; Arkhipova, Maria; Farkas, Attila; Maas, Gerhard; Jacob, Timo

2016-02-14

In this study titanium isopropoxide was dissolved in 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) and further in a custom-made guanidinium-based ionic liquid (N11N11NpipGuaTFSI). Electrochemical investigations were carried out by means of cyclic voltammetry (CV) and the initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). For BMITFSI we found one large cathodic reduction peak at a potential of -1.2 V vs. Pt, corresponding to the growth of monoatomic high islands. The obtained deposit was identified as elemental titanium by Auger Electron Spectroscopy (AES). Furthermore, we found a corresponding anodic peak at -0.3 V vs. Pt, which is associated with the dissolution of the islands. This observation leads to the assumption that titanium deposition from the imidazolium-based room-temperature ionic liquid (RTIL) proceeds in a one-step electron transfer. In contrast, for the guanidinium-based RTIL we found several peaks during titanium reduction and oxidation, which indicates a multi-step electron transfer in this alternative electrolyte.

Process for preparing a chemical compound enriched in isotope content

DOEpatents

Michaels, Edward D.

1982-01-01

A process to prepare a chemical enriched in isotope content which includes: (a) A chemical exchange reaction between a first and second compound which yields an isotopically enriched first compound and an isotopically depleted second compound; (b) the removal of a portion of the first compound as product and the removal of a portion of the second compound as spent material; (c) the conversion of the remainder of the first compound to the second compound for reflux at the product end of the chemical exchange reaction region; (d) the conversion of the remainder of the second compound to the first compound for reflux at the spent material end of the chemical exchange region; and the cycling of the additional chemicals produced by one conversion reaction to the other conversion reaction, for consumption therein. One of the conversion reactions is an oxidation reaction, and the energy that it yields is used to drive the other conversion reaction, a reduction. The reduction reaction is carried out in a solid polymer electrolyte electrolytic reactor. The overall process is energy efficient and yields no waste by-products.

Guided Lithium Metal Deposition and Improved Lithium Coulombic Efficiency through Synergistic Effects of LiAsF 6 and Cyclic Carbonate Additives

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

Ren, Xiaodi; Zhang, Yaohui; Engelhard, Mark H.

Spatial and morphology control over lithium (Li) metal nucleation/growth, as well as improving Li Coulombic efficiency (CE) are of the most challenging issues for rechargeable Li metal batteries. Here, we report that LiAsF6 and vinylene carbonate (VC) can work synergistically to address these challenges. It is revealed that AsF6- can be reduced to Li3As and LiF, which can act as seeds for Li growth and form a robust solid electrolyte interphase (SEI) layer, respectively. The addition of VC is critical because it not only enables uniform AsF6- reduction by passivating the defect sites on Cu substrate, but also improves themore » SEI layer flexibility during the reductive polymerization process. As a result, highly compact, uniform and dendrite-free Li film with vertically aligned columns structure can be obtained with greatly increased Li CE, and the Li metal batteries using the electrolyte with both LiAsF6 and VC additives can have much improved cycle life.« less

Role of DDL processes during electrolytic reduction of Cu(II) in a low oxygen environment.

PubMed

Brosky, Rebekah T; Pamukcu, Sibel

2013-11-15

Heavy metals typically accumulate in reduced bottom sediments after being discharged into waterways by industrial and municipal processes. A laboratory experiment was conducted in order to determine if abundance of clay in the bottom sediments of a Cu-contaminated aqueous ecosystem could enhance electrolytic reduction of the heavy metal. Cu(NO3)2 · 2.5H2O was added to simulate a moderately contaminated system with 650 μg Cu/ml kaolinite clay-water slurry. A constant electrical potential of 1.0 V/cm was applied across platinum wire electrodes inserted into the continuously stirred system for four days while the system ORP(2) was monitored and periodic sub-samples were taken for analysis. The electrical as well as the chemical results indicate that the quantity of Cu(II) being reduced to Cu(I), especially within the aqueous phase, is increased within the first 48 h of experimentation by the presence of kaolinite clay up to 0.05 mg clay/l slurry. Copyright © 2013 Elsevier B.V. All rights reserved.

40 CFR 60.14 - Modification.

Code of Federal Regulations, 2012 CFR

2012-07-01

... not be considered a modification. (5) The addition or use of any system or device whose primary function is the reduction of air pollutants, except when an emission control system is removed or is...

40 CFR 60.14 - Modification.

Code of Federal Regulations, 2014 CFR

2014-07-01

... not be considered a modification. (5) The addition or use of any system or device whose primary function is the reduction of air pollutants, except when an emission control system is removed or is...

40 CFR 60.14 - Modification.

Code of Federal Regulations, 2011 CFR

2011-07-01

... not be considered a modification. (5) The addition or use of any system or device whose primary function is the reduction of air pollutants, except when an emission control system is removed or is...

40 CFR 60.14 - Modification.

Code of Federal Regulations, 2013 CFR

2013-07-01

... not be considered a modification. (5) The addition or use of any system or device whose primary function is the reduction of air pollutants, except when an emission control system is removed or is...

Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.

Polymer membrane based electrolytic cell and process for the direct generation of hydrogen peroxide in liquid streams

NASA Technical Reports Server (NTRS)

White, James H. (Inventor); Schwartz, Michael (Inventor); Sammells, Anthony F. (Inventor)

1997-01-01

An electrolytic cell for generating hydrogen peroxide is provided including a cathode containing a catalyst for the reduction of oxygen, and an anode containing a catalyst for the oxidation of water. A polymer membrane, semipermeable to either protons or hydroxide ions is also included and has a first face interfacing to the cathode and a second face interfacing to the anode so that when a stream of water containing dissolved oxygen or oxygen bubbles is passed over the cathode and a stream of water is passed over the anode, and an electric current is passed between the anode and the cathode, hydrogen peroxide is generated at the cathode and oxygen is generated at the anode.

Toposelective electrochemical desorption of thiol SAMs from neighboring polycrystalline gold surfaces.

PubMed

Tencer, Michal; Berini, Pierre

2008-11-04

We describe a method for the selective desorption of thiol self-assembled monolayers from gold surfaces having micrometer-scale separations on a substrate. In an electrolyte solution, the electrical resistance between the adjacent areas can be much lower than the resistance between a surface and the counter electrode. Also, both reductive and oxidative thiol desorption may occur. Therefore, the potentials of the surfaces must be independently controlled with a multichannel potentiostat and operating windows for a given thiol/electrolyte system must be established. In this study operating windows were established for 1-dodecanethiol-based SAMs in phosphate buffer, phosphate-buffered saline, and sodium hydroxide solution, and selective SAM removal was successfully performed in a four-electrode configuration.

Structural features of the nonionic surfactants stabilizing long-lived bubble nuclei

NASA Technical Reports Server (NTRS)

Darrigo, J. S.

1980-01-01

A study of the effects of various electrolytes and one organic compound on bubble production in agarose gels is presented. Several preparations of ultrapure agarose were compared for 42 electrolytes and phenol to identify trends in bubble formation. The anion and cation sequences of bubble suppression are similar to processes for salting out of nonionic surfactants. The reduction of bubble number by polyvalent ions and 1% phenol suggests that the polar portions of these nonionic surfactants represent amide groups. The evidence for amide groups is consistent with the relative positions of Mg(2+) in all cation sequences; this result makes it unlikely that either linkages contribute to the hydrophilicity of the nonionic surfactants stabilizing bubble nuclei in the different aqueous gels tested.

Electrode materials: a challenge for the exploitation of protonic solid oxide fuel cells

PubMed Central

Fabbri, Emiliana; Pergolesi, Daniele; Traversa, Enrico

2010-01-01

High temperature proton conductor (HTPC) oxides are attracting extensive attention as electrolyte materials alternative to oxygen-ion conductors for use in solid oxide fuel cells (SOFCs) operating at intermediate temperatures (400–700 °C). The need to lower the operating temperature is dictated by cost reduction for SOFC pervasive use. The major stake for the deployment of this technology is the availability of electrodes able to limit polarization losses at the reduced operation temperature. This review aims to comprehensively describe the state-of-the-art anode and cathode materials that have so far been tested with HTPC oxide electrolytes, offering guidelines and possible strategies to speed up the development of protonic SOFCs. PMID:27877342

Abuse Response of 18650 Li-Ion Cells with Different Cathodes Using EC:EMC/LiPF6 and EC:PC:DMC/LiPF6 Electrolytes

DOE PAGES

Roth, Emmanuel Peter

2008-01-01

We report Lithium-Ion batteries are being considered as a high-energy density replacement for Nickel Metal Hydride (NiMH) batteries in Hybrid Electric Vehicles (HEVs) and in the new Plug-In Hybrids (PHEVs). Although these cells can result in significant reduction in weight and volume, they have several safety related issues that still need to be addressed. We report here on the thermal response of Li-ion cells specifically assembled in our laboratory to test new materials, electrolytes and additives. Finally, improvements in the thermal abuse tolerance of cells are reported and discussed in terms of the need for overall battery system safety.

The Electrochemical Performance of Silicon Nanoparticles in Concentrated Electrolyte.

PubMed

Chang, Zeng-Hua; Wang, Jian-Tao; Wu, Zhao-Hui; Gao, Min; Wu, Shuai-Jin; Lu, Shi-Gang

2018-06-11

Silicon is a promising material for anodes in energy-storage devices. However, excessive growth of a solid-electrolyte interphase (SEI) caused by the severe volume change during the (de)lithiation processes leads to dramatic capacity fading. Here, we report a super-concentrated electrolyte composed of lithium bis(fluorosulfonyl)imide (LiFSI) and propylene carbonate (PC) with a molar ratio of 1:2 to improve the cycling performance of silicon nanoparticles (SiNPs). The SiNP electrode shows a remarkably improved cycling performance with an initial delithiation capacity of approximately 3000 mAh g -1 and a capacity of approximately 2000 mAh g -1 after 100 cycles, exhibiting about 6.8 times higher capacity than the cells with dilute electrolyte LiFSI-(PC) 8 . Raman spectra reveal that most of the PC solvent and FSI anions are complexed by Li + to form a specific solution structure like a fluid polymeric network. The reduction of FSI anions starts to play an important role owing to the increased concentration of contact ion pairs (CIPs) or aggregates (AGGs), which contribute to the formation of a more mechanically robust and chemically stable complex SEI layer. The complex SEI layer can effectively suppress the morphology evolution of silicon particles and self-limit the excessive growth, which mitigates the crack propagation of the silicon electrode and the deterioration of the kinetics. This study will provide a new direction for screening cycling-stable electrolytes for silicon-based electrodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Designer interphases for the lithium-oxygen electrochemical cell

PubMed Central

Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I.; Tu, Zhengyuan; Lau, Sampson; Zachman, Michael J.; Kourkoutis, Lena F.; Archer, Lynden A.

2017-01-01

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells. PMID:28439557

The coupling between stability and ion pair formation in magnesium electrolytes from first-principles quantum mechanics and classical molecular dynamics

DOE PAGES

Rajput, Nav Nidhi; Qu, Xiaohuui; Sa, Niya; ...

2015-02-10

Here in this work we uncover a novel effect between concentration dependent ion pair formation and anion stability at reducing potentials, e.g., at the metal anode. Through comprehensive calculations using both first-principles as well as well-benchmarked classical molecular dynamics over a matrix of electrolytes, covering solvents and salt anions with a broad range in chemistry, we elucidate systematic correlations between molecular level interactions and composite electrolyte properties, such as electrochemical stability, solvation structure, and dynamics. We find that Mg electrolytes are highly prone to ion pair formation, even at modest concentrations, for a wide range of solvents with different dielectricmore » constants, which have implications for dynamics as well as charge transfer. Specifically, we observe that, at Mg metal potentials, the ion pair undergoes partial reduction at the Mg cation center (Mg 2+ -> Mg +), which competes with the charge transfer mechanism and can activate the anion to render it susceptible to decomposition. Specifically, TFSI exhibits a significant bond weakening while paired with the transient, partially reduced Mg +. In contrast, BH 4 $-$ and BF 4 $-$ are shown to be chemically stable in a reduced ion pair configuration. Furthermore, we observe that higher order glymes as well as DMSO improve the solubility of Mg salts, but only the longer glyme chains reduce the dynamics of the ions in solution. This information provides critical design metrics for future electrolytes as it elucidates a close connection between bulk solvation and cathodic stability as well as the dynamics of the salt.« less

Lipid Profile and Electrolyte Composition in Diabetic Rats Treated With Leaf Extract of Musa sapientum.

PubMed

Adewoye, E O; Ige, A O

2016-01-01

Diabetes mellitus affects lipid levels resulting in diabetic dyslipidemia as well as electrolyte loss from the body. Musa sapientum has been reported to possess antidiabetic properties. This study assessed the lipid profile and electrolyte composition in alloxan-induced diabetic rats treated with methanol leaf extract of M. sapientum (cMEMSL). Diabetes was induced with alloxan (120 mg/kg i.p.). Seventy-five male albino rats were divided into 5 groups of 15 rats each. Group 1 was control; groups 2-5 were made diabetic and treated with 0.2 ml 0.9% NaCl, cMEMSL (250 mg/kg and 500 mg/kg), and glibenclamide (5 mg/kg), respectively, for 14 days. Blood samples were obtained from the retro orbital sinus after light anesthesia from 5 animals in each group on days 2, 7, and 14 for lipids and electrolyte analysis. Lipid profile of diabetic treated (cMEMSL and glibenclamide) animals showed significant reduction (p < .05) in total cholesterol, triglyceride, and low density lipoprotein (LDL) levels. The high density lipoprotein (HDL) level in the treatment groups increased significantly (p < .05) compared with diabetic untreated. Sodium, potassium, and phosphate ions significantly increased in all diabetic treatment groups while chloride ion significantly decreased compared with diabetic untreated. There was no significant difference in calcium and bicarbonate ion concentration in all the groups. This study has showed additional properties of Musa sapientum to include its ability to restore electrolyte balance, reduce cholesterol, triglyceride, LDL, and increase the HDL levels in diabetic animals.

Acoustic results of supersonic tip speed fan blade modification

NASA Technical Reports Server (NTRS)

Jutras, R. R.; Kazin, S. B.

1974-01-01

A supersonic tip speed single stage fan was modified with the intent of reducing multiple pure tone (MPT) or buzz saw noise. There were three modifications to the blades from the original design. The modifications to the blade resulted in an increase in cascade throat area causing the shock to start at a lower corrected fan speed. The acoustic results without acoustically absorbing liners showed substantial reduction in multiple pure tone levels. However, an increase in the blade passing frequency noise at takeoff fan speed accompanied the MPT reduction. The net result however, was a reduction in the maximum 1000-foot (304.8 m) altitude level flyover PNL. For the case with acoustic treatment in the inlet outer wall, the takeoff noise increased relative to an acoustically treated baseline. This was largely due to the increased blade passing frequency noise which was not effectively reduced by the liner.

A review of different behavior modification strategies designed to reduce sedentary screen behaviors in children.

PubMed

Steeves, Jeremy A; Thompson, Dixie L; Bassett, David R; Fitzhugh, Eugene C; Raynor, Hollie A

2012-01-01

Previous research suggests that reducing sedentary screen behaviors may be a strategy for preventing and treating obesity in children. This systematic review describes strategies used in interventions designed to either solely target sedentary screen behaviors or multiple health behaviors, including sedentary screen behaviors. Eighteen studies were included in this paper; eight targeting sedentary screen behaviors only, and ten targeting multiple health behaviors. All studies used behavior modification strategies for reducing sedentary screen behaviors in children (aged 1-12 years). Nine studies only used behavior modification strategies, and nine studies supplemented behavior modification strategies with an electronic device to enhance sedentary screen behaviors reductions. Many interventions (50%) significantly reduced sedentary screen behaviors; however the magnitude of the significant reductions varied greatly (-0.44 to -3.1 h/day) and may have been influenced by the primary focus of the intervention, number of behavior modification strategies used, and other tools used to limit sedentary screen behaviors.

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.

Professional Advanced Research and Analysis

NASA Technical Reports Server (NTRS)

Coulman, George A.

1996-01-01

Reported here is a summary of studies examining some problems in an energy conversion system. Regenerative fuel cell systems have been suggested for future manned space missions, but to meet the needed specific power requirements substantial improvements in the state-of-the-art technologies are needed. Similar improvements are needed, with emphasis on cost reduction in addition to higher conversion efficiency, for fuel cell systems that have potential for terrestrial applications. Polymer Electrolyte Membrane (PEM) fuel cells have been identified as promising candidates for development that would lead to the desired cost reduction and increased efficiency.

Investigating Electrochemical Processes in Secondary Batteries

NASA Astrophysics Data System (ADS)

Cama, Christina A.

For the past twenty-six years, the lithium-ion battery has been the most popular recharge- able battery for portable devices and electric vehicles. Despite its success, the energy storage capability of lithium-ion batteries (LIBs) is significantly limited by both the electrodes and electrolytes employed. Typical LIBs rely on intercalation-type electrodes, that are not capable of storing more than 1 Li+ per formula unit. The energy storage capability of LIBs can be improved through the application of conversion-type materials and beyond lithium chemistries. This research involves multiple projects which explore the electrochemistry of conversion electrodes, magnesium-ion chemistry, and lithium-sulfur chemistry. Application of conversion-electrodes like copper ferrite, CuFe2O4, and magnetite, Fe3O4, are capable of lithium storage over five times greater than that achieved by electrodes used in commercial LIBs. The drawback to utilizing the conversion mechanism is that significant energy storage capability is lost during charge. In this research, X- ray characterization methods, including X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) are used to elucidate the lithiation and delithiation mechanism for CuFe2O4 and to understand the source of the irreversibility. These experiments provide significant insight into the reduction processes and cation migration within the structure. During lithiation, CuFe2O4 undergoes a three-step reduction mechanism involving (1) lithiation of CuFe2O4, (2) extrusion of copper metal nanoparticles and formation of rock- salt LiFeO2, followed by the (3) formation of iron metal nanoparticles. Upon delithiation, XAS spectra clearly demonstrate the feasibility of Fe0 oxidation to a rock-salt iron oxide; however, Cu0 oxidation is not observed. Additional experiments explored the kinetic limitations of lithiating Fe3O4 nanoparticles, with different crystallite sizes. The experiments demonstrate that the kinetics of the lithiation mechanism are influenced by the electroactive material’s agglomerate and crystallite size. The rate of lithiation involving small crystallites is dependent on diffusion within the agglomerates; however, as the crystallite size increases, the lithiation rate is inhibited by diffusion within both the agglomerate and the crystallite. Battery chemistries beyond lithium can also lead to energy storage capabilities an order of magnitude higher than LIBs. Both magnesium-ion and lithium-sulfur battery chemistries are investigated in this dissertation. The properties of ionic liquid electrolytes are explored as safer alternatives to harmful Grignard-reagent electrolytes commonly used for magnesium chemistries. Electrochemical evaluation of the ionic liquid electrolytes found that although better conductivity can be achieved with unsaturated electrolytes like imidizolium based electrolytes, greater oxidative voltages are possible with saturated electrolytes like the piperidinium and pyridinium based electrolytes. The higher oxidative voltage is a promising attribute for high voltage applications. Cathode additives, including FeS2 and microporous carbon, are studied to inhibit polysulfide dissolution within the electrolyte of Li|S batteries. Although FeS2 exhibited promising electrochemistry as its own cathode, it was found to be an ineffective additive within sulfur cathodes. Instead, the properties of microporous carbons are explored to identify an appropriate carbon additive to both increase conductivity and impede polysulfide dissolution. A wood based carbon exhibited high capacity and long cycle life at low rate compared to conventional microporous carbons. As a whole, this research has provided valuable insight into the electrochemical processes taking place within a battery, as well as the factors which affect these processes. Electrochemical, spectroscopic, and various scattering methods are used to probe processes which span from the reactions occurring within the electrode to the redox reactions which define the voltage limitations of the electrolyte. These studies demonstrate the impact of each battery component on the overall electrochemical performance and provide fundamental insight into battery operation.

Graphene-based materials via benzidine-assisted exfoliation and reduction of graphite oxide and their electrochemical properties

NASA Astrophysics Data System (ADS)

Vermisoglou, E. C.; Giannakopoulou, T.; Romanos, G.; Boukos, N.; Psycharis, V.; Lei, C.; Lekakou, C.; Petridis, D.; Trapalis, C.

2017-01-01

Benzidine, a compound bearing aromatic rings and terminal amino groups, was employed for the intercalation and simultaneous reduction of graphite oxide (GO). The aromatic diamine can be intercalated into GO as follows: (1) by grafting with the epoxy groups of GO, (2) by hydrogen bonding with the oxygen containing groups of GO. Stacking between benzidine aromatic rings and unoxidized domains of GO may occur through π-π interaction. The role of benzidine is influenced by pH conditions and the weight ratio GO/benzidine. Two weight ratios were tested i.e. 1:2 and 1:3. Under strong alkaline conditions through K2CO3 addition (pH ∼10.4-10.6) both intercalation and reduction of GO via amino groups occur, while under strong acidic conditions through HCl addition (pH ∼1.4-2.2) π-π stacking is preferred. When no base or acid is added (pH ∼5.2) and the weight ratio is 1:2, there are indications that reduction and π-π stacking occur, while at a GO/benzidine weight ratio 1:3 intercalation via amino groups and reduction seem to dominate. The aforementioned remarks render benzidine a multifunctional tool towards production of reduced graphene oxide. The effect of pH conditions and the GO/benzidine weight ratio on the quality and the electrochemical properties of the produced graphene-based materials were investigated. Cyclic voltammetry measurements using three-electrode cell and KCl aqueous solution as an electrolyte gave specific capacitance values up to ∼178 F/g. When electric double-layer capacitors (EDLC) were fabricated from these materials, the maximum capacitance in organic electrolyte i.e., tetraethyl ammonium tetrafluoroborate (TEABF4) in polycarbonate (PC) was ∼29 F/g.