Sample records for alkali metal battery

  1. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, Perry E.; Bell, Jerry E.; Harlow, Richard A.; Chase, Gordon G.

    1983-01-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed therebetween. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants therethrough at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed therebetween. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal therebetween. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal.

  2. Alkali metal/sulfur battery

    DOEpatents

    Anand, Joginder N.

    1978-01-01

    Alkali metal/sulfur batteries in which the electrolyte-separator is a relatively fragile membrane are improved by providing means for separating the molten sulfur/sulfide catholyte from contact with the membrane prior to cooling the cell to temperatures at which the catholyte will solidify. If the catholyte is permitted to solidify while in contact with the membrane, the latter may be damaged. The improvement permits such batteries to be prefilled with catholyte and shipped, at ordinary temperatures.

  3. Method of assembling and sealing an alkali metal battery

    DOEpatents

    Elkins, P.E.; Bell, J.E.; Harlow, R.A.; Chase, G.G.

    1983-03-01

    A method of initially assembling and then subsequently hermetically sealing a container portion of an alkali metal battery to a ceramic portion of such a battery is disclosed. Sealing surfaces are formed respectively on a container portion and a ceramic portion of an alkali metal battery. These sealing surfaces are brought into juxtaposition and a material is interposed there between. This interposed material is one which will diffuse into sealing relationship with both the container portion and the ceramic portion of the alkali metal battery at operational temperatures of such a battery. A pressure is applied between these sealing surfaces to cause the interposed material to be brought into intimate physical contact with such juxtaposed surfaces. A temporary sealing material which will provide a seal against a flow of alkali metal battery reactants there through at room temperatures and is applied over the juxtaposed sealing surfaces and material interposed there between. The entire assembly is heated to an operational temperature so that the interposed material diffuses into the container portion and the ceramic portion to form a hermetic seal there between. The pressure applied to the juxtaposed sealing surfaces is maintained in order to ensure the continuation of the hermetic seal. 4 figs.

  4. Ion conducting polymers and polymer blends for alkali metal ion batteries

    DOEpatents

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

    2017-08-29

    Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

  5. A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries.

    PubMed

    Peng, Hong-Jie; Huang, Jia-Qi; Zhang, Qiang

    2017-08-29

    Flexible energy storage systems are imperative for emerging flexible devices that are revolutionizing our life. Lithium-ion batteries, the current main power sources, are gradually approaching their theoretical limitation in terms of energy density. Therefore, alternative battery chemistries are urgently required for next-generation flexible power sources with high energy densities, low cost, and inherent safety. Flexible lithium-sulfur (Li-S) batteries and analogous flexible alkali metal-chalcogen batteries are of paramount interest owing to their high energy densities endowed by multielectron chemistry. In this review, we summarized the recent progress of flexible Li-S and analogous batteries. A brief introduction to flexible energy storage systems and general Li-S batteries has been provided first. Progress in flexible materials for flexible Li-S batteries are reviewed subsequently, with a detailed classification of flexible sulfur cathodes as those based on carbonaceous (e.g., carbon nanotubes, graphene, and carbonized polymers) and composite (polymers and inorganics) materials and an overview of flexible lithium anodes and flexible solid-state electrolytes. Advancements in other flexible alkali metal-chalcogen batteries are then introduced. In the next part, we emphasize the importance of cell packaging and flexibility evaluation, and two special flexible battery prototypes of foldable and cable-type Li-S batteries are highlighted. In the end, existing challenges and future development of flexible Li-S and analogous alkali metal-chalcogen batteries are summarized and prospected.

  6. Alkali metal ion battery with bimetallic electrode

    DOEpatents

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  7. Ion conducting fluoropolymer carbonates for alkali metal ion batteries

    DOEpatents

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

    2017-09-05

    Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

  8. High capacity nickel battery material doped with alkali metal cations

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1982-05-18

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  9. Cathode architectures for alkali metal / oxygen batteries

    DOEpatents

    Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

    2015-01-13

    Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

  10. Challenges and Prospect of Non-aqueous Non-alkali (NANA) Metal-Air Batteries.

    PubMed

    Gelman, Danny; Shvartsev, Boris; Ein-Eli, Yair

    2016-12-01

    Non-aqueous non-alkali (NANA) metal-air battery technologies promise to provide electrochemical energy storage with the highest specific energy density. Metal-air battery technology is particularly advantageous being implemented in long-range electric vehicles. Up to now, almost all the efforts in the field are focused on Li-air cells, but other NANA metal-air battery technologies emerge. The major concern, which the research community should be dealing with, is the limited and rather poor rechargeability of these systems. The challenges we are covering in this review are related to the initial limited discharge capacities and cell performances. By comprehensively reviewing the studies conducted so far, we show that the implementation of advanced materials is a promising approach to increase metal-air performance and, particularly, metal surface activation as a prime achievement leading to respectful discharge currents. In this review, we address the most critical areas that need careful research attention in order to achieve progress in the understanding of the physical and electrochemical processes in non-aqueous electrolytes applied in beyond lithium and zinc air generation of metal-air battery systems.

  11. Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

    DOEpatents

    Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

    2015-02-10

    Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

  12. Process to separate alkali metal salts from alkali metal reacted hydrocarbons

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

    Gordon, John Howard; Alvare, Javier; Larsen, Dennis

    A process to facilitate gravimetric separation of alkali metal salts, such as alkali metal sulfides and polysulfides, from alkali metal reacted hydrocarbons. The disclosed process is part of a method of upgrading a hydrocarbon feedstock by removing heteroatoms and/or one or more heavy metals from the hydrocarbon feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase containing alkali metal salts and reduced heavy metals, and an upgraded hydrocarbon feedstock. The inorganic phasemore » may be gravimetrically separated from the upgraded hydrocarbon feedstock after mixing at a temperature between about 350.degree. C. to 400.degree. C. for a time period between about 15 minutes and 2 hours.« less

  13. Alkali slurry ozonation to produce a high capacity nickel battery material

    DOEpatents

    Jackovitz, John F.; Pantier, Earl A.

    1984-11-06

    A high capacity battery material is made, consisting essentially of hydrated Ni(II) hydroxide, and about 5 wt. % to about 40 wt. % of Ni(IV) hydrated oxide interlayer doped with alkali metal cations selected from potassium, sodium and lithium cations.

  14. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

    1995-01-01

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  15. Method for intercalating alkali metal ions into carbon electrodes

    DOEpatents

    Doeff, M.M.; Ma, Y.; Visco, S.J.; DeJonghe, L.

    1995-08-22

    A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

  16. Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

    DOE PAGES

    Deng, Zhi; Mo, Yifei; Ong, Shyue Ping

    2016-03-25

    The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. Here, the scope of this review includes the monovalent lithium- and sodium-ion chemistries that aremore » currently of the most commercial interest.« less

  17. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  18. Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

    PubMed

    Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

    2016-06-06

    Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hydrothermal alkali metal recovery process

    DOEpatents

    Wolfs, Denise Y.; Clavenna, Le Roy R.; Eakman, James M.; Kalina, Theodore

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by treating them with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of an added base to establish a pH during the treatment step that is higher than would otherwise be possible without the addition of the base. During the treating process the relatively high pH facilitates the conversion of water-insoluble alkali metal compounds in the alkali metal residues into water-soluble alkali metal constituents. The resultant aqueous solution containing water-soluble alkali metal constituents is then separated from the residue solids, which consist of the treated particles and any insoluble materials formed during the treatment step, and recycled to the gasification process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, the base that is added during the treatment step is an alkali metal hydroxide obtained by water washing the residue solids produced during the treatment step.

  20. Metallic anodes for next generation secondary batteries.

    PubMed

    Kim, Hansu; Jeong, Goojin; Kim, Young-Ugk; Kim, Jae-Hun; Park, Cheol-Min; Sohn, Hun-Joon

    2013-12-07

    Li-air(O2) and Li-S batteries have gained much attention recently and most relevant research has aimed to improve the electrochemical performance of air(O2) or sulfur cathode materials. However, many technical problems associated with the Li metal anode have yet to be overcome. This review mainly focuses on the electrochemical behaviors and technical issues related to metallic Li anode materials as well as other metallic anode materials such as alkali (Na) and alkaline earth (Mg) metals, including Zn and Al when these metal anodes were employed for various types of secondary batteries.

  1. EXTINGUISHMENT OF ALKALI METAL FIRES

    DTIC Science & Technology

    low O2 partial pressures on alkali metal fires Extinguishment of alkali metal fires using in organic salt mixtures Extinguishment of alkali metal ... fires using inorganic salt foams Alkali metal jet stream ignition at various pressure conditions Bibliography

  2. Hydrothermal alkali metal catalyst recovery process

    DOEpatents

    Eakman, James M.; Clavenna, LeRoy R.

    1979-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water at a temperature between about 250.degree. F. and about 700.degree. F. and in the presence of added carbon monoxide. During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

  3. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  4. Methods of recovering alkali metals

    DOEpatents

    Krumhansl, James L; Rigali, Mark J

    2014-03-04

    Approaches for alkali metal extraction, sequestration and recovery are described. For example, a method of recovering alkali metals includes providing a CST or CST-like (e.g., small pore zeolite) material. The alkali metal species is scavenged from the liquid mixture by the CST or CST-like material. The alkali metal species is extracted from the CST or CST-like material.

  5. Aqueous alkali metal hydroxide insoluble cellulose ether membrane

    NASA Technical Reports Server (NTRS)

    Hoyt, H. E.; Pfluger, H. L. (Inventor)

    1969-01-01

    A membrane that is insoluble in an aqueous alkali metal hydroxide medium is described. The membrane is a resin which is a water-soluble C2-C4 hydroxyalkyl cellulose ether polymer and an insolubilizing agent for controlled water sorption, a dialytic and electrodialytic membrane. It is particularly useful as a separator between electrodes or plates in an alkaline storage battery.

  6. EXTINGUISHMENT OF ALKALI METAL FIRES

    DTIC Science & Technology

    Contents: Effect of inert gas nket and ow O2 partial pressures on alkali metal fires Extinguishment of small scale fires Extinguishment of alkali... metal fires using inorganic salt foam Alkali metal jet stream ignition at various pressure conditions

  7. Alkali metal for ultraviolet band-pass filter

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick (Inventor); Fraschetti, George A. (Inventor); Mccann, Timothy A. (Inventor); Mayall, Sherwood D. (Inventor); Dunn, Donald E. (Inventor); Trauger, John T. (Inventor)

    1993-01-01

    An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.

  8. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  9. EXTINGUISHMENT OF ALKALI METAL FIRES

    DTIC Science & Technology

    was found to be effective on low temperature (1000F) fires and was useful on alkali metal fires on or under insulation. Organic liquids were not...particularly effective on alkali metal fires . A section is presented on a typical alkali metal system which might be used to generate electrical power in space.

  10. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  11. Alkali metal hafnium oxide scintillators

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

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

    The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  12. Alkali metal recovery from carbonaceous material conversion process

    DOEpatents

    Sharp, David W.; Clavenna, LeRoy R.; Gorbaty, Martin L.; Tsou, Joe M.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced in the gasifier or similar reaction zone, alkali metal constitutents are recovered from the particles by withdrawing and passing the particles from the reaction zone to an alkali metal recovery zone in the substantial absence of molecular oxygen and treating the particles in the recovery zone with water or an aqueous solution in the substantial absence of molecular oxygen. The solution formed by treating the particles in the recovery zone will contain water-soluble alkali metal constituents and is recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preventing contact of the particles with oxygen as they are withdrawn from the reaction zone and during treatment in the recovery zone avoids the formation of undesirable alkali metal constituents in the aqueous solution produced in the recovery zone and insures maximum recovery of water-soluble alkali metal constituents from the alkali metal residues.

  13. Electroactive materials for rechargeable batteries

    DOEpatents

    Wu, Huiming; Amine, Khalil; Abouimrane, Ali

    2015-04-21

    An as-prepared cathode for a secondary battery, the cathode including an alkaline source material including an alkali metal oxide, an alkali metal sulfide, an alkali metal salt, or a combination of any two or more thereof.

  14. Method for the safe disposal of alkali metal

    DOEpatents

    Johnson, Terry R.

    1977-01-01

    Alkali metals such as those employed in liquid metal coolant systems can be safely reacted to form hydroxides by first dissolving the alkali metal in relatively inert metals such as lead or bismuth. The alloy thus formed is contacted with a molten salt including the alkali metal hydroxide and possibly the alkali metal carbonate in the presence of oxygen. This oxidizes the alkali metal to an oxide which is soluble within the molten salt. The salt is separated and contacted with steam or steam-CO.sub.2 mixture to convert the alkali metal oxide to the hydroxide. These reactions can be conducted with minimal hydrogen evolution and with the heat of reaction distributed between the several reaction steps.

  15. Apparatus enables accurate determination of alkali oxides in alkali metals

    NASA Technical Reports Server (NTRS)

    Dupraw, W. A.; Gahn, R. F.; Graab, J. W.; Maple, W. E.; Rosenblum, L.

    1966-01-01

    Evacuated apparatus determines the alkali oxide content of an alkali metal by separating the metal from the oxide by amalgamation with mercury. The apparatus prevents oxygen and moisture from inadvertently entering the system during the sampling and analytical procedure.

  16. PROCESS OF RECOVERING ALKALI METALS

    DOEpatents

    Wolkoff, J.

    1961-08-15

    A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

  17. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, Raymond D.; McPheeters, Charles C.

    1980-01-01

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  18. Method of handling radioactive alkali metal waste

    DOEpatents

    Wolson, R.D.; McPheeters, C.C.

    Radioactive alkali metal is mixed with particulate silica in a rotary drum reactor in which the alkali metal is converted to the monoxide during rotation of the reactor to produce particulate silica coated with the alkali metal monoxide suitable as a feed material to make a glass for storing radioactive material. Silica particles, the majority of which pass through a 95 mesh screen or preferably through a 200 mesh screen, are employed in this process, and the preferred weight ratio of silica to alkali metal is 7 to 1 in order to produce a feed material for the final glass product having a silica to alkali metal monoxide ratio of about 5 to 1.

  19. Electric vehicle battery research and development

    NASA Technical Reports Server (NTRS)

    Schwartz, H. J.

    1973-01-01

    High energy battery technology for electric vehicles is reviewed. The state-of-the-art in conventional batteries, metal-gas batteries, alkali-metal high temperature batteries, and organic electrolyte batteries is reported.

  20. Alkali metal carbon dioxide electrochemical system for energy storage and/or conversion of carbon dioxide to oxygen

    NASA Technical Reports Server (NTRS)

    Hagedorn, Norman H. (Inventor)

    1993-01-01

    An alkali metal, such as lithium, is the anodic reactant; carbon dioxide or a mixture of carbon dioxide and carbon monoxide is the cathodic reactant; and carbonate of the alkali metal is the electrolyte in an electrochemical cell for the storage and delivery of electrical energy. Additionally, alkali metal-carbon dioxide battery systems include a plurality of such electrochemical cells. Gold is a preferred catalyst for reducing the carbon dioxide at the cathode. The fuel cell of the invention produces electrochemical energy through the use of an anodic reactant which is extremely energetic and light, and a cathodic reactant which can be extracted from its environment and therefore exacts no transportation penalty. The invention is, therefore, especially useful in extraterrestrial environments.

  1. Electrolyte Chemistry for Simultaneous Stabilization of Potassium Metal and Superoxide in K-O₂ Batteries.

    PubMed

    Xiao, Neng; Gourdin, Gerald; Wu, Yiying

    2018-05-22

    In the superoxide batteries based on O2/O2- redox chemistry, identifying an electrolyte to stabilize both alkali metal and superoxide remains challenging due to their reactivity towards electrolyte components. Bis(fluorosulfonyl)imide (FSI-) has been recognized as a "magical anion" for passivating alkali metals. Herein, we illustrate the chemical reactions between FSI- and superoxide, and the resultant dilemma when considering an anode-compatible electrolyte vs. a cathode-compatible one in K-O2 batteries. On one side, the KFSI-dimethoxyethane (DME) electrolyte passivates the potassium metal anode via the cleavage of S-F bond and formation of a KF-rich solid electrolyte interface (SEI). Nevertheless, the KFSI salt is chemically unstable due to the nucleophilic attack by superoxide and/or hydroxide species. On the other hand, potassium bis(trifluorosulfonyl)imide (KTFSI) is stable for KO2, but results in mossy deposition and irreversible plating and stripping. In order to circumvent this dilemma, we develop an artificial SEI for K metal anode to achieve long cycle-life K-O2 batteries. This work contributes to the understanding of electrolyte chemistry and guides the development of stable electrolytes and artificial SEI in metal-O2 batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Upgrading platform using alkali metals

    DOEpatents

    Gordon, John Howard

    2014-09-09

    A process for removing sulfur, nitrogen or metals from an oil feedstock (such as heavy oil, bitumen, shale oil, etc.) The method involves reacting the oil feedstock with an alkali metal and a radical capping substance. The alkali metal reacts with the metal, sulfur or nitrogen content to form one or more inorganic products and the radical capping substance reacts with the carbon and hydrogen content to form a hydrocarbon phase. The inorganic products may then be separated out from the hydrocarbon phase.

  3. Controlled in-situ dissolution of an alkali metal

    DOEpatents

    Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

    2012-09-11

    A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

  4. Method of making alkali metal hydrides

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

    Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek

    A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

  5. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, David C.; Mailhe, Catherine C.; De Jonghe, Lutgard C.

    1986-01-01

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  6. Electrochemical devices utilizing molten alkali metal electrode-reactant

    DOEpatents

    Hitchcock, D.C.; Mailhe, C.C.; De Jonghe, L.C.

    1985-07-10

    Electrochemical cells are provided with a reactive metal to reduce the oxide of the alkali metal electrode-reactant. Cells employing a molten alkali metal electrode, e.g., sodium, in contact with a ceramic electrolyte, which is a conductor of the ions of the alkali metal forming the electrode, exhibit a lower resistance when a reactive metal, e.g., vanadium, is allowed to react with and reduce the alkali metal oxide. Such cells exhibit less degradation of the electrolyte and of the glass seals often used to joining the electrolyte to the other components of the cell under cycling conditions.

  7. Spill-Resistant Alkali-Metal-Vapor Dispenser

    NASA Technical Reports Server (NTRS)

    Klipstein, William

    2005-01-01

    A spill-resistant vessel has been developed for dispensing an alkali-metal vapor. Vapors of alkali metals (most commonly, cesium or rubidium, both of which melt at temperatures slightly above room temperature) are needed for atomic frequency standards, experiments in spectroscopy, and experiments in laser cooling. Although the present spill-resistant alkali-metal dispenser was originally intended for use in the low-gravity environment of outer space, it can also be used in normal Earth gravitation: indeed, its utility as a vapor source was confirmed by use of cesium in a ground apparatus. The vessel is made of copper. It consists of an assembly of cylinders and flanges, shown in the figure. The uppermost cylinder is a fill tube. Initially, the vessel is evacuated, the alkali metal charge is distilled into the bottom of the vessel, and then the fill tube is pinched closed to form a vacuum seal. The innermost cylinder serves as the outlet for the vapor, yet prevents spilling by protruding above the surface of the alkali metal, no matter which way or how far the vessel is tilted. In the event (unlikely in normal Earth gravitation) that any drops of molten alkali metal have been shaken loose by vibration and are floating freely, a mesh cap on top of the inner cylinder prevents the drops from drifting out with the vapor. Liquid containment of the equivalent of 1.2 grams of cesium was confirmed for all orientations with rubbing alcohol in one of the prototypes later used with cesium.

  8. Alkali Metal Handling Practices at NASA MSFC

    NASA Technical Reports Server (NTRS)

    Salvail, Patrick G.; Carter, Robert R.

    2002-01-01

    NASA Marshall Space Flight Center (MSFC) is NASA s principle propulsion development center. Research and development is coordinated and carried out on not only the existing transportation systems, but also those that may be flown in the near future. Heat pipe cooled fast fission cores are among several concepts being considered for the Nuclear Systems Initiative. Marshall Space Flight Center has developed a capability to handle high-purity alkali metals for use in heat pipes or liquid metal heat transfer loops. This capability is a low budget prototype of an alkali metal handling system that would allow the production of flight qualified heat pipe modules or alkali metal loops. The processing approach used to introduce pure alkali metal into heat pipe modules and other test articles are described in this paper.

  9. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohol, alkali metal salt. 721.4660... Substances § 721.4660 Alcohol, alkali metal salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance generically identified as alcohol, alkali metal salt (PMN P-91-151) is...

  10. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  11. Positive electrode for a lithium battery

    DOEpatents

    Park, Sang-Ho; Amine, Khalil

    2015-04-07

    A method for producing a lithium alkali transition metal oxide for use as a positive electrode material for lithium secondary batteries by a precipitation method. The positive electrode material is a lithium alkali transition metal composite oxide and is prepared by mixing a solid state mixed with alkali and transition metal carbonate and a lithium source. The mixture is thermally treated to obtain a small amount of alkali metal residual in the lithium transition metal composite oxide cathode material.

  12. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, Wen Y.

    1984-01-01

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  13. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  14. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  15. Salts of alkali metal anions and process of preparing same

    DOEpatents

    Dye, James L.; Ceraso, Joseph M.; Tehan, Frederick J.; Lok, Mei Tak

    1978-01-01

    Compounds of alkali metal anion salts of alkali metal cations in bicyclic polyoxadiamines are disclosed. The salts are prepared by contacting an excess of alkali metal with an alkali metal dissolving solution consisting of a bicyclic polyoxadiamine in a suitable solvent, and recovered by precipitation. The salts have a gold-color crystalline appearance and are stable in a vacuum at -10.degree. C. and below.

  16. Electrochemical cell utilizing molten alkali metal electrode-reactant

    DOEpatents

    Virkar, Anil V.; Miller, Gerald R.

    1983-11-04

    An improved electrochemical cell comprising an additive-modified molten alkali metal electrode-reactant and/or electrolyte is disclosed. Various electrochemical cells employing a molten alkali metal, e.g., sodium, electrode in contact with a cationically conductive ceramic membrane experience a lower resistance and a lower temperature coefficient of resistance whenever small amounts of selenium are present at the interface of the electrolyte and the molten alkali metal. Further, cells having small amounts of selenium present at the electrolyte-molten metal interface exhibit less degradation of the electrolyte under long term cycling conditions.

  17. Process for the disposal of alkali metals

    DOEpatents

    Lewis, Leroy C.

    1977-01-01

    Large quantities of alkali metals may be safely reacted for ultimate disposal by contact with a hot concentrated caustic solution. The alkali metals react with water in the caustic solution in a controlled reaction while steam dilutes the hydrogen formed by the reaction to a safe level.

  18. Batteries for storage of wind-generated energy

    NASA Technical Reports Server (NTRS)

    Schwartz, H. J.

    1973-01-01

    Cost effectiveness characteristics of conventional-, metal gas-, and high energy alkali metal-batteries for wind generated energy storage are considered. A lead-acid battery with a power density of 20 to 30 watt/hours per pound is good for about 1500 charge-discharge cycles at a cost of about $80 per kilowatt hour. A zinc-chlorine battery that stores chlorine as solid chlorine hydrate at temperatures below 10 C eliminates the need to handle gaseous chlorine; its raw material cost are low and inexpensive carbon can be used for the chlorine electrode. This system has the best chance to replace lead-acid. Exotic alkali metal batteries are deemed too costly at the present stage of development.

  19. Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries.

    PubMed

    Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Ma, Jianmin; Deng, Yonghong; Li, Yutao; Liu, Huakun; Dou, Shixue

    2017-10-01

    Lithium-ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium-ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated-graphite for LIBs, but also an effective strategy to develop diverse high-energy batteries for stationary energy storage in the future.

  20. Ultrathin Layered SnSe Nanoplates for Low Voltage, High-Rate, and Long-Life Alkali-Ion Batteries.

    PubMed

    Wang, Wei; Li, Peihao; Zheng, Henry; Liu, Qiao; Lv, Fan; Wu, Jiandong; Wang, Hao; Guo, Shaojun

    2017-12-01

    2D electrode materials with layered structures have shown huge potential in the fields of lithium- and sodium-ion batteries. However, their poor conductivity limits the rate performance and cycle stability of batteries. Herein a new colloid chemistry strategy is reported for making 2D ultrathin layered SnSe nanoplates (SnSe NPs) for achieving more efficient alkali-ion batteries. Due to the effect of weak Van der Waals forces, each semiconductive SnSe nanoplate stacks on top of each other, which can facilitate the ion transfer and accommodate volume expansion during the charge and discharge process. This unique structure as well as the narrow-bandgap semiconductor property of SnSe simultaneously meets the requirements of achieving fast ionic and electronic conductivities for alkali-ion batteries. They exhibit high capacity of 463.6 mAh g -1 at 0.05 A g -1 for Na-ion batteries and 787.9 mAh g -1 at 0.2 A g -1 for Li-ion batteries over 300 cycles, and also high stability for alkali-ion batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The Synthesis and Characterization of Ionic Liquids for Alkali-Metal Batteries and a Novel Electrolyte for Non-Humidified Fuel Cells

    NASA Astrophysics Data System (ADS)

    Tucker, Telpriore G.

    This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy. Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl 4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC. Battery testing based on [EMI+][FeCl4 -] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br 7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4 +][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements. Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases

  2. Alkali metal intercalates of molybdenum disulfide.

    NASA Technical Reports Server (NTRS)

    Somoano, R. B.; Hadek, V.; Rembaum, A.

    1973-01-01

    Study of some of the physicochemical properties of compounds obtained by subjecting natural molybdenite and single crystals of molybdenum disulfide grown by chemical vapor transport to intercalation with the alkali group of metals (Li, Na, K, Rb, and Cs) by means of the liquid ammonia technique. Reported data and results include: (1) the intercalation of the entire alkali metal group, (2) stoichiometries and X-ray data on all of the compounds, and (3) superconductivity data for all the intercalation compounds.

  3. Alkali Metal/Salt Thermal-Energy-Storage Systems

    NASA Technical Reports Server (NTRS)

    Phillips, Wayne W.; Stearns, John W.

    1987-01-01

    Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.

  4. COMPLEX FLUORIDES OF PLUTONIUM AND AN ALKALI METAL

    DOEpatents

    Seaborg, G.T.

    1960-08-01

    A method is given for precipitating alkali metal plutonium fluorides. such as KPuF/sub 5/, KPu/sub 2/F/sub 9/, NaPuF/sub 5/, and RbPuF/sub 5/, from an aqueous plutonium(IV) solution by adding hydrogen fluoride and alkali-metal- fluoride.

  5. Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)‐Ion Batteries

    PubMed Central

    Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Li, Yutao; Liu, Huakun; Dou, Shixue

    2017-01-01

    Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future. PMID:29051856

  6. Electronic structure of semiconducting alkali-metal silicides and germanides

    NASA Astrophysics Data System (ADS)

    Tegze, M.; Hafner, J.

    1989-11-01

    We present self-consistent linearized-muffin-tin-orbital calculations of the electronic structure of three alkali-metal germanides and silicides (KGe, NaGe, and NaSi). Like the alkali-metal-lead compounds investigated in our earlier work [M. Tegze and J. Hafner, Phys. Rev. B 39, 8263 (1989)] the Ge and Si compounds of the alkali metals form complex structures based on the packing of tetrahedral Ge4 and Si4 clusters. Our calculations show that all three compounds are narrow-gap semiconductors. The width of the energy gap depends on two main factors: the ratio of the intracluster to the intercluster interactions between the group-IV elements (which increases from Pb to Si) and the strength of the interactions between the alkali-metal atoms (which varies with the size ratio).

  7. Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

    Maroni, V.A.; Maciejewski, M.L.

    This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

  8. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

  9. 40 CFR 721.5452 - Alkali metal salt of halogenated organoborate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal salt of halogenated... Specific Chemical Substances § 721.5452 Alkali metal salt of halogenated organoborate (generic). (a... generically as alkali metal salt of halogenated organoborate (PMN P-00-0638) is subject to reporting under...

  10. 40 CFR 721.4660 - Alcohol, alkali metal salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohol, alkali metal salt. 721.4660 Section 721.4660 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4660 Alcohol, alkali metal sal...

  11. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  12. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  13. IUPAC-NIST Solubility Data Series. 75. Nonmetals in Liquid Alkali Metals

    NASA Astrophysics Data System (ADS)

    Borgstedt, Hans Ulrich; Guminski, Cezary; Borgstedt, Hans Ulrich; Guminski, Cezary

    2001-07-01

    Liquid alkali metals have several physical properties which favor their use in a number of important applications. For example, their large liquidus temperature range and their excellent heat transfer properties are important for use as heat transfer media. They are used in large nuclear reactors in which hundreds of tons of sodium are circulating, and in small parts of engines for cooling of valves. Since these metals are among the most electropositive elements, several of them (Li, Na) can be used in high specific capacity and high energy density batteries at moderately elevated temperatures. The compatibility of metallic constructional materials which are used to contain the liquid metals is strongly influenced by nonmetals present in the liquids. The physical properties of the liquid metals are also influenced by dissolved substances. Several nonmetals dissolved in alkali metals are able to form ternary compounds with components of the constructional materials. Thus, corrosion and compatibility studies have been accompanied by extensive chemical work related to the solutions of non-metallic substances in liquid alkali metals. All available solubility data of nonmetallic elements and some of their compounds in the five liquid alkali metal solvents (Li, Na, K, Rb, and Cs) are collected and compiled. Original publications with reliable data and information on the methods used to generate them are reported in individual Compilations. When numerical data are not given in a publication, the data are often read out from figures and converted into numerical data by the compilers. The precision of this procedure is indicated in the Compilations under Estimated Error. Evaluated solubility data are tabulated at the end of the Critical Evaluations: if there is agreement of at least two independent studies within the experimental error, the solubility values are assigned to the "recommended" category. Values are assigned as "tentative," if only one reliable result was

  14. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under this...

  15. Aqueous cathode for next-generation alkali-ion batteries.

    PubMed

    Lu, Yuhao; Goodenough, John B; Kim, Youngsik

    2011-04-20

    The lithium-ion batteries that ushered in the wireless revolution rely on electrode strategies that are being stretched to power electric vehicles. Low-cost, safe electrical-energy storage that enables better use of alternative energy sources (e.g., wind, solar, and nuclear) requires an alternative strategy. We report a demonstration of the feasibility of a battery having a thin, solid alkali-ion electrolyte separating a water-soluble redox couple as the cathode and lithium or sodium in a nonaqueous electrolyte as the anode. The cell operates without a catalyst and has high storage efficiency. The possibility of a flow-through mode for the cathode allows flexibility of the cell design for safe, large-capacity electrical-energy storage at an acceptable cost.

  16. A rechargeable lithium metal battery operating at intermediate temperatures using molten alkali bis(trifluoromethylsulfonyl)amide mixture as an electrolyte

    NASA Astrophysics Data System (ADS)

    Watarai, Atsushi; Kubota, Keigo; Yamagata, Masaki; Goto, Takuya; Nohira, Toshiyuki; Hagiwara, Rika; Ui, Koichi; Kumagai, Naoaki

    The physicochemical properties of molten alkali bis(trifluoromethylsulfonyl)amide, MTFSI (M = Li, K, Cs), mixture (x LiTFSI = 0.20, x KTFSI = 0.10, x CsTFSI = 0.70) were studied to develop a new rechargeable lithium battery operating at intermediate temperature (100-180 °C). The viscosity and ionic conductivity of this melt at 150 °C are 87.2 cP and 14.2 mS cm -1, respectively. The cyclic voltammetry revealed that the electrochemical window at 150 °C is as wide as 5.0 V, and that the electrochemical deposition/dissolution of lithium metal occurs at the cathode limit. A Li/MTFSI (M = Li, K, Cs)/LiFePO 4 cell showed an excellent cycle performance at a constant current rate of C/10 at 150 °C; 95% of the initial discharge capacity was maintained after 50 cycles. Except for the initial few cycles, the coulombic efficiencies were approximately 100% for all the cycles, indicating the stabilities of the molten MTFSI mixture and all the electrode materials.

  17. Electrochemical cell having an alkali-metal-nitrate electrode

    DOEpatents

    Roche, M.F.; Preto, S.K.

    1982-06-04

    A power-producing secondary electrochemical cell includes a molten alkali metal as the negative-electrode material and a molten-nitrate salt as the positive-electrode material. The molten material in the respective electrodes are separated by a solid barrier of alkali-metal-ion conducting material. A typical cell includes active materials of molten sodium separated from molten sodium nitrate and other nitrates in mixture by a layer of sodium ..beta..'' alumina.

  18. Alkali metal vapors - Laser spectroscopy and applications

    NASA Technical Reports Server (NTRS)

    Stwalley, W. C.; Koch, M. E.

    1980-01-01

    The paper examines the rapidly expanding use of lasers for spectroscopic studies of alkali metal vapors. Since the alkali metals (lithium, sodium, potassium, rubidium and cesium) are theoretically simple ('visible hydrogen'), readily ionized, and strongly interacting with laser light, they represent ideal systems for quantitative understanding of microscopic interconversion mechanisms between photon (e.g., solar or laser), chemical, electrical and thermal energy. The possible implications of such understanding for a wide variety of practical applications (sodium lamps, thermionic converters, magnetohydrodynamic devices, new lasers, 'lithium waterfall' inertial confinement fusion reactors, etc.) are also discussed.

  19. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN P...

  20. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN P...

  1. Neuropsychiatric manifestations of alkali metal deficiency and excess

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

    Yung, C.Y.

    1984-01-01

    The alkali metals from the Group IA of the periodic table (lithium, sodium, potassium, rubidium, cesium and francium) are reviewed. The neuropsychiatric aspects of alkali metal deficiencies and excesses (intoxications) are described. Emphasis was placed on lithium due to its clinical uses. The signs and symptoms of these conditions are characterized by features of an organic brain syndrome with delirium and encephalopathy prevailing. There are no clinically distinctive features that could be reliably used for diagnoses. Sodium and potassium are two essential alkali metals in man. Lithium is used as therapeutic agent in bipolar affective disorders. Rubidium has been investigatedmore » for its antidepressant effect in a group of psychiatric disorders. Cesium is under laboratory investigation for its role in carcinogenesis and in depressive illness. Very little is known of francium due to its great instability for experimental study.« less

  2. Origin of low sodium capacity in graphite and generally weak substrate binding of Na and Mg among alkali and alkaline earth metals.

    PubMed

    Liu, Yuanyue; Merinov, Boris V; Goddard, William A

    2016-04-05

    It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.

  3. Al/Cl2 molten salt battery

    NASA Technical Reports Server (NTRS)

    Giner, J.

    1972-01-01

    Molten salt battery has been developed with theoretical energy density of 5.2 j/kg (650 W-h/lb). Battery, which operates at 150 C, can be used in primary mode or as rechargeable battery. Battery has aluminum anode and chlorine cathode. Electrolyte is mixture of AlCl3, NaCl, and some alkali metal halide such as KCl.

  4. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject to...

  5. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject to...

  6. Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

    PubMed

    Kumai, T; Nomura, H

    1980-01-01

    The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

  7. Azo compounds as a family of organic electrode materials for alkali-ion batteries.

    PubMed

    Luo, Chao; Borodin, Oleg; Ji, Xiao; Hou, Singyuk; Gaskell, Karen J; Fan, Xiulin; Chen, Ji; Deng, Tao; Wang, Ruixing; Jiang, Jianjun; Wang, Chunsheng

    2018-02-27

    Organic compounds are desirable for sustainable Li-ion batteries (LIBs), but the poor cycle stability and low power density limit their large-scale application. Here we report a family of organic compounds containing azo group (N=N) for reversible lithiation/delithiation. Azobenzene-4,4'-dicarboxylic acid lithium salt (ADALS) with an azo group in the center of the conjugated structure is used as a model azo compound to investigate the electrochemical behaviors and reaction mechanism of azo compounds. In LIBs, ADALS can provide a capacity of 190 mAh g -1 at 0.5 C (corresponding to current density of 95 mA g -1 ) and still retain 90%, 71%, and 56% of the capacity when the current density is increased to 2 C, 10 C, and 20 C, respectively. Moreover, ADALS retains 89% of initial capacity after 5,000 cycles at 20 C with a slow capacity decay rate of 0.0023% per cycle, representing one of the best performances in all organic compounds. Superior electrochemical behavior of ADALS is also observed in Na-ion batteries, demonstrating that azo compounds are universal electrode materials for alkali-ion batteries. The highly reversible redox chemistry of azo compounds to alkali ions was confirmed by density-functional theory (DFT) calculations. It provides opportunities for developing sustainable batteries.

  8. Recent Advances on Sodium-Oxygen Batteries: A Chemical Perspective.

    PubMed

    Yadegari, Hossein; Sun, Xueliang

    2018-06-19

    Releasing greenhouse gases into the atmosphere because of widespread use of fossil fuels by humankind has resulted in raising the earth's temperature during the past few decades. Known as global warming, increasing the earth's temperature may in turn endanger civilization on the earth by starting a cycle of environmental changes including climate change and sea level rise. Therefore, replacing fossil fuels with more sustainable energy resources has been considered as one of the main strategies to tackle the global warming crisis. In this regard, energy saving devices are required to store the energy from sustainable resources like wind and solar when they are available and deliver them on demand. Moreover, developing plug-in electric vehicles (PEVs) as an alternative for internal combustion engines has been extensively pursued, since a major sector of fossil fuels is used for transportation purposes. However, currently available battery systems fail to meet the required demands for energy storage. Alkali metal-O 2 battery systems demonstrate a promising prospect as a high-energy density solution regarding the increasing demand of mankind for energy storage. Combining a metallic negative electrode with a breathing oxygen electrode, a metal-O 2 cell can be considered as a half battery/half fuel cell system. The negative electrode in the metal-O 2 cells operates a conversion reaction rather than intercalation mechanism, which eliminates the need for a host lattice. In addition, the positive electrode material (O 2 ) comes from the ambient air and hence is not stored in the battery. Therefore, the resultant battery systems exhibit the highest theoretical energy density, which is comparable to that of gasoline. Accordingly, an unprecedented amount of research activity was directed toward alkali metal-O 2 batteries in the past decade in response to the need for high-energy storage technology in electric transportation. This extensive research surge has resulted in a

  9. Solvent- and catalyst-free mechanochemical synthesis of alkali metal monohydrides

    DOE PAGES

    Hlova, Ihor Z.; Castle, Andra; Goldston, Jennifer F.; ...

    2016-07-06

    Alkali metal monohydrides, AH (A = Li–Cs) have been synthesized in quantitative yields at room temperature by reactive milling of alkali metals in the presence of hydrogen gas at 200 bar or less. The mechanochemical approach reported here eliminates problems associated with the malleability of alkali metals — especially Li, Na, and K — and promotes effective solid–gas reactions, ensuring their completion. This is achieved by incorporating a certain volume fraction of the corresponding hydride powder as a process control agent, which allows continuous and efficient milling primarily by coating the surface of metal particles, effectively blocking cold welding. Formationmore » of high-purity crystalline monohydrides has been confirmed by powder X-ray diffraction, solid-state NMR spectroscopy, and volumetric analyses of reactively desorbed H 2 from as-milled samples. The proposed synthesis method is scalable and particularly effective for extremely air-sensitive materials, such as alkali and alkaline earth metal hydrides. Furthermore, the technique may also be favorable for production in continuous reactors operating at room temperature, thereby reducing the total processing time, energy consumption and, hence, the cost of production of these hydrides or their derivatives and composites.« less

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

    DOEpatents

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

    2000-01-01

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

  11. Method and composition for testing for the presence of an alkali metal

    DOEpatents

    Guon, Jerold

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

  12. The interactions of sorbates with gallosilicates and alkali-metal exchanged gallosilicates

    NASA Astrophysics Data System (ADS)

    Limtrakul, J.; Kuno, M.; Treesukol, P.

    1999-11-01

    Structures, energetics and vibrational frequencies of the interaction of adsorbates with H-aluminosilicates (H-AlZ), H-gallosilicates (H-GaZ), alkali-metal exchanged aluminosilicates (X-AlZ) and alkali-metal exchanged gallosilicates (X-GaZ), where X being Li, Na, or K, have been carried out at B3LYP and HF levels of theory with 6-31G(d) as the basis set. The charge compensating alkali-metal ions can affect the catalytically active site (Si-O-T where T=Al or Ga) by weakening the Si-O, Al-O, and Ga-O bonds as compared to their anionic frameworks. Comparing the net stabilization energies, Δ ENSE, of the naked alkali-metal/H 2O adducts with those of the alkali-metal exchanged zeolite/H 2O systems, the latter amounts only to about 50% of the former, which is partly due to the destabilizing role of the negative zeolitic oxygen frameworks surrounding the cations. The interaction of sorbates with the alkali-metal exchanged gallosilicates can be employed to probe the field strength inside the catalytic frameworks as indicated by the plot of the binding energy, Δ E, versus 1/ RX-O w2, with R(X-O w) being the distance between the cationic nucleus and the oxygen atom of the adsorbate. The IR spectra of H 2O adsorbed on Na-AlZ are calculated to be 3584, 3651, and 1686 cm -1. The obtained results are in excellent agreement with the very recent experimental IR spectra of water adsorbed on Na-ZSM-5 of Zecchina et al. (J. Phys. Chem., 100 (1996) 16 484). Other important features, i.e. the correlation between Δ νOH and, Δ E, R(X-O w) , and 1/ RX-O w2, cationic size, demonstrate that the interactions of sorbates with alkali-metal exchanged gallosilicates are well approximated by electrostatic contribution.

  13. Advancing Lithium Metal Batteries

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

    Liu, Bin; Zhang, Ji-Guang; Xu, Wu

    Considering the unsatisfied energy density of traditional graphite anode-based lithium (Li)-ion batteries, any alterative high capacity anodes will be highly expected to be practically applied in future high energy battery systems. Li metal is regarded as one of the most promising anodes due to its ultrahigh capacity (3860 mAh g-1), the lowest standard negative electrochemical potential (-3.040 V) and the very low gravimetric density (0.534 g cm-3). However, dendrite growth and high reactivity of Li metal result in low cycling efficiency and severe safety concerns. The revival of research and development on Li metal anode in recent years has broughtmore » new in-depth understandings and key experimental achievements regarding Li metal protection and enhanced performances of Li-metal batteries. In this perspective article, we first concisely review the recent discoveries and then offer possible research directions for further development of Li metal batteries.« less

  14. Role of crystal field in mixed alkali metal effect: electron paramagnetic resonance study of mixed alkali metal oxyfluoro vanadate glasses.

    PubMed

    Honnavar, Gajanan V; Ramesh, K P; Bhat, S V

    2014-01-23

    The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF2-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V(4+) ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a "preferential substitution model". Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

  15. DFT study of the interaction between DOTA chelator and competitive alkali metal ions.

    PubMed

    Frimpong, E; Skelton, A A; Honarparvar, B

    2017-09-01

    1, 4, 7, 10-tetraazacyclododecane-1, 4, 7, 10-tetracetic acid (DOTA) is an important chelator for radiolabeling of pharmaceuticals. The ability of alkali metals found in the body to complex with DOTA and compete with radio metal ions can alter the radiolabeling process. Non-covalent interactions between DOTA complexed with alkali metals Li + , Na + , K + and Rb + , are investigated with density functional theory using B3LYP and ωB97XD functionals. Conformational possibilities of DOTA were explored with a varying number of carboxylic pendant arms of DOTA in close proximity to the ions. It is found that the case in which four arms of DOTA are interacting with ions is more stable than other conformations. The objective of this study is to explore the electronic structure properties upon complexation of alkali metals Li + Na + , K + and Rb + with a DOTA chelator. Interaction energies, relaxation energies, entropies, Gibbs free energies and enthalpies show that the stability of DOTA, complexed with alkali metals decreases down the group of the periodic table. Implicit water solvation affects the complexation of DOTA-ions leading to decreases in the stability of the complexes. NBO analysis through the natural population charges and the second order perturbation theory, revealed a charge transfer between DOTA and alkali metals. Conceptual DFT-based properties such as HOMO/LUMO energies, ΔE HOMO-LUMO and chemical hardness and softness indicated a decrease in the chemical stability of DOTA-alkali metal complexes down the alkali metal series. This study serves as a guide to researchers in the field of organometallic chelators, particularly, radiopharmaceuticals in finding the efficient optimal match between chelators and various metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Sealed aerospace metal-hydride batteries

    NASA Technical Reports Server (NTRS)

    Coates, Dwaine

    1992-01-01

    Nickel metal hydride and silver metal hydride batteries are being developed for aerospace applications. There is a growing market for smaller, lower cost satellites which require higher energy density power sources than aerospace nickel-cadmium at a lower cost than space nickel-hydrogen. These include small LEO satellites, tactical military satellites and satellite constellation programs such as Iridium and Brilliant Pebbles. Small satellites typically do not have the spacecraft volume or the budget required for nickel-hydrogen batteries. NiCd's do not have adequate energy density as well as other problems such as overcharge capability and memory effort. Metal hydride batteries provide the ideal solution for these applications. Metal hydride batteries offer a number of advantages over other aerospace battery systems.

  17. Is Electronegativity a Useful Descriptor for the "Pseudo-Alkali-Metal" NH4?

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

    Whiteside, Alexander; Xantheas, Sotiris S.; Gutowski, Maciej S.

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined the electronegativity of the "pseudo-alkali metal" ammonium (NH4) and evaluated its reliability as a descriptor in comparison to the electronegativities of the alkali metals. The computed properties of its binary complexes with astatine and of selected borohydrides confirm the similarity of NH4 to the alkali metal atoms, although the electronegativity of NH4 is relatively large in comparison to its cationic radius. We paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation, andmore » reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the polyatomic nature of NH4.« less

  18. Tuning the electronic structure of graphene through alkali metal and halogen atom intercalation

    NASA Astrophysics Data System (ADS)

    Ahmad, Sohail; Miró, Pere; Audiffred, Martha; Heine, Thomas

    2018-04-01

    The deposition, intercalation and co-intercalation of heavy alkali metals and light halogens atoms in graphene mono- and bilayers have been studied using first principles density-functional calculations. Both the deposition and the intercalation of alkali metals gives rise to n-type doping due to the formation of M+-C- pairs. The co-intercalation of a 1:1 ratio of alkali metals and halogens derives into the formation of ionic pairs among the intercalated species, unaltering the electronic structure of the layered material.

  19. Alkali metal yttrium neo-pentoxide double alkoxide precursors to alkali metal yttrium oxide nanomaterials

    DOE PAGES

    Boyle, Timothy J.; Neville, Michael L.; Sears, Jeremiah Matthew; ...

    2016-03-15

    In this study, a series of alkali metal yttrium neo-pentoxide ([AY(ONep) 4]) compounds were developed as precursors to alkali yttrium oxide (AYO 2) nanomaterials. The reaction of yttrium amide ([Y(NR 2) 3] where R=Si(CH 3) 3) with four equivalents of H-ONep followed by addition of [A(NR 2)] (A=Li, Na, K) or A o (A o=Rb, Cs) led to the formation of a complex series of A nY(ONep) 3+n species, crystallographically identified as [Y 2Li 3(μ 3-ONep)(μ 3-HONep)(μ-ONep) 5(ONep) 3(HONep) 2] (1), [YNa 2(μ 3-ONep) 4(ONep)] 2 (2), {[Y 2K 3(μ 3-ONep) 3(μ-ONep) 4(ONep) 2(ηξ-tol) 2][Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep)more » 4]•η x-tol]} (3), [Y 4K 2(μ 4-O)(μ 3-ONep) 8(ONep) 4] (3a), [Y 2Rb 3(μ 4-ONep) 3(μ-ONep) 6] (4), and [Y 2Cs 4(μ 6-O)(μ 3-ONep) 6(μ 3-HONep) 2(ONep) 2(η x-tol) 4]•tol (5). Compounds 1–5 were investigated as single source precursors to AYOx nanomaterials following solvothermal routes (pyridine, 185 °C for 24h). The final products after thermal processing were found by powder X-ray diffraction experiments to be Y 2O 3 with variable sized particles based on transmission electron diffraction. Energy dispersive X-ray spectroscopy studies indicated that the heavier alkali metal species were present in the isolated nanomaterials.« less

  20. Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

    DOEpatents

    Gordon, John Howard

    2014-09-09

    A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

  1. Highly reproducible alkali metal doping system for organic crystals through enhanced diffusion of alkali metal by secondary thermal activation.

    PubMed

    Lee, Jinho; Park, Chibeom; Song, Intek; Koo, Jin Young; Yoon, Taekyung; Kim, Jun Sung; Choi, Hee Cheul

    2018-05-16

    In this paper, we report an efficient alkali metal doping system for organic single crystals. Our system employs an enhanced diffusion method for the introduction of alkali metal into organic single crystals by controlling the sample temperature to induce secondary thermal activation. Using this system, we achieved intercalation of potassium into picene single crystals with closed packed crystal structures. Using optical microscopy and Raman spectroscopy, we confirmed that the resulting samples were uniformly doped and became K 2 picene single crystal, while only parts of the crystal are doped and transformed into K 2 picene without secondary thermal activation. Moreover, using a customized electrical measurement system, the insulator-to-semiconductor transition of picene single crystals upon doping was confirmed by in situ electrical conductivity and ex situ temperature-dependent resistivity measurements. X-ray diffraction studies showed that potassium atoms were intercalated between molecular layers of picene, and doped samples did not show any KH- nor KOH-related peaks, indicating that picene molecules are retained without structural decomposition. During recent decades, tremendous efforts have been exerted to develop high-performance organic semiconductors and superconductors, whereas as little attention has been devoted to doped organic crystals. Our method will enable efficient alkali metal doping of organic crystals and will be a resource for future systematic studies on the electrical property changes of these organic crystals upon doping.

  2. Process for carbonaceous material conversion and recovery of alkali metal catalyst constituents held by ion exchange sites in conversion residue

    DOEpatents

    Sharp, David W.

    1980-01-01

    In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered for the particles by contacting or washing them with an aqueous solution containing calcium or magnesium ions in an alkali metal recovery zone at a low temperature, preferably below about 249.degree. F. During the washing or leaching process, the calcium or magnesium ions displace alkali metal ions held by ion exchange sites in the particles thereby liberating the ions and producing an aqueous effluent containing alkali metal constituents. The aqueous effluent from the alkali metal recovery zone is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  3. Is electronegativity a useful descriptor for the pseudo-alkali metal NH4?

    PubMed

    Whiteside, Alexander; Xantheas, Sotiris S; Gutowski, Maciej

    2011-11-18

    Molecular ions in the form of "pseudo-atoms" are common structural motifs in chemistry, with properties that are transferrable between different compounds. We have determined one such property--the electronegativity--for the "pseudo-alkali metal" ammonium (NH(4)), and evaluated its reliability as a descriptor versus the electronegativities of the alkali metals. The computed properties of ammonium's binary complexes with astatine and of selected borohydrides confirm the similarity of NH(4) to the alkali metal atoms, although the electronegativity of NH(4) is relatively large in comparison to its cationic radius. We have paid particular attention to the molecular properties of ammonium (angular anisotropy, geometric relaxation and reactivity), which can cause deviations from the behaviour expected of a conceptual "true alkali metal" with this electronegativity. These deviations allow for the discrimination of effects associated with the molecular nature of NH(4). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Observation of Raman self-focusing in an alkali-metal vapor cell

    NASA Astrophysics Data System (ADS)

    Proite, N. A.; Unks, B. E.; Green, J. T.; Yavuz, D. D.

    2008-02-01

    We report an experimental demonstration of Raman self-focusing and self-defocusing in a far-off resonant alkali-metal atomic system. The key idea is to drive a hyperfine transition in an alkali-metal atom to a maximally coherent state with two laser beams. In this regime, the two-photon detuning from the Raman resonance controls the nonlinear index of the medium.

  5. Removal of oxides from alkali metal melts by reductive titration to electrical resistance-change end points

    DOEpatents

    Tsang, Floris Y.

    1980-01-01

    Alkali metal oxides dissolved in alkali metal melts are reduced with soluble metals which are converted to insoluble oxides. The end points of the reduction is detected as an increase in electrical resistance across an alkali metal ion-conductive membrane interposed between the oxide-containing melt and a material capable of accepting the alkali metal ions from the membrane when a difference in electrical potential, of the appropriate polarity, is established across it. The resistance increase results from blocking of the membrane face by ions of the excess reductant metal, to which the membrane is essentially non-conductive.

  6. Compression-Driven Enhancement of Electronic Correlations in Simple Alkali Metals

    NASA Astrophysics Data System (ADS)

    Fabbris, Gilberto; Lim, Jinhyuk; Veiga, Larissa; Haskel, Daniel; Schilling, James

    2015-03-01

    Alkali metals are the best realization of the nearly free electron model. This scenario appears to change dramatically as the alkalis are subjected to extreme pressure, leading to unexpected properties such as the departure from metallic behavior in Li and Na, and the occurrence of remarkable low-symmetry crystal structures in all alkalis. Although the mechanism behind these phase transitions is currently under debate, these are believed to be electronically driven. In this study the high-pressure electronic and structural ground state of Rb and Cs was investigated through low temperature XANES and XRD measurements combined with ab initio calculations. The results indicate that the pressure-induced localization of the conduction band triggers a Peierls-like mechanism, inducing the low symmetry phases. This localization process is evident by the pressure-driven increase in the number of d electrons, which takes place through strong spd hybridization. These experimental results indicate that compression turns the heavy alkali metals into strongly correlated electron systems. Work at Argonne was supported by DOE No. DE-AC02-06CH11357. Research at Washington University was supported by NSF DMR-1104742 and CDAC/DOE/NNSA DE-FC52-08NA28554.

  7. The role of halide ions on the electrochemical behaviour of iron in alkali solutions

    NASA Astrophysics Data System (ADS)

    Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

    2008-02-01

    Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

  8. Advances in high temperature components for AMTEC (alkali metal thermal-to-electric converter)

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

    Williams, R.M.; Jeffries-Nakamura, B.; Underwood, M.L.

    1991-12-31

    Long lifetimes are required for AMTEC (or sodium heat engine) components for aerospace and terrestrial applications, and the high heat input temperature as well as the alkali metal liquid and vapor environment places unusual demands on the materials used to construct AMTEC devices. In addition, it is important to maximize device efficiency and power density, while maintaining a long life capability. In addition to the electrode, which must provide both efficient electrode kinetics, transport of the alkali metal, and low electrical resistance, other high temperature components of the cell face equally demanding requirements. The beta{double_prime} alumina solid electrolyte (BASE), themore » seal between the BASE ceramic and its metallic transition to the hot alkali metal (liquid or vapor) source, and metallic components of the device are exposed to hot liquid alkali metal. Modification of AMTEC components may also be useful in optimizing the device for particular operating conditions. In particular, a potassium AMTEC may be expected to operate more efficiently at lower temperatures.« less

  9. Advances in high temperature components for AMTEC (alkali metal thermal-to-electric converter)

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

    Williams, R.M.; Jeffries-Nakamura, B.; Underwood, M.L.

    1991-01-01

    Long lifetimes are required for AMTEC (or sodium heat engine) components for aerospace and terrestrial applications, and the high heat input temperature as well as the alkali metal liquid and vapor environment places unusual demands on the materials used to construct AMTEC devices. In addition, it is important to maximize device efficiency and power density, while maintaining a long life capability. In addition to the electrode, which must provide both efficient electrode kinetics, transport of the alkali metal, and low electrical resistance, other high temperature components of the cell face equally demanding requirements. The beta{double prime} alumina solid electrolyte (BASE),more » the seal between the BASE ceramic and its metallic transition to the hot alkali metal (liquid or vapor) source, and metallic components of the device are exposed to hot liquid alkali metal. Modification of AMTEC components may also be useful in optimizing the device for particular operating conditions. In particular, a potassium AMTEC may be expected to operate more efficiently at lower temperatures.« less

  10. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  11. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  12. Alkali metal-refractory metal biphase electrode for AMTEC

    NASA Technical Reports Server (NTRS)

    Williams, Roger M. (Inventor); Bankston, Clyde P. (Inventor); Cole, Terry (Inventor); Khanna, Satish K. (Inventor); Jeffries-Nakamura, Barbara (Inventor); Wheeler, Bob L. (Inventor)

    1989-01-01

    An electrode having increased output with slower degradation is formed of a film applied to a beta-alumina solid electrolyte (BASE). The film comprises a refractory first metal M.sup.1 such as a platinum group metal, suitably platinum or rhodium, capable of forming a liquid or a strong surface adsorption phase with sodium at the operating temperature of an alkali metal thermoelectric converter (AMTEC) and a second refractory metal insoluble in sodium or the NaM.sup.1 liquid phase such as a Group IVB, VB or VIB metal, suitably tungsten, molybdenum, tantalum or niobium. The liquid phase or surface film provides fast transport through the electrode while the insoluble refractory metal provides a structural matrix for the electrode during operation. A trilayer structure that is stable and not subject to deadhesion comprises a first, thin layer of tungsten, an intermediate co-deposited layer of tungsten-platinum and a thin surface layer of platinum.

  13. Hall Determination of Atomic Radii of Alkali Metals

    ERIC Educational Resources Information Center

    Houari, Ahmed

    2008-01-01

    I will propose here an alternative method for determining atomic radii of alkali metals based on the Hall measurements of their free electron densities and the knowledge of their crystal structure. (Contains 2 figures.)

  14. Process for preparing higher oxides of the alkali and alkaline earth metals

    NASA Technical Reports Server (NTRS)

    Sadhukhan, P.; Bell, A. (Inventor)

    1978-01-01

    High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

  15. Stabilized Alkali-Metal Ultraviolet-Band-Pass Filters

    NASA Technical Reports Server (NTRS)

    Mardesich, Nick; Fraschetti, George A.; Mccann, Timothy; Mayall, Sherwood D.; Dunn, Donald E.; Trauger, John T.

    1995-01-01

    Layers of bismuth 5 to 10 angstrom thick incorporated into alkali-metal ultraviolet-band-pass optical filters by use of advanced fabrication techniques. In new filters layer of bismuth helps to reduce surface migration of sodium. Sodium layer made more stable and decreased tendency to form pinholes by migration.

  16. Method for inhibiting alkali metal corrosion of nickel-containing alloys

    DOEpatents

    DeVan, Jackson H.; Selle, James E.

    1983-01-01

    Structural components of nickel-containing alloys within molten alkali metal systems are protected against corrosion during the course of service by dissolving therein sufficient aluminum, silicon, or manganese to cause the formation and maintenance of a corrosion-resistant intermetallic reaction layer created by the interaction of the molten metal, selected metal, and alloy.

  17. Dendrite-Free Potassium–Oxygen Battery Based on a Liquid Alloy Anode

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

    Yu, Wei; Lau, Kah Chun; Lei, Yu

    The safety issue caused by the dendrite growth is not only a key research problem in lithium-ion batteries but also a critical concern in alkali metal (i.e., Li, Na, and K) oxygen batteries where a solid metal is usually used as the anode. Herein, we demonstrate the first dendrite-free K-O-2 battery at ambient temperature based on a liquid Na K alloy anode. The unique liquid liquid connection between the liquid alloy and the electrolyte in our alloy anode-based battery provides a homogeneous and robust anode electrolyte interface. Meanwhile, we manage to show that the Na K alloy is only compatiblemore » in K-O-2 batteries but not in Na-O-2 batteries, which is mainly attributed to the stronger reducibility of potassium and relatively more favorable thermodynamic formation of KO, over NaO2 during the discharge process. It is observed that our K-O-2 battery based on a liquid alloy anode shows a long cycle life (over 620 h) and a low discharge charge overpotential (about 0.05 V at initial cycles). Moreover, the mechanism investigation into the K-O-2 cell degradation shows that the 02 crossover effect and the ether electrolyte instability are the critical problems for K-O-2 batteries. In a word, this study provides a new route to solve the problems caused by the dendrite growth in alkali metal oxygen batteries.« less

  18. Alkali Metal Heat Pipe Life Issues

    NASA Technical Reports Server (NTRS)

    Reid, Robert S.

    2004-01-01

    One approach to space fission power system design is predicated on the use of alkali metal heat pipes, either as radiator elements, thermal management components, or as part of the core primary heat-transfer system. This synopsis characterizes long-life core heat pipes. References are included where more detailed information can be found. Specifics shown here are for demonstrational purposes and do not necessarily reflect current Project Prometheus point designs.

  19. A simple model for metal cation-phosphate interactions in nucleic acids in the gas phase: alkali metal cations and trimethyl phosphate.

    PubMed

    Ruan, Chunhai; Huang, Hai; Rodgers, M T

    2008-02-01

    Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies (BDEs) of complexes of alkali metal cations to trimethyl phosphate, TMP. Endothermic loss of the intact TMP ligand is the only dissociation pathway observed for all complexes. Theoretical calculations at the B3LYP/6-31G* level of theory are used to determine the structures, vibrational frequencies, and rotational constants of neutral TMP and the M+(TMP) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/6-311+G(2d,2p) level using the B3LYP/6-31G* optimized geometries. The agreement between theory and experiment is reasonably good for all complexes except Li+(TMP). The absolute M+-(TMP) BDEs are found to decrease monotonically as the size of the alkali metal cation increases. No activated dissociation was observed for alkali metal cation binding to TMP. The binding of alkali metal cations to TMP is compared with that to acetone and methanol.

  20. Na-Zn liquid metal battery

    NASA Astrophysics Data System (ADS)

    Xu, Junli; Kjos, Ole Sigmund; Osen, Karen Sende; Martinez, Ana Maria; Kongstein, Ole Edvard; Haarberg, Geir Martin

    2016-11-01

    A new kind of membrane free liquid metal battery was developed. The battery employs liquid sodium and zinc as electrodes both in liquid state, and NaCl-CaCl2 molten salts as electrolyte. The discharge flat voltage is in the range of about 1.4 V-1.8 V, and the cycle efficiency achieved is about 90% at low discharge current densities (below 40 mA cm-2). Moreover, this battery can also be charged and discharged at high current density with good performance. The discharge flat voltage is above 1.1 V when it is discharged at 100 mA cm-2, while it is about 0.8 V with 100% cycle efficiency when it is discharged at 200 mA cm-2. Compared to other reported liquid metal battery, this battery has lower cost, which suggests broad application prospect in energy storage systems for power grid.

  1. In situ formation of coal gasification catalysts from low cost alkali metal salts

    DOEpatents

    Wood, Bernard J.; Brittain, Robert D.; Sancier, Kenneth M.

    1985-01-01

    A carbonaceous material, such as crushed coal, is admixed or impregnated with an inexpensive alkali metal compound, such as sodium chloride, and then pretreated with a stream containing steam at a temperature of 350.degree. to 650.degree. C. to enhance the catalytic activity of the mixture in a subsequent gasification of the mixture. The treatment may result in the transformation of the alkali metal compound into another, more catalytically active, form.

  2. Gradient porous electrode architectures for rechargeable metal-air batteries

    DOEpatents

    Dudney, Nancy J.; Klett, James W.; Nanda, Jagjit; Narula, Chaitanya Kumar; Pannala, Sreekanth

    2016-03-22

    A cathode for a metal air battery includes a cathode structure having pores. The cathode structure has a metal side and an air side. The porosity decreases from the air side to the metal side. A metal air battery and a method of making a cathode for a metal air battery are also disclosed.

  3. Dendrite-Free Sodium-Metal Anodes for High-Energy Sodium-Metal Batteries.

    PubMed

    Sun, Bing; Li, Peng; Zhang, Jinqiang; Wang, Dan; Munroe, Paul; Wang, Chengyin; Notten, Peter H L; Wang, Guoxiu

    2018-05-31

    Sodium (Na) metal is one of the most promising electrode materials for next-generation low-cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co-doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N- and S-containing functional groups on the carbon nanotubes induce the NSCNTs to be highly "sodiophilic," which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na-metal-based anode (Na/NSCNT anode) exhibits a dendrite-free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium-oxygen (Na-O 2 ) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na-O 2 batteries with bare Na metal anodes. This work opens a new avenue for the development of next-generation high-energy-density sodium-metal batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Sodium-metal halide and sodium-air batteries.

    PubMed

    Ha, Seongmin; Kim, Jae-Kwang; Choi, Aram; Kim, Youngsik; Lee, Kyu Tae

    2014-07-21

    Impressive developments have been made in the past a few years toward the establishment of Na-ion batteries as next-generation energy-storage devices and replacements for Li-ion batteries. Na-based cells have attracted increasing attention owing to low production costs due to abundant sodium resources. However, applications of Na-ion batteries are limited to large-scale energy-storage systems because of their lower energy density compared to Li-ion batteries and their potential safety problems. Recently, Na-metal cells such as Na-metal halide and Na-air batteries have been considered to be promising for use in electric vehicles owing to good safety and high energy density, although less attention is focused on Na-metal cells than on Na-ion cells. This Minireview provides an overview of the fundamentals and recent progress in the fields of Na-metal halide and Na-air batteries, with the aim of providing a better understanding of new electrochemical systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Device and method for upgrading petroleum feedstocks and petroleum refinery streams using an alkali metal conductive membrane

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

    Gordon, John Howard; Alvare, Javier

    A reactor has two chambers, namely an oil feedstock chamber and a source chamber. An ion separator separates the oil feedstock chamber from the source chamber, wherein the ion separator allows alkali metal ions to pass from the source chamber, through the ion separator, and into the oil feedstock chamber. A cathode is at least partially housed within the oil feedstock chamber and an anode is at least partially housed within the source chamber. A quantity of an oil feedstock is within the oil feedstock chamber, the oil feedstock comprising at least one carbon atom and a heteroatom and/or onemore » or more heavy metals, the oil feedstock further comprising naphthenic acid. When the alkali metal ion enters the oil feedstock chamber, the alkali metal reacts with the heteroatom, the heavy metals and/or the naphthenic acid, wherein the reaction with the alkali metal forms inorganic products.« less

  6. Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

    PubMed

    Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

    2017-05-01

    Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Investigation of Anti-Relaxation Coatings for Alkali-Metal Vapor Cells using Surface Science Techniques

    DTIC Science & Technology

    2011-02-01

    worldwide. Lawrence Berkeley National Laboratory Peer Reviewed Title: Investigation of anti-Relaxation coatings for alkali-metal vapor cells using ...2010 Abstract: Many technologies based on cells containing alkali-metal atomic vapor benefit from the use of antirelaxation surface coatings in order to...preserve atomic spin polarization. In particular, paraffin has been used for this purpose for several decades and has been demonstrated to allow an

  8. Alkali metal protective garment and composite material

    DOEpatents

    Ballif, III, John L.; Yuan, Wei W.

    1980-01-01

    A protective garment and composite material providing satisfactory heat resistance and physical protection for articles and personnel exposed to hot molten alkali metals, such as sodium. Physical protection is provided by a continuous layer of nickel foil. Heat resistance is provided by an underlying backing layer of thermal insulation. Overlying outer layers of fireproof woven ceramic fibers are used to protect the foil during storage and handling.

  9. Li Metal Anodes and Rechargeable Lithium Metal Batteries. Springer Series in Materials Science

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

    Zhang, Jiguang; Xu, Wu; Henderson, Wesley A.

    Lithium (Li) metal is an ideal anode material for rechargeable batteries. With the urgent need for the “next generation” rechargeable batteries, such as Li-S, Li-air batteries as well as rechargeable Li metal batteries using Li intercalation compounds as the cathode, the use of Li metal anode has attracted significant interests in recent years. Unfortunately, rechargeable batteries based on Li metal anode have not yet been commercialized mainly due to two barriers: one is the growth of Li dendrites and associated safety hazard, and another is the low Coulombic efficiency (CE) of Li cycling and associated early battery failure due tomore » Li powdering and increasing cell impedance. To have a high CE, minimum side reactions between freshly/native deposited Li and electrolyte has to be minimized. These reactions are proportional to the chemical and electrochemical activity of native Li when they are in direct contact with surrounding electrolyte. They are also proportional to the surface area of deposited Li. This means that high CE of Li deposition/stripping always related to a low surface area Li deposition and suppressed Li dendrite growth. Therefore, the enhancement of CE is a more fundamental factors controlling long term, stable cycling of Li metal anode. In this book, we will first review the general models of the dendrite growth mechanism. The effect of SEI layer on the modeling of Li dendrite growth will also be discussed. Then we will discuss various instruments/tools that are critical for the investigation of Li dendrite growth. In the Chapter 3, various factors which affect CE of Li cycling and dendrite growth will be discussed together with an emphasize on enhancement of CE. Chapter 4 of the book will discuss the specific application of Li metal anode in several key rechargeable Li metal batteries, including Li-air batteries, Li-S batteries and Li metal batteries using intercalation compounds as cathode. At last, the perspective on the future

  10. Elliptical polarization of near-resonant linearly polarized probe light in optically pumped alkali metal vapor

    PubMed Central

    Li, Yingying; Wang, Zhiguo; Jin, Shilong; Yuan, Jie; Luo, Hui

    2017-01-01

    Optically pumped alkali metal atoms currently provide a sensitive solution for magnetic microscopic measurements. As the most practicable plan, Faraday rotation of linearly polarized light is extensively used in spin polarization measurements of alkali metal atoms. In some cases, near-resonant Faraday rotation is applied to improve the sensitivity. However, the near-resonant linearly polarized probe light is elliptically polarized after passing through optically pumped alkali metal vapor. The ellipticity of transmitted near-resonant probe light is numerically calculated and experimentally measured. In addition, we also analyze the negative impact of elliptical polarization on Faraday rotation measurements. From our theoretical estimate and experimental results, the elliptical polarization forms an inevitable error in spin polarization measurements. PMID:28216649

  11. Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Ito, S.; Feng, B.; Arita, M.; Someya, T.; Chen, W.-C.; Takayama, A.; Iimori, T.; Namatame, H.; Taniguchi, M.; Cheng, C.-M.; Tang, S.-J.; Komori, F.; Matsuda, I.

    2018-04-01

    Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

  12. Apparatuses for making cathodes for high-temperature, rechargeable batteries

    DOEpatents

    Meinhardt, Kerry D.; Sprenkle, Vincent L.; Coffey, Gregory W.

    2016-09-13

    The approaches and apparatuses for fabricating cathodes can be adapted to improve control over cathode composition and to better accommodate batteries of any shape and their assembly. For example, a first solid having an alkali metal halide, a second solid having a transition metal, and a third solid having an alkali metal aluminum halide are combined into a mixture. The mixture can be heated in a vacuum to a temperature that is greater than or equal to the melting point of the third solid. When the third solid is substantially molten liquid, the mixture is compressed into a desired cathode shape and then cooled to solidify the mixture in the desired cathode shape.

  13. Bipolar Nickel-Metal Hydride Battery Being Developed

    NASA Technical Reports Server (NTRS)

    Manzo, Michelle A.

    1998-01-01

    The NASA Lewis Research Center has contracted with Electro Energy, Inc., to develop a bipolar nickel-metal hydride battery design for energy storage on low-Earth-orbit satellites. The objective of the bipolar nickel-metal hydride battery development program is to approach advanced battery development from a systems level while incorporating technology advances from the lightweight nickel electrode field, hydride development, and design developments from nickel-hydrogen systems. This will result in a low-volume, simplified, less-expensive battery system that is ideal for small spacecraft applications. The goals of the program are to develop a 1-kilowatt, 28-volt (V), bipolar nickel-metal hydride battery with a specific energy of 100 watt-hours per kilogram (W-hr/kg), an energy density of 250 W-hr/liter and a 5-year life in low Earth orbit at 40-percent depth-of-discharge.

  14. First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

    NASA Astrophysics Data System (ADS)

    Kaneko, Tomoaki; Saito, Riichiro

    2017-11-01

    Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

  15. Methods and apparatuses for making cathodes for high-temperature, rechargeable batteries

    DOEpatents

    Meinhardt, Kerry D; Sprenkle, Vincent L; Coffey, Gregory W

    2014-05-20

    The approaches for fabricating cathodes can be adapted to improve control over cathode composition and to better accommodate batteries of any shape and their assembly. For example, a first solid having an alkali metal halide, a second solid having a transition metal, and a third solid having an alkali metal aluminum halide are combined into a mixture. The mixture can be heated in a vacuum to a temperature that is greater than or equal to the melting point of the third solid. When the third solid is substantially molten liquid, the mixture is compressed into a desired cathode shape and then cooled to solidify the mixture in the desired cathode shape.

  16. Rechargeable dual-metal-ion batteries for advanced energy storage.

    PubMed

    Yao, Hu-Rong; You, Ya; Yin, Ya-Xia; Wan, Li-Jun; Guo, Yu-Guo

    2016-04-14

    Energy storage devices are more important today than any time before in human history due to the increasing demand for clean and sustainable energy. Rechargeable batteries are emerging as the most efficient energy storage technology for a wide range of portable devices, grids and electronic vehicles. Future generations of batteries are required to have high gravimetric and volumetric energy, high power density, low price, long cycle life, high safety and low self-discharge properties. However, it is quite challenging to achieve the above properties simultaneously in state-of-the-art single metal ion batteries (e.g. Li-ion batteries, Na-ion batteries and Mg-ion batteries). In this contribution, hybrid-ion batteries in which various metal ions simultaneously engage to store energy are shown to provide a new perspective towards advanced energy storage: by connecting the respective advantages of different metal ion batteries they have recently attracted widespread attention due to their novel performances. The properties of hybrid-ion batteries are not simply the superposition of the performances of single ion batteries. To enable a distinct description, we only focus on dual-metal-ion batteries in this article, for which the design and the benefits are briefly discussed. We enumerate some new results about dual-metal-ion batteries and demonstrate the mechanism for improving performance based on knowledge from the literature and experiments. Although the search for hybrid-ion batteries is still at an early age, we believe that this strategy would be an excellent choice for breaking the inherent disadvantages of single ion batteries in the near future.

  17. Alkali metal intercalated fullerene-like MS(2) (M = W, Mo) nanoparticles and their properties.

    PubMed

    Zak, Alla; Feldman, Yishay; Lyakhovitskaya, Vera; Leitus, Gregory; Popovitz-Biro, Ronit; Wachtel, Ellen; Cohen, Hagai; Reich, Shimon; Tenne, Reshef

    2002-05-01

    Layered metal disulfides-MS(2) (M = Mo, W) in the form of fullerene-like nanoparticles and in the form of platelets (crystallites of the 2H polytype) have been intercalated by exposure to alkali metal (potassium and sodium) vapor using a two-zone transport method. The composition of the intercalated systems was established using X-ray energy dispersive spectrometer and X-ray photoelectron spectroscopy (XPS). The alkali metal concentration in the host lattice was found to depend on the kind of sample and the experimental conditions. Furthermore, an inhomogeneity of the intercalated samples was observed. The product consisted of both nonintercalated and intercalated phases. X-ray diffraction analysis and transmission electron microscopy of the samples, which were not exposed to the ambient atmosphere, showed that they suffered little change in their lattice parameters. On the other hand, after exposure to ambient atmosphere, substantial increase in the interplanar spacing (3-5 A) was observed for the intercalated phases. Insertion of one to two water molecules per intercalated metal atom was suggested as a possible explanation for this large expansion along the c-axis. Deintercalation of the hydrated alkali atoms and restacking of the MS(2) layers was observed in all the samples after prolonged exposure to the atmosphere. Electric field induced deintercalation of the alkali metal atoms from the host lattice was also observed by means of the XPS technique. Magnetic moment measurements for all the samples indicate a diamagnetic to paramagnetic transition after intercalation. Measurements of the transport properties reveal a semiconductor to metal transition for the heavily K intercalated 2H-MoS(2). Other samples show several orders of magnitude decrease in resistivity and two- to five-fold decrease in activation energies upon intercalation. These modifications are believed to occur via charge transfer from the alkali metal to the conduction band of the host lattice

  18. Metal pad instabilities in liquid metal batteries.

    PubMed

    Zikanov, Oleg

    2015-12-01

    A mechanical analogy is used to analyze the interaction between the magnetic field, electric current, and deformation of interfaces in liquid metal batteries. In the framework of a low-mode, nondissipative, linear stability model, it is found that, during charging or discharging, a sufficiently large battery is prone to instabilities of two types. One is similar to the metal pad instability known to exist in the aluminum reduction cells. Another type is new. It is related to the destabilizing effect of the Lorentz force formed by the azimuthal magnetic field induced by the base current, and the current perturbations caused by the local variations of the thickness of the electrolyte layer.

  19. Hydrometallurgical treatment of nickel-metal hydride battery electrodes

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

    Lyman, J.W.; Palmer, G.R.

    1995-12-31

    Nickel-metal hydride (Ni-MH) battery electrodes have been developed as a substitute for cadmium-containing negative electrodes. Use of NI-MH electrodes offers enhanced electrochemical properties in many instances as well as reduced environmental toxicity. Rechargeable batteries using NI-MH electrodes are also strong candidates for electric vehicles. During the production and secondary reclamation of these battery types, recycling procedures will be needed to prevent environmental impact caused by these wastes as well as to recover the value inherent in the scrap. The US Bureau of Mines (USBM) is investigating hydrometallurgical technology that separates and recovers purified metallic components from Ni-MH battery scrap ofmore » two types, AB{sub 2} and AB{sub 5}. An investigation of acid dissolution and metal recovery techniques has determined several processing alternatives that may be used to promote the successful recycling of much of the battery fabrication scrap and eventual secondary scrap. The metals recovered are Ni, Co, and rare earth metals. Although recovery techniques have been identified in principal, their applicability to mixed battery waste stream and economic attractiveness remain to be demonstrated.« less

  20. Calorimetric Study of Alkali Metal Ion (K +, Na +, Li +) Exchange in a Clay-Like MXene

    DOE PAGES

    Sharma, Geetu; Muthuswamy, Elayaraja; Naguib, Michael; ...

    2017-06-21

    Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. This work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti 3C 2T x, where T x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti 3C 2T x, ΔH imm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used tomore » obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na + and Li + ions. Water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.« less

  1. Calorimetric Study of Alkali Metal Ion (K +, Na +, Li +) Exchange in a Clay-Like MXene

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

    Sharma, Geetu; Muthuswamy, Elayaraja; Naguib, Michael

    Intercalation of ions in layered materials has been explored to improve the rate capability in Li-ion batteries and supercapacitors. This work investigates the energetics of alkali ion exchange in a clay-like MXene, Ti 3C 2T x, where T x stands for anionic surface moieties, by immersion calorimetry in aqueous solutions. The measured immersion enthalpies of clay-like Ti 3C 2T x, ΔH imm, at 25 °C in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.19 (±0.56), -5.90 (±0.31), -1.31 (±0.20), and -1.29 (±0.13) kJ/mol of MXene, respectively. Inductively coupled plasma mass spectrometry is used tomore » obtain the concentrations of alkali ions in the solid and aqueous phases. Using these concentrations, the enthalpies of exchange of alkali metal ions (Li+, Na+, and K+) are calculated; ΔHex in 1 M KCl, 1 M NaCl, 1 M LiCl, and nanopure water are -9.3 (±2.2), 21.0 (±0.9), -1.3 (±0.2), and 302.4 (±0.6) kJ/mol of MXene, respectively. Both immersion and exchange enthalpies are most exothermic for potassium. This suggests that K+ ions interact more strongly with anions present in the interlayers of this MXene than Na + and Li + ions. Water vapor adsorption calorimetry indicates very weak interaction of water with the MXene, while immersion calorimetry suggests a weakly hydrophilic nature of the MXene surface.« less

  2. Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

    PubMed

    Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

    2017-09-01

    High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Recycling of nickel-metal hydride battery scrap

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

    Lyman, J.W.; Palmer, G.R.

    1994-12-31

    Nickel-metal hydride (Ni-MH) battery technology is being developed as a NiCd replacement for applications in consumer cells and electric vehicle batteries. The U.S. Bureau of Mines is investigating hydrometallurgical recycling technology that separates and recovers individual components from Ni-MH battery scrap. Acid dissolution and metal recovery techniques such as precipitation and solvent extraction produced purified products of rare-earths, nickel, and other metals associated with AB{sub 2} and AB{sub 5} Ni-MH scrap. Tests were conducted on scrap cells of a single chemistry that had been de-canned to reduce iron content. Although recovery techniques have been identified in principal, their applicability tomore » mixed battery waste stream and economic attractiveness remain to be demonstrated. 14 refs.« less

  4. Evidence for alkali metal formation at a cathode interface of organic electroluminescent devices by thermal decomposition of alkali metal carboxylates during their vapor deposition

    NASA Astrophysics Data System (ADS)

    Ganzorig, Chimed; Fujihira, Masamichi

    2004-11-01

    This study examines the possibility of thermal decomposition of Na salts of acetate, benzoate, and fluoride during vacuum vapor deposition using a quartz crystal microbalance to measure negative frequency shift (Δf) caused by increasing mass deposited from the same amount of source materials. Cs acetate is also examined. We compare the negative frequency shift-source current (Δf -I) curves of the Na salts with those of organic materials such as tris(8-hydroxyquinoline)aluminum and N ,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine. CH3COONa and C6H5COONa exhibit much lower Δf than the organic materials. CH3COOCs gives much larger Δf than CH3COONa due to the higher atomic weight of Cs. These exhibit clear evidence for alkali metal formation by thermal decomposition during vapor deposition of alkali metal carboxylates.

  5. Thermodynamics of Liquid Alkali Metals and Their Binary Alloys

    NASA Astrophysics Data System (ADS)

    Thakor, P. B.; Patel, Minal H.; Gajjar, P. N.; Jani, A. R.

    2009-07-01

    The theoretical investigation of thermodynamic properties like internal energy, entropy, Helmholtz free energy, heat of mixing (ΔE) and entropy of mixing (ΔS) of liquid alkali metals and their binary alloys are reported in the present paper. The effect of concentration on the thermodynamic properties of Ac1Bc2 alloy of the alkali-alkali elements is investigated and reported for the first time using our well established local pseudopotential. To investigate influence of exchange and correlation effects, we have used five different local field correction functions viz; Hartree(H), Taylor(T), Ichimaru and Utsumi(IU), Farid et al. (F) and Sarkar et al. (S). The increase of concentration C2, increases the internal energy and Helmholtz free energy of liquid alloy Ac1Bc2. The behavior of present computation is not showing any abnormality in the outcome and hence confirms the applicability of our model potential in explaining the thermodynamics of liquid binary alloys.

  6. Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se2 solar cells on glass substrate

    NASA Astrophysics Data System (ADS)

    Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; Tayagaki, Takeshi; Guthrey, Harvey; Shibata, Hajime; Matsubara, Koji; Niki, Shigeru

    2018-03-01

    The precise control of alkali-metal concentrations in Cu(In,Ga)Se2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance from the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.

  7. Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se 2 solar cells on glass substrate

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

    Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo

    The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance frommore » the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.« less

  8. Effect of thermal annealing on the redistribution of alkali metals in Cu(In,Ga)Se 2 solar cells on glass substrate

    DOE PAGES

    Kamikawa, Yukiko; Nishinaga, Jiro; Ishizuka, Shogo; ...

    2018-03-07

    The precise control of alkali-metal concentrations in Cu(In,Ga)Se 2 (CIGS) solar cells via post deposition treatment (PDT) has recently attracted attention. When PDT is performed at an elevated temperature, an accompanying annealing effect is expected. Here, we investigate how thermal annealing affects the redistribution of alkali metals in CIGS solar cells on glass substrates and the properties of the solar cells. In addition, we investigate the origin of non-homogeneous alkali-metal depth profiles that are typical of CIGS grown using a three-stage process. In particular, we use secondary-ion mass spectrometry measurements of the ion concentration as a function of distance frommore » the CIGS surface to investigate the impact of thermal annealing on the distribution of alkali metals (Na, Ka, and Rb) and constituent elements (Ga and In) in the CIGS absorbers. We find that the depth profiles of the alkali metals strongly reflect the density of sites that tend to accommodate alkali metals, i.e., vacancies. Annealing at elevated temperature caused a redistribution of the alkali metals. The thermal-diffusion kinetics of alkali metals depends strongly on the species involved. We introduced low flux potassium fluoride (KF) to study a side effect of KF-PDT, i.e., Na removal from CIGS, separately from its predominant effects such as surface modification. When sufficient amounts of Na are supplied from the soda lime glass via annealing at an elevated temperature, the negative effect was not apparent. Conversely, when the Na supply was not sufficient, it caused a deterioration of the photovoltaic properties.« less

  9. Transversely diode-pumped alkali metal vapour laser

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

    Parkhomenko, A I; Shalagin, A M

    2015-09-30

    We have studied theoretically the operation of a transversely diode-pumped alkali metal vapour laser. For the case of high-intensity laser radiation, we have obtained an analytical solution to a complex system of differential equations describing the laser. This solution allows one to exhaustively determine all the energy characteristics of the laser and to find optimal parameters of the working medium and pump radiation (temperature, buffer gas pressure, and intensity and width of the pump spectrum). (lasers)

  10. Borohydride electro-oxidation in a molten alkali hydroxide eutectic mixture and a novel borohydride-periodate battery

    NASA Astrophysics Data System (ADS)

    Wang, Andrew; Gyenge, Előd L.

    2015-05-01

    The electrochemical oxidation of BH4- in a molten NaOH-KOH eutectic mixture (0.515:0.485 mole fractions), is investigated for the first time by cyclic voltammetry and electrochemical impedance spectroscopy. Anodically oxidized Ni is electrocatalytically more active than Pt for BH4- oxidation in the molten alkali electrolyte as shown by the more than three times higher exchange current density (i.e. 15.8 mA cm-2 vs. 4.6 mA cm-2 at 185 °C). Next the proof-of-concept for a novel BH4-/IO4- molten alkali electrolyte battery is presented. Using oxidized Ni mesh anode and Pt mesh cathode a maximum power density of 63 mW cm-2 is achieved at 185 °C.

  11. Theory of metal atom-water interactions and alkali halide dimers

    NASA Technical Reports Server (NTRS)

    Jordan, K. D.; Kurtz, H. A.

    1982-01-01

    Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

  12. High Energy-Density Electrodes for Alkali-Metal Battery Systems

    DTIC Science & Technology

    1977-11-29

    characteristics of real battery systems. In our laboratory, techniques for preparing well-characterized inter - calated Li TaS., and Na TaS. have been...to measure the variation of the chemical potential and diffusivity of sodium with composition x in Na TaSa where x varies from 0 to 1, 0, The...measure the chemical potential and diffusivity ■ Na (s)/Na (propylene carbonate)/Na TaSa (A) of sodium in Na TaSa . x Experimental Tantalum

  13. Thermal Coefficient of Redox Potential of Alkali Metals

    NASA Astrophysics Data System (ADS)

    Fukuzumi, Yuya; Hinuma, Yoyo; Moritomo, Yutaka

    2018-05-01

    The thermal coefficient (α) of redox potential (V) is a significant physical quantity that converts the thermal energy into electric energy. In this short note, we carefully determined α of alkali metals (A = Li and Na) against electrolyte solution. The obtained α is much larger than that expected from the specific heat (CpA) of solid A and depends on electrolyte solution. These observations indicate that the solvent has significant effect on α.

  14. Coordination effect-regulated CO2 capture with an alkali metal onium salts/crown ether system

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

    Yang, Zhen-Zhen; Jiang, Deen; Zhu, Xiang

    2014-01-01

    A coordination effect was employed to realize equimolar CO2 absorption, adopting easily synthesized amino group containing absorbents (alkali metal onium salts). The essence of our strategy was to increase the steric hindrance of cations so as to enhance a carbamic acid pathway for CO2 capture. Our easily synthesized alkali metal amino acid salts or phenolates were coordinated with crown ethers, in which highly sterically hindered cations were obtained through a strong coordination effect of crown ethers with alkali metal cations. For example, a CO2 capacity of 0.99 was attained by potassium prolinate/18-crown-6, being characterized by NMR, FT-IR, and quantum chemistrymore » calculations to go through a carbamic acid formation pathway. The captured CO2 can be stripped under very mild conditions (50 degrees C, N-2). Thus, this protocol offers an alternative for the development of technological innovation towards efficient and low energy processes for carbon capture and sequestration.« less

  15. Design principles for electrolytes and interfaces for stable lithium-metal batteries

    NASA Astrophysics Data System (ADS)

    Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan; Archer, Lynden A.

    2016-09-01

    The future of electrochemical energy storage hinges on the advancement of science and technology that enables rechargeable batteries that utilize reactive metals as anodes. With specific capacity more than ten times that of the LiC6 anode used in present-day lithium-ion batteries, cells based on Li-metal anodes are of particular interest. Effective strategies for stabilizing the anode in such cells are now understood to be a requirement for progress on exceptional storage technologies, including Li-S and Li-O2 batteries. Multiple challenges—parasitic reactions of Li-metal with liquid electrolytes, unstable and dendritic electrodeposition, and dendrite-induced short circuits—derailed early efforts to commercialize such lithium-metal batteries. Here we consider approaches for rationally designing electrolytes and Li-metal/electrolyte interfaces for stable, dendrite-free operation of lithium-metal batteries. On the basis of fundamental understanding of the failure modes of reactive metal anodes, we discuss the key variables that govern the stability of electrodeposition at the Li anode and propose a universal framework for designing stable electrolytes and interfaces for lithium-metal batteries.

  16. Understanding the initial irreversibility of metal sulfides for sodium-ion batteries via operando techniques

    DOE PAGES

    Wang, Liguang; Wang, Jiajun; Guo, Fangmin; ...

    2018-11-13

    Transition metal sulfides are promising high capacity anodes for sodium-ion batteries in terms of the conversion reaction with multiple alkali metal ions. Nonetheless, some inherent challenges such as sluggish sodium ion diffusion kinetics, large volume change, and poor cycle stability limit their implementation. Addressing these issues necessitates a comprehensive understanding the complex sodium ion storage mechanism particularly at the initial cycle. Here, taking nickel subsulfide as a model material, we reveal the complicated conversion reaction mechanism upon the first cycle by combining in operando 2D transmission X-ray microscopy with X-ray absorption spectroscopy, ex-situ 3D nano-tomography, high-energy X-ray diffraction and electrochemicalmore » impedance spectroscopy. This study demonstrates that the microstructure evolution, inherent slow sodium ions diffusion kinetics, and slow ion mobility at the two-phase interface contribute to the high irreversible capacity upon the first cycle. Finally, such understandings are critical for developing the conversion reaction materials with the desired electrochemical activity and stability.« less

  17. Understanding the initial irreversibility of metal sulfides for sodium-ion batteries via operando techniques

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

    Wang, Liguang; Wang, Jiajun; Guo, Fangmin

    Transition metal sulfides are promising high capacity anodes for sodium-ion batteries in terms of the conversion reaction with multiple alkali metal ions. Nonetheless, some inherent challenges such as sluggish sodium ion diffusion kinetics, large volume change, and poor cycle stability limit their implementation. Addressing these issues necessitates a comprehensive understanding the complex sodium ion storage mechanism particularly at the initial cycle. Here, taking nickel subsulfide as a model material, we reveal the complicated conversion reaction mechanism upon the first cycle by combining in operando 2D transmission X-ray microscopy with X-ray absorption spectroscopy, ex-situ 3D nano-tomography, high-energy X-ray diffraction and electrochemicalmore » impedance spectroscopy. This study demonstrates that the microstructure evolution, inherent slow sodium ions diffusion kinetics, and slow ion mobility at the two-phase interface contribute to the high irreversible capacity upon the first cycle. Finally, such understandings are critical for developing the conversion reaction materials with the desired electrochemical activity and stability.« less

  18. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4663...

  19. Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores

    PubMed Central

    Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D.; Hill, Anita J.; Wang, Huanting

    2018-01-01

    Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future. PMID:29487910

  20. Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores.

    PubMed

    Zhang, Huacheng; Hou, Jue; Hu, Yaoxin; Wang, Peiyao; Ou, Ranwen; Jiang, Lei; Liu, Jefferson Zhe; Freeman, Benny D; Hill, Anita J; Wang, Huanting

    2018-02-01

    Porous membranes with ultrafast ion permeation and high ion selectivity are highly desirable for efficient mineral separation, water purification, and energy conversion, but it is still a huge challenge to efficiently separate monatomic ions of the same valence and similar sizes using synthetic membranes. We report metal organic framework (MOF) membranes, including ZIF-8 and UiO-66 membranes with uniform subnanometer pores consisting of angstrom-sized windows and nanometer-sized cavities for ultrafast selective transport of alkali metal ions. The angstrom-sized windows acted as ion selectivity filters for selection of alkali metal ions, whereas the nanometer-sized cavities functioned as ion conductive pores for ultrafast ion transport. The ZIF-8 and UiO-66 membranes showed a LiCl/RbCl selectivity of ~4.6 and ~1.8, respectively, which are much greater than the LiCl/RbCl selectivity of 0.6 to 0.8 measured in traditional porous membranes. Molecular dynamics simulations suggested that ultrafast and selective ion transport in ZIF-8 was associated with partial dehydration effects. This study reveals ultrafast and selective transport of monovalent ions in subnanometer MOF pores and opens up a new avenue to develop unique MOF platforms for efficient ion separations in the future.

  1. [On-line analysis and mass concentration characters of the alkali metal ions of PM10 in Beijing].

    PubMed

    Zhang, Kai; Wang, Yue-Si; Wen, Tian-Xue; Liu, Guang-Ren; Hu, Bo; Zhao, Ya-Nan

    2008-01-01

    The mass concentration characters and the sources of water-soluble alkali metal ions in PM10 in 2004 and 2005 in Beijing were analyzed by using the system of rapid collection of particles. The result showed that the average concentration of Na+, K+, Mg2+ and Ca2+ was 0.5-1.4, 0.5-2.5, 0.1-0.5 and 0.6-5.8 microg/m3, respectively. The highest and lowest concentration appeared in different seasons for the alkali metal ions, which was related to the quality and source. The concentration of alkali metal ions was no difference between the heating period and no heating period, which meant the heating was not the main source. Sea salt and soil were the important sources of Na+. The source of K+ came from biomass burning and vegetation. Soil was the large source of Mg2+ and Ca2+. The alkali metal ions appeared different daily variation in different seasons. Precipitation could decrease the concentration of Na+, K+, Mg2+ and Ca2+, which was 10%-70%, 20%-80%, 10%-77%, 5%-80% respectively.

  2. Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

    PubMed

    Yin, Jun; Hu, Ying; Yoon, Juyoung

    2015-07-21

    All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

  3. Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

    PubMed

    Cheng, Fangyi; Chen, Jun

    2012-03-21

    Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

  4. Reactive Precipitation of Anhydrous Alkali Sulfide Nanocrystals with Concomitant Abatement of Hydrogen Sulfide and Cogeneration of Hydrogen.

    PubMed

    Li, Xuemin; Zhao, Yangzhi; Brennan, Alice; McCeig, Miranda; Wolden, Colin A; Yang, Yongan

    2017-07-21

    Anhydrous alkali sulfide (M 2 S, M=Li or Na) nanocrystals (NCs) are important materials central to the development of next generation cathodes and solid-state electrolytes for advanced batteries, but not commercially available at present. This work reports an innovative method to directly synthesize M 2 S NCs through alcohol-mediated reactions between alkali metals and hydrogen sulfide (H 2 S). In the first step, the alkali metal is complexed with alcohol in solution, forming metal alkoxide (ROM) and releasing hydrogen (H 2 ). Next, H 2 S is bubbled through the ROM solution, where both chemicals are completely consumed to produce phase-pure M 2 S NC precipitates and regenerate alcohol that can be recycled. The M 2 S NCs morphology may be tuned through the choice of the alcohol and solvent. Both synthetic steps are thermodynamically favorable (ΔG m o <-100 kJ mol -1 ), proceeding rapidly to completion at ambient temperature with almost 100 % atom efficiency. The net result, H 2 S+2 m→M 2 S+H 2 , makes good use of a hazardous chemical (H 2 S) and delivers two value-added products that naturally phase separate for easy recovery. This scalable approach provides an energy-efficient and environmentally benign solution to the production of nanostructured materials required in emerging battery technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Suppression of dendritic lithium growth in lithium metal-based batteries.

    PubMed

    Li, Linlin; Li, Siyuan; Lu, Yingying

    2018-06-19

    Lithium metal-based batteries offer promising prospects as alternatives to today's lithium-ion batteries, due to their ultra-high energy density. Unfortunately, the application of lithium metal is full of challenges and has puzzled researchers for more than 40 years. In this feature article, we describe the history of the development of lithium metal batteries and their existing key challenges, which include non-uniform electrodeposition, volume expansion, high reactivity of the lithium metal/unstable solid electrolyte interphase (SEI), and the shuttling of active cathode materials. Then, we focus on the growth mechanisms of uneven lithium electrodeposition and extend the discussion to the approaches to inhibit lithium dendrites. Finally, we discuss future directions that are expected to drive progress in the development of lithium metal batteries.

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

    PubMed

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

    2018-04-09

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

  7. Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

    PubMed

    Tang, Hongjian; Duan, Yufeng; Zhu, Chun; Cai, Tianyi; Li, Chunfeng; Cai, Liang

    2017-10-01

    Alkali metal-based sorbents are potential for oxidized mercury (Hg 2+ ) selective adsorption but show hardly effect to elemental mercury (Hg 0 ) in flue gas. Density functional theory (DFT) was employed to investigate the Hg 0 and HgCl 2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg 0 was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl 2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl 2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl 2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl 2 is identified as a Lewis acid and more reactive than Hg 0 . The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl 2 adsorption energies. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOEpatents

    Joshi, Ashok V [Salt Lake City, UT; Balagopal, Shekar [Sandy, UT; Pendelton, Justin [Salt Lake City, UT

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  9. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases

    PubMed Central

    Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

    2015-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin. PMID:26839810

  10. Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

    NASA Astrophysics Data System (ADS)

    Gökçe, Aytaç Gürhan; Ersan, Fatih

    2017-01-01

    First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

  11. Design principles for electrolytes and interfaces for stable lithium-metal batteries

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

    Tikekar, Mukul D.; Choudhury, Snehashis; Tu, Zhengyuan

    2016-09-08

    The future of electrochemical energy storage hinges on the advancement of science and technology that enables rechargeable batteries that utilize reactive metals as anodes. With specific capacity more than ten times that of the LiC6 anode used in present-day lithium-ion batteries, cells based on Li-metal anodes are of particular interest. Effective strategies for stabilizing the anode in such cells are now understood to be a requirement for progress on exceptional storage technologies, including Li–S and Li–O2 batteries. Multiple challenges—parasitic reactions of Li-metal with liquid electrolytes, unstable and dendritic electrodeposition, and dendrite-induced short circuits—derailed early efforts to commercialize such lithium-metal batteries.more » Here we consider approaches for rationally designing electrolytes and Li-metal/electrolyte interfaces for stable, dendrite-free operation of lithium-metal batteries. On the basis of fundamental understanding of the failure modes of reactive metal anodes, we discuss the key variables that govern the stability of electrodeposition at the Li anode and propose a universal framework for designing stable electrolytes and interfaces for lithium-metal batteries.« less

  12. Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

    PubMed

    Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

    2017-06-01

    We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

  13. Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

    PubMed

    Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

    2017-07-18

    The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Polymeric metallic electrodes for rechargeable battery applications

    NASA Technical Reports Server (NTRS)

    Somoano, R.

    1982-01-01

    A review is presented on the status of plastic metal electrodes, emphasizing the use of polyacetylene as a prototype polymeric material. The electrochemical characteristics of polyacetylene are examined; and the potential use of this material, as well as other types of plastic metal electrodes, in batteries is evaluated. Several problem areas which must be solved before polyacetylene can be widely used in battery applications are discussed, including the problem of electrolyte stability, the problem that the depth of discharge and the energy density is limited by the metal-semiconductor transition, and also the poor electrochemical performance of impure material.

  15. Crystallized alkali-silica gel in concrete from the late 1890s

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

    Peterson, Karl; Gress, David; Van Dam, Tom

    The Elon Farnsworth Battery, a concrete structure completed in 1898, is in an advanced state of disrepair. To investigate the potential for rehabilitation, cores were extracted from the battery. Petrographic examination revealed abundant deposits of alkali silica reaction products in cracks associated with the quartz rich metasedimentary coarse aggregate. The products of the alkali silica reaction are variable in composition and morphology, including both amorphous and crystalline phases. The crystalline alkali silica reaction products are characterized by quantitative X-ray energy dispersive spectrometry (EDX) and X-ray diffraction (XRD). The broad extent of the reactivity is likely due to elevated alkali levelsmore » in the cements used.« less

  16. Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes.

    PubMed

    Wang, Zhong-Li; Xu, Dan; Xu, Ji-Jing; Zhang, Xin-Bo

    2014-11-21

    With the development of renewable energy and electrified transportation, electrochemical energy storage will be more important in the future than it has ever been in the past. Although lithium-ion batteries (LIBs) are traditionally considered to be the most likeliest candidate thanks to their relatively long cycle life and high energy efficiency, their limited energy density as well as cost are still causing a bottleneck for their long-term application. Alternatively, metal-air batteries have been proposed as a very promising large-scale electricity storage technology with the replacement of the intercalation reaction mechanism by the catalytic redox reaction of a light weight metal-oxygen couple. Generally, based on the electrolyte, these metal-air batteries can be divided into aqueous and nonaqueous systems, corresponding to two typical batteries of Zn-air and Li-air, respectively. The prominent feature of both batteries are their extremely high theoretical energy density, especially for nonaqueous Li-air batteries, which far exceeds the best that can be achieved with LIBs. In this review, we focus on the major obstacle of sluggish kinetics of the cathode in both batteries, and summarize the fundamentals and recent advances related to the oxygen catalyst materials. According to the electrolyte, the aqueous and nonaqueous electrocatalytic mechanisms of the oxygen reduction and evolution reactions are discussed. Subsequently, seven groups of oxygen catalysts, which have played catalytic roles in both systems, are selectively reviewed, including transition metal oxides (single-metal oxides and mixed-metal oxides), functional carbon materials (nanostructured carbons and doped carbons), metal oxide-nanocarbon hybrid materials, metal-nitrogen complexes (non-pyrolyzed and pyrolyzed), transition metal nitrides, conductive polymers, and precious metals (alloys). Nonaqueous systems have the advantages of energy density and rechargeability over aqueous systems and have

  17. A nickel metal hydride battery for electric vehicles

    NASA Astrophysics Data System (ADS)

    Ovshinsky, S. R.; Fetcenko, M. A.; Ross, J.

    1993-04-01

    An efficient battery is the key technological element to the development of practical electric vehicles. The science and technology of a nickel metal hydride battery, which stores hydrogen in the solid hydride phase and has high energy density, high power, long life, tolerance to abuse, a wide range of operating temperature, quick-charge capability, and totally sealed maintenance-free operation, is described. A broad range of multi-element metal hydride materials that use structural and compositional disorder on several scales of length has been engineered for use as the negative electrode in this battery. The battery operates at ambient temperature, is made of nontoxic materials, and is recyclable. Demonstration of the manufacturing technology has been achieved.

  18. Two-Dimensional Metal Oxide Nanomaterials for Next-Generation Rechargeable Batteries.

    PubMed

    Mei, Jun; Liao, Ting; Kou, Liangzhi; Sun, Ziqi

    2017-12-01

    The exponential increase in research focused on two-dimensional (2D) metal oxides has offered an unprecedented opportunity for their use in energy conversion and storage devices, especially for promising next-generation rechargeable batteries, such as lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs), as well as some post-lithium batteries, including lithium-sulfur batteries, lithium-air batteries, etc. The introduction of well-designed 2D metal oxide nanomaterials into next-generation rechargeable batteries has significantly enhanced the performance of these energy-storage devices by providing higher chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier-/charge-transport kinetics, which have greatly promoted the development of nanotechnology and the practical application of rechargeable batteries. Here, the recent progress in the application of 2D metal oxide nanomaterials in a series of rechargeable LIBs, NIBs, and other post lithium-ion batteries is reviewed relatively comprehensively. Current opportunities and future challenges for the application of 2D nanomaterials in energy-storage devices to achieve high energy density, high power density, stable cyclability, etc. are summarized and outlined. It is believed that the integration of 2D metal oxide nanomaterials in these clean energy devices offers great opportunities to address challenges driven by increasing global energy demands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Bending-Tolerant Anodes for Lithium-Metal Batteries.

    PubMed

    Wang, Aoxuan; Tang, Shan; Kong, Debin; Liu, Shan; Chiou, Kevin; Zhi, Linjie; Huang, Jiaxing; Xia, Yong-Yao; Luo, Jiayan

    2018-01-01

    Bendable energy-storage systems with high energy density are demanded for conformal electronics. Lithium-metal batteries including lithium-sulfur and lithium-oxygen cells have much higher theoretical energy density than lithium-ion batteries. Reckoned as the ideal anode, however, Li has many challenges when directly used, especially its tendency to form dendrite. Under bending conditions, the Li-dendrite growth can be further aggravated due to bending-induced local plastic deformation and Li-filaments pulverization. Here, the Li-metal anodes are made bending tolerant by integrating Li into bendable scaffolds such as reduced graphene oxide (r-GO) films. In the composites, the bending stress is largely dissipated by the scaffolds. The scaffolds have increased available surface for homogeneous Li plating and minimize volume fluctuation of Li electrodes during cycling. Significantly improved cycling performance under bending conditions is achieved. With the bending-tolerant r-GO/Li-metal anode, bendable lithium-sulfur and lithium-oxygen batteries with long cycling stability are realized. A bendable integrated solar cell-battery system charged by light with stable output and a series connected bendable battery pack with higher voltage is also demonstrated. It is anticipated that this bending-tolerant anode can be combined with further electrolytes and cathodes to develop new bendable energy systems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The Alkali Metal Thermal-To-Electric Converter for Solar System Exploration

    NASA Technical Reports Server (NTRS)

    Ryan, M.

    1999-01-01

    AMTEC, the Alkali Metal Thermal to Electric Converter, is a direct thermal to electric energy conversion device; it has been demostrated to perform at high power densities, with open circuit voltages in single electrochemical cells up to 1.6 V and current desities up to 2.0 A/cm(sup 2).

  1. Molybdenum cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures

    NASA Astrophysics Data System (ADS)

    Matsuda, Kazuhiro; Tamura, Kozaburo; Katoh, Masahiro; Inui, Masanori

    2004-03-01

    We have developed a sample cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures. All parts of the cell are made of molybdenum which is resistant to the chemical corrosion of alkali metals. Single crystalline molybdenum disks electrolytically thinned down to 40 μm were used as the walls of the cell through which x rays pass. The crystal orientation of the disks was controlled in order to reduce the background from the cell. All parts of the cell were assembled and brazed together using a high-temperature Ru-Mo alloy. Energy dispersive x-ray diffraction measurements have been successfully carried out for fluid rubidium up to 1973 K and 16.2 MPa. The obtained S(Q) demonstrates the applicability of the molybdenum cell to x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures.

  2. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    NASA Astrophysics Data System (ADS)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  3. Investigating the effects of alkali metal Na addition on catalytic activity of HZSM-5 for methyl mercaptan elimination

    NASA Astrophysics Data System (ADS)

    Yu, Jie; He, Dedong; Chen, Dingkai; Liu, Jiangping; Lu, Jichang; Liu, Feng; Liu, Pan; Zhao, Yutong; Xu, Zhizhi; Luo, Yongming

    2017-10-01

    Na-modified HZSM-5 catalysts with different Na loading amounts were prepared by incipient-wetness impregnation method and their catalytic activities for methyl mercaptan catalytic elimination were analyzed. XRD, N2 adsorption-desorption, NH3-TPD, CO2-TPD and FT-IR measurements were carried out to investigate the effects of modification of alkali metal Na on the physicochemical properties of the HZSM-5 zeolite catalyst. Research results illustrated that the introduction of alkali metal Na can improve catalytic activity for CH3SH catalytic elimination. CH3SH can be almost completely converted over 3%-Na/HZSM-5 at 450 °C compared to pure HZSM-5 at 600 °C based on our experimental results and the results from previous research. The improved catalytic activity could be attributed to the regulated acid-base properties of the HZSM-5 catalysts by doping with alkali metal Na. High alkali concentration treatment, however, may destroy the framework structure of the catalyst sample, thus causing the poor stability performance of the obtained catalyst.

  4. Element specificity of ortho-positronium annihilation for alkali-metal loaded SiO2 glasses.

    PubMed

    Sato, K; Hatta, T

    2015-03-07

    Momentum distributions associated with ortho-positronium (o-Ps) pick-off annihilation photon are often influenced by light elements, as, e.g., carbon, oxygen, and fluorine. This phenomenon, so-called element specificity of o-Ps pick-off annihilation, has been utilized for studying the elemental environment around the open spaces. To gain an insight into the element specificity of o-Ps pick-off annihilation, the chemical shift of oxygen 1s binding energy and the momentum distributions associated with o-Ps pick-off annihilation were systematically investigated for alkali-metal loaded SiO2 glasses by means of X-ray photoelectron spectroscopy and positron-age-momentum correlation spectroscopy, respectively. Alkali metals introduced into the open spaces surrounded by oxygen atoms cause charge transfer from alkali metals to oxygen atoms, leading to the lower chemical shift for the oxygen 1s binding energy. The momentum distribution of o-Ps localized into the open spaces is found to be closely correlated with the oxygen 1s chemical shift. This correlation with the deepest 1s energy level evidences that the element specificity of o-Ps originates from pick-off annihilation with orbital electrons, i.e., dominantly with oxygen 2p valence electrons and s electrons with lower probability.

  5. Liquid metal batteries - materials selection and fluid dynamics

    NASA Astrophysics Data System (ADS)

    Weier, T.; Bund, A.; El-Mofid, W.; Horstmann, G. M.; Lalau, C.-C.; Landgraf, S.; Nimtz, M.; Starace, M.; Stefani, F.; Weber, N.

    2017-07-01

    Liquid metal batteries are possible candidates for massive and economically feasible large-scale stationary storage and as such could be key components of future energy systems based mainly or exclusively on intermittent renewable electricity sources. The completely liquid interior of liquid metal batteries and the high current densities give rise to a multitude of fluid flow phenomena that will primarily influence the operation of future large cells, but might be important for today’s smaller cells as well. The paper at hand starts with a discussion of the relative merits of using molten salts or ionic liquids as electrolytes for liquid metal cells and touches the choice of electrode materials. This excursus into electrochemistry is followed by an overview of investigations on magnetohydrodynamic instabilities in liquid metal batteries, namely the Tayler instability and electromagnetically excited gravity waves. A section on electro-vortex flows complements the discussion of flow phenomena. Focus of the flow related investigations lies on the integrity of the electrolyte layer and related critical parameters.

  6. A Study of the Hydration of the Alkali Metal Ions in Aqueous Solution

    PubMed Central

    2011-01-01

    The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O–D stretching bands of partially deuterated water bound to these metal ions and the O–D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M–O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M–O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M–O bond distances and coordination numbers also for the alkali metal ions even though the M–O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M–O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) Å, which corresponds to six-, seven-, eight- and

  7. Alkali-metal silicate binders and methods of manufacture

    NASA Technical Reports Server (NTRS)

    Schutt, J. B. (Inventor)

    1979-01-01

    A paint binder is described which uses a potassium or sodium silicate dispersion having a silicon dioxide to alkali-metal oxide mol ratio of from 4.8:1 to 6.0:1. The binder exhibits stability during both manufacture and storage. The process of making the binder is predictable and repeatable and the binder may be made with inexpensive components. The high mol ratio is achieved with the inclusion of a silicon dioxide hydrogel. The binder, which also employs a silicone, is in the final form of a hydrogel sol.

  8. Study of the reaction of tungsten carbide in molten alkali metal nitrates. Syntheses of divalent (s and d blocks) metal tungstates

    NASA Astrophysics Data System (ADS)

    Deloume, Jean-Pierre; Marote, Pedro; Sigala, Catherine; Matei, Cristian

    2003-08-01

    WC is tested as precursor to synthesize metal tungstates by reaction in molten alkali metal nitrates. This constitutes a complex redox system with two reducing agents, W and C, and an oxidizer having several oxidation states. The mass loss due to the evolution of gases reveals the reaction steps. The infrared analyses of the gas phase show what kind of reaction develops according to the temperature. WC produces a water-soluble alkali metal tungstate. The reaction of a mixture of WC and a divalent metal chloride (Mg, Ca, Ba, Ni, Cu, Zn) leads to water-insoluble metal tungstates. As the reactivity of the cations increases in the order Zn, Ni, Cu, the reaction of WC is modified by their presence. The physico-chemical characterizations of the products show that some of them are contaminated either by WC or by metal oxide. Some others are rather pure products. These differences, in relationship with the other analyses, allow to propose first reaction pathways of the tungsten carbide in molten salts.

  9. Metal chloride cathode for a battery

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V. (Inventor); Distefano, Salvador (Inventor); Bankston, C. Perry (Inventor)

    1991-01-01

    A method of fabricating a rechargeable battery is disclosed which includes a positive electrode which contains a chloride of a selected metal when the electrode is in its active state. The improvement comprises fabricating the positive electrode by: providing a porous matrix composed of a metal; providing a solution of the chloride of the selected metal; and impregnating the matrix with the chloride from the solution.

  10. Sodium-metal chloride batteries

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Attia, A. I.; Halpert, G.

    1992-01-01

    It was concluded that rapid development in the technology of sodium metal chloride batteries has been achieved in the last decade mainly due to the: expertise available with sodium sulfur system; safety; and flexibility in design and fabrication. Long cycle lives of over 1000 and high energy densities of approx. 100 Wh/kg have been demonstrated in both Na/FeCl2 and Na/NiCl2 cells. Optimization of porous cathode and solid electrolyte geometries are essential for further enhancing the battery performance. Fundamental studies confirm the capabilities of these systems. Nickel dichloride emerges as the candidate cathode material for high power density applications such as electric vehicle and space.

  11. Mixed Polyanion Glass Cathodes: Mixed Alkali Effect

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

    Kercher, A. K.; Chapel, A. S.; Kolopus, J. A.

    2017-01-01

    In lithium-ion batteries, mixed polyanion glass cathodes have demonstrated high capacities (200-500 mAh/g) by undergoing conversion and intercalation reactions. Mixed polyanion glasses typically have the same fundamental issues as other conversion cathodes, i.e.: large hysteresis, capacity fade, and 1st-cycle irreversible loss. A key advantage of glass cathodes is the ability to tailor their composition to optimize the desired physical properties and electrochemical performance. The strong dependence of glass physical properties (e.g., ionic diffusivity, electrical conductivity, and chemical durability) on the composition of alkali mixtures in a glass is well known and has been named the mixed alkali effect. The mixedmore » alkali effect on battery electrochemical properties is reported here for the first time. Depending on glass composition, the mixed alkali effect is shown to improve capacity retention during cycling (from 39% to 50% after 50 cycle test), to reduce the 1st-cycle irreversible loss (from 41% to 22%), and improve the high power (500 mA/g) capacity (from 50% to 67% of slow discharge capacity).« less

  12. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-31

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  13. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOEpatents

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  14. The solvated electron battery

    NASA Astrophysics Data System (ADS)

    Bennett, J.; Harney, D.; Mitchell, T.

    A novel ambient temperture secondary battery using sodium and sulfur dissolved in liquid ammonia is being developed at ELTECH Systems corpooration. The key element of the system is the solvated electron electrode, a metallic liquid which is formed by ammonia and a number of alkali and alkaline earth metals. These solutions are excellent ionic and electronic conductors and have been shown to contain 'free' solvated electrons as the anionic species in solution. Sulfur was chosen as the cathodic reactant because of its high solubility in ammonia, and also because of the high solubiity and good conductivity of the polysulfide reaction products. Development efforts have thus far concentrated on basic electrochemical measurements and establishment of system feasibility.

  15. Metal sulfide for battery applications

    NASA Astrophysics Data System (ADS)

    Guidotti, Ronald A.

    1988-08-01

    A number of metal sulfides can be used in batteries as a cathode (reducible) material as part of an electrochemical couple to provide energy. There are a number of physical and chemical characteristics that can be evaluated for screening potential candidates for use in batteries. These include: cell potential vs. Li, thermal and chemical stability, electrical conductivity, allotropic form (phase), reaction kinetics during discharge, type of discharge mechanism, and material rechargeability. These are reviewed in general, with emphasis on sulfides of copper, iron, and molybdenum which are currently being used as cathodes in Li and Li-alloy batteries. The presence of impurities can adversely impact performance when naturally occurring sulfide minerals are used for battery applications. Sandia National Laboratories uses natural pyrite (FeS2) for its high-temperature, thermally activated Li(Si)/FeS2 batteries. The purification and processing procedures for the FeS2 involves both chemical and physical methods. Flotation was found to yield comparable results as HF leaching for removal of silica, but without the negative health and environmental concerns associated with this technique.

  16. Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

    PubMed

    Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

    2016-02-01

    The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. pH tunability and influence of alkali metal basicity on the plasmonic resonance of silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Yadav, Vijay D.; Akhil Krishnan, R.; Borade, Lalit; Shirolikar, Seema; Jain, Ratnesh; Dandekar, Prajakta

    2017-07-01

    Localized surface plasmon resonance has been a unique and intriguing feature of silver nanoparticles (AgNPs) that has attracted immense attention. This has led to an array of applications for AgNPs in optics, sensors, plasmonic imaging etc. Although numerous applications have been reported consistently, the importance of buffer and reaction parameters during the synthesis of AgNPs, is still unclear. In the present study, we have demonstrated the influence of parameters like pH, temperature and buffer conditions (0.1 M citrate buffer) on the plasmonic resonance of AgNPs. We found that neutral and basic pH (from alkali metal) provide optimum interaction conditions for nucleation of plasmon resonant AgNPs. Interestingly, this was not observed in the non-alkali metal base (ammonia). Also, when the nanoparticles synthesized from alkali metal base were incorporated in different buffers, it was observed that the nanoparticles dissolved in the acidic buffer and had reduced plasmonic resonance intensity. This, however, was resolved in the basic buffer, increasing the plasmonic resonance intensity and confirming that nucleation of nanoparticles required basic conditions. The above inference has been supported by characterization of AgNPs using UV-Vis spectrophotometer, Fluorimetry analysis, Infrared spectrometer and TEM analysis. The study concluded that the plasmonic resonance of AgNPs occurs due to the interaction of alkali (Na) and transition metal (Ag) salt in basic/neutral conditions, at a specific temperature range, in presence of a capping agent (citric acid), providing a pH tune to the overall system.

  18. Alternate cathodes for sodium-metal chloride batteries

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Attia, A. I.; Halpert, G.

    1991-01-01

    Various metal chlorides were tested as possible cathode materials for sodium-metal batteries (in addition to Fe and Ni chlorides, which have been already developed to a stage of commercialization), using an electrochemical cell consisting of a pyrex tube, heated to 250 C, with the metal wire as working electrode, concentric Ni foil as counterelectrode, and high-purity Al as reference electrode. In particular, the aim of this study was to identify metal chlorides insoluble even in neutral melts, possible at the interface during overcharge, in order to eliminate the failure mode of the cell through a cationic exchange of the dissolved metal ions with sodium beta-double-prime alumina solid electrolyte. Results indicate that Mo and Co are likely alternatives to FeCl2 and NiCl2 cathodes in sodium batteries. The open circuit voltages of Na/CoCl(x) and Na/MoCl(x) cells at 250 C would be 2.55 V and 2.64 V, respectively.

  19. Impact on global metal flows arising from the use of portable rechargeable batteries.

    PubMed

    Rydh, Carl Johan; Svärd, Bo

    2003-01-20

    The use of portable rechargeable battery cells and their effects on global metal flows were assessed or the following three cases: (1) the base case, which reflects the situation in 1999 of the global production of batteries; (2) the global production of portable nickel-cadmium batteries in 1999, assumed to be replaced by other battery types; and (3) assessment of the projected battery market in 2009. The study included the following battery technologies: nickel-cadmium (NiCd); nickel-metal hydride (NiMH) (AB(5), AB(2)); and lithium-based batteries (Li-ion: Co, Ni, Mn; Li-polymer: V). Based on the lithospheric extraction indicator (LEI), which is the ratio of anthropogenic to natural metal flows, and the significance of battery production related to global metal mining, the potential environmental impact of metals used in different battery types was evaluated. The LEIs and average metal demand for the battery market in 1999, expressed as a percentage of global mining output in 1999, were estimated to be as follows: Ni 5.6 (2.0%); Cd 4.4 (37%); Li 0.65 (3.8%); V 0.33 (6.5%); Co 0.18 (15%); Nd 0.18 (8.4%); La 0.10 (9.5%); Ce 0.083 (4.4%); and Pr 0.073 (9.4%). The use of Ni and Cd is of the greatest environmental interest, due to their high LEIs. In the case of complete replacement of portable NiCd batteries by NiMH or Li-based batteries, the LEI for Ni (5.6) would change by -0.1-0.5% and the LEI for Cd would decrease from 4.4 to 3.0 (-31%). Meanwhile, the mobilization of metals considered less hazardous than Cd (LEI 0 < 5) would increase less than 7%. Based on this assessment, the replacement of NiCd batteries would result in decreased environmental impact. To decrease the impact on global metal flows arising from the use of portable batteries the following points should be considered: (1) development of battery technologies should aim at high energy density and long service life; (2) metals with high natural occurrence should be used; and (3) metals from disused

  20. Internally folded expanded metal electrode for battery construction

    NASA Technical Reports Server (NTRS)

    Pierce, Doug C. (Inventor); Korinek, Paul D. (Inventor); Morgan, Maurice C. (Inventor)

    1993-01-01

    A battery system is disclosed which includes folded grids of expanded metal inserted through non-conductive substrates and pasted with electrochemically active materials. In the most preferred embodiment, a frame is provided with a plastic insert, and slots are provided in the latter to receive the expanded metal grid. After suitable coinage of the grid and insertion through the plastic film, the grid is sealed and pasted on opposite sides with positive and negative active material. A battery is assembled using one or a plurality of the resulting electrode elements, with separators, to produce a high-power, lead-acid battery. The folded grid provides many of the design benefits of standard bipolar construction.

  1. Stabilizing lithium metal using ionic liquids for long-lived batteries

    PubMed Central

    Basile, A.; Bhatt, A. I.; O'Mullane, A. P.

    2016-01-01

    Suppressing dendrite formation at lithium metal anodes during cycling is critical for the implementation of future lithium metal-based battery technology. Here we report that it can be achieved via the facile process of immersing the electrodes in ionic liquid electrolytes for a period of time before battery assembly. This creates a durable and lithium ion-permeable solid–electrolyte interphase that allows safe charge–discharge cycling of commercially applicable Li|electrolyte|LiFePO4 batteries for 1,000 cycles with Coulombic efficiencies >99.5%. The tailored solid–electrolyte interphase is prepared using a variety of electrolytes based on the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide room temperature ionic liquid containing lithium salts. The formation is both time- and lithium salt-dependant, showing dynamic morphology changes, which when optimized prevent dendrite formation and consumption of electrolyte during cycling. This work illustrates that a simple, effective and industrially applicable lithium metal pretreatment process results in a commercially viable cycle life for a lithium metal battery. PMID:27292652

  2. Electronic and structural ground state of heavy alkali metals at high pressure

    DOE PAGES

    Fabbris, G.; Lim, J.; Veiga, L. S. I.; ...

    2015-02-17

    Here, alkali metals display unexpected properties at high pressure, including emergence of low symmetry crystal structures, that appear to occur due to enhanced electronic correlations among the otherwise nearly-free conduction electrons. We investigate the high pressure electronic and structural ground state of K, Rb, and Cs using x-ray absorption spectroscopy and x-ray diffraction measurements together with ab initio theoretical calculations. The sequence of phase transitions under pressure observed at low temperature is similar in all three heavy alkalis except for the absence of the oC84 phase in Cs. Both the experimental and theoretical results point to pressure-enhanced localization of themore » valence electrons characterized by pseudo-gap formation near the Fermi level and strong spd hybridization. Although the crystal structures predicted to host magnetic order in K are not observed, the localization process appears to drive these alkalis closer to a strongly correlated electron state.« less

  3. Electronic and structural ground state of heavy alkali metals at high pressure

    NASA Astrophysics Data System (ADS)

    Fabbris, G.; Lim, J.; Veiga, L. S. I.; Haskel, D.; Schilling, J. S.

    2015-02-01

    Alkali metals display unexpected properties at high pressure, including emergence of low-symmetry crystal structures, which appear to occur due to enhanced electronic correlations among the otherwise nearly free conduction electrons. We investigate the high-pressure electronic and structural ground state of K, Rb, and Cs using x-ray absorption spectroscopy and x-ray diffraction measurements together with a b i n i t i o theoretical calculations. The sequence of phase transitions under pressure observed at low temperature is similar in all three heavy alkalis except for the absence of the o C 84 phase in Cs. Both the experimental and theoretical results point to pressure-enhanced localization of the valence electrons characterized by pseudogap formation near the Fermi level and strong s p d hybridization. Although the crystal structures predicted to host magnetic order in K are not observed, the localization process appears to drive these alkalis closer to a strongly correlated electron state.

  4. Advanced Metal-Hydrides-Based Thermal Battery: A New Generation of High Density Thermal Battery Based on Advanced Metal Hydrides

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

    None

    HEATS Project: The University of Utah is developing a compact hot-and-cold thermal battery using advanced metal hydrides that could offer efficient climate control system for EVs. The team’s innovative designs of heating and cooling systems for EVs with high energy density, low-cost thermal batteries could significantly reduce the weight and eliminate the space constraint in automobiles. The thermal battery can be charged by plugging it into an electrical outlet while charging the electric battery and it produces heat and cold through a heat exchanger when discharging. The ultimate goal of the project is a climate-controlling thermal battery that can lastmore » up to 5,000 charge and discharge cycles while substantially increasing the driving range of EVs, thus reducing the drain on electric batteries.« less

  5. High-Energy-Density Metal-Oxygen Batteries: Lithium-Oxygen Batteries vs Sodium-Oxygen Batteries.

    PubMed

    Song, Kyeongse; Agyeman, Daniel Adjei; Park, Mihui; Yang, Junghoon; Kang, Yong-Mook

    2017-12-01

    The development of next-generation energy-storage devices with high power, high energy density, and safety is critical for the success of large-scale energy-storage systems (ESSs), such as electric vehicles. Rechargeable sodium-oxygen (Na-O 2 ) batteries offer a new and promising opportunity for low-cost, high-energy-density, and relatively efficient electrochemical systems. Although the specific energy density of the Na-O 2 battery is lower than that of the lithium-oxygen (Li-O 2 ) battery, the abundance and low cost of sodium resources offer major advantages for its practical application in the near future. However, little has so far been reported regarding the cell chemistry, to explain the rate-limiting parameters and the corresponding low round-trip efficiency and cycle degradation. Consequently, an elucidation of the reaction mechanism is needed for both lithium-oxygen and sodium-oxygen cells. An in-depth understanding of the differences and similarities between Li-O 2 and Na-O 2 battery systems, in terms of thermodynamics and a structural viewpoint, will be meaningful to promote the development of advanced metal-oxygen batteries. State-of-the-art battery design principles for high-energy-density lithium-oxygen and sodium-oxygen batteries are thus reviewed in depth here. Major drawbacks, reaction mechanisms, and recent strategies to improve performance are also summarized. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative.

    PubMed

    Požar, Josip; Nikšić-Franjić, Ivana; Cvetnić, Marija; Leko, Katarina; Cindro, Nikola; Pičuljan, Katarina; Borilović, Ivana; Frkanec, Leo; Tomišić, Vladislav

    2017-09-14

    The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N,N-dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na + cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL + complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL + stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1 H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N,N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed.

  7. Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

    NASA Astrophysics Data System (ADS)

    Hummelshøj, J. S.; Landis, D. D.; Voss, J.; Jiang, T.; Tekin, A.; Bork, N.; Dułak, M.; Mortensen, J. J.; Adamska, L.; Andersin, J.; Baran, J. D.; Barmparis, G. D.; Bell, F.; Bezanilla, A. L.; Bjork, J.; Björketun, M. E.; Bleken, F.; Buchter, F.; Bürkle, M.; Burton, P. D.; Buus, B. B.; Calborean, A.; Calle-Vallejo, F.; Casolo, S.; Chandler, B. D.; Chi, D. H.; Czekaj, I.; Datta, S.; Datye, A.; DeLaRiva, A.; Despoja, V.; Dobrin, S.; Engelund, M.; Ferrighi, L.; Frondelius, P.; Fu, Q.; Fuentes, A.; Fürst, J.; García-Fuente, A.; Gavnholt, J.; Goeke, R.; Gudmundsdottir, S.; Hammond, K. D.; Hansen, H. A.; Hibbitts, D.; Hobi, E.; Howalt, J. G.; Hruby, S. L.; Huth, A.; Isaeva, L.; Jelic, J.; Jensen, I. J. T.; Kacprzak, K. A.; Kelkkanen, A.; Kelsey, D.; Kesanakurthi, D. S.; Kleis, J.; Klüpfel, P. J.; Konstantinov, I.; Korytar, R.; Koskinen, P.; Krishna, C.; Kunkes, E.; Larsen, A. H.; Lastra, J. M. G.; Lin, H.; Lopez-Acevedo, O.; Mantega, M.; Martínez, J. I.; Mesa, I. N.; Mowbray, D. J.; Mýrdal, J. S. G.; Natanzon, Y.; Nistor, A.; Olsen, T.; Park, H.; Pedroza, L. S.; Petzold, V.; Plaisance, C.; Rasmussen, J. A.; Ren, H.; Rizzi, M.; Ronco, A. S.; Rostgaard, C.; Saadi, S.; Salguero, L. A.; Santos, E. J. G.; Schoenhalz, A. L.; Shen, J.; Smedemand, M.; Stausholm-Møller, O. J.; Stibius, M.; Strange, M.; Su, H. B.; Temel, B.; Toftelund, A.; Tripkovic, V.; Vanin, M.; Viswanathan, V.; Vojvodic, A.; Wang, S.; Wellendorff, J.; Thygesen, K. S.; Rossmeisl, J.; Bligaard, T.; Jacobsen, K. W.; Nørskov, J. K.; Vegge, T.

    2009-07-01

    We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition metal atom (M2) plus two to five (BH4)- groups, i.e., M1M2(BH4)2-5, using a number of model structures with trigonal, tetrahedral, octahedral, and free coordination of the metal borohydride complexes. Of the over 700 investigated structures, about 20 were predicted to form potentially stable alloys with promising decomposition energies. The M1(Al/Mn/Fe)(BH4)4, (Li/Na)Zn(BH4)3, and (Na/K)(Ni/Co)(BH4)3 alloys are found to be the most promising, followed by selected M1(Nb/Rh)(BH4)4 alloys.

  8. Yarrowia lipolytica possesses two plasma membrane alkali metal cation/H+ antiporters with different functions in cell physiology.

    PubMed

    Papouskova, Klara; Sychrova, Hana

    2006-04-03

    The family of Nha antiporters mediating the efflux of alkali metal cations in exchange for protons across the plasma membrane is conserved in all yeast species. Yarrowia lipolytica is a dimorphic yeast, phylogenetically very distant from the model yeast Saccharomyces cerevisiae. A search in its sequenced genome revealed two genes (designated as YlNHA1 and YlNHA2) with homology to the S. cerevisiae NHA1 gene, which encodes a plasma membrane alkali metal cation/H+ antiporter. Upon heterologous expression of both YlNHA genes in S. cerevisiae, we showed that Y. lipolytica antiporters differ not only in length and sequence, but also in their affinity for individual substrates. While the YlNha1 protein mainly increased cell tolerance to potassium, YlNha2p displayed a remarkable transport capacity for sodium. Thus, Y. lipolytica is the first example of a yeast species with two plasma membrane alkali metal cation/H+ antiporters differing in their putative functions in cell physiology; cell detoxification vs. the maintenance of stable intracellular pH, potassium content and cell volume.

  9. Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries

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

    Adams, Brian D.; Zheng, Jianming; Ren, Xiaodi

    Lithium (Li) metal is an ideal anode material for high energy density batteries. However, its low Coulombic efficiency (CE) and formation of dendrites during the plating and stripping processes has hindered its applications in rechargeable Li metal batteries. The accurate measurement of Li CE is a critical factor to predict the cycle life of Li metal batteries, but the measurement of Li CE is affected by various factors that often leads to conflicting values reported in the literature. Here, we investigate various factors that affect the measurement of Li CE and propose a more accurate method of determining Li CE.more » It was also found that the capacity used for cycling greatly affects the stabilization cycles and the average CE. A higher cycling capacity leads to a shorter number of stabilization cycles and higher average CE. With a proper high-concentration ether-based electrolyte, Li metal can be cycled with a high average CE of 99.5 % for over 100 cycles at a high capacity of 6 mAh cm-2 suitable for practical applications.« less

  10. Alkali activation of recovered fuel-biofuel fly ash from fluidised-bed combustion: Stabilisation/solidification of heavy metals.

    PubMed

    Yliniemi, Juho; Pesonen, Janne; Tiainen, Minna; Illikainen, Mirja

    2015-09-01

    Recovered fuel-biofuel fly ash from a fluidized bed boiler was alkali-activated and granulated with a sodium-silicate solution in order to immobilise the heavy metals it contains. The effect of blast-furnace slag and metakaolin as co-binders were studied. Leaching standard EN 12457-3 was applied to evaluate the immobilisation potential. The results showed that Ba, Pb and Zn were effectively immobilised. However, there was increased leaching after alkali activation for As, Cu, Mo, Sb and V. The co-binders had minimal or even negative effect on the immobilisation. One exception was found for Cr, in which the slag decreased leaching, and one was found for Cu, in which the slag increased leaching. A sequential leaching procedure was utilized to gain a deeper understanding of the immobilisation mechanism. By using a sequential leaching procedure it is possible fractionate elements into watersoluble, acid-soluble, easily-reduced and oxidisable fractions, yielding a total 'bioavailable' amount that is potentially hazardous for the environment. It was found that the total bioavailable amount was lower following alkali activation for all heavy metals, although the water-soluble fraction was higher for some metals. Evidence from leaching tests suggests the immobilisation mechanism was chemical retention, or trapping inside the alkali activation reaction products, rather than physical retention, adsorption or precipitation as hydroxides. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Superior ionic and electronic properties of ReN2 monolayers for Na-ion battery electrodes.

    PubMed

    Zhang, Shi-Hao; Liu, Bang-Gui

    2018-08-10

    Excellent monolayer electrode materials can be used to design high-performance alkali-metal-ion batteries. Here, we propose two-dimensional ReN 2 monolayers as superior sodium-ion battery materials. Our total energy optimization results in a buckled tetragonal structure for the ReN 2 monolayer, and our phonon spectrum and elastic moduli prove that it is dynamically and mechanically stable. Further investigations show that it is metallic and still keeps its metallic feature after the adsorption of Na or K atoms, and the adsorption of Na (or K) atoms changes the lattice parameters by 3.2% (or 3.8%) at most. Its maximum capacity reaches 751 mA h g -1 for Na-ion batteries or 250 mA h g -1 for K-ion batteries, and the diffusion barrier is only 0.027 eV for the Na atom or 0.127 eV for the K atom. The small lattice changes, high storage capacity, metallic feature, and extremely low ion diffusion barriers make the ReN 2 monolayers a superior electrode material for Na-ion rechargeable batteries with ultrafast charging/discharging processes.

  12. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2.

    PubMed

    Maitra, Urmimala; House, Robert A; Somerville, James W; Tapia-Ruiz, Nuria; Lozano, Juan G; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A; Massel, Felix; Pickup, David M; Ramos, Silvia; Lu, Xingye; McNally, Daniel E; Chadwick, Alan V; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C; Roberts, Matthew R; Bruce, Peter G

    2018-03-01

    The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li + -O(2p)-Li + interactions). Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg 2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg 2+ remains in Na 2/3 [Mg 0.28 Mn 0.72 ]O 2 , which stabilizes oxygen.

  13. Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2

    NASA Astrophysics Data System (ADS)

    Maitra, Urmimala; House, Robert A.; Somerville, James W.; Tapia-Ruiz, Nuria; Lozano, Juan G.; Guerrini, Niccoló; Hao, Rong; Luo, Kun; Jin, Liyu; Pérez-Osorio, Miguel A.; Massel, Felix; Pickup, David M.; Ramos, Silvia; Lu, Xingye; McNally, Daniel E.; Chadwick, Alan V.; Giustino, Feliciano; Schmitt, Thorsten; Duda, Laurent C.; Roberts, Matthew R.; Bruce, Peter G.

    2018-03-01

    The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds as promising high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion and charge compensation by transition-metal (TM) ions. The additional capacity is provided through charge compensation by oxygen redox chemistry and some oxygen loss. It has been reported previously that oxygen redox occurs in O 2p orbitals that interact with alkali ions in the TM and alkali-ion layers (that is, oxygen redox occurs in compounds containing Li+-O(2p)-Li+ interactions). Na2/3[Mg0.28Mn0.72]O2 exhibits an excess capacity and here we show that this is caused by oxygen redox, even though Mg2+ resides in the TM layers rather than alkali-metal (AM) ions, which demonstrates that excess AM ions are not required to activate oxygen redox. We also show that, unlike the alkali-rich compounds, Na2/3[Mg0.28Mn0.72]O2 does not lose oxygen. The extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen, which promotes oxygen loss, whereas Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2, which stabilizes oxygen.

  14. Hazards, Safety and Design Considerations for Commercial Lithium-ion Cells and Batteries

    NASA Technical Reports Server (NTRS)

    Jeevarajan, Judith

    2007-01-01

    This viewgraph presentation reviews the features of the Lithium-ion batteries, particularly in reference to the hazards and safety of the battery. Some of the characteristics of the Lithium-ion cell are: Highest Energy Density of Rechargeable Battery Chemistries, No metallic lithium, Leading edge technology, Contains flammable electrolyte, Charge cut-off voltage is critical (overcharge can result in fire), Open circuit voltage higher than metallic lithium anode types with similar organic electrolytes. Intercalation is a process that places small ions in crystal lattice. Small ions (such as lithium, sodium, and the other alkali metals) can fit in the interstitial spaces in a graphite lattice. These metallic ions can go farther and force the graphitic planes apart to fit two, three, or more layers of metallic ions between the carbon sheets. Other features of the battery/cell are: The graphite is conductive, Very high energy density compared to NiMH or NiCd, Corrosion of aluminum occurs very quickly in the presence of air and electrolyte due to the formation of HF from LiPF6 and HF is highly corrosive. Slides showing the Intercalation/Deintercalation and the chemical reactions are shown along with the typical charge/discharge for a cylindrical cell. There are several graphs that review the hazards of the cells.

  15. Theoretical analysis of oxygen diffusion at startup in an alkali metal heat pipe with gettered alloy walls

    NASA Technical Reports Server (NTRS)

    Tower, L. K.

    1973-01-01

    The diffusion of oxygen into, or out of, a gettered alloy exposed to oxygenated alkali liquid metal coolant, a situation arising in some high temperature heat transfer systems, was analyzed. The relation between the diffusion process and the thermochemistry of oxygen in the alloy and in the alkali metal was developed by making several simplifying assumptions. The treatment is therefore theoretical in nature. However, a practical example pertaining to the startup of a heat pipe with walls of T-111, a tantalum alloy, and lithium working fluid illustrates the use of the figures contained in the analysis.

  16. Integrated oil production and upgrading using molten alkali metal

    DOEpatents

    Gordon, John Howard

    2016-10-04

    A method that combines the oil retorting process (or other process needed to obtain/extract heavy oil or bitumen) with the process for upgrading these materials using sodium or other alkali metals. Specifically, the shale gas or other gases that are obtained from the retorting/extraction process may be introduced into the upgrading reactor and used to upgrade the oil feedstock. Also, the solid materials obtained from the reactor may be used as a fuel source, thereby providing the heat necessary for the retorting/extraction process. Other forms of integration are also disclosed.

  17. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan. Revision 1

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

    None

    The Hanford Site, located northwest of the city of Richland, Washington, houses reactors, chemical-separation systems, and related facilities used for the production of special nuclear materials, as well as for activities associated with nuclear energy development. The 300 Area of the Hanford Site contains reactor fuel manufacturing facilities and several research and development laboratories. The 3718-F Alkali Metal Treatment and Storage Facility (3718-F Facility), located in the 300 Area, was used to store and treat alkali metal wastes. Therefore, it is subject to the regulatory requirements for the storage and treatment of dangerous wastes. Closure will be conducted pursuant tomore » the requirements of the Washington Administrative Code (WAC) 173-303-610 (Ecology 1989) and 40 CFR 270.1. Closure also will satisfy the thermal treatment facility closure requirements of 40 CFR 265.381. This closure plan presents a description of the 3718-F Facility, the history of wastes managed, and the approach that will be followed to close the facility. Only hazardous constituents derived from 3718-F Facility operations will be addressed.« less

  18. Radioisotope powered alkali metal thermoelectric converter design for space systems

    NASA Technical Reports Server (NTRS)

    Sievers, R. K.; Bankston, C. P.

    1988-01-01

    The design concept of an alkali-metal thermoelectric converter (AMTEC) for 15-30-percent-efficient conversion of heat from the General Purpose (radioisotope) Heat Source (GPHS) on spacecraft is presented. The basic physical principles of the conversion cycle are outlined; a theoretical model is derived; a modular design is described and illustrated with drawings; and the overall AMTEC/GPHS system design is characterized. Predicted performance data are presented in extensive tables and graphs and discussed in detail.

  19. A metal-free organic-inorganic aqueous flow battery.

    PubMed

    Huskinson, Brian; Marshak, Michael P; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R; Galvin, Cooper J; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

    2014-01-09

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals

  20. The effect of the carbon nanotube buffer layer on the performance of a Li metal battery

    NASA Astrophysics Data System (ADS)

    Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

    2016-05-01

    Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a

  1. Batteries for electric road vehicles.

    PubMed

    Goodenough, John B; Braga, M Helena

    2018-01-15

    The dependence of modern society on the energy stored in a fossil fuel is not sustainable. An immediate challenge is to eliminate the polluting gases emitted from the roads of the world by replacing road vehicles powered by the internal combustion engine with those powered by rechargeable batteries. These batteries must be safe and competitive in cost, performance, driving range between charges, and convenience. The competitive performance of an electric car has been demonstrated, but the cost of fabrication, management to ensure safety, and a short cycle life have prevented large-scale penetration of the all-electric road vehicle into the market. Low-cost, safe all-solid-state cells from which dendrite-free alkali-metal anodes can be plated are now available; they have an operating temperature range from -20 °C to 80 °C and they permit the design of novel high-capacity, high-voltage cathodes providing fast charge/discharge rates. Scale-up to large multicell batteries is feasible.

  2. Characterization of spent nickel-metal hydride batteries and a preliminary economic evaluation of the recovery processes.

    PubMed

    Lin, Sheng-Lun; Huang, Kuo-Lin; Wang, I-Ching; Chou, I-Cheng; Kuo, Yi-Ming; Hung, Chung-Hsien; Lin, Chitsan

    2016-03-01

    Valuable metal materials can be recovered from spent nickel-metal hydride (NiMH) batteries. However, little attention has been paid to the metal compositions of individual components of NiMH batteries, although this is important for the selection of the appropriate recycling process. In this study, NiMH batteries were manually disassembled to identify the components and to characterize the metals in each of these. A preliminary economic analysis was also conducted to evaluate the recovery of valuable metals from spent NiMH batteries using thermal melting versus simple mechanical separation. The results of this study show that metallic components account for more than 60% of battery weight. The contents of Ni, Fe, Co, and rare earth elements (REEs) (i.e., valuable metals of interest for recovery) in a single battery were 17.9%, 15.4%, 4.41%, and 17.3%, respectively. Most of the Fe was in the battery components of the steel cathode collector, cathode cap, and anode metal grid, while Ni (>90%) and Co (>90%) were mainly in the electrode active materials (anode and cathode metal powders). About 1.88 g of REEs (Ce, La, and Y) could be obtained from one spent NiMH battery. The estimated profits from recovering valuable metals from spent NiMH batteries by using thermal melting and mechanical processes are 2,329 and 2,531 USD/ton, respectively, when including a subsidy of 1,710 USD/ton. The findings of this study are very useful for further research related to technical and economic evaluations of the recovery of valuable metals from spent NiMH batteries. The spent nickel-metal hydride (NiMH) batteries were manually disassembled and their components were identified. The metals account for more than 60% of battery weight, when Ni, Fe, Co, and rare earth elements (REEs) were 17.9%, 15.4%, 4.41%, and 17.3%, respectively, in a single battery. The estimated profits of recovering valuable metals from NiMH batteries by using thermal melting and mechanical processing are 2,329 and

  3. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, Anthony A.

    1985-01-01

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

  4. Nickel-metal hydride battery development. Final technical report

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

    NONE

    1995-06-01

    Rechargeable batteries are used as the power source for a broad range of portable equipment. Key battery selection criteria typically are weight, volume, first cost, life cycle cost, and environmental impact. Rechargeable batteries are favored from a life cycle cost and environmental impact standpoint over primary batteries. The nickel-metal hydride (Ni-MH) battery system has emerged as the battery of choice for many applications based on its superior characteristics when judged on the above criteria against other battery types. In most cases commercial Ni-MH batteries are constructed with coiled electrodes in cylindrical metal containers. Electro Energy, Inc. (EEI) has been developingmore » a novel flat bipolar configuration of the Ni-MH system that offers weight, volume, and cost advantages when compared to cylindrical cells. The unique bipolar approach consists of fabricating individual flat wafer cells in conductive, carbon-filled, plastic face plates. The individual cells contain a nonconductive plastic border which is heat sealed around the perimeter to make a totally sealed unit cell. Multi-cell batteries are fabricated by stacking the individual wafer cells in such a way that the positive face of one cell contacts the negative face of the adjacent cell. The stack is then contained in an outer housing with end contacts. The purpose of this program was to develop, evaluate, and demonstrate the capabilities of the EEI Ni-MH battery system for consumer applications. The work was directed at the development and evaluation of the compact bipolar construction for its potential advantages of high power and energy density. Experimental investigations were performed on various nickel electrode types, hydride electrode formulations, and alternate separator materials. Studies were also directed at evaluating various oxygen recombination techniques for low pressure operation during charge and overcharge.« less

  5. Fluconazole affects the alkali-metal-cation homeostasis and susceptibility to cationic toxic compounds of Candida glabrata.

    PubMed

    Elicharova, Hana; Sychrova, Hana

    2014-08-01

    Candida glabrata is a salt-tolerant and fluconazole (FLC)-resistant yeast species. Here, we analyse the contribution of plasma-membrane alkali-metal-cation exporters, a cation/proton antiporter and a cation ATPase to cation homeostasis and the maintenance of membrane potential (ΔΨ). Using a series of single and double mutants lacking CNH1 and/or ENA1 genes we show that the inability to export potassium and toxic alkali-metal cations leads to a slight hyperpolarization of the plasma membrane of C. glabrata cells; this hyperpolarization drives more cations into the cells and affects cation homeostasis. Surprisingly, a much higher hyperpolarization of C. glabrata plasma membrane was produced by incubating cells with subinhibitory concentrations of FLC. FLC treatment resulted in a substantially increased sensitivity of cells to various cationic drugs and toxic cations that are driven into the cell by negative-inside plasma-membrane potential. The effect of the combination of FLC plus cationic drug treatment was enhanced by the malfunction of alkali-metal-cation transporters that contribute to the regulation of membrane potential and cation homeostasis. In summary, we show that the combination of subinhibitory concentrations of FLC and cationic drugs strongly affects the growth of C. glabrata cells. © 2014 The Authors.

  6. Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells.

    PubMed

    Zhao, Wangen; Yao, Zhun; Yu, Fengyang; Yang, Dong; Liu, Shengzhong Frank

    2018-02-01

    Organic-inorganic hybrid halide perovskites are proven to be a promising semiconductor material as the absorber layer of solar cells. However, the perovskite films always suffer from nonuniform coverage or high trap state density due to the polycrystalline characteristics, which degrade the photoelectric properties of thin films. Herein, the alkali metal ions which are stable against oxidation and reduction are used in the perovskite precursor solution to induce the process of crystallization and nucleation, then affect the properties of the perovskite film. It is found that the addition of the alkali metal ions clearly improves the quality of perovskite film: enlarges the grain sizes, reduces the defect state density, passivates the grain boundaries, increases the built-in potential ( V bi ), resulting to the enhancement in the power conversion efficiency of perovskite thin film solar cell.

  7. Anode-Free Rechargeable Lithium Metal Batteries

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

    Qian, Jiangfeng; Adams, Brian D.; Zheng, Jianming

    2016-08-18

    Anode-free rechargeable lithium (Li) batteries (AFLBs) are phenomenal energy storage systems due to their significantly increased energy density and reduced cost relative to Li-ion batteries, as well as ease of assembly owing to the absence of an active (reactive) anode material. However, significant challenges, including Li dendrite growth and low cycling Coulombic efficiency (CE), have prevented their practical implementation. Here, we report for the first time an anode-free rechargeable lithium battery based on a Cu||LiFePO4 cell structure with an extremely high CE (> 99.8%). This results from the utilization of both an exceptionally stable electrolyte and optimized charge/discharge protocols whichmore » minimize the corrosion of the in-situ formed Li metal anode.« less

  8. Raman and nuclear magnetic resonance investigation of alkali metal vapor interaction with alkene-based anti-relaxation coating

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

    Tretiak, O. Yu., E-mail: otretiak@genphys.ru; Balabas, M. V.; Blanchard, J. W.

    2016-03-07

    The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonancemore » investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.« less

  9. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, A.A.

    1985-07-02

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

  10. Structural and dynamical trends in alkali-metal silanides characterized by neutron-scattering methods

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

    Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean -Noel

    Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH 3, where M = K, Rb, Cs, K 0.5Rb 0.5, K 0.5Cs 0.5, and Rb 0.5Cs 0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (α) and ordered (β) phases for temperatures above and below about 200–250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a redmore » shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order–disorder (β–α) phase transition, and measurements upon cooling of the α-phase revealed the known strong hysteresis for reversion back to the β-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH 3 – anions in the α- and β-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. Lastly, this dynamical result might provide some insights concerning the enthalpy–entropy compensation effect previously observed for these potentially promising hydrogen storage materials.« less

  11. Structural and dynamical trends in alkali-metal silanides characterized by neutron-scattering methods

    DOE PAGES

    Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean -Noel; ...

    2016-09-02

    Structural, vibrational, and dynamical properties of the mono- and mixed-alkali silanides (MSiH 3, where M = K, Rb, Cs, K 0.5Rb 0.5, K 0.5Cs 0.5, and Rb 0.5Cs 0.5) were investigated by various neutron experiments, including neutron powder diffraction (NPD), neutron vibrational spectroscopy (NVS), neutron-scattering fixed-window scans (FWSs), and quasielastic neutron scattering (QENS) measurements. Structural characterization showed that the mixed compounds exhibit disordered (α) and ordered (β) phases for temperatures above and below about 200–250 K, respectively, in agreement with their monoalkali correspondents. Vibrational and dynamical properties are strongly influenced by the cation environment; in particular, there is a redmore » shift in the band energies of the librational and bending modes with increasing lattice size as a result of changes in the bond lengths and force constants. Additionally, slightly broader spectral features are observed in the case of the mixed compounds, indicating the presence of structural disorder caused by the random distribution of the alkali-metal cations within the lattice. FWS measurements upon heating showed that there is a large increase in reorientational mobility as the systems go through the order–disorder (β–α) phase transition, and measurements upon cooling of the α-phase revealed the known strong hysteresis for reversion back to the β-phase. Interestingly, at a given temperature, among the different alkali silanide compounds, the relative reorientational mobilities of the SiH 3 – anions in the α- and β-phases tended to decrease and increase, respectively, with increasing alkali-metal mass. Lastly, this dynamical result might provide some insights concerning the enthalpy–entropy compensation effect previously observed for these potentially promising hydrogen storage materials.« less

  12. The effect of the carbon nanotube buffer layer on the performance of a Li metal battery.

    PubMed

    Zhang, Ding; Zhou, Yi; Liu, Changhong; Fan, Shoushan

    2016-06-07

    Lithium (Li) metal is one of the most promising candidates as an anode for the next-generation energy storage systems because of its high specific capacity and lowest negative electrochemical potential. But the growth of Li dendrites limits the application of the Li metal battery. In this work, a type of modified Li metal battery with a carbon nanotube (CNT) buffer layer inserted between the separator and the Li metal electrode was reported. The electrochemical results show that the modified batteries have a much better rate capability and cycling performance than the conventional Li metal batteries. The mechanism study by electrochemical impedance spectroscopy reveals that the modified battery has a smaller charge transfer resistance and larger Li ion diffusion coefficient during the deposition process on the Li electrode than the conventional Li metal batteries. Symmetric battery tests show that the interfacial behavior of the Li metal electrode with the buffer layer is more stable than the naked Li metal electrode. The morphological characterization of the CNT buffer layer and Li metal lamina reveals that the CNT buffer layer has restrained the growth of Li dendrites. The CNT buffer layer has great potential to solve the safety problem of the Li metal battery.

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

    DOEpatents

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

    2016-05-31

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

  14. Extraction process for removing metallic impurities from alkalide metals

    DOEpatents

    Royer, L.T.

    1987-03-20

    A development is described for removing metallic impurities from alkali metals by employing an extraction process wherein the metallic impurities are extracted from a molten alkali metal into molten lithium metal due to the immiscibility of the alkali metals in lithium and the miscibility of the metallic contaminants or impurities in the lithium. The purified alkali metal may be readily separated from the contaminant-containing lithium metal by simple decanting due to the differences in densities and melting temperatures of the alkali metals as compared to lithium.

  15. Modified secondary lithium metal batteries with the polyaniline-carbon nanotube composite buffer layer.

    PubMed

    Zhang, Ding; Yin, Yanli; Liu, Changhong; Fan, Shoushan

    2015-01-07

    A modified secondary lithium metal battery inserted with a polyaniline-carbon nanotube nanoporous composite buffer layer was fabricated. This unique and simple design of battery has the great potential to decrease the safety risk of the secondary Li metal battery in cycles of recharging processes and improve its cycle life in the future.

  16. Ovonic nickel metal hydride batteries for space applications

    NASA Technical Reports Server (NTRS)

    Venkatesan, S.; Corrigan, D. A.; Fetcenko, M. A.; Gifford, P. R.; Dhar, S. K.; Ovshinsky, S. R.

    1993-01-01

    Ovonic nickel-metal hydride (NiMH) rechargeable batteries are easily adaptable to a variety of applications. Small consumer NiMH cells were developed and are now being manufactured by licensees throughout the world. This technology was successfully scaled up in larger prismatic cells aimed at electric vehicle applications. Sealed cells aimed at satellite power applications were also built and cycle tested by OBC and other outside agencies. Prototype batteries with high specific energy (over 80 Wh/kg), high energy density (245 Wh/L), and excellent power capability (400 W/kg) were produced. Ovonic NiMH batteries demonstrated an excellent cycle life of over 10,000 cycles at 30 percent DOD. Presently, Ovonic Battery Company is working on an advanced version of this battery for space applications as part of an SBIR contract from NASA.

  17. Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties

    DOE PAGES

    Sougrati, Moulay T.; Darwiche, Ali; Liu, Xiaohiu; ...

    2016-03-16

    Here we report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as a negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on 57Fe M ssbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe NCN into Li/Na NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not requiremore » heavy treatments (nanoscale tailoring, sophisticated textures, coating etc.) to obtain long cycle life with density current as high as 9 A/g -1 for hundreds of charge/discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M x(NCN) y with M = Mn, Cr, Zn can cycle successfully versus lithium and sodium. Ultimately, their electrochemical activity and performances open the way to the design of a novel family of anode materials.« less

  18. Electron core ionization in compressed alkali metal cesium

    NASA Astrophysics Data System (ADS)

    Degtyareva, V. F.

    2018-01-01

    Elements of groups I and II in the periodic table have valence electrons of s-type and are usually considered as simple metals. Crystal structures of these elements at ambient pressure are close-packed and high-symmetry of bcc and fcc-types, defined by electrostatic (Madelung) energy. Diverse structures were found under high pressure with decrease of the coordination number, packing fraction and symmetry. Formation of complex structures can be understood within the model of Fermi sphere-Brillouin zone interactions and supported by Hume-Rothery arguments. With the volume decrease there is a gain of band structure energy accompanied by a formation of many-faced Brillouin zone polyhedra. Under compression to less than a half of the initial volume the interatomic distances become close to or smaller than the ionic radius which should lead to the electron core ionization. At strong compression it is necessary to assume that for alkali metals the valence electron band overlaps with the upper core electrons, which increases the valence electron count under compression.

  19. Magnesium-antimony liquid metal battery for stationary energy storage.

    PubMed

    Bradwell, David J; Kim, Hojong; Sirk, Aislinn H C; Sadoway, Donald R

    2012-02-01

    Batteries are an attractive option for grid-scale energy storage applications because of their small footprint and flexible siting. A high-temperature (700 °C) magnesium-antimony (Mg||Sb) liquid metal battery comprising a negative electrode of Mg, a molten salt electrolyte (MgCl(2)-KCl-NaCl), and a positive electrode of Sb is proposed and characterized. Because of the immiscibility of the contiguous salt and metal phases, they stratify by density into three distinct layers. Cells were cycled at rates ranging from 50 to 200 mA/cm(2) and demonstrated up to 69% DC-DC energy efficiency. The self-segregating nature of the battery components and the use of low-cost materials results in a promising technology for stationary energy storage applications. © 2012 American Chemical Society

  20. Metal-air battery research and development

    NASA Astrophysics Data System (ADS)

    Behrin, E.; Cooper, J. F.

    1982-05-01

    This report summarizes the activities of the Metal-air Battery Program during the calendar year 1981. The principal objective is to develop a refuelable battery as an automotive energy source for general-purpose electric vehicles and to conduct engineering demonstrations of its ability to provide vehicles with the range, acceleration, and rapid refueling capability of current internal-combustion-engine automobiles. The second objective is to develop an electrically-rechargeable battery for specific-mission electric vehicles, such as commuter vehicles, that can provide low-cost transportation. The development progression is to: (1) develop a mechanically rechargeable aluminum-air power cell using model electrodes, (2) develop cost-effective anode and cathode materials and structures as required to achieve reliability and efficiency goals, and to establish the economic competitiveness of this technology, and (3) develop and integrated propulsion system utilizing the power cell.

  1. Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

    PubMed

    Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

    2015-12-09

    The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

  2. Alkali metal/halide thermal energy storage systems performance evaluation

    NASA Technical Reports Server (NTRS)

    Phillips, W. M.; Stearns, J. W.

    1986-01-01

    A pseudoheat-pipe heat transfer mechanism has been demonstrated effective in terms of both total heat removal efficiency and rate, on the one hand, and system isothermal characteristics, on the other, for solar thermal energy storage systems of the kind being contemplated for spacecraft. The selection of appropriate salt and alkali metal substances for the system renders it applicable to a wide temperature range. The rapid heat transfer rate obtainable makes possible the placing of the thermal energy storage system around the solar receiver canister, and the immersing of heat transfer fluid tubes in the phase change salt to obtain an isothermal heat source.

  3. Method of making a light weight battery plaque

    NASA Technical Reports Server (NTRS)

    Reid, M. A.; Post, R. E.; Soltis, D. G. (Inventor)

    1984-01-01

    A nickel plaque which may be coated with a suitable metal or compound to make an electrode for a fuel cell or battery is fabricated by directing nickel sensitizer, catalyst and plating solutions through a porous plastic substrate in the order named and at prescribed temperatures and flow rates. A boride compound dissolved in the plating solution decreases the electrical resistance of the plaque. Certain substrates may require treatment in an alkali solution to dissolve filler materials thereby increasing porosity to a required 65%.

  4. Magnetohydrodynamic effects in liquid metal batteries

    NASA Astrophysics Data System (ADS)

    Stefani, F.; Galindo, V.; Kasprzyk, C.; Landgraf, S.; Seilmayer, M.; Starace, M.; Weber, N.; Weier, T.

    2016-07-01

    Liquid metal batteries (LMBs) consist of two liquid metal electrodes and a molten salt ionic conductor sandwiched between them. The density ratios allow for a stable stratification of the three layers. LMBs were already considered as part of energy conversion systems in the 1960s and have recently received renewed interest for economical large-scale energy storage. In this paper, we concentrate on the magnetohydrodynamic aspects of this cell type with special focus on electro-vortex flows and possible effects of the Tayler instability.

  5. Analysis of the Alkali Metal Diatomic Spectra; Using molecular beams and ultracold molecules

    NASA Astrophysics Data System (ADS)

    Kim, Jin-Tae

    2014-12-01

    This ebook illustrates the complementarity of molecular beam (MB) spectra and ultracold molecule (UM) spectra in unraveling the complex electronic spectra of diatomic alkali metal molecules, using KRb as a prime example. Researchers interested in molecular spectroscopy, whether physicist, chemist, or engineer, may find this ebook helpful and may be able to apply similar ideas to their molecules of interest.

  6. Post-harvest processing methods for reduction of silica and alkali metals in wheat straw.

    PubMed

    Thompson, David N; Shaw, Peter G; Lacey, Jeffrey A

    2003-01-01

    Silica and alkali metals in wheat straw limit its use for bioenergy and gasification. Slag deposits occur via the eutectic melting of SiO2 with K2O, trapping chlorides at surfaces and causing corrosion. A minimum melting point of 950 degrees C is desirable, corresponding to an SiO2:K2O weight ratio of about 3:1. Mild chemical treatments were used to reduce Si, K, and Cl, while varying temperature, concentration, % solids, and time. Dilute acid was more effective at removing K and Cl, while dilute alkali was more effective for Si. Reduction of minerals in this manner may prove economical for increasing utilization of the straw for combustion or gasification.

  7. Structure factor of liquid alkali metals using a classical-plasma reference system

    NASA Astrophysics Data System (ADS)

    Pastore, G.; Tosi, M. P.

    1984-06-01

    This paper presents calculations of the liquid structure factor of the alkali metals near freezing, starting from the classical plasma of bare ions as reference liquid. The indirect ion-ion interaction arising from electronic screening is treated by an optimized random phase approximation (ORPA), imposing physical requirements as in the original ORPA scheme developed by Weeks, Chandler and Andersen for liquids with strongly repulsive core potentials. A comparison of the results with computer simulation data for a model of liquid rubidium shows that the present approach overcomes the well-known difficulties met in applying to these metals the standard ORPA based on a reference liquid of neutral hard spheres. The optimization scheme is also shown to be equivalent to a reduction of the range of the indirect interaction in momentum space, as proposed empirically in an earlier work. Comparison with experiment for the other alkalis shows that a good overall representation of the data can be obtained for sodium, potassium and cesium, but not for lithium, when one uses a very simple form of the electron-ion potential adjusted to the liquid compressibility. The small-angle scattering region is finally examined more carefully in the light of recent data of Waseda, with a view to possible refinements of the pseudopotential model.

  8. Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

    PubMed

    Cao, Hujun; Richter, Theresia M M; Pistidda, Claudio; Chaudhary, Anna-Lisa; Santoru, Antonio; Gizer, Gökhan; Niewa, Rainer; Chen, Ping; Klassen, Thomas; Dornheim, Martin

    2015-11-01

    The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Extremely Stable Sodium Metal Batteries Enabled by Localized High-Concentration Electrolytes

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

    Zheng, Jianming; Chen, Shuru; Zhao, Wengao

    Sodium (Na) metal is a promising anode for Na ion batteries. However, the high reactivity of Na metal with electrolytes and the low Na metal cycling efficiency have limited its practical application in rechargeable Na metal batteries. High concentration electrolytes (HCE, ≥4 M) consisting of sodium bis(fluorosulfonyl)imide (NaFSI) and ether solvent could ensure the stable cycling of Na metal with high coulombic efficiency, but suffer from high viscosity, poor wetting ability, and high salt cost. Here, we report that the salt concentration could be significantly reduced (≤ 1.5 M) by diluting with a hydrofluoroether (HFE) as ‘inert’ diluent, which maintainsmore » the solvation structures of HCE, thereby forming a localized high concentration electrolyte (LHCE). A LHCE (2.1 M NaFSI/DME-BTFE (solvent molar ratio 1:2)) has been demonstrated to enable the dendrite-free Na deposition with high coulombic efficiency of > 99%, fast-charging (20C) and stable cycling (90.8% retention after 40,000 cycles) of Na||Na3V2(PO4)3 batteries.« less

  10. Self-discharge mechanism of sealed-type nickel/metal-hydride battery

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

    Ikoma, Munehisa; Hoshina, Yasuko; Matsumoto, Isao

    1996-06-01

    Factors affecting the self-discharge rate of a nickel/metal-hydride (Ni-MH) battery, generally much higher than that of nickel/cadmium (Ni-Cd) battery, are investigated, and the self-discharge mechanism is discussed. Ammonia and amine participate in the shuttle reaction like nitrate ion in the Ni-Cd battery, resulting in acceleration of the self-discharge. When nonwoven fabric made of sulfonated-polypropylene is used as a separator instead of conventional polyamide separator, the self-discharge rate of the Ni-MH battery is strongly depressed, to the same level as that of Ni-Cd battery.

  11. Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

    PubMed

    Ramanathan, Rajesh; Walia, Sumeet; Kandjani, Ahmad Esmaielzadeh; Balendran, Sivacarendran; Mohammadtaheri, Mahsa; Bhargava, Suresh Kumar; Kalantar-zadeh, Kourosh; Bansal, Vipul

    2015-02-03

    A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

  12. Metal-CO2 Batteries on the Road: CO2 from Contamination Gas to Energy Source.

    PubMed

    Xie, Zhaojun; Zhang, Xin; Zhang, Zhang; Zhou, Zhen

    2017-04-01

    Rechargeable nonaqueous metal-air batteries attract much attention for their high theoretical energy density, especially in the last decade. However, most reported metal-air batteries are actually operated in a pure O 2 atmosphere, while CO 2 and moisture in ambient air can significantly impact the electrochemical performance of metal-O 2 batteries. In the study of CO 2 contamination on metal-O 2 batteries, it has been gradually found that CO 2 can be utilized as the reactant gas alone; namely, metal-CO 2 batteries can work. On the other hand, investigations on CO 2 fixation are in focus due to the potential threat of CO 2 on global climate change, especially for its steadily increasing concentration in the atmosphere. The exploitation of CO 2 in energy storage systems represents an alternative approach towards clean recycling and utilization of CO 2 . Here, the aim is to provide a timely summary of recent achievements in metal-CO 2 batteries, and inspire new ideas for new energy storage systems. Moreover, critical issues associated with reaction mechanisms and potential directions for future studies are discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Electrolytic systems and methods for making metal halides and refining metals

    DOEpatents

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  14. Development of battery management system for nickel-metal hydride batteries in electric vehicle applications

    NASA Astrophysics Data System (ADS)

    Jung, Do Yang; Lee, Baek Haeng; Kim, Sun Wook

    Electric vehicle (EV) performance is very dependent on traction batteries. For developing electric vehicles with high performance and good reliability, the traction batteries have to be managed to obtain maximum performance under various operating conditions. Enhancement of battery performance can be accomplished by implementing a battery management system (BMS) that plays an important role in optimizing the control mechanism of charge and discharge of the batteries as well as monitoring the battery status. In this study, a BMS has been developed for maximizing the use of Ni-MH batteries in electric vehicles. This system performs several tasks: the control of charging and discharging, overcharge and over-discharge protection, the calculation and display of state-of-charge (SOC), safety, and thermal management. The BMS is installed in and tested in a DEV5-5 electric vehicle developed by Daewoo Motor Co. and the Institute for Advanced Engineering in Korea. Eighteen modules of a Panasonic nickel-metal hydride (Ni-MH) battery, 12 V, 95 A h, are used in the DEV5-5. High accuracy within a range of 3% and good reliability are obtained. The BMS can also improve the performance and cycle-life of the Ni-MH battery peak, as well as the reliability and the safety of the electric vehicles.

  15. Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations.

    PubMed

    Lee, Edmond P F; Wright, Timothy G

    2005-10-08

    The heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) have been studied by high-level ab initio calculations. The RCCSD(T) method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a (2)Pi ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from (2)Pi to (2)Sigma(+) as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest (3)Sigma(-) and (3)Pi states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.

  16. Surface Tension of Liquid Alkali, Alkaline, and Main Group Metals: Theoretical Treatment and Relationship Investigations

    NASA Astrophysics Data System (ADS)

    Aqra, Fathi; Ayyad, Ahmed

    2011-09-01

    An improved theoretical method for calculating the surface tension of liquid metals is proposed. A recently derived equation that allows an accurate estimate of surface tension to be made for the large number of elements, based on statistical thermodynamics, is used for a means of calculating reliable values for the surface tension of pure liquid alkali, alkaline earth, and main group metals at the melting point, In order to increase the validity of the model, the surface tension of liquid lithium was calculated in the temperature range 454 K to 1300 K (181 °C to 1027 °C), where the calculated surface tension values follow a straight line behavior given by γ = 441 - 0.15 (T-Tm) (mJ m-2). The calculated surface excess entropy of liquid Li (- dγ/ dT) was found to be 0.15 mJ m-2 K-1, which agrees well with the reported experimental value (0.147 mJ/m2 K). Moreover, the relations of the calculated surface tension of alkali metals to atomic radius, heat of fusion, and specific heat capacity are described. The results are in excellent agreement with the existing experimental data.

  17. Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice? [Metal-Air Batteries: Future Electrochemical Energy Storage of Choice?

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

    Li, Yanguang; Lu, Jun

    Metal-air batteries have much higher theoretical energy density than lithium-ion batteries, and are frequently advocated as the solution toward next-generation electrochemical energy storage for applications including electric vehicles or grid energy storage. Yet they have not fulfilled their full potentials as limited by challenges associated with the metal anode, air cathode and electrolyte. These challenges would have to be properly resolved before metal-air batteries can become a practical reality and be deployed on a large scale. Here we survey the current status and latest advances in metal-air battery research for both aqueous (e.g. Zn-air) and non-aqueous (e.g. Li-air) systems. Themore » general technical issues confronting their developments are overviewed, and our perspective on possible solutions is offered.« less

  18. Metal–Air Batteries: Will They Be the Future Electrochemical Energy Storage Device of Choice? [Metal-Air Batteries: Future Electrochemical Energy Storage of Choice?

    DOE PAGES

    Li, Yanguang; Lu, Jun

    2017-05-05

    Metal-air batteries have much higher theoretical energy density than lithium-ion batteries, and are frequently advocated as the solution toward next-generation electrochemical energy storage for applications including electric vehicles or grid energy storage. Yet they have not fulfilled their full potentials as limited by challenges associated with the metal anode, air cathode and electrolyte. These challenges would have to be properly resolved before metal-air batteries can become a practical reality and be deployed on a large scale. Here we survey the current status and latest advances in metal-air battery research for both aqueous (e.g. Zn-air) and non-aqueous (e.g. Li-air) systems. Themore » general technical issues confronting their developments are overviewed, and our perspective on possible solutions is offered.« less

  19. Theoretical study of mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes.

    PubMed

    Groen, Cornelis Petrus; Oskam, Ad; Kovács, Attila

    2003-02-10

    The structure, bonding, and vibrational properties of the mixed MLaX(4) (M = Na, K, Cs; X = F, Cl, Br, I) rare earth/alkali metal halide complexes have been studied using the MP2 method in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. From the three characteristic structures, possessing 1- (C(3)(v)), 2- (C(2)(v)), or 3-fold coordination (C(3)(v)) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are stable isomers with close dissociation energies. In general, for the complexes existing of lighter alkali metals and halogens, the bidentate structure corresponds to the global minimum of the potential energy surface, while the heavier analogues favor the tridentate structure. At experimentally relevant temperatures (T > 800 K), however, the isomerization entropy leads to a domination of the bidentate structures over the tridentate forms for all complexes. An important effect of the size of the alkali metal is manifested in the larger stabilities of the K and Cs complexes. The natural atomic charges are in agreement with strong electrostatic interactions in the title complexes. The marginal covalent contributions show a slight increasing trend in the heavier analogues. The calculated vibrational data indicate that infrared spectroscopy may be an effective tool for experimental investigation and characterization of MLaX(4) molecules.

  20. Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

    PubMed

    Gagné, Olivier Charles; Hawthorne, Frank Christopher

    2016-08-01

    Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

  1. Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: morphology and performance as a cathode material for lithium ion batteries.

    PubMed

    Kim, Yongseon

    2012-05-01

    Li(Ni(0.8)Co(0.1)Mn(0.1))O(2) (NCM811) was synthesized using alkali chlorides as a flux and the performance as a cathode material for lithium ion batteries was examined. Primary particles of the powder were segregated and grown separately in the presence of liquid state fluxes, which induced each particle to be composed of one primary particle with well-developed facet planes, not the shape of agglomerates as appears with commercial NCMs. The new NCM showed far less gas emission during high temperature storage at charged states, and higher volumetric capacity thanks to its high bulk density. The material is expected to provide optimal performances for pouch type lithium ion batteries, which require high volumetric capacity and are vulnerable to deformation caused by gas generation from the electrode materials.

  2. Impedance and self-discharge mechanism studies of nickel metal hydride batteries for energy storage applications

    NASA Astrophysics Data System (ADS)

    Zhu, Wenhua; Zhu, Ying; Tatarchuk, Bruce

    2013-04-01

    Nickel metal hydride battery packs have been found wide applications in the HEVs (hybrid electric vehicles) through the on-board rapid energy conservation and efficient storage to decrease the fossil fuel consumption rate and reduce CO2 emissions as well as other harmful exhaust gases. In comparison to the conventional Ni-Cd battery, the Ni-MH battery exhibits a relatively higher self-discharge rate. In general, there are quite a few factors that speed up the self-discharge of the electrodes in the sealed nickel metal hydride batteries. This disadvantage eventually reduces the overall efficiency of the energy conversion and storage system. In this work, ac impedance data were collected from the nickel metal hydride batteries. The self-discharge mechanism and battery capacity degradation were analyzed and discussed for further performance improvement.

  3. Advanced High Energy Density Secondary Batteries with Multi‐Electron Reaction Materials

    PubMed Central

    Luo, Rui; Huang, Yongxin; Li, Li

    2016-01-01

    Secondary batteries have become important for smart grid and electric vehicle applications, and massive effort has been dedicated to optimizing the current generation and improving their energy density. Multi‐electron chemistry has paved a new path for the breaking of the barriers that exist in traditional battery research and applications, and provided new ideas for developing new battery systems that meet energy density requirements. An in‐depth understanding of multi‐electron chemistries in terms of the charge transfer mechanisms occuring during their electrochemical processes is necessary and urgent for the modification of secondary battery materials and development of secondary battery systems. In this Review, multi‐electron chemistry for high energy density electrode materials and the corresponding secondary battery systems are discussed. Specifically, four battery systems based on multi‐electron reactions are classified in this review: lithium‐ and sodium‐ion batteries based on monovalent cations; rechargeable batteries based on the insertion of polyvalent cations beyond those of alkali metals; metal–air batteries, and Li–S batteries. It is noted that challenges still exist in the development of multi‐electron chemistries that must be overcome to meet the energy density requirements of different battery systems, and much effort has more effort to be devoted to this. PMID:27840796

  4. Spin relaxation in ultracold collisions of molecular radicals with alkali-metal atoms

    NASA Astrophysics Data System (ADS)

    Tscherbul, Timur; Klos, Jacek; Zukowski, Piotr

    2016-05-01

    We present accurate quantum scattering calculations of spin relaxation in ultracold collisions of alkali-metal atoms and polar 2 Σ molecules CaH, SrF, and SrOH. The calculations employ state-of-the-art ab initio interaction potentials and a rigorous quantum theory of atom-molecule collisions in a magnetic field based on the total angular momentum representation. We will further discuss the relevance of the results to atom-molecule sympathetic cooling experiments in a magnetic trap.

  5. Alkali Metal CO2 Sorbents and the Resulting Metal Carbonates: Potential for Process Intensification of Sorption-Enhanced Steam Reforming.

    PubMed

    Memon, Muhammad Zaki; Zhao, Xiao; Sikarwar, Vineet Singh; Vuppaladadiyam, Arun K; Milne, Steven J; Brown, Andy P; Li, Jinhui; Zhao, Ming

    2017-01-03

    Sorption-enhanced steam reforming (SESR) is an energy and cost efficient approach to produce hydrogen with high purity. SESR makes it economically feasible to use a wide range of feedstocks for hydrogen production such as methane, ethanol, and biomass. Selection of catalysts and sorbents plays a vital role in SESR. This article reviews the recent research aimed at process intensification by the integration of catalysis and chemisorption functions into a single material. Alkali metal ceramic powders, including Li 2 ZrO 3 , Li 4 SiO 4 and Na 2 ZrO 3 display characteristics suitable for capturing CO 2 at low concentrations (<15% CO 2 ) and high temperatures (>500 °C), and thus are applicable to precombustion technologies such as SESR, as well as postcombustion capture of CO 2 from flue gases. This paper reviews the progress made in improving the operational performance of alkali metal ceramics under conditions that simulate power plant and SESR operation, by adopting new methods of sorbent synthesis and doping with additional elements. The paper also discusses the role of carbonates formed after in situ CO 2 chemisorption during a steam reforming process in respect of catalysts for tar cracking.

  6. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

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

    Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai

    2017-03-01

    Lithium (Li) metal battery is an attractive energy storage system owing to the ultrahigh specific capacity and the lowest redox potential of Li metal anode. However, safety concern associated with dendrite growth and limited cycle life especially at a high charge current density are two critical challenges hindering the practical applications of rechargeable Li metal batteries. Here, we report for the first time that an optimal amount (0.05 M) of LiPF6 as additive in the LiTFSI-LiBOB dual-salt/carbonate-based electrolyte can significantly enhance the charging capability and the long-term cycle life of Li metal batteries with a moderately high cathode loading ofmore » 1.75 mAh cm-2. Unprecedented stable-cycling (97.1% capacity retention after 500 cycles) along with very limited increase in electrode over-potential has been achieved at a high current density of 1.75 mA cm-2. This unparalleled fast charging and stable cycling performance is contributed from both the stabilized Al cathode current collector, and, more importantly, the robust and conductive SEI layer formed on Li metal anode in the presence of the LiPF6 additive.« less

  7. Ultralow-power local laser control of the dimer density in alkali-metal vapors through photodesorption

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

    Jha, Pankaj K.; Scully, Marlan O.; Princeton University, Princeton, New Jersey 08544

    2012-08-27

    Ultralow-power diode-laser radiation is employed to induce photodesorption of cesium from a partially transparent thin-film cesium adsorbate on a solid surface. Using resonant Raman spectroscopy, we demonstrate that this photodesorption process enables an accurate local optical control of the density of dimer molecules in alkali-metal vapors.

  8. Pseudopotential theoretical study of the alkali metals under arbitrary pressure: Density, bulk modulus, and shear moduli

    NASA Astrophysics Data System (ADS)

    Rasky, Daniel J.; Milstein, Frederick

    1986-02-01

    Milstein and Hill previously derived formulas for computing the bulk and shear moduli, κ, μ, and μ', at arbitrary pressures, for cubic crystals in which interatomic interaction energies are modeled by pairwise functions, and they carried out the moduli computations using the complete family of Morse functions. The present study extends their work to a pseudopotential description of atomic binding. Specifically: (1) General formulas are derived for determining these moduli under hydrostatic loading within the framework of a pseudopotential model. (2) A two-parameter pseudopotential model is used to describe atomic binding of the alkali metals, and the two parameters are determined from experimental data (the model employs the Heine-Abarenkov potential with the Taylor dielectric function). (3) For each alkali metal (Li, Na, K, Rb, and Cs), the model is used to compute the pressure-versus-volume behavior and, at zero pressure, the binding energy, the density, and the elastic moduli and their pressure derivatives; the theoretical behavior is found to be in excellent agreement with experiment. (4) Calculations are made of κ, μ, and μ' of the bcc alkali metals over wide ranges of hydrostatic compression and expansion. (5) The pseudopotential results are compared with those of arbitrary-central-force models (wherein κ-(2/3)μ=μ'+2P) and with the specific Morse-function results. The pressures, bulk moduli, and zero-pressure shear moduli (as determined for the Morse and pseudopotential models) are in excellent agreement, but important differences appear in the shear moduli under high compressions. The computations in the present paper are for the bcc metals; a subsequent paper will extend this work to include both the bcc and fcc structures, at compressions and expansions where elastic stability or lattice cohesion is, in practice, lost.

  9. 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

  10. 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

  11. Silicon halide-alkali metal flames as a source of solar grade silicon

    NASA Technical Reports Server (NTRS)

    Olsen, D. B.; Miller, W. J.

    1979-01-01

    The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

  12. Long life lithium batteries with stabilized electrodes

    DOEpatents

    Amine, Khalil [Downers Grove, IL; Liu, Jun [Naperville, IL; Vissers, Donald R [Naperville, IL; Lu, Wenquan [Darien, IL

    2009-03-24

    The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

  13. Thin-film silicon for flexible metal-air batteries.

    PubMed

    Garamoun, Ahmed; Schubert, Markus B; Werner, Jürgen H

    2014-12-01

    Due to its high energy density, theoretical studies propose silicon as a promising candidate material for metal-air batteries. Herein, for the first time, experimental results detail the use of n-type doped amorphous silicon and silicon carbide as fuel in Si-air batteries. Thin-film silicon is particularly interesting for flexible and rolled batteries with high specific energies. Our Si-air batteries exhibit a specific capacity of 269 Ah kg(-1) and an average cell voltage of 0.85 V at a discharge current density of 7.9 μA cm(-2) , corresponding to a specific energy of 229 Wh kg(-1) . Favorably in terms of safety, low concentrated alkaline solution serves as electrolyte. Discharging of the Si-air cells continues as long as there is silicon available for oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Development of a nickel/metal hydride battery (Ni/MH) system for EV application

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

    Ikoma, M.; Hamada, S.; Morishita, N.

    1994-12-31

    In order to satisfy basic battery characteristics for electric vehicles (EV) such as specific energy, specific power and cycle life that are required for driving on urban streets, the authors have selected the valve-regulated lead acid battery as a conventional battery and the nickel/metal-hydride battery as an advanced battery, and have been studying their development in order to put them into practical use by 1998. Regarding the nickel/metal-hydride battery, excellent nickel positive electrode with high temperature charge efficiency accomplished with additives such as Ca compounds, and an exceedingly good hydrogen absorbing alloy negative electrode with high capacity and long cyclemore » life, achieved by adjustment of alloy composition, surface treatment, and control of binder and conductive additive have been developed to overcome difficulties in the scale-up of battery size. Modular batteries using this technology possess specific energy twice (70 Wh/kg) that of the lead-acid battery, and have superior specific power (160 Wh/kg) and cycle life. 5 refs.« less

  15. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

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

    Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai

    2017-03-01

    Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI-LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75mAh cm(-2), a cyclability of 97.1% capacity retention after 500 cycles along withmore » very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm(-2). The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.« less

  16. Bipolar Nickel-Metal Hydride Battery Development Project

    NASA Technical Reports Server (NTRS)

    Cole, John H.

    1999-01-01

    This paper reviews the development of the Electro Energy, Inc.'s bipolar nickel metal hydride battery. The advantages of the design are that each cell is individually sealed, and that there are no external cell terminals, no electrode current collectors, it is compatible with plastic bonded electrodes, adaptable to heat transfer fins, scalable to large area, capacity and high voltage. The design will allow for automated flexible manufacturing, improved energy and power density and lower cost. The development and testing of the battery's component are described. Graphic presentation of the results of many of the tests are included.

  17. M13 virus-directed synthesis of nanostructured metal oxides for lithium-oxygen batteries.

    PubMed

    Oh, Dahyun; Qi, Jifa; Han, Binghong; Zhang, Geran; Carney, Thomas J; Ohmura, Jacqueline; Zhang, Yong; Shao-Horn, Yang; Belcher, Angela M

    2014-08-13

    Transition metal oxides are promising electrocatalysts for both water oxidations and metal-air batteries. Here, we report the virus-mediated synthesis of cobalt manganese oxide nanowires (NWs) to fabricate high capacity Li-O2 battery electrodes. Furthermore, we hybridized Ni nanoparticles (NPs) on bio Co3O4 NWs to improve the round trip efficiency as well as the cycle life of Li-O2 batteries. This biomolecular directed synthesis method is expected to provide a selection platform for future energy storage electrocatalysts.

  18. Method of treating alkali metal sulfide and carbonate mixtures

    DOEpatents

    Kohl, Arthur L.; Rennick, Robert D.; Savinsky, Martin W.

    1978-01-01

    A method of removing and preferably recovering sulfur values from an alkali metal sulfide and carbonate mixture comprising the steps of (1) introducing the mixture in an aqueous medium into a first carbonation zone and reacting the mixture with a gas containing a major amount of CO.sub.2 and a minor amount of H.sub.2 S; (2) introducing the resultant product from step 1 into a stripping zone maintained at subatmospheric pressure, and contacting this product with steam to produce a gaseous mixture, comprising H.sub.2 S and water vapor, and a liquor of reduced sulfide content; (3) introducing the liquor of reduced sulfide content into a second carbonation zone, and reacting the liquor with substantially pure gaseous CO.sub.2 in an amount sufficient to precipitate bicarbonate crystals and produce an offgas containing CO.sub.2 and H.sub.2 S for use in step 1; (4) recovering the bicarbonate crystals from step 3, and thermally decomposing the crystals to produce an alkaline metal carbonate product and a substantially pure CO.sub.2 offgas for use in step 3.

  19. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

    2008-09-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

  20. Lithium Metal-Copper Vanadium Oxide Battery with a Block Copolymer Electrolyte

    DOE PAGES

    Devaux, Didier; Wang, Xiaoya; Thelen, Jacob L.; ...

    2016-09-08

    Lithium (Li) batteries comprising multivalent positive active materials such as copper vanadium oxide have high theoretical capacity. These batteries with a conventional liquid electrolyte exhibit limited cycle life because of copper dissolution into the electrolyte. In this paper, we report here on the characterization of solid-state Li metal batteries with a positive electrode based on α-Cu 6.9V 6O 18.9 (α-CuVO 3). We replaced the liquid electrolyte by a nanostructured solid block copolymer electrolyte comprising of a mixture of polystyrene-b-poly(ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. In situ X-ray diffraction was used to follow the Li insertion/de-insertion mechanism into themore » α-CuVO 3 host material and its reversibility. In situ X-ray scattering revealed that the multistep electrochemical reactions involved are similar in the presence of liquid or solid electrolyte. The capacity fade of the solid-state batteries is less rapid than that of α-CuVO 3–Li metal batteries with a conventional liquid electrolyte. Hard X-ray microtomography revealed that upon cycling, voids and Cu-rich agglomerates were formed at the interface between the Li metal and the SEO electrolyte. Finally, the void volume and the volume occupied by the Cu-rich agglomerates were independent of C-rate and cycle number.« less

  1. Implementation of Hydrodynamic Simulation Code in Shock Experiment Design for Alkali Metals

    NASA Astrophysics Data System (ADS)

    Coleman, A. L.; Briggs, R.; Gorman, M. G.; Ali, S.; Lazicki, A.; Swift, D. C.; Stubley, P. G.; McBride, E. E.; Collins, G.; Wark, J. S.; McMahon, M. I.

    2017-10-01

    Shock compression techniques enable the investigation of extreme P-T states. In order to probe off-Hugoniot regions of P-T space, target makeup and laser pulse parameters must be carefully designed. HYADES is a hydrodynamic simulation code which has been successfully utilised to simulate shock compression events and refine the experimental parameters required in order to explore new P-T states in alkali metals. Here we describe simulations and experiments on potassium, along with the techniques required to access off-Hugoniot states.

  2. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M [Naperville, IL; Kim, Jeom-Soo [Naperville, IL; Johnson, Christopher S [Naperville, IL

    2008-01-01

    An uncycled electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula Li.sub.(2+2x)/(2+x)M'.sub.2x/(2+x)M.sub.(2-2x)/(2+x)O.sub.2-.delta., in which 0.ltoreq.x<1 and .delta. is less than 0.2, and in which M is a non-lithium metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. Methods of preconditioning the electrodes are disclosed as are electrochemical cells and batteries containing the electrodes.

  3. Stabilized Lithium-Metal Surface in a Polysulfide-Rich Environment of Lithium-Sulfur Batteries.

    PubMed

    Zu, Chenxi; Manthiram, Arumugam

    2014-08-07

    Lithium-metal anode degradation is one of the major challenges of lithium-sulfur (Li-S) batteries, hindering their practical utility as next-generation rechargeable battery chemistry. The polysulfide migration and shuttling associated with Li-S batteries can induce heterogeneities of the lithium-metal surface because it causes passivation by bulk insulating Li2S particles/electrolyte decomposition products on a lithium-metal surface. This promotes lithium dendrite formation and leads to poor lithium cycling efficiency with complicated lithium surface chemistry. Here, we show copper acetate as a surface stabilizer for lithium metal in a polysulfide-rich environment of Li-S batteries. The lithium surface is protected from parasitic reactions with the organic electrolyte and the migrating polysulfides by an in situ chemical formation of a passivation film consisting of mainly Li2S/Li2S2/CuS/Cu2S and electrolyte decomposition products. This passivation film also suppresses lithium dendrite formation by controlling the lithium deposition sites, leading to a stabilized lithium surface characterized by a dendrite-free morphology and improved surface chemistry.

  4. Thigh burns from exploding e-cigarette lithium ion batteries: First case series.

    PubMed

    Nicoll, K J; Rose, A M; Khan, M A A; Quaba, O; Lowrie, A G

    2016-06-01

    E-cigarette (EC) use has risen meteorically over the last decade. The majority of these devices are powered by re-chargeable lithium ion batteries, which can represent a fire hazard if damaged, over-heated, over-charged or stored inappropriately. There are currently no reports in the medical literature of lithium ion battery burns related to EC use and no guidance on the appropriate management of lithium ion battery associated injuries. We report two individual cases of burn resulting from explosion of EC re-chargeable lithium ion batteries. Both patients required in-patient surgical management. We provide evidence that lithium ion battery explosions can be associated with mixed thermal and alkali chemical burns, resulting from the significant discharge of thermal energy and the dispersal of corrosive lithium ion compounds. We would recommend, as with other elemental metal exposures, caution in exposing lithium ion battery burns to water irrigation. Early and thorough cleaning and debridement of such burns, to remove residual lithium contamination, may limit the risk of burn wound extension and potentially improve outcomes. Copyright © 2016 Elsevier Ltd and ISBI. All rights reserved.

  5. Long life lithium batteries with stabilized electrodes

    DOEpatents

    Amine, Khalil; Liu, Jun; Vissers, Donald R; Lu, Wenquan

    2015-04-21

    The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In certain electrolytes, the alkali metal salt is a bis(chelato)borate and the additives include substituted or unsubstituted linear, branched or cyclic hydrocarbons comprising at least one oxygen atom and at least one aryl, alkenyl or alkynyl group. In other electrolytes, the additives include a substituted aryl compound or a substituted or unsubstituted heteroaryl compound wherein the additive comprises at least one oxygen atom. There are also provided methods of making the electrolytes and batteries employing the electrolytes. The invention also provides for electrode materials. Cathodes of the present invention may be further stabilized by surface coating the particles of the spinel or olivine with a material that can neutralize acid or otherwise lessen or prevent leaching of the manganese or iron ions. In some embodiments the coating is polymeric and in other embodiments the coating is a metal oxide such as ZrO.sub.2, TiO.sub.2, ZnO, WO.sub.3, Al.sub.2O.sub.3, MgO, SiO.sub.2, SnO.sub.2 AlPO.sub.4, Al(OH).sub.3, a mixture of any two or more thereof.

  6. Absorption Spectroscopy of Rubidium in an Alkali Metal Dispenser Cell and Bleached Wave Analysis

    DTIC Science & Technology

    2015-03-26

    Department of Engineering Physics Graduate School of Engineering and Management Air Force Institute of Technology Air University Air Education and...at atmospheric temperatures and pressures, so none of the safety measures needed with pure solid alkali metal would be required. AMDs can also be...Institute of Technology Graduate School of Engineering and Management (AFIT/ENP) 2950 Hobson Way WPAFB OH 45433-7765 8. PERFORMING ORGANIZATION

  7. Sodium-metal chloride battery research at JPL

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Attia, A. I.; Halpert, G.

    1991-01-01

    Sodium metal chloride batteries have certain distinct advantages over sodium sulfur batteries such as increased safety, inherent overcharge capability and lower operation temperatures. Two systems, i.e., Na/FeCl2 and Na/NiCl2 were developed extensively elsewhere and evaluated for various applications including electric vehicles and space. Their performance has been very encouraging and prompted a detailed fundamental study of these cathodes here at the Jet Propulsion Laboratory. A brief review of our studies on these new cathode materials is presented here. The initial efforts focussed on the methods of fabrication of the electrodes and their electrochemical characterization. Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics and identifying the rate limiting processes in the reduction of metal chloride cathodes. Nickel chloride emerged from these studies as the most promising candidate material and was taken up for further detailed study on its passivation - a rate limiting process - under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have higher energy density, has been assessed. Based on the criteria established from the voltammetric response of FeCl2, NiCl2, and CuCl2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt chlorides appear promising.

  8. Ionic conductivity of β-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

    PubMed

    Yang, Ling-Yun; Fu, Xiao-Bin; Chen, Tai-Qiang; Pan, Li-Kun; Ji, Peng; Yao, Ye-Feng; Chen, Qun

    2015-04-20

    Highly conductive, crystalline, polymer electrolytes, β-cyclodextrin (β-CD)-polyethylene oxide (PEO)/LiAsF6 and β-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, β-CD, and LiAsF6 /NaAsF6 . The assembled β-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Thermal behavior of heat-pipe-assisted alkali-metal thermoelectric converters

    NASA Astrophysics Data System (ADS)

    Lee, Ji-Su; Lee, Wook-Hyun; Chi, Ri-Guang; Chung, Won-Sik; Lee, Kye-Bock; Rhi, Seok-Ho; Jeong, Seon-Yong; Park, Jong-Chan

    2017-11-01

    The alkali-metal thermal-to-electric converter (AMTEC) changes thermal energy directly into electrical energy using alkali metals, such as sodium and potassium, as the working fluid. The AMTEC system primarily consists of beta-alumina solid electrolyte (BASE) tubes, low and high-pressure chambers, an evaporator, and a condenser and work through continuous sodium circulation, similar to conventional heat pipes. When the sodium ions pass through the BASE tubes with ion conductivity, this ion transfer generates electricity. The efficiency of the AMTEC directly depends on the temperature difference between the top and bottom of the system. The optimum design of components of the AMTEC, including the condenser, evaporator, BASE tubes, and artery wick, can improve power output and efficiency. Here, a radiation shield was installed in the low-pressure chamber of the AMTEC and was investigated experimentally and numerically to determine an optimum design for preventing radiation heat loss through the condenser and the wall of AMTEC container. A computational fluid dynamics (CFD) simulation was carried out to decide the optimum size of the low-pressure chamber. The most suitable height and diameter of the chamber were 270 mm and 180 mm, respectively, with eight BASE tubes, which were 150 mm high, 25 mm in diameter, and 105 mm in concentric diameter. Increasing the temperature ratio ( T Cond /T B ) led to high power output. The minimum dimensionless value (0.4611) for temperature ( T Cond /T B ) appeared when the radiation shield was made of 500-mesh nickel. Simulation results for the best position and shape for the radiation shield, revealed that maximum power was generated when a stainless steel shield was installed in between the BASE tubes and condenser.

  10. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    PubMed

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

  11. Lithium-antimony-lead liquid metal battery for grid-level energy storage

    NASA Astrophysics Data System (ADS)

    Wang, Kangli; Jiang, Kai; Chung, Brice; Ouchi, Takanari; Burke, Paul J.; Boysen, Dane A.; Bradwell, David J.; Kim, Hojong; Muecke, Ulrich; Sadoway, Donald R.

    2014-10-01

    The ability to store energy on the electric grid would greatly improve its efficiency and reliability while enabling the integration of intermittent renewable energy technologies (such as wind and solar) into baseload supply. Batteries have long been considered strong candidate solutions owing to their small spatial footprint, mechanical simplicity and flexibility in siting. However, the barrier to widespread adoption of batteries is their high cost. Here we describe a lithium-antimony-lead liquid metal battery that potentially meets the performance specifications for stationary energy storage applications. This Li||Sb-Pb battery comprises a liquid lithium negative electrode, a molten salt electrolyte, and a liquid antimony-lead alloy positive electrode, which self-segregate by density into three distinct layers owing to the immiscibility of the contiguous salt and metal phases. The all-liquid construction confers the advantages of higher current density, longer cycle life and simpler manufacturing of large-scale storage systems (because no membranes or separators are involved) relative to those of conventional batteries. At charge-discharge current densities of 275 milliamperes per square centimetre, the cells cycled at 450 degrees Celsius with 98 per cent Coulombic efficiency and 73 per cent round-trip energy efficiency. To provide evidence of their high power capability, the cells were discharged and charged at current densities as high as 1,000 milliamperes per square centimetre. Measured capacity loss after operation for 1,800 hours (more than 450 charge-discharge cycles at 100 per cent depth of discharge) projects retention of over 85 per cent of initial capacity after ten years of daily cycling. Our results demonstrate that alloying a high-melting-point, high-voltage metal (antimony) with a low-melting-point, low-cost metal (lead) advantageously decreases the operating temperature while maintaining a high cell voltage. Apart from the fact that this finding

  12. Lithium-antimony-lead liquid metal battery for grid-level energy storage.

    PubMed

    Wang, Kangli; Jiang, Kai; Chung, Brice; Ouchi, Takanari; Burke, Paul J; Boysen, Dane A; Bradwell, David J; Kim, Hojong; Muecke, Ulrich; Sadoway, Donald R

    2014-10-16

    The ability to store energy on the electric grid would greatly improve its efficiency and reliability while enabling the integration of intermittent renewable energy technologies (such as wind and solar) into baseload supply. Batteries have long been considered strong candidate solutions owing to their small spatial footprint, mechanical simplicity and flexibility in siting. However, the barrier to widespread adoption of batteries is their high cost. Here we describe a lithium-antimony-lead liquid metal battery that potentially meets the performance specifications for stationary energy storage applications. This Li||Sb-Pb battery comprises a liquid lithium negative electrode, a molten salt electrolyte, and a liquid antimony-lead alloy positive electrode, which self-segregate by density into three distinct layers owing to the immiscibility of the contiguous salt and metal phases. The all-liquid construction confers the advantages of higher current density, longer cycle life and simpler manufacturing of large-scale storage systems (because no membranes or separators are involved) relative to those of conventional batteries. At charge-discharge current densities of 275 milliamperes per square centimetre, the cells cycled at 450 degrees Celsius with 98 per cent Coulombic efficiency and 73 per cent round-trip energy efficiency. To provide evidence of their high power capability, the cells were discharged and charged at current densities as high as 1,000 milliamperes per square centimetre. Measured capacity loss after operation for 1,800 hours (more than 450 charge-discharge cycles at 100 per cent depth of discharge) projects retention of over 85 per cent of initial capacity after ten years of daily cycling. Our results demonstrate that alloying a high-melting-point, high-voltage metal (antimony) with a low-melting-point, low-cost metal (lead) advantageously decreases the operating temperature while maintaining a high cell voltage. Apart from the fact that this

  13. A metal-free organic-inorganic aqueous flow battery

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

    Huskinson, B; Marshak, MP; Suh, C

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metalsmore » and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox

  14. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries.

    PubMed

    Li, M M; Yang, C C; Wang, C C; Wen, Z; Zhu, Y F; Zhao, M; Li, J C; Zheng, W T; Lian, J S; Jiang, Q

    2016-06-07

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world's dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials-hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g(-1), which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  15. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    PubMed Central

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-01-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g−1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles. PMID:27270184

  16. Design of Hydrogen Storage Alloys/Nanoporous Metals Hybrid Electrodes for Nickel-Metal Hydride Batteries

    NASA Astrophysics Data System (ADS)

    Li, M. M.; Yang, C. C.; Wang, C. C.; Wen, Z.; Zhu, Y. F.; Zhao, M.; Li, J. C.; Zheng, W. T.; Lian, J. S.; Jiang, Q.

    2016-06-01

    Nickel metal hydride (Ni-MH) batteries have demonstrated key technology advantages for applications in new-energy vehicles, which play an important role in reducing greenhouse gas emissions and the world’s dependence on fossil fuels. However, the poor high-rate dischargeability of the negative electrode materials—hydrogen storage alloys (HSAs) limits applications of Ni-MH batteries in high-power fields due to large polarization. Here we design a hybrid electrode by integrating HSAs with a current collector of three-dimensional bicontinuous nanoporous Ni. The electrode shows enhanced high-rate dischargeability with the capacity retention rate reaching 44.6% at a discharge current density of 3000 mA g-1, which is 2.4 times that of bare HSAs (18.8%). Such a unique hybrid architecture not only enhances charge transfer between nanoporous Ni and HSAs, but also facilitates rapid diffusion of hydrogen atoms in HSAs. The developed HSAs/nanoporous metals hybrid structures exhibit great potential to be candidates as electrodes in high-performance Ni-MH batteries towards applications in new-energy vehicles.

  17. Understanding the molecular mechanism of pulse current charging for stable lithium-metal batteries

    PubMed Central

    Li, Qi; Tan, Shen; Li, Linlin; Lu, Yingying; He, Yi

    2017-01-01

    High energy and safe electrochemical storage are critical components in multiple emerging fields of technologies. Rechargeable lithium-metal batteries are considered to be promising alternatives for current lithium-ion batteries, leading to as much as a 10-fold improvement in anode storage capacity (from 372 to 3860 mAh g−1). One of the major challenges for commercializing lithium-metal batteries is the reliability and safety issue, which is often associated with uneven lithium electrodeposition (lithium dendrites) during the charging stage of the battery cycling process. We report that stable lithium-metal batteries can be achieved by simply charging cells with square-wave pulse current. We investigated the effects of charging period and frequency as well as the mechanisms that govern this process at the molecular level. Molecular simulations were performed to study the diffusion and the solvation structure of lithium cations (Li+) in bulk electrolyte. The model predicts that loose association between cations and anions can enhance the transport of Li+ and eventually stabilize the lithium electrodeposition. We also performed galvanostatic measurements to evaluate the cycling behavior and cell lifetime under pulsed electric field and found that the cell lifetime can be more than doubled using certain pulse current waveforms. Both experimental and simulation results demonstrate that the effectiveness of pulse current charging on dendrite suppression can be optimized by choosing proper time- and frequency-dependent pulses. This work provides a molecular basis for understanding the mechanisms of pulse current charging to mitigating lithium dendrites and designing pulse current waveforms for stable lithium-metal batteries. PMID:28776039

  18. Metal-Air Batteries: (Latest citations from the Aerospace Database)

    NASA Technical Reports Server (NTRS)

    1997-01-01

    The bibliography contains citations concerning applications of metal-air batteries. Topics include systems that possess different practical energy densities at specific powers. Coverage includes the operation of air electrodes at different densities and performance results. The systems are used in electric vehicles as a cost-effective method to achieve reliability and efficiency. Zinc-air batteries are covered more thoroughly in a separate bibliography. (Contains 50-250 citations and includes a subject term index and title list.)

  19. Chemical effects of alkali atoms on critical temperature in superconducting alkali-doped fullerides

    NASA Astrophysics Data System (ADS)

    Hetfleisch, F.; Gunnarsson, O.; Srama, R.; Han, J. E.; Stepper, M.; Roeser, H.-P.; Bohr, A.; Lopez, J. S.; Mashmool, M.; Roth, S.

    2018-03-01

    Alkali metal doped fullerides (A3C60) are superconductors with critical temperatures, Tc, extending up to 38 K. Tc is known to depend strongly on the lattice parameter a, which can be adjusted by physical or chemical pressure. In the latter case an alkali atom is replaced by a different sized one, which changes a. We have collected an extensive data base of experimental data for Tc from very early up to recent measurements. We disentangle alkali atom chemical effects on Tc, beyond the well-known consequences of changing a. It is found that Tc, for a fixed a, is typically increased as smaller alkali atoms are replaced by larger ones, except for very large a. Possible reasons for these results are discussed. Although smaller in size than the lattice parameter contribution, the chemical effect is not negligible and should be considered in future physical model developments.

  20. Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries with High Sulfur Mass Loading.

    PubMed

    Chen, Lin; Huang, Zhennan; Shahbazian-Yassar, Reza; Libera, Joseph A; Klavetter, Kyle C; Zavadil, Kevin R; Elam, Jeffrey W

    2018-02-28

    Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm 2 . After 140 cycles at a high current rate of ∼1 mA/cm 2 , alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.

  1. Alkali Metal Ion Complexes with Phosphates, Nucleotides, Amino Acids, and Related Ligands of Biological Relevance. Their Properties in Solution.

    PubMed

    Crea, Francesco; De Stefano, Concetta; Foti, Claudia; Lando, Gabriele; Milea, Demetrio; Sammartano, Silvio

    2016-01-01

    Alkali metal ions play very important roles in all biological systems, some of them are essential for life. Their concentration depends on several physiological factors and is very variable. For example, sodium concentrations in human fluids vary from quite low (e.g., 8.2 mmol dm(-3) in mature maternal milk) to high values (0.14 mol dm(-3) in blood plasma). While many data on the concentration of Na(+) and K(+) in various fluids are available, the information on other alkali metal cations is scarce. Since many vital functions depend on the network of interactions occurring in various biofluids, this chapter reviews their complex formation with phosphates, nucleotides, amino acids, and related ligands of biological relevance. Literature data on this topic are quite rare if compared to other cations. Generally, the stability of alkali metal ion complexes of organic and inorganic ligands is rather low (usually log K < 2) and depends on the charge of the ligand, owing to the ionic nature of the interactions. At the same time, the size of the cation is an important factor that influences the stability: very often, but not always (e.g., for sulfate), it follows the trend Li(+) > Na(+) > K(+) > Rb(+) > Cs(+). For example, for citrate it is: log K ML = 0.88, 0.80, 0.48, 0.38, and 0.13 at 25 °C and infinite dilution. Some considerations are made on the main aspects related to the difficulties in the determination of weak complexes. The importance of the alkali metal ion complexes was also studied in the light of modelling natural fluids and in the use of these cations as probes for different processes. Some empirical relationships are proposed for the dependence of the stability constants of Na(+) complexes on the ligand charge, as well as for correlations among log K values of NaL, KL or LiL species (L = generic ligand).

  2. Hybrid electrolytes for lithium metal batteries

    NASA Astrophysics Data System (ADS)

    Keller, Marlou; Varzi, Alberto; Passerini, Stefano

    2018-07-01

    This perspective article discusses the most recent developments in the field of hybrid electrolytes, here referred to electrolytes composed of two, well-defined ion-conducting phases, for high energy density lithium metal batteries. The two phases can be both solid, as e.g., two inorganic conductors or one inorganic and one polymer conductor, or, differently, one liquid and one inorganic conductor. In this latter case, they are referred as quasi-solid hybrid electrolytes. Techniques for the appropriate characterization of hybrid electrolytes are discussed emphasizing the importance of ionic conduction and interfacial properties. On this view, multilayer systems are also discussed in more detail. Investigations on Lewis acid-base interactions, activation energies for lithium-ion transfer between the phases, and the formation of an interphase between the components are reviewed and analyzed. The application of different hybrid electrolytes in lithium metal cells with various cathode compositions is also discussed. Fabrication methods for the feasibility of large-scale applications are briefly analyzed and different cell designs and configurations, which are most suitable for the integration of hybrid electrolytes, are determined. Finally, the specific energy of cells containing different hybrid electrolytes is estimated to predict possible enhancement in energy with respect to the current lithium-ion battery technology.

  3. Alkali-Resistant Mechanism of a Hollandite DeNOx Catalyst.

    PubMed

    Hu, Pingping; Huang, Zhiwei; Gu, Xiao; Xu, Fei; Gao, Jiayi; Wang, Yue; Chen, Yaxin; Tang, Xingfu

    2015-06-02

    A thorough understanding of the deactivation mechanism by alkalis is of great importance for rationally designing improved alkali-resistant deNOx catalysts, but a traditional ion-exchange mechanism cannot often accurately describe the nature of the deactivation, thus hampering the development of superior catalysts. Here, we establish a new exchange-coordination mechanism on the basis of the exhaustive study on the strong alkali resistance of a hollandite manganese oxide (HMO) catalyst. A combination of isothermal adsorption measurements of ammonia with X-ray absorption near-edge structure spectra and X-ray photoelectron spectra reveals that alkali metal ions first react with protons from Brønsted acid sites of HMO via the ion exchange. Synchrotron X-ray diffraction patterns and extended X-ray absorption fine structure spectra coupled with theoretical calculations demonstrate that the exchanged alkali metal ions are subsequently stabilized at size-suitable cavities in the HMO pores via a coordination model with an energy savings. This exchange-coordination mechanism not only gives a wholly convincing explanation for the intrinsic nature of the deactivation of the reported catalysts by alkalis but also provides a strategy for rationally designing improved alkali-resistant deNOx catalysts in general.

  4. High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes.

    PubMed

    Chen, Shuru; Zheng, Jianming; Mei, Donghai; Han, Kee Sung; Engelhard, Mark H; Zhao, Wengao; Xu, Wu; Liu, Jun; Zhang, Ji-Guang

    2018-03-25

    Rechargeable lithium-metal batteries (LMBs) are regarded as the "holy grail" of energy-storage systems, but the electrolytes that are highly stable with both a lithium-metal anode and high-voltage cathodes still remain a great challenge. Here a novel "localized high-concentration electrolyte" (HCE; 1.2 m lithium bis(fluorosulfonyl)imide in a mixture of dimethyl carbonate/bis(2,2,2-trifluoroethyl) ether (1:2 by mol)) is reported that enables dendrite-free cycling of lithium-metal anodes with high Coulombic efficiency (99.5%) and excellent capacity retention (>80% after 700 cycles) of Li||LiNi 1/3 Mn 1/3 Co 1/3 O 2 batteries. Unlike the HCEs reported before, the electrolyte reported in this work exhibits low concentration, low cost, low viscosity, improved conductivity, and good wettability that make LMBs closer to practical applications. The fundamental concept of "localized HCEs" developed in this work can also be applied to other battery systems, sensors, supercapacitors, and other electrochemical systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Nickel-metal hydride (Ni-MH) batteries for aircraft power

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

    Erbacher, J.K.; Kruchek, C.L.; Vukson, S.P.

    1995-12-31

    Commercial nickel metal hydride (Ni-MH) batteries are under evaluation for potential application as a replacement for existing Ni-Cd and Pb-Acid batteries currently used by the USAF. Replacement of these batteries is desirable due to the high cost of maintenance and acquisition, the environmental hazards associated with worker exposure to hazardous materials, and the high cost of reclamation programs for these existing batteries. Both cylindrical and prismatic AB5 cells show promise for this application, but will require alloy and single cell development to reduce self-discharge, increase discharge and charge rates, and expand the temperature range to meet austere military environments. Testedmore » AB{sub 2} cylindrical cell technology appear inadequate to meet military requirements although these cells show better charge capability at 71 C than AB{sub 5} cylindrical or prismatic cells.« less

  6. Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

    NASA Astrophysics Data System (ADS)

    Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

    2017-05-01

    Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

  7. Non-pulsed electrochemical impregnation of flexible metallic battery plaques

    DOEpatents

    Maskalick, Nicholas J.

    1982-01-01

    A method of loading active battery material into porous, flexible, metallic battery plaques, comprises the following steps: precipitating nickel hydroxide active material within the plaque, by making the plaque cathodic, at a high current density, in an electro-precipitation cell also containing a consumable nickel anode and a solution comprising nickel nitrate, having a pH of between 2.0 and 2.8; electrochemically oxidizing the precipitate in caustic formation solution; and repeating the electro-precipitation step at a low current density.

  8. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

    DOE PAGES

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; ...

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  9. Recovery of Metal Values from Spent Zinc-Carbon Dry Cell Batteries

    NASA Astrophysics Data System (ADS)

    Khan, Majharul Haque; Gulshan, Fahmida; Kurny, A. S. W.

    2013-04-01

    Spent zinc-carbon dry cell batteries were characterized in the process of recovery of metal values. Zinc, manganese and steel were the major metallic materials constituting 63 % of the weight of spent batteries. Different components of the spent batteries were separately processed to extract the metallic values. A maximum of 92 % of total amount of zinc contained in the anodes could be extracted with a purity of over 99.0 % from the anodes by heating at 600 °C for 10 min in presence of 12 % NH4Cl flux. Spent electrolyte paste containing manganese and zinc as major metallic elements, was leached in sulfuric acid solution in presence of hydrogen peroxide as a reducing agent. The optimum condition for leaching was found to be concentration of sulfuric acid: 2.5 M, concentration of hydrogen peroxide: 10 %, temperature: 60 °C, stirring speed: 600 rpm and solid/liquid ratio 1:12. A maximum of 88 % manganese contained in the paste could be dissolved within 27 min of leaching under the optimized conditions. Dissolution of zinc under the same conditions was 97 %. A maximum of 69.89 % of manganese and 83.29 % of zinc contained in the leach liquor could be precipitated in the form of manganese carbonate and zinc oxalate.

  10. Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

    NASA Astrophysics Data System (ADS)

    Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

    2014-06-01

    A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

  11. Azimuthal swirl in liquid metal electrodes and batteries

    NASA Astrophysics Data System (ADS)

    Ashour, Rakan; Kelley, Douglas

    2016-11-01

    Liquid metal batteries consist of two molten metals with different electronegativity separated by molten salt. In these batteries, critical performance related factors such as the limiting current density are governed by fluid mixing in the positive electrode. In this work we present experimental results of a swirling flow in a layer of molten lead-bismuth alloy driven by electrical current. Using in-situ ultrasound velocimetery, we show that poloidal circulation appears at low current density, whereas azimuthal swirl becomes dominant at higher current density. The presence of thermal gradients produces buoyant forces, which are found to compete with those produced by current injection. Taking the ratio of the characteristic electromagnetic to buoyant flow velocity, we are able to predict the current density at which the flow becomes electromagnetically driven. Scaling arguments are also used to show that swirl is generated through self-interaction between the electrical current in the electrode with its own magnetic field.

  12. Non-Adiabatic Atomic Transitions: Computational Cross Section Calculations of Alkali Metal-Noble Gas Collisions

    DTIC Science & Technology

    2011-09-01

    there a one time transfer of prob- ability between Coriolis coupled states. One possible way to answer this question would be to literally create and... time -dependent numerical algorithm was developed using FORTRAN 90 to predict S-Matrix elements for alkali metal - noble gas (MNg) collisions. The...committee and the physics department for their time and effort to see me through the completion of my doctorate degree. Charlton D. Lewis, II v Table of

  13. High-energy-density, aqueous, metal-polyiodide redox flow batteries

    DOEpatents

    Li, Bin; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

    2017-08-29

    Improved metal-based redox flow batteries (RFBs) can utilize a metal and a divalent cation of the metal (M.sup.2+) as an active redox couple for a first electrode and electrolyte, respectively, in a first half-cell. For example, the metal can be Zn. The RFBs can also utilize a second electrolyte having I.sup.-, anions of I.sub.x (for x.gtoreq.3), or both in an aqueous solution, wherein the I.sup.- and the anions of I.sub.x (for x.gtoreq.3) compose an active redox couple in a second half-cell.

  14. Progress in the development of Ovonic nickel-metal hydride batteries

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

    Venkatesan, S.; Corrigan, D.A.; Gifford, P.R.

    1993-05-01

    Proprietary, multicomponent hydrogen storage alloys using the principles of atomic engineering form the heart of Ovonic Nickel-Metal Hydride (Ni/MH) battery technology. This battery system, in development for 10 years, has been licensed to several manufacturers both for consumer cells and electric vehicle batteries. These cells have achieved a specific energy of over 80 Wh/kg, a peak power in excess of 200 W/kg, and over 1000 cycles at 100% depth of discharge. They also have an intrinsic ability to withstand overcharge and overdischarge abuse. Ovonic Ni/MH batteries are environmentally friendly and can be recycled. Performance data will be presented showing themore » successful scale-up of this technology for electric vehicle applications.« less

  15. Thermal management improvement of an air-cooled high-power lithium-ion battery by embedding metal foam

    NASA Astrophysics Data System (ADS)

    Mohammadian, Shahabeddin K.; Rassoulinejad-Mousavi, Seyed Moein; Zhang, Yuwen

    2015-11-01

    Effect of embedding aluminum porous metal foam inside the flow channels of an air-cooled Li-ion battery module was studied to improve its thermal management. Four different cases of metal foam insert were examined using three-dimensional transient numerical simulations. The effects of permeability and porosity of the porous medium as well as state of charge were investigated on the standard deviation of the temperature field and maximum temperature inside the battery in all four cases. Compared to the case of no porous insert, embedding aluminum metal foam in the air flow channel significantly improved the thermal management of Li-ion battery cell. The results also indicated that, decreasing the porosity of the porous structure decreases both standard deviation of the temperature field and maximum temperature inside the battery. Moreover, increasing the permeability of the metal foam drops the maximum temperature inside the battery while decreasing this property leads to improving the temperature uniformity. Our results suggested that, among the all studied cases, desirable temperature uniformity and maximum temperature were achieved when two-third and the entire air flow channel is filled with aluminum metal foam, respectively.

  16. 3718-F Alkali Metal Treatment and Storage Facility Closure Plan

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

    None

    Since 1987, Westinghouse Hanford Company has been a major contractor to the U.S. Department of Energy-Richland Operations Office and has served as co-operator of the 3718-F Alkali Metal Treatment and Storage Facility, the waste management unit addressed in this closure plan. The closure plan consists of a Part A Dangerous waste Permit Application and a RCRA Closure Plan. An explanation of the Part A Revision (Revision 1) submitted with this document is provided at the beginning of the Part A section. The closure plan consists of 9 chapters and 5 appendices. The chapters cover: introduction; facility description; process information; wastemore » characteristics; groundwater; closure strategy and performance standards; closure activities; postclosure; and references.« less

  17. Development of processes for the production of solar grade silicon from halides and alkali metals

    NASA Technical Reports Server (NTRS)

    Dickson, C. R.; Gould, R. K.

    1980-01-01

    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

  18. Preparation and Use of Alkali Metals (Li and Na) in Alumina and Silica Gel as Reagents in Organic Syntheses

    NASA Astrophysics Data System (ADS)

    Jalloh, Fatmata

    This work describes the development of alkali metals (Li and Na) encapsulated in silica and alumina gel (SG and AG), and their applications in organic syntheses. The methods elucidated involved the thermal incorporation of these metals into the pores of SG and AG, serving as solid-state reagents. The encapsulation method/approach addresses the problems associated with the high reactivity of these metals that limit their synthetic utility in research laboratories, pharmaceutical, and manufacturing industries. These problems include their sensitivity to air and moisture, pyrophoricity, difficulty in handling, non-commercial availability, and instability of some of the organoalkali metals reagents. Herein, we describe the developments to synthesize alkali metal precursor (Li-AG) in solid form that offer safer organolithium reagents. This precursor reduces or eliminates the danger associated with the traditional handling of organolithium reagents stored in flammable organic solvents. The use of Li-AG to prepare and deliver organolithium reagents from organic halides and ethers, as needed especially for those that are commercially not available is put forward. In addition, exploration of additional applications of Na-SG and Na-AG reagents in the demethoxylation of Weinreb amides to secondary amines, and Bouveault-Blanc type reduction of amides to amines are described.

  19. Interaction of Cu(+) with cytosine and formation of i-motif-like C-M(+)-C complexes: alkali versus coinage metals.

    PubMed

    Gao, Juehan; Berden, Giel; Rodgers, M T; Oomens, Jos

    2016-03-14

    The Watson-Crick structure of DNA is among the most well-known molecular structures of our time. However, alternative base-pairing motifs are also known to occur, often depending on base sequence, pH, or the presence of cations. Pairing of cytosine (C) bases induced by the sharing of a single proton (C-H(+)-C) may give rise to the so-called i-motif, which occurs primarily in expanded trinucleotide repeats and the telomeric region of DNA, particularly at low pH. At physiological pH, silver cations were recently found to stabilize C dimers in a C-Ag(+)-C structure analogous to the hemiprotonated C-dimer. Here we use infrared ion spectroscopy in combination with density functional theory calculations at the B3LYP/6-311G+(2df,2p) level to show that copper in the 1+ oxidation state induces an analogous formation of C-Cu(+)-C structures. In contrast to protons and these transition metal ions, alkali metal ions induce a different dimer structure, where each ligand coordinates the alkali metal ion in a bidentate fashion in which the N3 and O2 atoms of both cytosine ligands coordinate to the metal ion, sacrificing hydrogen-bonding interactions between the ligands for improved chelation of the metal cation.

  20. Structures of Hydrated Alkali Metal Cations, M+(H2O)nAr (m = Li, Na, K, rb and Cs, n = 3-5), Using Infrared Photodissociation Spectroscopy and Thermodynamic Analysis

    NASA Astrophysics Data System (ADS)

    Ke, Haochen; van der Linde, Christian; Lisy, James M.

    2014-06-01

    Alkali metal cations play vital roles in chemical and biochemical systems. Lithium is widely used in psychiatric treatment of manic states and bipolar disorder; Sodium and potassium are essential elements, having major biological roles as electrolytes, balancing osmotic pressure on body cells and assisting the electroneurographic signal transmission; Rubidium has seen increasing usage as a supplementation for manic depression and depression treatment; Cesium doped compounds are used as essential catalysts in chemical production and organic synthesis. Since hydrated alkali metal cations are ubiquitous and the basic form of the alkali metal cations in chemical and biochemical systems, their structural and thermodynamic properties serve as the foundation for modeling more complex chemical and biochemical processes, such as ion transport and ion size-selectivity of ionophores and protein channels. By combining mass spectrometry and infrared photodissociation spectroscopy, we have characterized the structures and thermodynamic properties of the hydrated alkali metal cations, i.e. M+(H2O)nAr, (M = Li, Na, K, Rb and Cs, n = 3-5). Ab initio calculations and RRKM-EE (evaporative ensemble) calculations were used to assist in the spectral assignments and thermodynamic analysis. Results showed that the structures of hydrated alkali metal cations were determined predominantly by the competition between non-covalent interactions, i.e. the water---water hydrogen bonding interactions and the water---cation electrostatic interactions. This balance, however, is very delicate and small changes, i.e. different cations, different levels of hydration and different effective temperatures clearly impact the balance.

  1. A low cost, high energy density and long cycle life potassium-sulfur battery for grid-scale energy storage

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

    Lu, Xiaochuan; Bowden, Mark E.; Sprenkle, Vincent L.

    2015-08-15

    Alkali metal-sulfur batteries are attractive for energy storage applications because of their high energy density. Among the batteries, lithium-sulfur batteries typically use liquid in the battery electrolyte, which causes problems in both performance and safety. Sodium-sulfur batteries can use a solid electrolyte such as beta alumina but this requires a high operating temperature. Here we report a novel potassium-sulfur battery with K+-conducting beta-alumina as the electrolyte. Our studies indicate that liquid potassium exhibits much better wettability on the surface of beta-alumina compared to liquid sodium at lower temperatures. Based on this observation, we develop a potassium-sulfur battery that can operatemore » at as low as 150°C with excellent performance. In particular, the battery shows excellent cycle life with negligible capacity fade in 1000 cycles because of the dense ceramic membrane. This study demonstrates a new battery with a high energy density, long cycle life, low cost and high safety, which is ideal for grid-scale energy storage.« less

  2. Alkali-earth metal bridges formed in biofilm matrices regulate the uptake of fluoroquinolone antibiotics and protect against bacterial apoptosis.

    PubMed

    Kang, Fuxing; Wang, Qian; Shou, Weijun; Collins, Chris D; Gao, Yanzheng

    2017-01-01

    Bacterially extracellular biofilms play a critical role in relieving toxicity of fluoroquinolone antibiotic (FQA) pollutants, yet it is unclear whether antibiotic attack may be defused by a bacterial one-two punch strategy associated with metal-reinforced detoxification efficiency. Our findings help to assign functions to specific structural features of biofilms, as they strongly imply a molecularly regulated mechanism by which freely accessed alkali-earth metals in natural waters affect the cellular uptake of FQAs at the water-biofilm interface. Specifically, formation of alkali-earth-metal (Ca 2+ or Mg 2+ ) bridge between modeling ciprofloxacin and biofilms of Escherichia coli regulates the trans-biofilm transport rate of FQAs towards cells (135-nm-thick biofilm). As the addition of Ca 2+ and Mg 2+ (0-3.5 mmol/L, CIP: 1.25 μmol/L), the transport rates were reduced to 52.4% and 63.0%, respectively. Computational chemistry analysis further demonstrated a deprotonated carboxyl in the tryptophan residues of biofilms acted as a major bridge site, of which one side is a metal and the other is a metal girder jointly connected to the carboxyl and carbonyl of a FQA. The bacterial growth rate depends on the bridging energy at anchoring site, which underlines the environmental importance of metal bridge formed in biofilm matrices in bacterially antibiotic resistance. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Metal-mediated aminocatalysis provides mild conditions: Enantioselective Michael addition mediated by primary amino catalysts and alkali-metal ions

    PubMed Central

    Leven, Matthias; Neudörfl, Jörg M

    2013-01-01

    Summary Four catalysts based on new amides of chiral 1,2-diamines and 2-sulfobenzoic acid have been developed. The alkali-metal salts of these betaine-like amides are able to form imines with enones, which are activated by Lewis acid interaction for nucleophilic attack by 4-hydroxycoumarin. The addition of 4-hydroxycoumarin to enones gives ee’s up to 83% and almost quantitative yields in many cases. This novel type of catalysis provides an effective alternative to conventional primary amino catalysis were strong acid additives are essential components. PMID:23400419

  4. Development of Li-Metal Battery Cell Chemistries at NASA Glenn Research Center

    NASA Technical Reports Server (NTRS)

    Lvovich, Vadim F.

    2015-01-01

    State-of-the-Art lithium-ion battery technology is limited by specific energy and thus not sufficiently advanced to support the energy storage necessary for aerospace needs, such as all-electric aircraft and many deep space NASA exploration missions. In response to this technological gap, our research team at NASA Glenn Research Center has been active in formulating concepts and developing testing hardware and components for Li-metal battery cell chemistries. Lithium metal anodes combined with advanced cathode materials could provide up to five times the specific energy versus state-of-the-art lithium-ion cells (1000 Whkg versus 200 Whkg). Although Lithium metal anodes offer very high theoretical capacity, they have not been shown to successfully operate reversibly.

  5. Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery.

    PubMed

    Wang, Wei; Xu, Wu; Cosimbescu, Lelia; Choi, Daiwon; Li, Liyu; Yang, Zhenguo

    2012-07-07

    A nonaqueous, hybrid metal-organic redox flow battery based on tailored anthraquinone structure is demonstrated to have an energy efficiency of ~82% and a specific discharge energy density similar to those of aqueous redox flow batteries, which is due to the significantly improved solubility of anthraquinone in supporting electrolytes.

  6. A Universal Organic Cathode for Ultrafast Lithium- and Multivalent Metal Batteries.

    PubMed

    Fan, Xiulin; Wang, Fei; Ji, Xiao; Wang, Ruixing; Gao, Tao; Hou, Singyuk; Chen, Ji; Deng, Tao; Li, Xiaogang; Chen, Long; Luo, Chao; Wang, Luning; Wang, Chunsheng

    2018-04-27

    Low-cost multivalent battery chemistries (Mg 2+ , Al 3+ ) have been extensively investigated for large-scale energy storage applications. However, their commercialization is plagued by the poor power density and cycle life of cathodes. A universal polyimides@CNT (PI@CNT) cathode is now presented that can reversibly store various cations with different valences (Li + , Mg 2+ , Al 3+ ) at an extremely fast rate. The ion-coordination charge storage mechanism of PI@CNT is systemically investigated. Full cells using PI@CNT cathodes and corresponding metal anodes exhibit long cycle life (>10000 cycles), fast kinetics (>20 C), and wide operating temperature range (-40 to 50 °C), making the low-cost industrial polyimides universal cathodes for different multivalent metal batteries. The stable ion-coordinated mechanism opens a new foundation for the development of high-energy and high-power multivalent batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Study of the factors influencing the metals solubilisation from a mixture of waste batteries by response surface methodology.

    PubMed

    Tanong, Kulchaya; Coudert, Lucie; Chartier, Myriam; Mercier, Guy; Blais, Jean-François

    2017-12-01

    This paper presents an innovative process for the recovery of valuable metals from a mixture of spent batteries. Different types of batteries, including alkaline, zinc-carbon (Zn-C), nickel cadmium (Ni-Cd), nickel metal hydride (Ni-MH), lithium ion (Li-ion) and lithium metallic (Li-M) batteries, were mixed according to the proportion of the Canadian sales of batteries. A Box-Behnken design was applied to find the optimum leaching conditions allowing a maximum of valuable metal removals from a mixture of spent batteries in the presence of an inorganic acid and a reducing agent. The results highlighted the positive effect of sodium metabisulfite on the performance of metals removal, especially for Mn. The solid/liquid ratio and the concentration of H 2 SO 4 were the main factors affecting the leaching behavior of valuable metals (Zn, Mn, Cd, Ni) present in spent batteries. Finally, the optimum leaching conditions were found as follows: one leaching step, solid/liquid ratio = 10.9%, [H 2 SO 4 ] = 1.34 M, sodium metabisulfite (Na 2 S 2 O 5 ) = 0.45 g/g of battery powder and retention time = 45 min. Under such conditions, the removal yields achieved were 94% for Mn, 81% for Cd, 99% for Zn, 96% for Co and 68% for Ni.

  8. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    NASA Astrophysics Data System (ADS)

    Patki, Gauri Dilip

    mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (<100nm diameter) and ball-milled silicon powder (325 mesh). The increase in rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from <100 nm to ˜10 nm particles, the hydrogen production rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

  9. Role of perfluoropolyether-based electrolytes in lithium metal batteries: Implication for suppressed Al current collector corrosion and the stability of Li metal/electrolytes interfaces

    NASA Astrophysics Data System (ADS)

    Cong, Lina; Liu, Jia; Armand, Michel; Mauger, Alain; Julien, Christian M.; Xie, Haiming; Sun, Liqun

    2018-03-01

    The development of safe and high performance lithium metal batteries represents a major technological challenge for this new century. Historically, intrinsic instabilities of conventional liquid organic electrolytes induced battery failures and safety issues that hinder the practical utilization of advanced rechargeable lithium metal batteries. Herein, we report a multifunctional perfluoropolyether-based liquid polymer electrolyte (PFPE-MC/LiTFSI), presenting a unique "anion-solvent" interaction. This interaction optimizes the interfacial chemistry of lithium metal batteries, which effectively inhibits the corrosion of aluminum current collectors, suppresses lithium dendrite growth, and also facilitates the formation of a thin and stable SEI layer on Li anode. Even at a high current density of 0.7 mA cm-2, the lithium dendrites do not form after 1360 h of continuous operation. The LiFePO4|PFPE-MC/LiTFSI|Li cell delivers a stable cycling performance with over 99.9% columbic efficiency either at ambient temperature or high temperature, which is significantly superior to those using traditional carbonate electrolytes. In addition, PFPE-MC/LiTFSI electrolyte also possesses eye-catching properties, such as being non-flammable, non-volatile, non-hygroscopic, and existing in the liquid state between -90 °C and 200 °C, which further ensures the high safety of the lithium metal batteries, making this electrolyte promising for the development of high energy lithium metal batteries.

  10. Heating rates in collisionally opaque alkali-metal atom traps: Role of secondary collisions

    NASA Astrophysics Data System (ADS)

    Beijerinck, H. C. W.

    2000-12-01

    Grazing collisions with background gas are the major cause of trap loss and trap heating in atom traps. To first order, these effects do not depend on the trap density. In collisionally opaque trapped atom clouds, however, scattered atoms with an energy E larger than the effective trap depth Eeff, which are destined to escape from the atom cloud, will have a finite probability for a secondary collision. This results in a contribution to the heating rate that depends on the column density of the trapped atoms, i.e., the product of density and characteristic size of the trap. For alkali-metal atom traps, secondary collisions are quite important due to the strong long-range interaction with like atoms. We derive a simple analytical expression for the secondary heating rate, showing a dependency proportional to E1/2eff. When extrapolating to a vanishing column density, only primary collisions with the background gas will contribute to the heating rate. This contribution is rather small, due to the weak long-range interaction of the usual background gas species in an ultrahigh-vacuum system-He, Ne, or Ar-with the trapped alkali-metal atoms. We conclude that the transition between trap-loss collisions and heating collisions is determined by a cutoff energy 200 μK<=Eeff<=400 μK, much smaller than the actual trap depth E in most magnetic traps. Atoms with an energy Eeffalkali-metal atoms Li through Cs as a function of the effective trap depth, the column density of the trap, and the species in the background gas. The predictions of our model are in good agreement with the experimental data of Myatt for heating rates in high-density 87Rb-atom magnetic traps at JILA, including the effect of the rf shield and the composition of the background gas. It is shown that collisions with atoms from the Oort

  11. Recovery of metals from a mixture of various spent batteries by a hydrometallurgical process.

    PubMed

    Tanong, Kulchaya; Coudert, Lucie; Mercier, Guy; Blais, Jean-Francois

    2016-10-01

    Spent batteries contain hazardous materials, including numerous metals (cadmium, lead, nickel, zinc, etc.) that are present at high concentrations. Therefore, proper treatment of these wastes is necessary to prevent their harmful effects on human health and the environment. Current recycling processes are mainly applied to treat each type of spent battery separately. In this laboratory study, a hydrometallurgical process has been developed to simultaneously and efficiently solubilize metals from spent batteries. Among the various chemical leaching agents tested, sulfuric acid was found to be the most efficient and cheapest reagent. A Box-Behnken design was used to identify the influence of several parameters (acid concentration, solid/liquid ratio, retention time and number of leaching steps) on the removal of metals from spent batteries. According to the results, the solid/liquid ratio and acid concentration seemed to be the main parameters influencing the solubilization of zinc, manganese, nickel, cadmium and cobalt from spent batteries. According to the results, the highest metal leaching removals were obtained under the optimal leaching conditions (pulp density = 180 g/L (w/v), [H2SO4] = 1 M, number of leaching step = 3 and leaching time = 30 min). Under such optimum conditions, the removal yields obtained were estimated to be 65% for Mn, 99.9% for Cd, 100% for Zn, 74% for Co and 68% for Ni. Further studies will be performed to improve the solubilization of Mn and to selectively recover the metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High Concentration Electrolyte Layer

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

    Zheng, Jianming; Yan, Pengfei; Mei, Donghai

    2016-02-08

    Lithium (Li) metal has been extensively investigated as an anode for rechargeable battery applications due to its ultrahigh specific capacity and the lowest redox potential. However, significant challenges including dendrite growth and low Coulombic efficiency are still hindering the practical applications of rechargeable Li metal batteries. Here, we demonstrate that long-term cycling of Li metal batteries can be realized by the formation of a transient high concentration electrolyte layer near the surface of Li metal anode during high rate discharge process. The highly concentrated Li+ ions in this transient layer will immediately solvate with the available solvent molecules and facilitatemore » the formation of a stable and flexible SEI layer composed of a poly(ethylene carbonate) framework integrated with other organic/inorganic lithium salts. This SEI layer largely suppresses the corrosion of Li metal anode by free organic solvents and enables the long-term operation of Li metal batteries. The fundamental findings in this work provide a new direction for the development and operation of Li metal batteries that could be operated at high current densities for a wide range of applications.« less

  13. Intracellular acidification-induced alkali metal cation/H+ exchange in human neutrophils

    PubMed Central

    1987-01-01

    Pretreatment of isolated human neutrophils (resting pHi congruent to 7.25 at pHo 7.40) with 30 mM NH4Cl for 30 min leads to an intracellular acidification (pHi congruen to 6.60) when the NH4Cl prepulse is removed. Thereafter, in 140 mM Na+ medium, pHi recovers exponentially with time (initial rate, approximately 0.12 pH/min) to reach the normal resting pHi by approximately 20 min, a process that is accomplished mainly, if not exclusively, though an exchange of internal H+ for external Na+. This Na+/H+ countertransport is stimulated by external Na+ (Km congruent to 21 mM) and by external Li+ (Km congruent to 14 mM), though the maximal transport rate for Na+ is about twice that for Li+. Both Na+ and Li+ compete as substrates for the same translocation sites on the exchange carrier. Other alkali metal cations, such as K+, Rb+, or Cs+, do not promote pHi recovery, owing to an apparent lack of affinity for the carrier. The exchange system is unaffected by ouabain or furosemide, but can be competitively inhibited by the diuretic amiloride (Ki congruent to 8 microM). The influx of Na+ or Li+ is accompanied by an equivalent counter-reflux of H+, indicating a 1:1 stoichiometry for the exchange reaction, a finding consistent with the lack of voltage sensitivity (i.e., electroneutrality) of pHi recovery. These studies indicate that the predominant mechanism in human neutrophils for pHi regulation after intracellular acidification is an amiloride-sensitive alkali metal cation/H+ exchange that shares a number of important features with similar recovery processes in a variety of other mammalian cell types. PMID:3694176

  14. Metal-organic framework-based separator for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Bai, Songyan; Liu, Xizheng; Zhu, Kai; Wu, Shichao; Zhou, Haoshen

    2016-07-01

    Lithium-sulfur batteries are a promising energy-storage technology due to their relatively low cost and high theoretical energy density. However, one of their major technical problems is the shuttling of soluble polysulfides between electrodes, resulting in rapid capacity fading. Here, we present a metal-organic framework (MOF)-based battery separator to mitigate the shuttling problem. We show that the MOF-based separator acts as an ionic sieve in lithium-sulfur batteries, which selectively sieves Li+ ions while efficiently suppressing undesired polysulfides migrating to the anode side. When a sulfur-containing mesoporous carbon material (approximately 70 wt% sulfur content) is used as a cathode composite without elaborate synthesis or surface modification, a lithium-sulfur battery with a MOF-based separator exhibits a low capacity decay rate (0.019% per cycle over 1,500 cycles). Moreover, there is almost no capacity fading after the initial 100 cycles. Our approach demonstrates the potential for MOF-based materials as separators for energy-storage applications.

  15. New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

    NASA Technical Reports Server (NTRS)

    Bugga, Ratnakumar V.; West, William C.; Kindler, Andrew; Smart, Marshall C.

    2013-01-01

    Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The

  16. James C. McGroddy Prize Talk: Superconductivity in alkali-metal doped Carbon-60

    NASA Astrophysics Data System (ADS)

    Hebard, Arthur

    2008-03-01

    Carbon sixty (C60), which was first identified in 1985 in laser desorption experiments, is unquestionably an arrestingly beautiful molecule. The high symmetry of the 12 pentagonal and 20 hexagonal faces symmetrically arrayed in a soccer-ball like structure invites special attention and continues to stimulate animated speculation. The availability in 1990 of macroscopic amounts of purified C60 derived from carbon-arc produced soot allowed the growth and characterization of both bulk and thin-film samples. Crystalline C60 is a molecular solid held together by weak van der Waals forces. The fcc structure has a 74% packing fraction thus allowing ample opportunity (26% available volume) for the intercalation of foreign atoms into the interstitial spaces of the three dimensional host. This opportunity catalyzed much of the collaborative work amongst chemists, physicists and materials scientists at Bell Laboratories, and resulted in the discovery of superconductivity in alkali-metal doped C60 with transition temperatures (Tc) in the mid-30-kelvin range. In this talk I will review how the successes of this initial team effort stimulated a worldwide collaboration between experimentalists and theorists to understand the promise and potential of an entirely new class of superconductors containing only two elements, carbon and an intercalated alkali metal. Although the cuprates still hold the record for the highest Tc, there are still open scientific questions about the mechanism that gives rise to such unexpectedly high Tc's in the non-oxide carbon-based superconductors. The doped fullerenes have unusual attributes (e.g., narrow electronic bands, high disorder, anomalous energy scales, and a tantalizing proximity to a metal-insulator Mott transition), which challenge conventional thinking and at the same time provide useful insights into new directions for finding even higher Tc materials. The final chapter of the `soot to superconductivity' story has yet to be written.

  17. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

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

    Yi, Tanghong; Chen, Wei; Cheng, Lei

    Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K + ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed themore » existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

  18. Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life.

    PubMed

    He, Mingfu; Lau, Kah Chun; Ren, Xiaodi; Xiao, Neng; McCulloch, William D; Curtiss, Larry A; Wu, Yiying

    2016-12-05

    Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Herein we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3 mol kg -1 ). Raman spectra of NaTFSI/DMSO electrolytes and ab initio molecular dynamics simulation reveal the Na + solvation number in DMSO and the formation of Na(DMSO) 3 (TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2 ) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Concentrated Electrolyte for the Sodium-Oxygen Battery: Solvation Structure and Improved Cycle Life

    DOE PAGES

    He, Mingfu; Lau, Kah Chun; Ren, Xiaodi; ...

    2016-11-03

    Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O 2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O 2 battery. Here in this paper, we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3molkg -1). Raman spectra of NaTFSI/DMSO electrolytes and abinitio molecular dynamics simulation reveal the Na + solvation number in DMSO and themore » formation of Na(DMSO) 3(TFSI)-like solvation structure. The majority of DMSO molecules solvating Na + in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O 2 batteries can be cycled forming sodium superoxide (NaO 2) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.« less

  20. The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

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

    Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.

    1986-08-01

    The alkali metal thermoelectric converter is a direct energy conversion device, utilizing a high alkali metal activity gradient to generate electrical power. Its operation is based on the unique ion conductive properties of beta''-alumina solid electrolyte. The major barrier to application of this device is identification of an electrode which can maintain optimum power densities for operation times of >10,000h. Thin, porous molybdenum electrodes have shown the best performance characteristics, but show a variety of time dependent phenomena, including eventual degradation to power densities 3-5 times lower than initial values. Several Na-Mo-O compounds, including Na/sub 2/MoO/sub 4/ and Na/sub 2/Mo/submore » 3/O/sub 6/, are formed during AMTEC operation. These compounds may be responsible for enhanced Na transport through Mo electrodes via sodium ion conduction, and eventual performance degradation due to their volatilization and decomposition. No decomposition of beta''-alumina has been observed under simulated AMTEC operating conditions up to 1373 K. In this paper, we present a model for chemical reactions occurring in porous molybdenum electrodes. The model is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, x-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell.« less

  1. Neutral glycoconjugated amide-based calix[4]arenes: complexation of alkali metal cations in water.

    PubMed

    Cindro, Nikola; Požar, Josip; Barišić, Dajana; Bregović, Nikola; Pičuljan, Katarina; Tomaš, Renato; Frkanec, Leo; Tomišić, Vladislav

    2018-02-07

    Cation complexation in water presents a unique challenge in calixarene chemistry, mostly due to the fact that a vast majority of calixarene-based cation receptors is not soluble in water or their solubility has been achieved by introducing functionalities capable of (de)protonation. Such an approach inevitably involves the presence of counterions which compete with target cations for the calixarene binding site, and also rather often requires the use of ion-containing buffer solutions in order to control the pH. Herein we devised a new strategy towards the solution of this problem, based on introducing carbohydrate units at the lower or upper rim of calix[4]arenes which comprise efficient cation binding sites. In this context, we prepared neutral, water-soluble receptors with secondary or tertiary amide coordinating groups, and studied their complexation with alkali metal cations in aqueous and methanol (for the comparison purpose) solutions. Complexation thermodynamics was quantitatively characterized by UV spectrometry and isothermal titration calorimetry, revealing that one of the prepared tertiary amide derivatives is capable of remarkably efficient (log K ≈ 5) and selective binding of sodium cations among alkali metal cations in water. Given the ease of the synthetic procedure used, and thus the variety of accessible analogues, this study can serve as a platform for the development of reagents for diverse purposes in aqueous media.

  2. Reviving the lithium metal anode for high-energy batteries

    NASA Astrophysics Data System (ADS)

    Lin, Dingchang; Liu, Yayuan; Cui, Yi

    2017-03-01

    Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li-S and Li-air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.

  3. Rare-gas impurities in alkali metals: Relation to optical absorption

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

    Meltzer, D.E.; Pinski, F.J.; Stocks, G.M.

    1988-04-15

    An investigation of the nature of rare-gas impurity potentials in alkali metals is performed. Results of calculations based on simple models are presented, which suggest the possibility of resonance phenomena. These could lead to widely varying values for the exponents which describe the shape of the optical-absorption spectrum at threshold in the Mahan--Nozieres--de Dominicis theory. Detailed numerical calculations are then performed with the Korringa-Kohn-Rostoker coherent-potential-approximation method. The results of these highly realistic calculations show no evidence for the resonance phenomena, and lead to predictions for the shape of the spectra which are in contradiction to observations. Absorption and emission spectramore » are calculated for two of the systems studied, and their relation to experimental data is discussed.« less

  4. Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

    PubMed Central

    Doeff, Marca M.; Chen, Guoying; Cabana, Jordi; Richardson, Thomas J.; Mehta, Apurva; Shirpour, Mona; Duncan, Hugues; Kim, Chunjoong; Kam, Kinson C.; Conry, Thomas

    2013-01-01

    Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g. changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g. on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done. PMID:24300777

  5. Characterization of electrode materials for lithium ion and sodium ion batteries using synchrotron radiation techniques.

    PubMed

    Doeff, Marca M; Chen, Guoying; Cabana, Jordi; Richardson, Thomas J; Mehta, Apurva; Shirpour, Mona; Duncan, Hugues; Kim, Chunjoong; Kam, Kinson C; Conry, Thomas

    2013-11-11

    Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g. changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g. on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

  6. A Quantitative Tunneling/Desorption Model for the Exchange Current at the Porous Electrode/Beta - Alumina/Alkali Metal Gas Three Phase Zone at 700-1300K

    NASA Technical Reports Server (NTRS)

    Williams, R. M.; Ryan, M. A.; Saipetch, C.; LeDuc, H. G.

    1996-01-01

    The exchange current observed at porous metal electrodes on sodium or potassium beta -alumina solid electrolytes in alkali metal vapor is quantitatively modeled with a multi-step process with good agreement with experimental results.

  7. Advanced analytical electron microscopy for alkali-ion batteries

    DOE PAGES

    Qian, Danna; Ma, Cheng; Meng, Ying Shirley; ...

    2015-06-26

    Lithium-ion batteries are a leading candidate for electric vehicle and smart grid applications. However, further optimizations of the energy/power density, coulombic efficiency and cycle life are still needed, and this requires a thorough understanding of the dynamic evolution of each component and their synergistic behaviors during battery operation. With the capability of resolving the structure and chemistry at an atomic resolution, advanced analytical transmission electron microscopy (AEM) is an ideal technique for this task. The present review paper focuses on recent contributions of this important technique to the fundamental understanding of the electrochemical processes of battery materials. A detailed reviewmore » of both static (ex situ) and real-time (in situ) studies will be given, and issues that still need to be addressed will be discussed.« less

  8. Monitoring of photoluminescence decay by alkali and alkaline earth metal cations using a photoluminescent bolaamphiphile self-assembly as an optical probe.

    PubMed

    Kim, Sunhyung; Kwak, Jinyoung; Lee, Sang-Yup

    2014-05-01

    Photoluminescence (PL) decay induced by the displacement of an ionic fluorescence component, Tb(3+), with alkali and alkaline earth metal cations was investigated using photoluminescent spherical self-assemblies as optical probes. The photoluminescent spherical self-assembly was prepared by the self-organization of a tyrosine-containing bolaamphiphile molecule with a photosensitizer and Tb(3+) ion. The lanthanide ion, Tb(3+), electrically bound to the carboxyl group of the bolaamphiphile molecule, was displaced by alkali and alkaline earth metal cations that had stronger electrophilicity. The PL of the self-assembly decayed remarkably due to the substitution of lanthanide ions with alkali and alkaline earth metal cations. The PL decay showed a positive correlation with cation concentration and was sensitive to the cation valency. Generally, the PL decay was enhanced by the electrophilicity of the cations. However, Ca(2+) showed greater PL decay than Mg(2+) because Ca(2+) could create various complexes with the carboxyl groups of the bolaamphiphile molecule. Microscopic and spectroscopic investigations were conducted to study the photon energy transfer and displacement of Tb(3+) by the cation exchange. This study demonstrated that the PL decay by the displacement of the ionic fluorescent compound was applied to the detection of various cations in aqueous media and is applicable to the development of future optical sensors. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Cation and anion dependence of stable geometries and stabilization energies of alkali metal cation complexes with FSA(-), FTA(-), and TFSA(-) anions: relationship with physicochemical properties of molten salts.

    PubMed

    Tsuzuki, Seiji; Kubota, Keigo; Matsumoto, Hajime

    2013-12-19

    Stable geometries and stabilization energies (Eform) of the alkali metal complexes with bis(fluorosulfonyl)amide, (fluorosulfonyl)(trifluoromethylslufonyl)amide and bis(trifluoromethylsulfonyl)amide (FSA(-), FTA(-) and TFSA(-)) were studied by ab initio molecular orbital calculations. The FSA(-) complexes prefer the bidentate structures in which two oxygen atoms of two SO2 groups have contact with the metal cation. The FTA(-) and TFSA(-) complexes with Li(+) and Na(+) prefer the bidentate structures, while the FTA(-) and TFSA(-) complexes with Cs(+) prefer tridentate structures in which the metal cation has contact with two oxygen atoms of an SO2 group and one oxygen atom of another SO2 group. The two structures are nearly isoenergetic in the FTA(-) and TFSA(-) complexes with K(+) and Rb(+). The magnitude of Eform depends on the alkali metal cation significantly. The Eform calculated for the most stable TFSA(-) complexes with Li(+), Na(+), K(+), Rb(+) and Cs(+) cations at the MP2/6-311G** level are -137.2, -110.5, -101.1, -89.6, and -84.1 kcal/mol, respectively. The viscosity and ionic conductivity of the alkali TFSA molten salts have strong correlation with the magnitude of the attraction. The viscosity increases and the ionic conductivity decreases with the increase of the attraction. The melting points of the alkali TFSA and alkali BETA molten salts also have correlation with the magnitude of the Eform, which strongly suggests that the magnitude of the attraction play important roles in determining the melting points of these molten salts. The anion dependence of the Eform calculated for the complexes is small (less than 2.9 kcal/mol). This shows that the magnitude of the attraction is not the cause of the low melting points of alkali FTA molten salts compared with those of corresponding alkali TFSA molten salts. The electrostatic interactions are the major source of the attraction in the complexes. The electrostatic energies for the most stable TFSA

  10. Fast ion transport at solid-solid interfaces in hybrid battery anodes

    NASA Astrophysics Data System (ADS)

    Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J.; Wei, Shuya; Zhang, Kaihang; Kourkoutis, Lena F.; Archer, Lynden A.

    2018-04-01

    Carefully designed solid-electrolyte interphases are required for stable, reversible and efficient electrochemical energy storage in batteries. We report that hybrid battery anodes created by depositing an electrochemically active metal (for example, Sn, In or Si) on a reactive alkali metal electrode by a facile ion-exchange chemistry lead to very high exchange currents and stable long-term performance of electrochemical cells based on Li and Na electrodes. By means of direct visualization and ex situ electrodeposition studies, Sn-Li anodes are shown to be stable at 3 mA cm-2 and 3 mAh cm-2. Prototype full cells in which the hybrid anodes are paired with high-loading LiNi0.8Co0.15Al0.05O2(NCA) cathodes are also reported. As a second demonstration, we create and study Sn-Na hybrid anodes and show that they can be cycled stably for more than 1,700 hours with minimal voltage divergence. Charge storage at the hybrid anodes is reported to involve a combination of alloying and electrodeposition reactions.

  11. Rydberg States of Alkali Metal Atoms on Superfluid Helium Droplets - Theoretical Considerations

    NASA Astrophysics Data System (ADS)

    Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

    2017-06-01

    The bound states of electrons on the surface of superfluid helium have been a research topic for several decades. One of the first systems treated was an electron bound to an ionized helium cluster. Here, a similar system is considered, which consists of a helium droplet with an ionized dopant inside and an orbiting electron on the outside. In our theoretical investigation we select alkali metal atoms (AK) as central ions, stimulated by recent experimental studies of Rydberg states for Na, Rb, and Cs attached to superfluid helium nanodroplets. Experimental spectra , obtained by electronic excitation and subsequent ionization, showed blueshifts for low lying electronic states and redshifts for Rydberg states. In our theoretical treatment the diatomic AK^+-He potential energy curves are first computed with ab initio methods. These potentials are then used to calculate the solvation energy of the ion in a helium droplet as a function of the number of atoms. Additional potential terms, derived from the obtained helium density distribution, are added to the undisturbed atomic pseudopotential in order to simulate a 'modified' potential felt by the outermost electron. This allows us to compute a new set of eigenstates and eigenenergies, which we compare to the experimentally observed energy shifts for highly excited alkali metal atoms on helium nanodroplets. A. Golov and S. Sekatskii, Physica B, 1994, 194, 555-556 E. Loginov, C. Callegari, F. Ancilotto, and M. Drabbels, J. Phys. Chem. A, 2011, 115, 6779-6788 F. Lackner, G. Krois, M. Koch, and W. E. Ernst, J. Phys. Chem. Lett., 2012, 3, 1404-1408 F. Lackner, G. Krois, M. Theisen, M. Koch, and W. E. Ernst, Phys. Chem. Chem. Phys., 2011, 13, 18781-18788

  12. Effect of charging on silicene with alkali metal atom adsorption

    NASA Astrophysics Data System (ADS)

    Li, Manman; Li, Zhongyao; Gong, Shi-Jing

    2018-02-01

    Based on first-principles calculations, we studied the effects of charging on the structure, binding energy and electronic properties of silicene with alkali metal (AM) atom (Li, Na or K) adsorption. In AMSi2, electron doping enlarges the lattice constant of silicene, while the influence of hole doping is non-monotonic. In AMSi8, the lattice constant increases/decreases almost linearly with the increase in electron/hole doping. In addition, the AM-Si vertical distance can be greatly enlarged by excessive hole doping in both AMSi2 and AMSi8 systems. When the hole doping is as large as  +e per unit cell, both AMSi2 and AMSi8 can be transformed from metal to semiconductor. However, the binding energy would be negative in the AM+ Si2 semiconductor. It suggests AM+ Si2 is unstable in this case. In addition, the electron doping and the AM-Si vertical distance would greatly influence the band gap of silicene in LiSi8 and NaSi8, while the band gap in KSi8 is relatively stable. Therefore, KSi8 may be a more practicable material in nanotechnology.

  13. Lithium metal oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kang, Sun-Ho

    2010-06-08

    An uncycled preconditioned electrode for a non-aqueous lithium electrochemical cell including a lithium metal oxide having the formula xLi.sub.2-yH.sub.yO.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 in which 0metal ion with an average trivalent oxidation state selected from two or more of the first row transition metals or lighter metal elements in the periodic table, and M' is one or more ions with an average tetravalent oxidation state selected from the first and second row transition metal elements and Sn. The xLi.sub.2-yH.sub.y.xM'O.sub.2.(1-x)Li.sub.1-zH.sub.zMO.sub.2 material is prepared by preconditioning a precursor lithium metal oxide (i.e., xLi.sub.2M'O.sub.3.(1-x)LiMO.sub.2) with a proton-containing medium with a pH<7.0 containing an inorganic acid. Methods of preparing the electrodes are disclosed, as are electrochemical cells and batteries containing the electrodes.

  14. H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

    1987-01-01

    For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

  15. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M [Naperville, IL; Johnson, Christopher S [Naperville, IL; Amine, Khalil [Downers Grove, IL; Kim, Jaekook [Naperville, IL

    2004-01-13

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2 M'O.sub.3 in which 0batteries are disclosed with anode, cathode and electrolyte as are batteries of several cells connected in parallel or series or both.

  16. Strong texturing of lithium metal in batteries

    DOE PAGES

    Shi, Feifei; Pei, Allen; Vailionis, Arturas; ...

    2017-10-30

    Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type ofmore » additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO 3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.« less

  17. Strong texturing of lithium metal in batteries

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

    Shi, Feifei; Pei, Allen; Vailionis, Arturas

    Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type ofmore » additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO 3 and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. In conclusion, this understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.« less

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

    PubMed Central

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

    2017-01-01

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

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

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

    Fu, Kun; Gong, Yunhui; Liu, Boyang

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

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

    DOE PAGES

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

    2017-04-07

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

  1. Lithium metal protection enabled by in-situ olefin polymerization for high-performance secondary lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    An, Yongling; Zhang, Zhen; Fei, Huifang; Xu, Xiaoyan; Xiong, Shenglin; Feng, Jinkui; Ci, Lijie

    2017-09-01

    Lithium metal is considered to be the optimal choice of next-generation anode materials due to its ultrahigh theoretical capacity and the lowest redox potential. However, the growth of dendritic and mossy lithium for rechargeable Li metal batteries lead to the possible short circuiting and subsequently serious safety issues during charge/discharge cycles. For the further practical applications of Li anode, here we report a facile method for fabricating robust interfacial layer via in-situ olefin polymerization. The resulting polymer layer effectively suppresses the formation of Li dendrites and enables the long-term operation of Li metal batteries. Using Li-S cells as a test system, we also demonstrate an improved capacity retention with the protection of tetramethylethylene-polymer. Our results indicate that this method could be a promising strategy to tackle the intrinsic problems of lithium metal anodes and promote the development of Li metal batteries.

  2. Lithium salts for advanced lithium batteries: Li-metal, Li-O 2, and Li-S

    DOE PAGES

    Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik; ...

    2015-06-01

    Presently lithium hexafluorophosphate (LiPF 6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Li-metal), lithium-oxygen (Li-O 2), and lithium sulphur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical andmore » chemical reactions and conditions within such cells. Furthermore, this review explores the critical role Li-salts play in ensuring in these batteries viability.« less

  3. Recovering metal values hydrometallurgically from spent dry battery cells

    NASA Astrophysics Data System (ADS)

    Rabah, M. A.; Barakat, M. A.; Mahrous, Y. Sh.

    1999-12-01

    A hydro-pyrometallurgical method was used to recover metal values from spent dry battery cells. Water-soluble ingredients were filtered, and solid residue was sorted by magnetic separation and water flotation. Parameters affecting the recovery efficiency were also studied. Results revealed that metallic parts, carbon rods, and paper were safely recovered; pure NH4Cl, MnO2, and ZnCl2 salts were obtained. Maximum recovery efficiencies reached 93 percent for manganese and 99.5 percent for zinc and NH4.

  4. Control of wavepacket dynamics in mixed alkali metal clusters by optimally shaped fs pulses

    NASA Astrophysics Data System (ADS)

    Bartelt, A.; Minemoto, S.; Lupulescu, C.; Vajda, Š.; Wöste, L.

    We have performed adaptive feedback optimization of phase-shaped femtosecond laser pulses to control the wavepacket dynamics of small mixed alkali-metal clusters. An optimization algorithm based on Evolutionary Strategies was used to maximize the ion intensities. The optimized pulses for NaK and Na2K converged to pulse trains consisting of numerous peaks. The timing of the elements of the pulse trains corresponds to integer and half integer numbers of the vibrational periods of the molecules, reflecting the wavepacket dynamics in their excited states.

  5. High-energy redox-flow batteries with hybrid metal foam electrodes.

    PubMed

    Park, Min-Sik; Lee, Nam-Jin; Lee, Seung-Wook; Kim, Ki Jae; Oh, Duk-Jin; Kim, Young-Jun

    2014-07-09

    A nonaqueous redox-flow battery employing [Co(bpy)3](+/2+) and [Fe(bpy)3](2+/3+) redox couples is proposed for use in large-scale energy-storage applications. We successfully demonstrate a redox-flow battery with a practical operating voltage of over 2.1 V and an energy efficiency of 85% through a rational cell design. By utilizing carbon-coated Ni-FeCrAl and Cu metal foam electrodes, the electrochemical reactivity and stability of the nonaqueous redox-flow battery can be considerably enhanced. Our approach intoduces a more efficient conversion of chemical energy into electrical energy and enhances long-term cell durability. The cell exhibits an outstanding cyclic performance of more than 300 cycles without any significant loss of energy efficiency. Considering the increasing demands for efficient energy storage, our achievement provides insight into a possible development pathway for nonaqueous redox-flow batteries with high energy densities.

  6. Alkali metals levels in the human brain tissue: Anatomical region differences and age-related changes.

    PubMed

    Ramos, Patrícia; Santos, Agostinho; Pinto, Edgar; Pinto, Nair Rosas; Mendes, Ricardo; Magalhães, Teresa; Almeida, Agostinho

    2016-12-01

    The link between trace elements imbalances (both "toxic" and "essential") in the human brain and neurodegenerative disease has been subject of extensive research. More recently, some studies have highlighted the potential role of the homeostasis deregulation of alkali metals in specific brain regions as key factor in the pathogenesis of neurodegenerative diseases such as multiple sclerosis and Alzheimer's disease. Using flame atomic emission spectrometry and inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion of the samples, alkali metals (Na, K, Li, Rb and Cs) were determined in 14 different areas of the human brain (frontal cortex, superior and middle temporal gyri, caudate nucleus, putamen, globus pallidus, cingulated gyrus, hippocampus, inferior parietal lobule, visual cortex of the occipital lobe, midbrain, pons, medulla and cerebellum) of adult individuals (n=42; 71±12, range: 50-101 years old) with no known history and evidence of neurodegenerative, neurological or psychiatric disorder. Potassium was found as the most abundant alkali metal, followed by Na, Rb, Cs and Li. Lithium, K and Cs distribution showed to be quite heterogeneous. On the contrary, Rb and Na appeared quite homogeneously distributed within the human brain tissue. The lowest levels of Na, K, Rb and Li were found in the brainstem (midbrain, medulla and pons) and cerebellum, while the lowest levels of Cs were found in the frontal cortex. The highest levels of K (mean±sd; range 15.5±2.5; 8.9-21.8mg/g) Rb (17.2±6.1; 3.9-32.4μg/g and Cs (83.4±48.6; 17.3-220.5ng/g) were found in putamen. The highest levels of Na and Li were found in the frontal cortex (11.6±2.4; 6.6-17.1mg/g) and caudate nucleus (7.6±4.6 2.2-21.3ng/g), respectively. Although K, Cs and Li levels appear to remain largely unchanged with age, some age-related changes were observed for Na and Rb levels in particular brain regions (namely in the hippocampus). Copyright © 2016 Elsevier GmbH. All

  7. An all-solid-state metal hydride - Sulfur lithium-ion battery

    NASA Astrophysics Data System (ADS)

    López-Aranguren, Pedro; Berti, Nicola; Dao, Anh Ha; Zhang, Junxian; Cuevas, Fermín; Latroche, Michel; Jordy, Christian

    2017-07-01

    A metal hydride is used for the first time as anode in a complete all-solid-state battery with sulfur as cathode and LiBH4 as solid electrolyte. The hydride is a nanocomposite made of MgH2 and TiH2 counterparts. The battery exhibits a high reversible capacity of 910 mAh g-1 with discharge plateaus at 1.8 V and 1.4 V. Moreover, the capacity remains to 85% of the initial value over the 25 first charge/discharge cycles.

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

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

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

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

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

    DOE PAGES

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

    2017-10-06

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

  10. Alkali metal thermal to electric conversion

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

    Sievers, R.K.; Ivanenok, J.F. III; Hunt, T.K.

    1995-10-01

    With potential efficiencies of up to 40%, AMTEC technology offers reliability and fuel flexibility for aerospace and ground power applications. Alkali Metal Thermal to Electric Conversion (AMTEC), a direct power-conversion technology, is emerging from the laboratory for use in a number of applications that require lightweight, long-running, efficient power systems. AMTEC is compatible with many heat and fuel sources, and it offers the reliability of direct (that is, no moving parts) thermal to electric conversion. These features make it an attractive technology for small spacecraft used in deep-space missions and for ground power applications, such as self-powered furnaces and themore » generators used in recreational vehicles. Researchers at Ford Scientific Laboratories, in Dearborn, Michigan, first conceived AMTEC technology in 1968 when they identified and patented a converter known as the sodium heat engine. This heat engine was based on the unique properties of {beta}-alumina solid electrolyte (BASE), a ceramic material that is an excellent sodium ion conductor but a poor electronic conductor. BASE was used to form a structural barrier across which a sodium concentration gradient could be produced from thermal energy. The engine provided a way to isothermally expand sodium through the BASE concentration gradient without moving mechanical components. Measured power density and calculated peak efficiencies were impressive, which led to funding from the Department of Energy for important material technology development.« less

  11. Spectroscopic studies of transition metal ions in molten alkali metal carboxylates

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

    Maroni, V.A.; Maciejewski, M.L.

    Electronic absorption and C-13 NMR spectroscopic studies were carried out to investigate the structure of (i) alkali metal formate (Fm) and acetate (Ac) eutectic melts and (ii) solutions of 3d transition metal (TM) cations in these eutectics. Measurements were made over the temperature range 90..-->..190/sup 0/C. The most stable oxidation states of the individual TMs in the Fm and Ac eutectics were: Ti/sup 3 +/, V/sup 3 +/, VO/sup 2 +/, Cr/sup 3 +/, Mn/sup 2 +/, Fe/sup 2 +/, Co/sup 2 +/, Ni/sup 2 +/, and Cu/sup 2 +/. The ligand field absorption spectra obtained in these carboxylate meltsmore » bore a consistent resemblance to the spectra of these same cations in aqueous media, but the absorptivities were generally higher than are observed for the hexaquo complexes. The results were interpreted in terms of the existence of bidentate coordination in some (if not all) cases, leading to noncentrosymmetric complexation geometries. Key results of the NMR measurements included the apparent observation of two different carboxylate anion environments in Ni/sup 2 +/ solutions. C-13 spin-lattice relaxation of the carboxylate anions in the TM-free eutectics was found to be controlled by dipolar coupling to another nucleus. In the TM-containing solutions, the spin-lattice relaxation times were reduced by a factor of 10 to 1000, evidencing the expected shift to electron-nuclear dipolar coupling. Activation energies for viscous flow derived from the spin-lattice relaxation measurements on TM-free melts were in the 10..-->..11 kcal/mol range, reflecting the highly ordered, glassy nature of the eutectics studied.« less

  12. Carbonation of metal silicates for long-term CO2 sequestration

    DOEpatents

    Blencoe, James G; Palmer, Donald A; Anovitz, Lawrence M; Beard, James S

    2014-03-18

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  13. Capacity extended bismuth-antimony cathode for high-performance liquid metal battery

    NASA Astrophysics Data System (ADS)

    Dai, Tao; Zhao, Yue; Ning, Xiao-Hui; Lakshmi Narayan, R.; Li, Ju; Shan, Zhi-wei

    2018-03-01

    Li-Bi based liquid metal batteries (LMBs) have attracted interest due to their potential for solving grid scale energy storage problems. In this study, the feasibility of replacing the bismuth cathode with a bismuth-antimony alloy cathode in lithium based LMBs is investigated. The influence of the Bi:Sb ratio on voltage characteristics is evaluated via the constant current discharge method and electrochemical titration. On observing the cross section of the electrode at various stages of discharge, it is determined that both Sb and Bi form solid intermetallics with Li on the cathode. Additionally, the addition of Bi not only reduces the melting temperature of the Bi:Sb intermetallic but also actively contributes to the electrode capacity. Thereafter, a Li|LiCl-LiF|Sb-Bi liquid metal battery with 3 A h nameplate capacity, assembled and cycled at 1 C rate, is found to possess a stable capacity for over 160 cycles. The overall performance of this battery is discussed in the context of cost effectiveness, energy and coulombic efficiencies.

  14. The Role of Dissolved Gas in Ionic Liquid Electrolytes for Secondary Lithium Metal Batteries

    DTIC Science & Technology

    2013-01-07

    devices use lithium-ion batteries comprised of a graphite anode and metal oxide cathode . Lithium, being the third-lightest element, is already synonymous...support shuttling lithium ions (battery cycling) such as the separator, electrolyte, and cathode and anode superstructures contribute most of the...ability of electro-deposit lithium non-dendritically. When lithium is electrodeposited , as during battery charging, it tends to form needle-like

  15. A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

    PubMed

    Abirami, Mari; Hwang, Soo Min; Yang, Juchan; Senthilkumar, Sirugaloor Thangavel; Kim, Junsoo; Go, Woo-Seok; Senthilkumar, Baskar; Song, Hyun-Kon; Kim, Youngsik

    2016-12-07

    Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn 3 [Co(CN) 6 ] 2 ·nH 2 O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g -1 hard carbon during 100 cycles (energy efficiencies of 74-79%).

  16. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

    PubMed

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2017-10-05

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Effect of Alkali Metal Cations on Slow Inactivation of Cardiac Na+ Channels

    PubMed Central

    Townsend, Claire; Horn, Richard

    1997-01-01

    Human heart Na+ channels were expressed transiently in both mammalian cells and Xenopus oocytes, and Na+ currents measured using 150 mM intracellular Na+. The kinetics of decaying outward Na+ current in response to 1-s depolarizations in the F1485Q mutant depends on the predominant cation in the extracellular solution, suggesting an effect on slow inactivation. The decay rate is lower for the alkali metal cations Li+, Na+, K+, Rb+, and Cs+ than for the organic cations Tris, tetramethylammonium, N-methylglucamine, and choline. In whole cell recordings, raising [Na+]o from 10 to 150 mM increases the rate of recovery from slow inactivation at −140 mV, decreases the rate of slow inactivation at relatively depolarized voltages, and shifts steady-state slow inactivation in a depolarized direction. Single channel recordings of F1485Q show a decrease in the number of blank (i.e., null) records when [Na+]o is increased. Significant clustering of blank records when depolarizing at a frequency of 0.5 Hz suggests that periods of inactivity represent the sojourn of a channel in a slow-inactivated state. Examination of the single channel kinetics at +60 mV during 90-ms depolarizations shows that neither open time, closed time, nor first latency is significantly affected by [Na+]o. However raising [Na+]o decreases the duration of the last closed interval terminated by the end of the depolarization, leading to an increased number of openings at the depolarized voltage. Analysis of single channel data indicates that at a depolarized voltage a single rate constant for entry into a slow-inactivated state is reduced in high [Na+]o, suggesting that the binding of an alkali metal cation, perhaps in the ion-conducting pore, inhibits the closing of the slow inactivation gate. PMID:9234168

  18. 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.

  19. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M [Naperville, IL; Johnson, Christopher S [Naperville, IL; Amine, Khalil [Oakbrook, IL

    2008-12-23

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0batteries are disclosed with anode, cathode and electrolyte as are batteries of several cells connected in parallel or series or both.

  20. Lithium Metal Oxide Electrodes For Lithium Cells And Batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

    2004-01-20

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2 M'O.sub.3 in which 0batteries are disclosed with anode, cathode and electrolyte as are batteries of several cells connected in parallel or series or both.

  1. Lithium metal oxide electrodes for lithium cells and batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

    2006-11-14

    A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0batteries are disclosed with anode, cathode and electrolyte as are batteries of several cells connected in parallel or series or both.

  2. Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

    NASA Technical Reports Server (NTRS)

    Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

    2006-01-01

    The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

  3. Controllable Electrochemical Fabrication of KO2-Decorated Binder-Free Cathodes for Rechargeable Lithium-Oxygen Batteries.

    PubMed

    Yu, Wei; Wang, Huwei; Qin, Lei; Hu, Junyang; Liu, Liang; Li, Baohua; Zhai, Dengyun; Kang, Feiyu

    2018-05-23

    Understanding the electrochemical property of superoxides in alkali metal oxygen batteries is critical for the design of a stable oxygen battery with high capacity and long cycle performance. In this work, a KO 2 -decorated binder-free cathode is fabricated by a simple and efficient electrochemical strategy. KO 2 nanoparticles are uniformly coated on the carbon nanotube film (CNT-f) through a controllable discharge process in the K-O 2 battery, and the KO 2 -decorated CNT-f is innovatively introduced into the Li-O 2 battery as the O 2 diffusion electrode. The Li-O 2 battery based on the KO 2 -decorated CNT-f cathode can deliver enhanced discharge capacity, reduced charge overpotential, and more stable cycle performance compared with the battery in the absence of KO 2 . In situ formed KO 2 particles on the surface of CNT-f cathode assist to form Li 2 O 2 nanosheets in the Li-O 2 battery, which contributes to the improvement of discharge capacity and cycle life. Interestingly, the analysis of KO 2 -decorated CNT-f cathodes, after discharge and cycle tests, reveals that the electrochemically synthesized KO 2 seems not a conventional electrocatalyst but a partially dissolvable and decomposable promoter in Li-O 2 batteries.

  4. A Molten Salt Lithium-Oxygen Battery.

    PubMed

    Giordani, Vincent; Tozier, Dylan; Tan, Hongjin; Burke, Colin M; Gallant, Betar M; Uddin, Jasim; Greer, Julia R; McCloskey, Bryan D; Chase, Gregory V; Addison, Dan

    2016-03-02

    Despite the promise of extremely high theoretical capacity (2Li + O2 ↔ Li2O2, 1675 mAh per gram of oxygen), many challenges currently impede development of Li/O2 battery technology. Finding suitable electrode and electrolyte materials remains the most elusive challenge to date. A radical new approach is to replace volatile, unstable and air-intolerant organic electrolytes common to prior research in the field with alkali metal nitrate molten salt electrolytes and operate the battery above the liquidus temperature (>80 °C). Here we demonstrate an intermediate temperature Li/O2 battery using a lithium anode, a molten nitrate-based electrolyte (e.g., LiNO3-KNO3 eutectic) and a porous carbon O2 cathode with high energy efficiency (∼95%) and improved rate capability because the discharge product, lithium peroxide, is stable and moderately soluble in the molten salt electrolyte. The results, supported by essential state-of-the-art electrochemical and analytical techniques such as in situ pressure and gas analyses, scanning electron microscopy, rotating disk electrode voltammetry, demonstrate that Li2O2 electrochemically forms and decomposes upon cycling with discharge/charge overpotentials as low as 50 mV. We show that the cycle life of such batteries is limited only by carbon reactivity and by the uncontrolled precipitation of Li2O2, which eventually becomes electrically disconnected from the O2 electrode.

  5. A review of the high temperature oxidation of uranium oxides in molten salts and in the solid state to form alkali metal uranates, and their composition and properties

    NASA Astrophysics Data System (ADS)

    Griffiths, Trevor R.; Volkovich, Vladimir A.

    An extensive review of the literature on the high temperature reactions (both in melts and in the solid state) of uranium oxides (UO 2, U 3O 8 and UO 3) resulting in the formation of insoluble alkali metal (Li to Cs) uranates is presented. Their uranate(VI) and uranate(V) compounds are examined, together with mixed and oxygen-deficient uranates. The reactions of uranium oxides with carbonates, oxides, per- and superoxides, chlorides, sulfates, nitrates and nitrites under both oxidising and non-oxidising conditions are critically examined and systematised, and the established compositions of a range of uranate(VI) and (V) compounds formed are discussed. Alkali metal uranates(VI) are examined in detail and their structural, physical, thermodynamic and spectroscopic properties considered. Chemical properties of alkali metal uranates(VI), including various methods for their reduction, are also reported. Errors in the current theoretical treatment of uranate(VI) spectra are identified and the need to develop routes for the preparation of single crystals is stressed.

  6. Metallic Sn‐Based Anode Materials: Application in High‐Performance Lithium‐Ion and Sodium‐Ion Batteries

    PubMed Central

    Ying, Hangjun

    2017-01-01

    Abstract With the fast‐growing demand for green and safe energy sources, rechargeable ion batteries have gradually occupied the major current market of energy storage devices due to their advantages of high capacities, long cycling life, superior rate ability, and so on. Metallic Sn‐based anodes are perceived as one of the most promising alternatives to the conventional graphite anode and have attracted great attention due to the high theoretical capacities of Sn in both lithium‐ion batteries (LIBs) (994 mA h g−1) and sodium‐ion batteries (847 mA h g−1). Though Sony has used Sn–Co–C nanocomposites as its commercial LIB anodes, to develop even better batteries using metallic Sn‐based anodes there are still two main obstacles that must be overcome: poor cycling stability and low coulombic efficiency. In this review, the latest and most outstanding developments in metallic Sn‐based anodes for LIBs and SIBs are summarized. And it covers the modification strategies including size control, alloying, and structure design to effectually improve the electrochemical properties. The superiorities and limitations are analyzed and discussed, aiming to provide an in‐depth understanding of the theoretical works and practical developments of metallic Sn‐based anode materials. PMID:29201624

  7. Metallic Sn-Based Anode Materials: Application in High-Performance Lithium-Ion and Sodium-Ion Batteries.

    PubMed

    Ying, Hangjun; Han, Wei-Qiang

    2017-11-01

    With the fast-growing demand for green and safe energy sources, rechargeable ion batteries have gradually occupied the major current market of energy storage devices due to their advantages of high capacities, long cycling life, superior rate ability, and so on. Metallic Sn-based anodes are perceived as one of the most promising alternatives to the conventional graphite anode and have attracted great attention due to the high theoretical capacities of Sn in both lithium-ion batteries (LIBs) (994 mA h g -1 ) and sodium-ion batteries (847 mA h g -1 ). Though Sony has used Sn-Co-C nanocomposites as its commercial LIB anodes, to develop even better batteries using metallic Sn-based anodes there are still two main obstacles that must be overcome: poor cycling stability and low coulombic efficiency. In this review, the latest and most outstanding developments in metallic Sn-based anodes for LIBs and SIBs are summarized. And it covers the modification strategies including size control, alloying, and structure design to effectually improve the electrochemical properties. The superiorities and limitations are analyzed and discussed, aiming to provide an in-depth understanding of the theoretical works and practical developments of metallic Sn-based anode materials.

  8. Probing the chemistry of nickel/metal hydride battery cells using electrochemical impedance spectroscopy

    NASA Technical Reports Server (NTRS)

    Isaac, Bryan J.

    1994-01-01

    Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for investigating the chemical and physical processes occurring at electrode surfaces. It offers information about electron transfer at interfaces, kinetics of reactions, and diffusion characteristics of the bulk phase between the electrodes. For battery cells, this technique offers another advantage in that it can be done without taking the battery apart. This non-destructive analysis technique can thus be used to gain a better understanding of the processes occurring within a battery cell. This also raises the possibility of improvements in battery design and identification or prediction of battery characteristics useful in industry and aerospace applications. EIS as a technique is powerful and capable of yielding significant information about the cell, but it also requires that the many parameters under investigation can be resolved. This implies an understanding of the processes occurring in a battery cell. Many battery types were surveyed in this work, but the main emphasis was on nickel/metal hydride batteries.

  9. Theoretical investigation of the use of nanocages with an adsorbed halogen atom as anode materials in metal-ion batteries.

    PubMed

    Razavi, Razieh; Abrishamifar, Seyyed Milad; Rajaei, Gholamreza Ebrahimzadeh; Kahkha, Mohammad Reza Rezaei; Najafi, Meysam

    2018-02-21

    The applicability of C 44 , B 22 N 22 , Ge 44 , and Al 22 P 22 nanocages, as well as variants of those nanocages with an adsorbed halogen atom, as high-performance anode materials in Li-ion, Na-ion, and K-ion batteries was investigated theoretically via density functional theory. The results obtained indicate that, among the nanocages with no adsorbed halogen atom, Al 22 P 22 would be the best candidate for a novel anode material for use in metal-ion batteries. Calculations also suggest that K-ion batteries which utilize these nanocages as anode materials would give better performance and would yield higher cell voltages than the corresponding Li-ion and Na-ion batteries with nanocage-based anodes. Also, the results for the nanocages with an adsorbed halogen atom imply that employing them as anode materials would lead to higher cell voltages and better metal-ion battery performance than if the nanocages with no adsorbed halogen atom were to be used as anode materials instead. Results further implied that nanocages with an adsorbed F atom would give higher cell voltages and better battery performance than nanocages with an adsorbed Cl or Br atom. We were ultimately able to conclude that a K-ion battery that utilized Al 21 P 22 with an adsorbed F atom as its anode material would afford the best metal-ion battery performance; we therefore propose this as a novel highly efficient metal-ion battery. Graphical abstract The results of a theoretical investigation indicated that Al 22 P 22 is a better candidate for a high-performance anode material in metal-ion batteries than Ge 44 is. Calculations also showed that K-ion batteries with nanocage-based anodes would produce higher cell voltages and perform better than the equivalent Li-ion and Na-ion batteries with nanocage-based anodes, and that anodes based on nanocages with an adsorbed F atom would perform better than anodes based on nanocages with an adsorbed Cl or Br atom.

  10. Nanocluster metal films as thermoelectric material for radioisotope mini battery unit

    NASA Astrophysics Data System (ADS)

    Borisyuk, P. V.; Krasavin, A. V.; Tkalya, E. V.; Lebedinskii, Yu. Yu.; Vasiliev, O. S.; Yakovlev, V. P.; Kozlova, T. I.; Fetisov, V. V.

    2016-10-01

    The paper is devoted to studying the thermoelectric and structural properties of films based on metal nanoclusters (Au, Pd, Pt). The experimental results of the study of single nanoclusters' tunneling conductance obtained with scanning tunneling spectroscopy are presented. The obtained data allowed us to evaluate the thermoelectric power of thin film consisting of densely packed individual nanoclusters. It is shown that such thin films can operate as highly efficient thermoelectric materials. A scheme of miniature thermoelectric radioisotope power source based on the thorium-228 isotope is proposed. The efficiency of the radioisotope battery using thermoelectric converters based on nanocluster metal films is shown to reach values up to 1.3%. The estimated characteristics of the device are comparable with the parameters of up-to-date radioisotope batteries based on nickel-63.

  11. Carbonation of metal silicates for long-term CO.sub.2 sequestration

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

    Blencoe, James G.; Palmer, Donald A.; Anovitz, Lawrence M.

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to producemore » a carbonate of the metal formerly contained in the metal silicate of step (a).« less

  12. Carbonation of metal silicates for long-term CO.sub.2 sequestration

    DOEpatents

    Blencoe, James G [Harriman, TN; Palmer, Donald A [Oliver Springs, TN; Anovitz, Lawrence M [Knoxville, TN; Beard, James S [Martinsville, VA

    2012-02-14

    In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

  13. Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

    PubMed

    Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

    2016-01-11

    As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Challenges and issues facing lithium metal for solid-state rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Mauger, A.; Armand, M.; Julien, C. M.; Zaghib, K.

    2017-06-01

    The commercial use of lithium metal batteries was delayed because of dendrite formation on the surface of the lithium electrode, and the difficulty finding a suitable electrolyte that has both the mechanical strength and ionic conductivity required for solid electrolytes. Recently, strategies have developed to overcome these difficulties, so that these batteries are currently an option for different applications, including electric cars. In this work, we review these strategies, and discuss the different routes that are promising for progress in the near future.

  15. Thermally-responsive, nonflammable phosphonium ionic liquid electrolytes for lithium metal batteries: operating at 100 degrees celsius.

    PubMed

    Lin, X; Kavian, R; Lu, Y; Hu, Q; Shao-Horn, Y; Grinstaff, M W

    2015-11-13

    Rechargeable batteries such as Li ion/Li metal batteries are widely used in the electronics market but the chemical instability of the electrolyte limits their use in more demanding environmental conditions such as in automotive, oil exploration, or mining applications. In this study, a series of alkyl phosphonium ionic liquid electrolyte are described with high thermal stability and solubility for LiTFSI. A lithium metal battery (LMB) containing a tailored phosphonium ionic liquid/LiTFSI electrolyte operates at 100 °C with good specific capacities and cycling stability. Substantial capacity is maintained during 70 cycles or 30 days. Instant on-off battery operation is realized via the significant temperature dependence of the electrolyte material, demonstrating the robustness and potential for use at high temperature.

  16. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

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

    Yi, Tanghong; Chen, Wei; Cheng, Lei

    Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

  17. Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

    DOE PAGES

    Yi, Tanghong; Chen, Wei; Cheng, Lei; ...

    2017-01-20

    Reversible intercalation reactions provide the basis for modern battery electrodes. In spite of the decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A xK 1–xFeF 3 (A = Li, Na). By starting with KFeF 3, approximately 75% of K+ ions were subsequently replaced by Li + and Na + through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopymore » confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe 2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. Our study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.« less

  18. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-01

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  19. Progress and recent developments in sodium-metal chloride batteries

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Attia, A. I.; Halpert, G.

    1991-01-01

    Significant strides have been made in the development of high-temperature rechargeable sodium batteries utilizing transition metal chloride cathodes in the last decade, mainly due to the expertise available on Na/S batteries. These systems have already performed attractively in the various feasibility studies and have an excellent safety record. Despite the encouraging figures obtained for specific energies, certain design changes such as modifying the geometry of the beta alumina electrolyte and optimization of the porous cathodes for enhanced electrolyte flow need to be made to achieve high power densities required in applications such as electric vehicles and space. The chemistry of MCl2 cathodes, electrode fabrication, and design options are discussed, and performance data are examined.

  20. Current status of environmental, health, and safety issues of nickel metal-hydride batteries for electric vehicles

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

    Corbus, D; Hammel, C J; Mark, J

    1993-08-01

    This report identifies important environment, health, and safety issues associated with nickel metal-hydride (Ni-MH) batteries and assesses the need for further testing and analysis. Among the issues discussed are cell and battery safety, workplace health and safety, shipping requirements, and in-vehicle safety. The manufacture and recycling of Ni-MH batteries are also examined. This report also overviews the ``FH&S`` issues associated with other nickel-based electric vehicle batteries; it examines venting characteristics, toxicity of battery materials, and the status of spent batteries as a hazardous waste.

  1. Doppler-free satellites of resonances of electromagnetically induced transparency and absorption on the D 2 lines of alkali metals

    NASA Astrophysics Data System (ADS)

    Sargsyan, A.; Sarkisyan, D.; Staedter, D.; Akulshin, A. M.

    2006-11-01

    The peculiarities of intra-Doppler structures that are observed in the atomic absorption spectrum of alkali metals with the help of two independent lasers have been studied. These structures accompany ultranarrow coherent resonances of electromagnetically induced transparency and absorption. With the D 2 line of rubidium taken as an example, it is shown that, in the scheme of unidirectional waves, the maximum number of satellite resonances caused by optical pumping selective with respect to the atomic velocity is equal to seven, while only six resonances are observed in the traditional scheme of saturated absorption with counterpropagating waves of the same frequency. The spectral position of the resonances and their polarity depend on the frequency of the saturating radiation, while their number and relative amplitude depend also on the experimental geometry. These features are of general character and should show themselves in the absorption spectrum on the D 2 lines of all alkali metals. An explanation of these features is given. The calculated spectral separations between the resonances are compared to the experimental ones, and their possible application is discussed.

  2. Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries)

    NASA Astrophysics Data System (ADS)

    Kim, Hojong; Boysen, Dane A.; Ouchi, Takanari; Sadoway, Donald R.

    2013-11-01

    Calcium is an attractive electrode material for use in grid-scale electrochemical energy storage due to its low electronegativity, earth abundance, and low cost. The feasibility of combining a liquid Ca-Bi positive electrode with a molten salt electrolyte for use in liquid metal batteries at 500-700 °C was investigated. Exhibiting excellent reversibility up to current densities of 200 mA cm-2, the calcium-bismuth liquid alloy system is a promising positive electrode candidate for liquid metal batteries. The measurement of low self-discharge current suggests that the solubility of calcium metal in molten salt electrolytes can be sufficiently suppressed to yield high coulombic efficiencies >98%. The mechanisms giving rise to Ca-Bi electrode overpotentials were investigated in terms of associated charge transfer and mass transport resistances. The formation of low density Ca11Bi10 intermetallics at the electrode-electrolyte interface limited the calcium deposition rate capability of the electrodes; however, the co-deposition of barium into bismuth from barium-containing molten salts suppressed Ca-Bi intermetallic formation thereby improving the discharge capacity.

  3. Calcium-Antimony Alloys as Electrodes for Liquid Metal Batteries

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

    Ouchi, T; Kim, H; Ning, XH

    The performance of a calcium-antimony (Ca-Sb) alloy serving as the positive electrode in a Ca vertical bar vertical bar Sb liquid metal battery was investigated in an electrochemical cell, Ca(in Bi) vertical bar LiCl-NaCl-CaCl2 vertical bar Ca(in Sb). The equilibrium potential of the Ca-Sb electrode was found to lie on the interval, 1.2-0.95 V versus Ca, in good agreement with electromotive force (emf) measurements in the literature. During both alloying and dealloying of Ca at the Sb electrode, the charge transfer and mass transport at the interface are facile enough that the electrode potential varies linearly from 0.95 to 0.75more » V vs Ca(s) as current density varies from 50 to 500 mA cm(-2). The discharge capacity of the Ca vertical bar vertical bar Sb cells increases as the operating temperature increases due to the higher solubility and diffusivity of Ca in Sb. The cell was successfully cycled with high coulombic efficiency (similar to 100%) and small fade rate (<0.01% cycle(-1)). These data combined with the favorable costs of these metals and salts make the Ca vertical bar vertical bar Sb liquid metal battery attractive for grid-scale energy storage. (C) The Author(s) 2014. Published by ECS. All rights reserved.« less

  4. Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

    PubMed Central

    Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C.; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J.; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J.

    2017-01-01

    Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source. PMID:28233864

  5. Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

    PubMed

    Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J

    2017-02-24

    Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

  6. Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger

    NASA Astrophysics Data System (ADS)

    Horeh, N. Bahaloo; Mousavi, S. M.; Shojaosadati, S. A.

    2016-07-01

    In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.

  7. Exploring the possibilities of two-dimensional transition metal carbides as anode materials for sodium batteries.

    PubMed

    Yang, Eunjeong; Ji, Hyunjun; Kim, Jaehoon; Kim, Heejin; Jung, Yousung

    2015-02-21

    Recently a group of two-dimensional materials called MXenes have been discovered and they have demonstrated their potential in Li rechargeable batteries. Herein, the Na storage and ion migration properties of M2C-type MXenes (M = Ti, V, Cr, Mn, Fe, Co, Ni, Nb, Mo) were investigated using density functional theory (DFT) calculations, and were compared to the Li case. Based on the average voltage and migration barrier of surface ions, we suggest that M = Ti, V, Cr, Mn, and Mo are suitable for sodium ion battery (SIB) anodes. These screened M2C materials can provide a theoretical capacity of 190-288 mA h g(-1) by accommodating two alkali ions per formula unit. They also exhibit an activation barrier of 0.1-0.2 eV for ionic motion, suggesting that the M2C materials are promising for high-power applications. The underlying aspects of the voltage differences between M2C materials are also discussed using electrostatic considerations.

  8. In Situ Neutron Depth Profiling of Lithium Metal-Garnet Interfaces for Solid State Batteries.

    PubMed

    Wang, Chengwei; Gong, Yunhui; Dai, Jiaqi; Zhang, Lei; Xie, Hua; Pastel, Glenn; Liu, Boyang; Wachsman, Eric; Wang, Howard; Hu, Liangbing

    2017-10-11

    The garnet-based solid state electrolyte (SSE) is considered a promising candidate to realize all solid state lithium (Li) metal batteries. However, critical issues require additional investigation before practical applications become possible, among which high interfacial impedance and low interfacial stability remain the most challenging. In this work, neutron depth profiling (NDP), a nondestructive and uniquely Li-sensitive technique, has been used to reveal the interfacial behavior of garnet SSE in contact with metallic Li through in situ monitoring of Li plating-stripping processes. The NDP measurement demonstrates predictive capabilities for diagnosing short-circuits in solid state batteries. Two types of cells, symmetric Li/garnet/Li (LGL) cells and asymmetric Li/garnet/carbon-nanotubes (LGC), are fabricated to emulate the behavior of Li metal and Li-free Li metal anodes, respectively. The data imply the limitation of Li-free Li metal anode in forming reliable interfacial contacts, and strategies of excessive Li and better interfacial engineering need to be investigated.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

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

  10. Designing and Diagnosing Novel Electrode Materials for Na-ion Batteries: Potential Alternatives to Current Li-ion Batteries

    NASA Astrophysics Data System (ADS)

    Xu, Jing

    Owing to outstanding energy density, Li-ion batteries have dominated the portable electronic industry for the past 20 years and they are now moving forward powering electric vehicles. In light of concerns over limited lithium reserve and rising lithium costs in the future, Na-ion batteries have re-emerged as potential alternatives for large scale energy storage. On the other hand, though both sodium and lithium are alkali metals sharing many chemical similarities, research on Na-ion batteries is still facing many challenges due to the larger size and unique bonding characteristics of Na ions. In this thesis, a series of sodium transition metal oxides are investigated as cathode materials for Na-ion batteries. P2 - Na2/3[Ni1/3 Mn2/3]O2 is firstly studied with a combination of first principles calculation and experiment, and battery performance is improved by excluding the phase transformation region. Li substituted compound, P2-Na0.8[Li0.12Ni0.22Mn0.66]O 2, is then explored. Its crystal / electronic structure evolution upon cycling is tracked by combing in situ synchrotron X-ray diffraction, ex situ X-ray absorption spectroscopy and solid state NMR. It is revealed that the presence of Li-ions in the transition metal layer allows increased amount of Na-ions to maintain the P2 structure during cycling. The design principles for the P2 type Na cathodes are devised based on this in-depth understanding and an optimized composition is proposed. The idea of Li substitution is then transferred to O3 type cathode. The new material, O3 - Na0.78 Li0.18Ni0.25Mn0.583O2, shows discharge capacity of 240 mAh/g, which is the highest capacity and highest energy density so far among cathode materials in Na-ion batteries. With significant progress on cathode materials, a comprehensive understanding of Na2Ti3O7 as anode for Na-ion batteries is discussed. The electrochemical performance is enhanced, due to increased electronic conductivity and reduced SEI formation with carbon coating

  11. Coverage dependent work function of graphene on a Cu(111) substrate with intercalated alkali metals

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

    Cook, Brandon G.; Russakoff, Arthur; Varga, Kalman

    2015-05-26

    Using first-principles calculations, it is shown that the work function of graphene on copper can be adjusted by varying the concentration of intercalated alkali metals. Using density functional theory, we calculate the modulation of work function when Li, Na, or K are intercalated between graphene and a Cu(111) surface. Furthermore, the physical origins of the change in work function are explained in terms of phenomenological models accounting for the formation and depolarization of interfacial dipoles and the shift in the Fermi-level induced via charge transfer.

  12. Facile synthesis of nanostructured transition metal oxides as electrodes for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Opra, Denis P.; Gnedenkov, Sergey V.; Sokolov, Alexander A.; Minaev, Alexander N.; Kuryavyi, Valery G.; Sinebryukhov, Sergey L.

    2017-09-01

    At all times, energy storage is one of the greatest scientific challenge. Recently, Li-ion batteries are under special attention due to high working voltage, long cycle life, low self-discharge, reliability, no-memory effect. However, commercial LIBs usage in medium- and large-scale energy storage are limited by the capacity of lithiated metal oxide cathode and unsafety of graphite anode at high-rate charge. In this way, new electrode materials with higher electrochemical performance should be designed to satisfy a requirement in both energy and power. As it known, nanostructured transition metal oxides are promising electrode materials because of their elevated specific capacity and high potential vs. Li/Li+. In this work, the perspective of an original facile technique of pulsed high-voltage plasma discharge in synthesis of nanostructured transition metal oxides as electrodes for lithium-ion batteries has been demonstrated.

  13. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium–sulfur batteries

    PubMed Central

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-01-01

    Lithium–sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium–sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density. PMID:28262801

  14. Correction: A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    PubMed

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-12-22

    Correction for 'A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide' by Chee Koon Ng et al., Chem. Commun., 2016, 52, 11842-11845.

  15. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

    NASA Astrophysics Data System (ADS)

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

    2015-12-01

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

  16. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles.

    PubMed

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A

    2015-12-04

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries.

  17. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles

    PubMed Central

    Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha; Archer, Lynden A.

    2015-01-01

    Rough electrodeposition, uncontrolled parasitic side-reactions with electrolytes and dendrite-induced short-circuits have hindered development of advanced energy storage technologies based on metallic lithium, sodium and aluminium electrodes. Solid polymer electrolytes and nanoparticle-polymer composites have shown promise as candidates to suppress lithium dendrite growth, but the challenge of simultaneously maintaining high mechanical strength and high ionic conductivity at room temperature has so far been unmet in these materials. Here we report a facile and scalable method of fabricating tough, freestanding membranes that combine the best attributes of solid polymers, nanocomposites and gel-polymer electrolytes. Hairy nanoparticles are employed as multifunctional nodes for polymer crosslinking, which produces mechanically robust membranes that are exceptionally effective in inhibiting dendrite growth in a lithium metal battery. The membranes are also reported to enable stable cycling of lithium batteries paired with conventional intercalating cathodes. Our findings appear to provide an important step towards room-temperature dendrite-free batteries. PMID:26634644

  18. A new class of solid oxide metal-air redox batteries for advanced stationary energy storage

    NASA Astrophysics Data System (ADS)

    Zhao, Xuan

    Cost-effective and large-scale energy storage technologies are a key enabler of grid modernization. Among energy storage technologies currently being researched, developed and deployed, rechargeable batteries are unique and important that can offer a myriad of advantages over the conventional large scale siting- and geography- constrained pumped-hydro and compressed-air energy storage systems. However, current rechargeable batteries still need many breakthroughs in material optimization and system design to become commercially viable for stationary energy storage. This PhD research project investigates the energy storage characteristics of a new class of rechargeable solid oxide metal-air redox batteries (SOMARBs) that combines a regenerative solid oxide fuel cell (RSOFC) and hydrogen chemical-looping component. The RSOFC serves as the "electrical functioning unit", alternating between the fuel cell and electrolysis mode to realize discharge and charge cycles, respectively, while the hydrogen chemical-looping component functions as an energy storage unit (ESU), performing electrical-chemical energy conversion in situ via a H2/H2O-mediated metal/metal oxide redox reaction. One of the distinctive features of the new battery from conventional storage batteries is the ESU that is physically separated from the electrodes of RSOFC, allowing it to freely expand and contract without impacting the mechanical integrity of the entire battery structure. This feature also allows an easy switch in the chemistry of this battery. The materials selection for ESU is critical to energy capacity, round-trip efficiency and cost effectiveness of the new battery. Me-MeOx redox couples with favorable thermodynamics and kinetics are highly preferable. The preliminary theoretical analysis suggests that Fe-based redox couples can be a promising candidate for operating at both high and low temperatures. Therefore, the Fe-based redox-couple systems have been selected as the baseline for this

  19. Analysis of a hydrometallurgical route to recover base metals from spent rechargeable batteries by liquid-liquid extraction with Cyanex 272

    NASA Astrophysics Data System (ADS)

    Mantuano, Danuza Pereira; Dorella, Germano; Elias, Renata Cristina Alves; Mansur, Marcelo Borges

    A hydrometallurgical route is proposed to recover zinc and manganese from spent alkaline batteries in order to separate base metals such as nickel, copper, aluminium, cadmium, lithium and cobalt which constitute the main metallic species of spent NiCd, NiMH and Li-ion rechargeable batteries. The route comprises the following main steps: (1) sorting batteries by type, (2) battery dismantling to separate the spent battery dust from plastic, iron scrap and paper, (3) leaching of the dust with sulphuric acid and (4) metal separation by a liquid-liquid extraction using Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) as extractant. The metal content of NiCd, NiMH and Li-ion batteries from three distinct manufacturers has been evaluated. A factorial design of experiments was used to investigate the leaching step using operational variables such as temperature, H 2SO 4 concentration, S/L ratio and H 2O 2 concentration. Analysis of metal separation by the liquid-liquid extraction with Cyanex 272 identified a pH 1/2 2.5-3.0 for zinc and aluminium, pH 1/2 4.0-4.5 for manganese, cadmium, copper and cobalt, pH 1/2 6.5 for nickel and pH 1/2 8.0 for lithium. These results indicate that batteries must be previously sorted by type and treated separately. In addition, data fitting to an equilibrium model proposed for the reactive test system by the European Federation of Chemical Engineering (EFChE) have indicated that MR 2(RH) 2 and MR 2 complexes (where M = Zn, Mn, Co, Cd and Cu) co-exist in the organic phase with Cyanex 272 depending on the loading conditions. The route has been found technically viable to separate the main metallic species of all batteries considered in this study.

  20. Development of nickel/metal-hydride batteries for EVs and HEVs

    NASA Astrophysics Data System (ADS)

    Taniguchi, Akihiro; Fujioka, Noriyuki; Ikoma, Munehisa; Ohta, Akira

    This paper is to introduce the nickel/metal-hydride (Ni/MH) batteries for electric vehicles (EVs) and hybrid electric vehicles (HEVs) developed and mass-produced by our company. EV-95 for EVs enables a vehicle to drive approximately 200 km per charge. As the specific power is extremely high, more than 200 W/kg at 80% depth of discharge (DOD), the acceleration performance is equivalent to that of gasoline fuel automobiles. The life characteristic is also superior. This battery gives the satisfactory result of more than 1000 cycles in bench tests and approximately 4-year on-board driving. EV-28 developed for small EVs comprises of a compact and light battery module with high specific power of 300 W/kg at 80% DOD by introducing a new technology for internal cell connection. Meanwhile, our cylindrical battery for the HEV was adopted into the first generation Toyota Prius in 1997 which is the world's first mass-product HEV, and has a high specific power of 600 W/kg. Its life characteristic was found to be equivalent to more than 100,000 km driving. Furthermore, a new prismatic module in which six cells are connected internally was used for the second generation Prius in 2000. The prismatic battery comprises of a compact and light battery pack with a high specific power of 1000 W/kg, which is approximately 1.7 times that of conventional cylindrical batteries, as a consequence of the development of a new internal cell connection and a new current collection structure.

  1. Method of coating metal surfaces to form protective metal coating thereon

    DOEpatents

    Krikorian, Oscar H.; Curtis, Paul G.

    1992-01-01

    A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof.

  2. Method of coating metal surfaces to form protective metal coating thereon

    DOEpatents

    Krikorian, O.H.; Curtis, P.G.

    1992-03-31

    A process is disclosed for forming a protective metal coating on a metal surface using a flux consisting of an alkali metal fluoride, an alkaline earth metal fluoride, an alkali metal fluoaluminate, an alkali metal fluosilicate, and mixtures thereof. The flux, in particulate form, is mixed with particles of a metal coating material which may comprise aluminum, chromium, mixtures thereof, and alloys containing at least 50 wt. % aluminum and the particulate mixture is applied to the metal surface in a single step, followed by heating the coated metal surface to a temperature sufficient to cause the metal coating material to react with the metal surface to form a protective reaction product in the form of a metal coating bonded to the metal surface. The metal surface which reacts with the metal coating material to form the protective coating may comprise Fe, Co, Ni, Ti, V, Cr, Mn, Zr, Nb, Mo, Tc, Hf, Ta, W, Re and alloys thereof. 1 figure.

  3. Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium–Sulfur Batteries

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

    Li, Guoxing; Huang, Qingquan; He, Xin

    Lithium–sulfur (Li–S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li–S batteries. In this paper, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Limore » salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π–π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li–S batteries with good cycling stability (1000 cycles) and slow capacity decay. Finally, this work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.« less

  4. Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium-Sulfur Batteries.

    PubMed

    Li, Guoxing; Huang, Qingquan; He, Xin; Gao, Yue; Wang, Daiwei; Kim, Seong H; Wang, Donghai

    2018-02-27

    Lithium-sulfur (Li-S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li-S batteries. In this work, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Li salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π-π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li-S batteries with good cycling stability (1000 cycles) and slow capacity decay. This work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.

  5. Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium–Sulfur Batteries

    DOE PAGES

    Li, Guoxing; Huang, Qingquan; He, Xin; ...

    2018-01-29

    Lithium–sulfur (Li–S) batteries are promising candidates for high-energy storage devices due to high theoretical capacities of both the sulfur cathode and lithium (Li) metal anode. Considerable efforts have been devoted to improving sulfur cathodes. However, issues associated with Li anodes, such as low Coulombic efficiency (CE) and growth of Li dendrites, remain unsolved due to unstable solid-electrolyte interphase (SEI) and lead to poor capacity retention and a short cycling life of Li–S batteries. In this paper, we demonstrate a facile and effective approach to fabricate a flexible and robust hybrid SEI layer through co-deposition of aromatic-based organosulfides and inorganic Limore » salts using poly(sulfur-random-1,3-diisopropenylbenzene) as an additive in an electrolyte. The aromatic-based organic components with planar backbone conformation and π–π interaction in the SEI layers can improve the toughness and flexibility to promote stable and high efficient Li deposition/dissolution. The as-formed durable SEI layer can inhibit dendritic Li growth, enhance Li deposition/dissolution CE (99.1% over 420 cycles), and in turn enable Li–S batteries with good cycling stability (1000 cycles) and slow capacity decay. Finally, this work demonstrates a route to address the issues associated with Li metal anodes and promote the development of high-energy rechargeable Li metal batteries.« less

  6. High-temperature, high-pressure hydrothermal synthesis, characterization, and structural relationships of mixed-alkali metals uranyl silicates

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

    Chen, Yi-Hsin; Liu, Hsin-Kuan; Chang, Wen-Jung

    2016-04-15

    Three mixed-alkali metals uranyl silicates, Na{sub 3}K{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}]·2H{sub 2}O (1), Na{sub 3}Rb{sub 3}[(UO{sub 2}){sub 3}(Si{sub 2}O{sub 7}){sub 2}] (2), and Na{sub 6}Rb{sub 4}[(UO{sub 2}){sub 4}Si{sub 12}O{sub 33}] (3), have been synthesized by high-temperature, high-pressure hydrothermal reactions at 550 °C and 1440 bar, and characterized by single-crystal X-ray diffraction, photoluminescence, and thermogravimetric analysis. Compound 1 and 2 are isostructural and contain layers of uranyl disilicate. The smaller cation, Na{sup +}, is located in the intralayer channels, whereas the larger cations, K{sup +} and Rb{sup +}, and water molecule are located in the interlayer region. The absencemore » of lattice water in 2 can be understood according to the valence-matching principle. The structure is related to that of a previously reported mixed-valence uranium(V,VI) silicate. Compound 3 adopts a 3D framework structure and contains a unique unbranched dreier fourfold silicate chain with the structural formula {uB,4"1_∞}[{sup 3}Si{sub 12}O{sub 33}] formed of Q{sup 2}, Q{sup 3}, and Q{sup 4} Si. The connectivity of the Si atoms in the Si{sub 12}O{sub 33}{sup 18−} anion can be interpreted on the basis of Zintl–Klemm concept. Crystal data for compound 1: triclinic, P-1, a=5.7981(2) Å, b=7.5875(3) Å, c=12.8068(5) Å, α=103.593(2)°, β=102.879(2)°, γ=90.064(2)°, V=533.00(3) Å{sup 3}, Z=1, R1=0.0278; compound 2: triclinic, P-1, a=5.7993(3) Å, b=7.5745(3) Å, c=12.9369(6) Å, α=78.265(2)°, β=79.137(2)°, γ=89.936(2)°, V=546.02(4) Å{sup 3}, Z=1, R1=0.0287; compound 3: monoclinic, C2/m, a=23.748(1) Å, b=7.3301(3) Å, c=15.2556(7) Å, β=129.116(2)°, V=2060.4(2) Å{sup 3}, Z=2, R1=0.0304. - Graphical abstract: Three mixed-alkali metals uranyl silicates were synthesized under hydrothermal conditions at 550 °C and 1400 bar and structurally characterized by single-crystal X-ray diffraction. Two of them have a layer

  7. Used battery collection in central Mexico: metal content, legislative/management situation and statistical analysis.

    PubMed

    Guevara-García, José Antonio; Montiel-Corona, Virginia

    2012-03-01

    A statistical analysis of a used battery collection campaign in the state of Tlaxcala, Mexico, is presented. This included a study of the metal composition of spent batteries from formal and informal markets, and a critical discussion about the management of spent batteries in Mexico with respect to legislation. A six-month collection campaign was statistically analyzed: 77% of the battery types were "AA" and 30% of the batteries were from the informal market. A substantial percentage (36%) of batteries had residual voltage in the range 1.2-1.4 V, and 70% had more than 1.0 V; this may reflect underutilization. Metal content analysis and recovery experiments were performed with the five formal and four more frequent informal trademarks. The analysis of Hg, Cd and Pb showed there is no significant difference in content between formal and informal commercialized batteries. All of the analyzed trademarks were under the permissible limit levels of the proposed Mexican Official Norm (NOM) NMX-AA-104-SCFI-2006 and would be classified as not dangerous residues (can be thrown to the domestic rubbish); however, compared with the EU directive 2006/66/EC, 8 out of 9 of the selected battery trademarks would be rejected, since the Mexican Norm content limit is 20, 7.5 and 5 fold higher in Hg, Cd and Pb, respectively, than the EU directive. These results outline the necessity for better regulatory criteria in the proposed Mexican NOM in order to minimize the impact on human health and the environment of this type of residues. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Highly Stable Lithium Metal Batteries Enabled by Regulating the Solvation of Lithium Ions in Nonaqueous Electrolytes.

    PubMed

    Zhang, Xue-Qiang; Chen, Xiang; Cheng, Xin-Bing; Li, Bo-Quan; Shen, Xin; Yan, Chong; Huang, Jia-Qi; Zhang, Qiang

    2018-05-04

    Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO 3 ) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiN x O y on a working lithium metal anode with dendrite-free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO 3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first-principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A pre-lithiation method for sulfur cathode used for future lithium metal free full battery

    NASA Astrophysics Data System (ADS)

    Wu, Yunwen; Yokoshima, Tokihiko; Nara, Hiroki; Momma, Toshiyuki; Osaka, Tetsuya

    2017-02-01

    Lithium metal free sulfur battery paired by lithium sulfide (Li2S) is a hot point in recent years because of its potential for relatively high capacity and its safety advantage. Due to the insulating nature and high sensitivity to moisture of Li2S, it calls for new way to introduce Li ion into S cathode besides the method of directly using the Li2S powder for the battery pre-lithiation. Herein, we proposed a pre-lithiation method to lithiate the polypyrrole (PPy)/S/Ketjenblack (KB) electrode into PPy/Li2S/KB cathode at room temperature. By this process, the fully lithiated PPy/Li2S/KB cathode showed facilitated charge transfer than the original PPy/S/KB cathode, leading to better cycling performance at high C-rates and disappearance of over potential phenomenon. In this work, the ion-selective PPy layer has been introduced on the cathode surface by an electrodeposition method, which can suppress the polysulfide dissolution from the cathode source. The lithium metal free full battery coupled by the prepared Li2S/KB cathode and graphite anode exhibited excellent cycling performance. Hence, we believe this comprehensive fabrication approach of Li2S cathode will pave a way for the application of new type lithium metal free secondary battery.

  10. The Study of Anti-/Pro-Oxidant, Lipophilic, Microbial and Spectroscopic Properties of New Alkali Metal Salts of 5-O-Caffeoylquinic Acid

    PubMed Central

    Kalinowska, Monika; Bajko, Ewelina; Matejczyk, Marzena; Kaczyński, Piotr; Łozowicka, Bożena; Lewandowski, Włodzimierz

    2018-01-01

    Lithium, sodium, potassium, rubidium and caesium salts of 5-O-caffeoylquinic acid (chlorogenic acid, 5-CQA) were synthesized and described by FT-IR (infrared spectroscopy), FT-Raman (Raman spectroscopy), UV (UV absorption spectroscopy), 1H (400.15 MHz), 13C (100.63 MHz) NMR (nuclear magnetic resonance spectroscopy). The quantum–chemical calculations at the B3LYP/6-311++G** level were done in order to obtain the optimal structures, IR spectra, NBO (natural bond orbital) atomic charges, HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) orbitals and chemical reactivity parameters for 5-CQA and Li, Na and K 5-CQAs (chlorogenates). The DPPH (α, α-diphenyl-β-picrylhydrazyl) and FRAP (ferric reducing antioxidant power) assays were used for the preliminary estimation of the antioxidant properties of alkali metal chlorogenates and chlorogenic acid. In the DPPH assay the EC50 parameter were equal to 7.39 μM for 5-CQA and was in the range of 4.50–5.89 μM for salts. The FRAP values for two different concentrations (5 and 2.5 μM) of the studied compounds were respectively 114.22 and 72.53 μM Fe2+ for 5-CQA, whereas for salts they were 106.92–141.13 and 78.93–132.00 μM Fe2+. The 5-CQA and its alkali metal salts possess higher antioxidant properties than commonly applied antioxidants (BHA, BHT, l-ascorbic acid). The pro-oxidant action of these compounds on trolox oxidation was studied in the range of their concentration 0.05–0.35 μM. The lipophilicity (logkw) of chlorogenates and chlorogenic acid was determined by RP-HPLC (reverse phase—high performance liquid chromatography) using five different columns (C8, PHE (phenyl), CN (cyano), C18, IAM (immobilized artificial membrane)). The compounds were screened for their in vitro antibacterial activity against E. coli, Bacillus sp., Staphylococcus sp., Streptococcus pyogenes and antifungal activity against Candida sp. The 5-CQA possessed lower antibacterial (minimal

  11. Cell Concepts of Metal-Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications.

    PubMed

    Medenbach, Lukas; Adelhelm, Philipp

    2017-09-29

    There is great interest in using sulfur as active component in rechargeable batteries thanks to its low cost and high specific charge (1672 mAh/g). The electrochemistry of sulfur, however, is complex and cell concepts are required, which differ from conventional designs. This review summarizes different strategies for utilizing sulfur in rechargeable batteries among membrane concepts, polysulfide concepts, all-solid-state concepts as well as high-temperature systems. Among the more popular lithium-sulfur and sodium-sulfur batteries, we also comment on recent results on potassium-sulfur and magnesium-sulfur batteries. Moreover, specific properties related to the type of light metal are discussed.

  12. The Incorporation of Lithium Alloying Metals into Carbon Matrices for Lithium Ion Battery Anodes

    NASA Astrophysics Data System (ADS)

    Hays, Kevin A.

    An increased interest in renewable energies and alternative fuels has led to recognition of the necessity of wide scale adoption of the electric vehicle. Automotive manufacturers have striven to produce an electric vehicle that can match the range of their petroleum-fueled counterparts. However, the state-of-the-art lithium ion batteries used to power the current offerings still do not come close to the necessary energy density. The energy and power densities of the lithium ion batteries must be increased significantly if they are going to make electric vehicles a viable option. The chemistry of the lithium ion battery, based on lithium cobalt oxide cathodes and graphite anodes, is limited by the amount of lithium the cathode can provide and the anode will accept. While these materials have proven themselves in portable electronics over the past two decades, plausible higher energy alternatives do exist. The focus is of this study is on anode materials that could achieve a capacity of more than 3 times greater than that of graphite anodes. The lithium alloying anode materials investigated and reported herein include tin, arsenic, and gallium arsenide. These metals were synthesized with nanoscale dimensions, improving their electrochemical and mechanical properties. Each exhibits their own benefits and challenges, but all display opportunities for incorporation in lithium ion batteries. Tin is incorporated in multilayer graphene nanoshells by introducing small amounts of metal in the core and, separately, on the outside of these spheres. Electrolyte decomposition on the anode limits cycle life of the tin cores, however, tin vii oxides introduced outside of the multilayer graphene nanoshells have greatly improved long term battery performance. Arsenic is a lithium alloying metal that has largely been ignored by the research community to date. One of the first long term battery performance tests of arsenic is reported in this thesis. Anodes were made from nanoscale

  13. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    PubMed Central

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  14. All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production

    NASA Astrophysics Data System (ADS)

    Schnell, Joscha; Günther, Till; Knoche, Thomas; Vieider, Christoph; Köhler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther

    2018-04-01

    Challenges and requirements for the large-scale production of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass production, possible solutions for the production chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the production processes for a sulfide based all-solid-state battery with conventional lithium-ion cell production is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass production of all-solid-state batteries, giving insight into promising manufacturing technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.

  15. Sodium-Oxygen Batteries: A Comparative Review from Chemical and Electrochemical Fundamentals to Future Perspective.

    PubMed

    Yadegari, Hossein; Sun, Qian; Sun, Xueliang

    2016-09-01

    Alkali metal-oxygen (Li-O2 , Na-O2 ) batteries have attracted a great deal of attention recently due to their high theoretical energy densities, comparable to gasoline, making them attractive candidates for application in electrical vehicles. However, the limited cycling life and low energy efficiency (high charging overpotential) of these cells hinder their commercialization. The Li-O2 battery system has been extensively studied in this regard during the past decade. Compared to the numerous reports of Li-O2 batteries, the research on Na-O2 batteries is still in its infancy. Although, Na-O2 batteries show a number of attractive properties such as low charging overpotential and high round-trip energy efficiency, their cycling life is currently limited to a few tens of cycles. Therefore, understanding the chemistry behind Na-O2 cells is critical towards enhancing their performance and advancing their development. Chemical and electrochemical reactions of Na-O2 batteries are reviewed and compared with those of Li-O2 batteries in the present review, as well as recent works on the chemical composition and morphology of the discharge products in these batteries. Furthermore, the determining kinetics factors for controlling the chemical composition of the discharge products in Na-O2 cells are discussed and the potential research directions toward improving Na-O2 cells are proposed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Two-Dimensional Phosphorene-Derived Protective Layers on a Lithium Metal Anode for Lithium-Oxygen Batteries.

    PubMed

    Kim, Youngjin; Koo, Dongho; Ha, Seongmin; Jung, Sung Chul; Yim, Taeeun; Kim, Hanseul; Oh, Seung Kyo; Kim, Dong-Min; Choi, Aram; Kang, Yongku; Ryu, Kyoung Han; Jang, Minchul; Han, Young-Kyu; Oh, Seung M; Lee, Kyu Tae

    2018-05-04

    Lithium-oxygen (Li-O 2 ) batteries are desirable for electric vehicles because of their high energy density. Li dendrite growth and severe electrolyte decomposition on Li metal are, however, challenging issues for the practical application of these batteries. In this connection, an electrochemically active two-dimensional phosphorene-derived lithium phosphide is introduced as a Li metal protective layer, where the nanosized protective layer on Li metal suppresses electrolyte decomposition and Li dendrite growth. This suppression is attributed to thermodynamic properties of the electrochemically active lithium phosphide protective layer. The electrolyte decomposition is suppressed on the protective layer because the redox potential of lithium phosphide layer is higher than that of electrolyte decomposition. Li plating is thermodynamically unfavorable on lithium phosphide layers, which hinders Li dendrite growth during cycling. As a result, the nanosized lithium phosphide protective layer improves the cycle performance of Li symmetric cells and Li-O 2 batteries with various electrolytes including lithium bis(trifluoromethanesulfonyl)imide in N,N-dimethylacetamide. A variety of ex situ analyses and theoretical calculations support these behaviors of the phosphorene-derived lithium phosphide protective layer.

  17. Alkali and alkaline earth metal salts of tetrazolone: structurally interesting and excellently thermostable.

    PubMed

    He, Piao; Wu, Le; Wu, Jin-Ting; Yin, Xin; Gozin, Michael; Zhang, Jian-Guo

    2017-07-04

    Tetrazolone (5-oxotetrazole) was synthesized by a moderate strategy through three steps (addition, cyclization and catalytic hydrogenation) avoiding the unstable intermediate diazonium, as reported during the previous preparation. Alkali and alkaline earth metal salts with lithium (1), sodium (2), potassium (3), rubidium (4) caesium (5), magnesium (6), calcium (7), strontium (8) and barium (9) were prepared and fully characterized using elemental analysis, IR and NMR spectroscopy, DSC and TG analysis. All metal salts were characterized via single-crystal X-ray diffraction. They crystallize in common space groups with high densities ranging from 1.479 (1) to 3.060 g cm -3 (5). Furthermore, the crystal structures of 7, 8 and 9 reveal interesting porous energetic coordination polymers with strong hydrogen bond interactions. All new salts have good thermal stabilities with decomposition temperature between 215.0 °C (4) and 328.2 °C (7), significantly higher than that of the reported nitrogen-rich salt neutral tetrazolone. The sensitivities towards impact and friction were tested using standard methods, and all the tetrazolone-based compounds investigated can be classified into insensitive. The flame test of these metal salts supports their potential use as perchlorate-free pyrotechnics or eco-friendly insensitive energetic materials.

  18. Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

    PubMed

    Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

    2016-01-14

    In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

  19. Alkali metals in addition to acidic pH activate the EvgS histidine kinase sensor in Escherichia coli.

    PubMed

    Eguchi, Yoko; Utsumi, Ryutaro

    2014-09-01

    Two-component signal transduction systems (TCSs) in bacteria perceive environmental stress and transmit the information via phosphorelay to adjust multiple cellular functions for adaptation. The EvgS/EvgA system is a TCS that confers acid resistance to Escherichia coli cells. Activation of the EvgS sensor initiates a cascade of transcription factors, EvgA, YdeO, and GadE, which induce the expression of a large group of acid resistance genes. We searched for signals activating EvgS and found that a high concentration of alkali metals (Na(+), K(+)) in addition to low pH was essential for the activation. EvgS is a histidine kinase, with a large periplasmic sensor region consisting of two tandem PBPb (bacterial periplasmic solute-binding protein) domains at its N terminus. The periplasmic sensor region of EvgS was necessary for EvgS activation, and Leu152, located within the first PBPb domain, was involved in the activation. Furthermore, chimeras of EvgS and PhoQ histidine kinases suggested that alkali metals were perceived at the periplasmic sensor region, whereas the cytoplasmic linker domain, connecting the transmembrane region and the histidine kinase domain, was required for low-pH perception. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

  20. Effect of Different Binders on the Electrochemical Performance of Metal Oxide Anode for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Wang, Rui; Feng, Lili; Yang, Wenrong; Zhang, Yinyin; Zhang, Yanli; Bai, Wei; Liu, Bo; Zhang, Wei; Chuan, Yongming; Zheng, Ziguang; Guan, Hongjin

    2017-10-01

    When testing the electrochemical performance of metal oxide anode for lithium-ion batteries (LIBs), binder played important role on the electrochemical performance. Which binder was more suitable for preparing transition metal oxides anodes of LIBs has not been systematically researched. Herein, five different binders such as polyvinylidene fluoride (PVDF) HSV900, PVDF 301F, PVDF Solvay5130, the mixture of styrene butadiene rubber and sodium carboxymethyl cellulose (SBR+CMC), and polyacrylonitrile (LA133) were studied to make anode electrodes (compared to the full battery). The electrochemical tests show that using SBR+CMC and LA133 binder which use water as solution were significantly better than PVDF. The SBR+CMC binder remarkably improve the bonding capacity, cycle stability, and rate performance of battery anode, and the capacity retention was about 87% after 50th cycle relative to the second cycle. SBR+CMC binder was more suitable for making transition metal oxides anodes of LIBs.

  1. Redox shuttles for overcharge protection of lithium batteries

    DOEpatents

    Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

    2010-12-14

    The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  2. In situ electrochemical investigations of the kinetic and thermodynamic properties of nickel-metal hydride traction batteries

    NASA Astrophysics Data System (ADS)

    Yang, Xiao Guang; Liaw, Bor Yann

    Although large ampere hour nickel-metal hydride (Ni-MH) traction batteries are in the stage of being commercialized for electric and hybrid vehicle applications, little is known about their performance characteristics. By using a standard Hg/HgO reference electrode in a commercial Ni-MH battery, we were able to conduct in situ measurements to determine both kinetic and thermodynamic properties of the system, including the characteristics of individual electrodes. Using the galvanostatic intermittent titration technique (GITT), we simultaneously and effectively determined the open-circuit voltage of the battery, the equilibrium electrode potentials, and the diffusion coefficient of proton and hydrogen in the nickel and metal hydride electrode, respectively, as a function of the states of charge (SOC). Using the current-step excitation technique, we found that the internal resistance of the battery primarily comes from the metal hydride electrode, which is greater by one order of magnitude than that of the Ni electrode. The cyclic linear micro-polarization experiments, on the other hand, showed that the charge-transfer resistance of the electrochemical reaction at the metal hydride electrode is about twice larger than that of the Ni counterpart above 20% SOC. In comparison, the internal resistance is an order of magnitude smaller than those of the electrochemical charge-transfer reactions. The micro-polarization technique also allowed us to calculate the exchange current densities of the respective electrode electrochemical reactions and the associated specific exchange current densities. These in situ, simple but detailed, characterizations of the thermodynamic and kinetic properties of the Ni-MH system provided valuable information for better understanding of the battery performance.

  3. Experimental investigation of thermal characteristics of lithium ion battery using phase change materials combined with metallic foams and fins

    NASA Astrophysics Data System (ADS)

    Deng, Y. C.; Zhang, H. Y.; Xia, X.

    2016-08-01

    Phase change materials are of great interest in energy storage and energy management applications due to their high latent heat and excellent cycling stability. In this paper, the thermal characteristics of phase change materials (PCM) for thermal management of cylindrical 18650 lithium-ion battery (LIB) were experimentally investigated. A commercial paraffin wax with a melting temperaturerange between 47 - 53.8oC was used in this study. A metal cylinder with a heater was used to emulate the heat generation from a battery, which was surrounded with the paraffin PCM and containted in a metal housing. The experiment was conducted in an environmental test chamber with controlled ambient temperatures and power inputs. Both the battery temperature and the housing wall temperature were measured during steady-state heating and cyclic heating conditions. Since PCM has low thermal conductivity, thermal enhancement techniques were investigated by adding metal foams (MFs) or combining metallic foam and fins into the PCM to enhance the thermal conductivity. The battery temperatures were measured for all the cases and the results were analyzed and discussed.

  4. Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progresses and perspectives.

    PubMed

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

    2018-02-14

    Lithium metal (Li°) - based rechargeable batteries (LMBs), such as Li° anode vs. intercalation and/or conversion type cathode batteries, lithium-sulphur (Li-S), and lithium-oxygen (O2)/air (Li-O2/air) are becoming increasingly important for electrifying the modern transportation system, enabling sustainable mobility in the near future. Though some rechargeable LMBs batteries (e.g., Li°/LiFePO4 batteries from Bolloré Bluecar®, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is still hampered due to the existence of a number of formidable challenges, including lithium dendrite growth, electrolyte instability towards high voltage intercalation type cathode, poor electronic and ionic conductivities of sulphur (S8) and O2, as well as their corresponding reduction products (e.g., Li2S and Li2O), dissolution and shuttling of polysulphide (PS) intermediates etc. This ultimately results in short cycle life, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. Among other mitigating strategies, the use of electrolyte additives is considered as one of the most economical, and effective approach for circumventing these dilemmas. Set out to offer an in-depth insight into the rapidly growing research on the account of electrolyte additives for rechargeable LMBs, this review presents an overview of the various functional additives, that are being applied in Li-anode/intercalation cathode-based, Li-S and Li-O2 batteries. This review is believed to assess the status quo of the research and thereby arouse new thoughts and opportunities, opening new avenues for the practical realization of these appealing devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. A Review of Sodium-Metal Chloride Battery Activity At JPL

    NASA Technical Reports Server (NTRS)

    Ratnakumar, B. V.; Attia, A. I.; Halpert, G.

    1991-01-01

    Following the disclosures by Coetzer et al. on the use of transition metal chlorides in chloroaluminates as alternate cathodes to sulfur in rechargeable sodium batteries, several laboratories, including the Jet Propulsion Laboratory, focused their attention on these systems. These systems have certain distinct advantages over sodium-sulfur batteries such as increased safety, inherent overcharge capability, and lower operating temperatures. Two systems, i.e., Na/FeCl2 and NaNiCl2, were developed extensively and evaluated in various applications including electric vehicles and space. Their performance has been very encouraging and warrants a detailed fundamental study on these cathodes. At the Jet Propulsion Laboratory a program was initiated two years back to understand the electrochemical behavior of FeCl2 and NiCl2, and to identify and evaluate other transition metal chlorides of promise. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization. Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics, and identifying the rate-limiting processes in te reduction of metal chloride cathodes. Nickel chloride emerged form these studies as the most promising candidate material and was taken up for further detailed study on its passivation- a rate limiting process-under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have a higher energy density, has been assessed. On the basis of the criteria established from the voltammetric response of FeCl2, NiCl2, and CuCl2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt appear promising.

  6. Spectroscopic and theoretical investigations of alkali metal linoleates and oleinates

    NASA Astrophysics Data System (ADS)

    Świsłocka, Renata; Regulska, Ewa; Jarońko, Paweł; Lewandowski, Włodzimierz

    2017-11-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the linoleic (cis-9,cis-12-octadecadienoic) and oleic (cis-9-octadecenoic) acids was investigated. The complementary analytical methods: vibrational (IR, Raman) and electronic (UV) molecular absorption spectroscopy as well as DFT quantum mechanical calculations (charge distribution, angles between bonds, bond lengths, theoretical IR and NMR spectra) were carried out. The regular shifts of bands connected with carboxylate anion in the spectra of studied salts were observed. Some bonds and angles reduced or elongated in the series: acid→Li→Na→K linoleates/oleinates. The highest changes were noted for bond lengths and angles concerning COO- ion. The electronic charge distribution in studied molecules was also discussed. Total atomic charges of carboxylate anion decrease as a result of the replacement of hydrogen atom with alkali metal cation. The increasing values of dipole moment and decreasing values of total energy in the order: linoleic/oleic acid→lithium→sodium→potassium linoleates/oleinates indicate an increase in stability of the compounds.

  7. Development of Novel Metal Hydride-Carbon Nanomaterial Based Nanocomposites as Anode Electrode Materials for Lithium Ion Battery

    DTIC Science & Technology

    2014-06-30

    The aim of this study is to develop metal hydride-carbon nanomaterial based nanocomposites as anode electrode materials for high capacity lithium ion battery and...henceforth to develop high energy density, and good cyclic stability lithium ion battery .

  8. Targeting high value metals in lithium-ion battery recycling via shredding and size-based separation.

    PubMed

    Wang, Xue; Gaustad, Gabrielle; Babbitt, Callie W

    2016-05-01

    Development of lithium-ion battery recycling systems is a current focus of much research; however, significant research remains to optimize the process. One key area not studied is the utilization of mechanical pre-recycling steps to improve overall yield. This work proposes a pre-recycling process, including mechanical shredding and size-based sorting steps, with the goal of potential future scale-up to the industrial level. This pre-recycling process aims to achieve material segregation with a focus on the metallic portion and provide clear targets for subsequent recycling processes. The results show that contained metallic materials can be segregated into different size fractions at different levels. For example, for lithium cobalt oxide batteries, cobalt content has been improved from 35% by weight in the metallic portion before this pre-recycling process to 82% in the ultrafine (<0.5mm) fraction and to 68% in the fine (0.5-1mm) fraction, and been excluded in the larger pieces (>6mm). However, size fractions across multiple battery chemistries showed significant variability in material concentration. This finding indicates that sorting by cathode before pre-treatment could reduce the uncertainty of input materials and therefore improve the purity of output streams. Thus, battery labeling systems may be an important step towards implementation of any pre-recycling process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Directing lateral growth of lithium dendrites in micro-compartmented anode arrays for safe lithium metal batteries.

    PubMed

    Zou, Peichao; Wang, Yang; Chiang, Sum-Wai; Wang, Xuanyu; Kang, Feiyu; Yang, Cheng

    2018-01-31

    Uncontrolled growth of lithium dendrites during cycling has remained a challenging issue for lithium metal batteries. Thus far, various approaches have been proposed to delay or suppress dendrite growth, yet little attention has been paid to the solutions that can make batteries keep working when lithium dendrites are already extensively present. Here we develop an industry-adoptable technology to laterally direct the growth of lithium dendrites, where all dendrites are retained inside the compartmented copper current collector in a given limited cycling capacity. This featured electrode layout renders superior cycling stability (e.g., smoothly running for over 150 cycles at 0.5 mA cm -2 ). Numerical simulations indicate that reduced dendritic stress and damage to the separator are achieved when the battery is abusively running over the ceiling capacity to generate protrusions. This study may contribute to a deeper comprehension of metal dendrites and provide a significant step towards ultimate safe batteries.

  10. Sodium sulfur battery seal

    DOEpatents

    Mikkor, Mati

    1981-01-01

    This disclosure is directed to an improvement in a sodium sulfur battery construction in which a seal between various battery compartments is made by a structure in which a soft metal seal member is held in a sealing position by holding structure. A pressure applying structure is used to apply pressure on the soft metal seal member when it is being held in sealing relationship to a surface of a container member of the sodium sulfur battery by the holding structure. The improvement comprises including a thin, well-adhered, soft metal layer on the surface of the container member of the sodium sulfur battery to which the soft metal seal member is to be bonded.

  11. Bonding and Mobility of Alkali Metals in Helicenes.

    PubMed

    Barroso, Jorge; Murillo, Fernando; Martínez-Guajardo, Gerardo; Ortíz-Chi, Filiberto; Pan, Sudip; Fernández-Herrera, María A; Merino, Gabriel

    2018-06-04

    In this work, we analyze the interaction of alkali metal cations with [6]- and [14]helicene and the cation mobility of therein. We found that the distortion of the carbon skeleton is the cause that some of the structures that are local minima for the smallest cations are not energetically stable for K+, Rb+, and Cs+. Also, the most favorable complexes are those where the cation is interacting with two rings forming a metallocene-like structure, except for the largest cation Cs+, where the distortion provoked by the size of the cation desestabilizes the complex. As far as mobility is concerned, the smallest cations, particularly Na+, are the ones that can move most efficiently. In [6]helicene, the mobility is limited by the capture of the cation forming the metallocene-like structure. In larger helicenes, the energy barriers for the cation to move are similar both inside and outside the helix. However, complexes with the cation between two layers are more energetically favored so that the movement will be preferred in that region. The bonding analysis reveals that interactions with no less than 50% of orbitalic contribution are taking place for the series of E+-[6]helicene. Particularly, the complexes of Li+ stand out showing a remarkably orbitalic character bonding (72.5 - 81.6%). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Life cycle environmental assessment of lithium-ion and nickel metal hydride batteries for plug-in hybrid and battery electric vehicles.

    PubMed

    Majeau-Bettez, Guillaume; Hawkins, Troy R; Strømman, Anders Hammer

    2011-05-15

    This study presents the life cycle assessment (LCA) of three batteries for plug-in hybrid and full performance battery electric vehicles. A transparent life cycle inventory (LCI) was compiled in a component-wise manner for nickel metal hydride (NiMH), nickel cobalt manganese lithium-ion (NCM), and iron phosphate lithium-ion (LFP) batteries. The battery systems were investigated with a functional unit based on energy storage, and environmental impacts were analyzed using midpoint indicators. On a per-storage basis, the NiMH technology was found to have the highest environmental impact, followed by NCM and then LFP, for all categories considered except ozone depletion potential. We found higher life cycle global warming emissions than have been previously reported. Detailed contribution and structural path analyses allowed for the identification of the different processes and value-chains most directly responsible for these emissions. This article contributes a public and detailed inventory, which can be easily be adapted to any powertrain, along with readily usable environmental performance assessments.

  13. Thick-film nickel-metal-hydride battery based on porous ceramic substrates

    NASA Astrophysics Data System (ADS)

    Do, Jing-Shan; Yu, Sen-Hao; Cheng, Suh-Fen

    Nickel-metal-hydride (Ni-MH) batteries are prepared with thick-film and thin-film technologies based on porous ceramic substrates. The porosity and the mean pore diameter of BP ceramic substrates prepared from the argils increases from 19.81% and 0.0432 μm to 29.81% and 0.224 μm, respectively, upon increasing the ethyl cellulose content in the BP argil from 0 to 0.79%. The pore diameter of Al 2O 3 substrates prepared from Al 2O 3 powder is mainly distributed in the range 0.01-0.5 μm. The distribution of the pore diameters of BP ceramic substrates lies in two ranges, namely: 0.04-2 μm and 10-300 μm. Using BP ceramic plates and Al 2O 3 plates as substrates to fabricate thick-film Ni-MH batteries, the optimal electroactive material utilization in the batteries is 77.0 and 71.1%, respectively. On increasing the screen-printing number for preparing the cathode (Ni(OH) 2) from 1 to 3, the discharge capacity of the thick-film battery increases from 0.2917 to 0.7875 mAh, and the utilization in the battery decreases from 71.0 to 53.0%.

  14. Composite Li metal anode with vertical graphene host for high performance Li-S batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Y. J.; Liu, S. F.; Wang, X. L.; Zhong, Y.; Xia, X. H.; Wu, J. B.; Tu, J. P.

    2018-01-01

    Efficient and stable operation of a lithium metal anode has become the enabling factor for next-generation high energy density storage system. Here, vertical graphene (VG) arrays are used as the scaffold structure for high performance Li metal batteries. The melt infusion method is employed to encapsulate Li inside the VG scaffold structure, and the lithiophilic Si layer is coated onto the array surface by magnetron sputtering to assist this melt-infusion process. The porous scaffold structure can control the volume expansion and inhibit the formation of dendritic lithium significantly, leading to the excellent electrochemical performance of the Li composite anode. In addition, the Li-S full batteries with the composite anode display enhanced cycling reversibility.

  15. A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives.

    PubMed

    Horvat, Gordan; Frkanec, Leo; Cindro, Nikola; Tomišić, Vladislav

    2017-09-13

    The complexation of alkali metal cations by lower rim N,N-dihexylacetamide (L1) and newly synthesized N-hexyl-N-methylacetamide (L2) calix[4]arene tertiary-amide derivatives was thoroughly studied at 25 °C in acetonitrile (MeCN), benzonitrile (PhCN), and methanol (MeOH) by means of direct and competitive microcalorimetric titrations, and UV and 1 H NMR spectroscopies. In addition, by measuring the ligands' solubilities, the solution (transfer) Gibbs energies of the ligands and their alkali metal complexes were obtained. The inclusion of solvent molecules in the free and complexed calixarene hydrophobic cavities was also investigated. Computational (classical molecular dynamics) investigations of the studied systems were also carried out. The obtained results were compared with those previously obtained by studying the complexation ability of an N-hexylacetamidecalix[4]arene secondary-amide derivative (L3). The stability constants of 1 : 1 complexes were determined in all solvents used (the values obtained by different methods being in excellent agreement), as were the corresponding complexation enthalpies and entropies. Almost all of the examined reactions were enthalpically controlled. The most striking exceptions were reactions of Li + with both ligands in methanol, for which the entropic contribution to the reaction Gibbs energy was substantial due the entropically favourable desolvation of the smallest lithium cation. The thermodynamic stabilities of the complexes were quite solvent dependent (the stability decreased in the solvent order: MeCN > PhCN ≫ MeOH), which could be accounted for by considering the differences in the solvation of the ligand and free and complexed alkali metal cations in the solvents used. Comparison of the stability constants of the ligand L1 and L2 complexes clearly revealed that the higher electron-donating ability of the hexyl with respect to the methyl group is of considerable importance in determining the equilibria of the

  16. Behavior of Lithium Metal Anodes under Various Capacity Utilization and High Current Density in Lithium Metal Batteries

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

    Jiao, Shuhong; Zheng, Jianming; Li, Qiuyan

    Lithium (Li) metal batteries (LMBs) are regarded as the most promising power sources for electric vehicles. Besides the Li dendrite growth and low Li Coulombic efficiency, how to well match Li metal anode with a high loading (normally over 3.0 mAh cm-2) cathode is another key challenge to achieve the real high energy density battery. In this work, we systematically investigate the effects of the Li metal capacity usage in each cycle, manipulated by varying the cathode areal loading, on the stability of Li metal anode and the cycling performance of LMBs using the LiNi1/3Mn1/3Co1/3O2 (NMC) cathode and an additive-containingmore » dual-salt/carbonate-solvent electrolyte. It is demonstrated that the Li||NMC cells show decent long-term cycling performance even with NMC areal capacity loading up to ca. 4.0 mAh cm-2 and at a charge current density of 1.0 mA cm-2. The increase of the Li capacity usage in each cycle causes variation in the components of the solid electrolyte interphase (SEI) layer on Li metal anode and generates more ionic conductive species from this electrolyte. Further study reveals for the first time that the degradation of Li metal anode and the thickness of SEI layer on Li anode show linear relationship with the areal capacity of NMC cathode. Meanwhile, the expansion rate of consumed Li and the ratio of SEI thickness to NMC areal loading are kept almost the same value with increasing cathode loading, respectively. These fundamental findings provide new perspectives on the rational evaluation of Li metal anode stability for the development of rechargeable LMBs.« less

  17. Metal-air flow batteries using oxygen enriched electrolyte

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

    Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh

    A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

  18. Metal-air flow batteries using oxygen enriched electrolyte

    DOEpatents

    Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh; Chen, Xujie

    2017-08-01

    A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

  19. Brazilian policy on battery disposal and its practical effects on battery recycling

    NASA Astrophysics Data System (ADS)

    Crocce Romano Espinosa, Denise; Moura Bernardes, Andréa; Alberto Soares Tenório, Jorge

    The disposal of batteries is a problem that has grown in the last few years, due to the increase in the use of portable devices. Batteries may contain toxic metals such as cadmium, mercury and lead, so their disposal must be controlled. Brazil was the first country in Latin America to regulate the disposal and treatment of batteries. Limits were established on the concentration of heavy metals within batteries, so that they could be disposed along with domestic waste. Since batteries are products used broadly, it is very difficult to control their disposal. In order to have an efficient collection, the population must be engaged, and that can only happen if they are informed about the laws and regulations regarding the subject, as well as the importance of disposing of batteries with higher concentrations of heavy metals or toxic substances separately from domestic garbage. Around the world, there are some long-established recycling processes for batteries. In Brazil, automotive (lead-acid) batteries have been recycled for several years, whereas the recycling of other types of batteries is just starting. This work does an analysis of the Brazilian law for battery recycling and presents some suggestions and examples of the initiatives of other countries, in order to manage of this kind of dangerous waste.

  20. Research Investigation Directed Toward Extending the Useful Range of the Electromagnetic Spectrum. [atomic spectra and electronic structure of alkali metals

    NASA Technical Reports Server (NTRS)

    Hartmann, S. R.; Happer, W.

    1974-01-01

    The report discusses completed and proposed research in atomic and molecular physics conducted at the Columbia Radiation Laboratory from July 1972 to June 1973. Central topics described include the atomic spectra and electronic structure of alkali metals and helium, molecular microwave spectroscopy, the resonance physics of photon echoes in some solid state systems (including Raman echoes, superradiance, and two photon absorption), and liquid helium superfluidity.

  1. 3D Fiber-Network-Reinforced Bicontinuous Composite Solid Electrolyte for Dendrite-free Lithium Metal Batteries.

    PubMed

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

    2018-02-28

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

  2. Rechargeable Metal-Air Proton-Exchange Membrane Batteries for Renewable Energy Storage.

    PubMed

    Nagao, Masahiro; Kobayashi, Kazuyo; Yamamoto, Yuta; Yamaguchi, Togo; Oogushi, Akihide; Hibino, Takashi

    2016-02-01

    Rechargeable proton-exchange membrane batteries that employ organic chemical hydrides as hydrogen-storage media have the potential to serve as next-generation power sources; however, significant challenges remain regarding the improvement of the reversible hydrogen-storage capacity. Here, we address this challenge through the use of metal-ion redox couples as energy carriers for battery operation. Carbon, with a suitable degree of crystallinity and surface oxygenation, was used as an effective anode material for the metal redox reactions. A Sn 0.9 In 0.1 P 2 O 7 -based electrolyte membrane allowed no crossover of vanadium ions through the membrane. The V 4+ /V 3+ , V 3+ /V 2+ , and Sn 4+ /Sn 2+ redox reactions took place at a more positive potential than that for hydrogen reduction, so that undesired hydrogen production could be avoided. The resulting electrical capacity reached 306 and 258 mAh g -1 for VOSO 4 and SnSO 4 , respectively, and remained at 76 and 91 % of their respective initial values after 50 cycles.

  3. Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

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

    Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

    2014-08-14

    The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X -(H 2O), X = F, Cl, Br, I, and alkali metal-water, M +(H 2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits tomore » the ab initio data that are between one and two orders of magnitude better in the χ 2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.« less

  4. Metal-Free Aqueous Flow Battery with Novel Ultrafiltered Lignin as Electrolyte

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

    Mukhopadhyay, Alolika; Hamel, Jonathan; Katahira, Rui

    As the number of generation sources from intermittent renewable technologies on the electric grid increases, the need for large-scale energy storage devices is becoming essential to ensure grid stability. Flow batteries offer numerous advantages over conventional sealed batteries for grid storage. In this work, for the first time, we investigated lignin, the second most abundant wood derived biopolymer, as an anolyte for the aqueous flow battery. Lignosulfonate, a water-soluble derivative of lignin, is environmentally benign, low cost and abundant as it is obtained from the byproduct of paper and biofuel manufacturing. The lignosulfonate utilizes the redox chemistry of quinone tomore » store energy and undergoes a reversible redox reaction. Here, we paired lignosulfonate with Br2/Br-, and the full cell runs efficiently with high power density. Also, the large and complex molecular structure of lignin considerably reduces the electrolytic crossover, which ensures very high capacity retention. The flowcell was able to achieve current densities of up to 20 mA/cm2 and charge polarization resistance of 15 ohm cm2. This technology presents a unique opportunity for a low-cost, metal-free flow battery capable of large-scale sustainable energy storage.« less

  5. Solar photovoltaic charging of high voltage nickel metal hydride batteries using DC power conversion

    NASA Astrophysics Data System (ADS)

    Kelly, Nelson A.; Gibson, Thomas L.

    There are an increasing number of vehicle choices available that utilize batteries and electric motors to reduce tailpipe emissions and increase fuel economy. The eventual production of electricity and hydrogen in a renewable fashion, such as using solar energy, can achieve the long-term vision of having no tailpipe environmental impact, as well as eliminating the dependence of the transportation sector on dwindling supplies of petroleum for its energy. In this report we will demonstrate the solar-powered charging of the high-voltage nickel-metal hydride (NiMH) battery used in the GM 2-mode hybrid system. In previous studies we have used low-voltage solar modules to produce hydrogen via the electrolysis of water and to directly charge lithium-ion battery modules. Our strategy in the present work was to boost low-voltage PV voltage to over 300 V using DC-DC converters in order to charge the high-voltage NiMH battery, and to regulate the battery charging using software to program the electronic control unit supplied with the battery pack. A protocol for high-voltage battery charging was developed, and the solar to battery charging efficiency was measured under a variety of conditions. We believe this is the first time such high-voltage batteries have been charged using solar energy in order to prove the concept of efficient, solar-powered charging for battery-electric vehicles.

  6. High energy density aluminum battery

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

    Brown, Gilbert M.; Parans Paranthaman, Mariappan; Dai, Sheng

    Compositions and methods of making are provided for a high energy density lithium-aluminum battery. The battery comprises an anode comprising aluminum metal. The battery further comprises a cathode comprising a lithium metal oxide. The battery further comprises an electrolyte capable of supporting reversible deposition and stripping of aluminum at the anode, and reversible intercalation and deintercalation of lithium at the cathode.

  7. Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel-metal-hydride batteries

    NASA Astrophysics Data System (ADS)

    Rodrigues, Luiz Eduardo Oliveira Carmo; Mansur, Marcelo Borges

    The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.2-10.9%), cobalt (5.1-5.5%), rare earth elements (15.3-29.0%) and cadmium (2.8%). The presence of cadmium reveals that some Ni-Cd batteries are possibly labeled as NiMH ones. The leaching of nickel and cobalt from the NiMH battery powder with sulfuric acid is efficient; operating variables temperature and concentration of H 2O 2 has no significant effect for the conditions studied. A mixture of rare earth elements is separated by precipitation with NaOH. Finally, solvent extraction with D2EHPA (di-2-ethylhexyl phosphoric acid) followed by Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) can separate cadmium, cobalt and nickel from the leach liquor. The effect of the main operating variables of both leaching and solvent extraction steps are discussed aiming to maximize metal separation for recycling purposes.

  8. Influence of alkali metal cations/type of activator on the structure of alkali-activated fly ash - ATR-FTIR studies

    NASA Astrophysics Data System (ADS)

    Król, M.; Rożek, P.; Chlebda, D.; Mozgawa, W.

    2018-06-01

    Coal fly ash as a secondary aluminosiliceous raw material that is commonly used in the so-called geopolymerization process has been activated with different alkali hydroxides solutions: LiOH, NaOH and KOH. Changes in the aluminosilicate structure of the material during alkali-activation have been analyzed in detail on the basis of ATR/FT-IR spectra. These changes mainly affect both the integral intensity and FWHM of bands in the range of 1200-950 cm-1, however dehydration and carbonation process can be also analyzed based on obtaining results.

  9. In Situ-Formed Hierarchical Metal-Organic Flexible Cathode for High-Energy Sodium-Ion Batteries.

    PubMed

    Huang, Ying; Fang, Chun; Zeng, Rui; Liu, Yaojun; Zhang, Wang; Wang, Yanjie; Liu, Qingju; Huang, Yunhui

    2017-12-08

    Metal-organic compounds are a family of electrode materials with structural diversity and excellent thermal stability for rechargeable batteries. Here, we fabricated a hierarchical nanocomposite with metal-organic cuprous tetracyanoquinodimethane (CuTCNQ) in a 3 D conductive carbon nanofibers (CNFs) network by in situ growth, and evaluated it as flexible cathode for sodium-ion batteries (SIBs). CuTCNQ in such flexible composite electrode is able to exhibit a high capacity of 252 mAh g -1 at 0.1 C and highly reversible stability for 1200 cycles within the voltage range of 2.5-4.1 V (vs. Na + /Na). A high specific energy of 762 Wh kg -1 was obtained with high average potential of 3.2 V (vs. Na + /Na). The in situ-formed electroactive metal-organic composites with tailored nanoarchitecture provide a promising alternative choice for high-performance cathode materials in SIBs with high energy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Combinatorial electrochemical cell array for high throughput screening of micro-fuel-cells and metal/air batteries.

    PubMed

    Jiang, Rongzhong

    2007-07-01

    An electrochemical cell array was designed that contains a common air electrode and 16 microanodes for high throughput screening of both fuel cells (based on polymer electrolyte membrane) and metal/air batteries (based on liquid electrolyte). Electrode materials can easily be coated on the anodes of the electrochemical cell array and screened by switching a graphite probe from one cell to the others. The electrochemical cell array was used to study direct methanol fuel cells (DMFCs), including high throughput screening of electrode catalysts and determination of optimum operating conditions. For screening of DMFCs, there is about 6% relative standard deviation (percentage of standard deviation versus mean value) for discharge current from 10 to 20 mAcm(2). The electrochemical cell array was also used to study tin/air batteries. The effect of Cu content in the anode electrode on the discharge performance of the tin/air battery was investigated. The relative standard deviations for screening of metal/air battery (based on zinc/air) are 2.4%, 3.6%, and 5.1% for discharge current at 50, 100, and 150 mAcm(2), respectively.

  11. On the origin of alkali metals in Europa exosphere

    NASA Astrophysics Data System (ADS)

    Ozgurel, Ozge; Pauzat, Françoise; Ellinger, Yves; Markovits, Alexis; Mousis, Olivier; LCT, LAM

    2016-10-01

    At a time when Europa is considered as a plausible habitat for the development of an early form of life, of particular concern is the origin of neutral sodium and potassium atoms already detected in its exosphere (together with magnesium though in smaller abundance), since these atoms are known to be crucial for building the necessary bricks of prebiotic species. However their origin and history are still poorly understood. The most likely sources could be exogenous and result from the contamination produced by Io's intense volcanism and/or by meteoritic bombardment. These sources could also be endogenous if these volatile elements originate directly from Europa's icy mantle. Here we explore the possibility that neutral sodium and potassium atoms were delivered to the satellite's surface via the upwelling of ices formed in contact with the hidden ocean. These metallic elements would have been transferred as ions to the ocean at early epochs after Europa's formation, by direct contact of water with the rocky core. During Europa's subsequent cooling, the icy layers formed at the top of the ocean would have kept trapped the sodium and potassium, allowing their future progression to the surface and final identification in the exosphere of the satellite. To support this scenario, we have used chemistry numerical models based on first principle periodic density functional theory (DFT). These models are shown to be well adapted to the description of compact ice and are capable to describe the trapping and neutralization of the initial ions in the ice matrix. The process is found relevant for all the elements considered, alkali metals like Na and K, as well as for Mg and probably for Ca, their respective abundances depending essentially of their solubility and chemical capabilities to blend with water ices.

  12. Structural and electronic engineering of 3DOM WO3 by alkali metal doping for improved NO2 sensing performance

    NASA Astrophysics Data System (ADS)

    Wang, Zhihua; Fan, Xiaoxiao; Han, Dongmei; Gu, Fubo

    2016-05-01

    Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and excellent selectivity. More importantly, the response of 3DOM WO3/Li to 500 ppb NO2 was up to 55 at room temperature (25 °C). The especially high response to ppb level NO2 at room temperature (25 °C) in this work has a very important practical significance. The best sensing performance of 3DOM WO3/Li could be ascribed to the most structure defects and the highest carrier mobility. And the possible gas sensing mechanism based on the model of the depletion layer was proposed to demonstrate that both structural and electronic properties are responsible for the NO2 sensing behavior.Novel alkali metal doped 3DOM WO3 materials were prepared using a simple colloidal crystal template method. Raman, XRD, SEM, TEM, XPS, PL, Hall and UV-Vis techniques were used to characterize the structural and electronic properties of all the products, while the corresponding sensing performances targeting ppb level NO2 were determined at different working temperatures. For the overall goal of structural and electronic engineering, the co-effect of structural and electronic properties on the improved NO2 sensing performance of alkali metal doped 3DOM WO3 was studied. The test results showed that the gas sensing properties of 3DOM WO3/Li improved the most, with the fast response-recovery time and

  13. Metal-organic frameworks for lithium ion batteries and supercapacitors

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

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefitmore » from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.« less

  14. Feasibility of a nickel-metal hydride battery for totally implantable artificial hearts.

    PubMed

    Okamoto, E; Yoshida, T; Fujiyoshi, M; Shimanaka, M; Takeuchi, A; Mitamura, Y; Mikami, T

    1996-01-01

    An implantable rechargeable battery is one of the key technologies for totally implantable artificial hearts. The nickel-metal hydride (Ni-MH) battery is promising for its high energy density of 1.5-2.0 times that of a nickel-cadmium battery. In this study, the effects of pulsatile discharge loads on the operating time and cycle life of Ni-MH batteries at 39 degrees C were studied. Two battery cells (TH-3M, 1,200 mAh, phi 14.5 x 49 mm; Toshiba, Tokyo, Japan) in series were charge/discharge cycled at 39 degrees C using a charge current of 1CA (1,200 mA) and then were fully discharged to 1.0 V/cell under either pulsatile discharge loads, which mimicked a systole (1 A for 0.3 sec) and a diastole (0.4 A for 0.3 sec), or a non pulsatile discharge load equivalent to the average of the pulsatile loads (0.7 A). Each cycle life test was interrupted on the 482nd cycle under pulsatile load, and on the 423rd cycle under non pulsatile load, because of malfunction of each battery charger. The tests showed that the pulsatile discharge cells had significantly (p < 0.001) less operating time (74.0 +/- 7.15 min) throughout the test period (up to 482 days) compared to the cells under equivalent non pulsatile discharge loads (93.7 +/- 7.74 min). The pulsatile-discharged Ni-MH cells provide significantly less operating time than the constantly discharged cells; the Ni-MH battery has an operating time of over 78 min and a cycle life of almost 500 cycles at 39 degrees C. In conclusion, the Ni-MH battery is feasible as an implantable back-up battery for a totally implantable artificial heart system.

  15. Prelithiation of silicon-carbon nanotube anodes for lithium ion batteries by stabilized lithium metal powder (SLMP).

    PubMed

    Forney, Michael W; Ganter, Matthew J; Staub, Jason W; Ridgley, Richard D; Landi, Brian J

    2013-09-11

    Stabilized lithium metal powder (SLMP) has been applied during battery assembly to effectively prelithiate high capacity (1500-2500 mAh/g) silicon-carbon nanotube (Si-CNT) anodes, eliminating the 20-40% first cycle irreversible capacity loss. Pressure-activation of SLMP is shown to enhance prelithiation and enable capacity matching between Si-CNT anodes and lithium nickel cobalt aluminum oxide (NCA) cathodes in full batteries with minimal added mass. The prelithiation approach enables high energy density NCA/Si-CNT batteries achieving >1000 cycles at 20% depth-of-discharge.

  16. Effect of alkali metal ions on the pyrrole and pyridine π-electron systems in pyrrole-2-carboxylate and pyridine-2-carboxylate molecules: FT-IR, FT-Raman, NMR and theoretical studies

    NASA Astrophysics Data System (ADS)

    Świderski, G.; Wojtulewski, S.; Kalinowska, M.; Świsłocka, R.; Lewandowski, W.

    2011-05-01

    The FT-IR, FT-Raman and 1H and 13C NMR spectra of pyrrole-2-carboxylic acid (PCA) and lithium, sodium, potassium, rubidium and caesium pyrrole-2-carboxylates were recorded, assigned and compared in the Li → Na → K → Rb → Cs salt series. The effect of alkali metal ions on the electronic system of ligands was discussed. The obtained results were compared with previously reported ones for pyridine-2-carboxylic acid and alkali metal pyridine-2-carboxylates. Calculations for pyrrole-2-carboxylic acid and Li, Na, K pyrrole-2-carboxylates in B3LYP/6-311++G ** level and Møller-Plesset method in MP2/6-311++G ** level were made. Bond lengths, angles and dipole moments as well as aromaticity indices (HOMA, EN, GEO, I 6) for the optimized structures of pyrrole-2-carboxylic acid (PCA) and lithium, sodium, potassium pyrrole-2-carboxylates were also calculated. The degree of perturbation of the aromatic system of ligand under the influence of metals in the Li → Cs series was investigated with the use of statistical methods (linear correlation), calculated aromaticity indices and Mulliken, NBO and ChelpG population analysis method. Additionally, the Bader theory (AIM) was applied to setting the characteristic of the bond critical points what confirmed the influence of alkali metals on the pyrrole ring.

  17. Electrochemical properties of a lithium-impregnated metal foam anode for thermal batteries

    NASA Astrophysics Data System (ADS)

    Choi, Yu-Song; Yu, Hye-Ryeon; Cheong, Hae-Won

    2015-02-01

    Lithium-impregnated metal foam anodes (LIMFAs) are fabricated and investigated. The LIMFAs are prepared by the impregnation of lithium into molten-salt-coated nickel metal foam. A single cell with the LIMFA exhibits a specific capacity of 3009 As g-1. For comparison, a single cell with a LiSi alloy anode is also discharged, demonstrating a specific capacity of 1050 As g-1. These significant improvements can be attributed to the large amount of lithium impregnated into the metal foam as well as the molten lithium holding capability of the foam. Due to their excellent electrochemical properties, LIMFAs are suitable for use in thermal batteries.

  18. Method of electrode fabrication and an electrode for metal chloride battery

    DOEpatents

    Bloom, I.D.; Nelson, P.A.; Vissers, D.R.

    1993-03-16

    A method of fabricating an electrode for use in a metal chloride battery and an electrode are provided. The electrode has relatively larger and more uniform pores than those found in typical electrodes. The fabrication method includes the steps of mixing sodium chloride particles selected from a predetermined size range with metal particles selected from a predetermined size range, and then rigidifying the mixture. The electrode exhibits lower resistivity values of approximately 0.5 [Omega]cm[sup 2] than those resistivity values of approximately 1.0-1.5 [Omega]cm[sup 2] exhibited by currently available electrodes.

  19. Method of electrode fabrication and an electrode for metal chloride battery

    DOEpatents

    Bloom, Ira D.; Nelson, Paul A.; Vissers, Donald R.

    1993-01-01

    A method of fabricating an electrode for use in a metal chloride battery and an electrode are provided. The electrode has relatively larger and more uniform pores than those found in typical electrodes. The fabrication method includes the steps of mixing sodium chloride particles selected from a predetermined size range with metal particles selected from a predetermined size range, and then rigidifying the mixture. The electrode exhibits lower resistivity values of approximately 0.5 .OMEGA.cm.sup.2 than those resistivity values of approximately 1.0-1.5 .OMEGA.cm.sup.2 exhibited by currently available electrodes.

  20. Long-Range Adiabatic Corrections to the Ground Molecular State of Alkali-Metal Dimers.

    NASA Astrophysics Data System (ADS)

    Marinescu, M.; Dalgarno, A.

    1997-04-01

    The structure of the long-range limit of the diagonal adiabatic corrections to the ground molecular state of diatomic molecules, may be expressed as a series of inverse powers of internuclear distance, R. The coefficients of this expansion are proportional to the inverse of the nuclear mass. Thus, they may be interpreted as a nuclear mass-dependent corrections to the dispersion coefficients. Using perturbation theory we have calculated the long-range coefficients of the diagonal adiabatic corrections up to the order of R-10. The final expressions are in terms of integrals over imaginary frequencies of products of atomic matrix elements involving Green's functions of complex energy. Thus, in our approach the molecular problem is reduced to an atomic one. Numerical evaluations have been done for all alkali-metal dimers. We acknowledge the support of the U.S. Dept. of Energy.

  1. Optical properties from time-dependent current-density-functional theory: the case of the alkali metals Na, K, Rb, and Cs

    NASA Astrophysics Data System (ADS)

    Ferradás, R.; Berger, J. A.; Romaniello, Pina

    2018-06-01

    We present the optical conductivity as well as the electron-energy loss spectra of the alkali metals Na, K, Rb, and Cs calculated within time-dependent current-density functional theory. Our ab initio formulation describes from first principles both the Drude-tail and the interband absorption of these metals as well as the most dominant relativistic effects. We show that by using a recently derived current functional [Berger, Phys. Rev. Lett. 115, 137402 (2015)] we obtain an overall good agreement with experiment at a computational cost that is equivalent to the random-phase approximation. We also highlight the importance of the choice of the exchange-correlation potential of the ground state.

  2. Sloshing instability and electrolyte layer rupture in liquid metal batteries

    NASA Astrophysics Data System (ADS)

    Weber, Norbert; Beckstein, Pascal; Herreman, Wietze; Horstmann, Gerrit Maik; Nore, Caroline; Stefani, Frank; Weier, Tom

    2017-05-01

    Liquid metal batteries (LMBs) are discussed today as a cheap grid scale energy storage, as required for the deployment of fluctuating renewable energies. Built as stable density stratification of two liquid metals separated by a thin molten salt layer, LMBs are susceptible to short-circuit by fluid flows. Using direct numerical simulation, we study a sloshing long wave interface instability in cylindrical cells, which is already known from aluminium reduction cells. After characterising the instability mechanism, we investigate the influence of cell current, layer thickness, density, viscosity, conductivity and magnetic background field. Finally we study the shape of the interface and give a dimensionless parameter for the onset of sloshing as well as for the short-circuit.

  3. Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium-Sulfur Batteries

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

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

    2016-03-29

    With the significant progress made in the development of cathodes in lithium-sulfur (Li-S) batteries, the stability of Li metal anodes becomes a more urgent challenge in these batteries. Here we report the systematic investigation of the stability of the anode/electrolyte interface in Li-S batteries with concentrated electrolytes containing various lithium salts. It is found that Li-S batteries using LiTFSI-based electrolytes are more stable than those using LiFSI-based electrolytes. The decreased stability is because the N-S bond in the FSI- anion is fairly weak and the scission of this bond leads to the formation of lithium sulfate (LiSOx) in the presencemore » of polysulfide species. In contrast, even the weakest bond (C-S) in the TFSI- anion is stronger than the N-S bond in the FSI- anion. In the LiTFSI-based electrolyte, the lithium metal anode tends to react with polysulfide to form lithium sulfide (LiSx) which is more reversible than LiSOx formed in the LiTFSI-based electrolyte. This fundamental difference in the bond strength of the salt anions in the presence of polysulfide species leads to a large difference in the stability of the anode-electrolyte interface and performance of the Li-S batteries with electrolytes composed of these salts. Therefore, anion selection is one of the key parameters in the search for new electrolytes for stable operation of Li-S batteries.« less

  4. Development of operationally stable inverted organic light-emitting diode prepared without using alkali metals (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Fukagawa, Hirohiko; Morii, Katsuyuki; Hasegawa, Munehiro; Gouda, Shun; Tsuzuki, Toshimitsu; Shimizu, Takahisa; Yamamoto, Toshihiro

    2015-10-01

    The OLED is one of the key devices for realizing future flexible displays and lightings. One of the biggest challenges left for the OLED fabricated on a flexible substrate is the improvement of its resistance to oxygen and moisture. A high barrier layer [a water vapor transmission rate (WVTR) of about 10-6 g/m2/day] is proposed to be necessary for the encapsulation of conventional OLEDs. Some flexible high barrier layers have recently been demonstrated; however, such high barrier layers require a complex process, which makes flexible OLEDs expensive. If an OLED is prepared without using air-sensitive materials such as alkali metals, no stringent encapsulation is necessary for such an OLED. In this presentation, we will discuss our continuing efforts to develop an inverted OLED (iOLED) prepared without using alkali metals. iOLEDs with a bottom cathode are considered to be effective for realizing air-stable OLEDs since the electron injection layer (EIL) can be prepared by fabrication processes that might damage the organic layers, resulting in the enhanced range of materials suitable for EILs. We have demonstrated that a highly efficient and relatively air-stable iOLED can be realized by employing poly(ethyleneimine) as an EIL. Dark spot formation was not observed after 250 days in the poly(ethyleneimine)-based iOLED encapsulated by a barrier film with a WVTR of 10-4 g/m2/day. In addition, we have demonstrated the fabrication of a highly operational stable iOLED utilizing a newly developed EIL. The iOLED exhibits an expected half-lifetime of over 10,000 h from an initial luminance of 1,000 cd/m2.

  5. [Novel process utilizing alkalis assisted hydrothermal process to stabilize heavy metals both from municipal solid waste or medical waste incinerator fly ash and waste water].

    PubMed

    Wang, Lei; Jin, Jian; Li, Xiao-dong; Chi, Yong; Yan, Jian-hua

    2010-08-01

    An alkalis assisted hydrothermal process was induced to stabilize heavy metals both from municipal solid waste or medical waste incinerator fly ash and waste water. The results showed that alkalis assisted hydrothermal process removed the heavy metals effectively from the waste water, and reduced leachability of fly ash after process. The heavy metal leachabilities of fly ash studied in this paper were Mn 17,300 microg/L,Ni 1650 microg/L, Cu 2560 microg/L, Zn 189,000 microg/L, Cd 1970 microg/L, Pb 1560 microg/L for medical waste incinerator fly ash; Mn 17.2 microg/L, Ni 8.32 microg/L, Cu 235.2 microg/L, Zn 668.3 microg/L, Cd 2.81 microg/L, Pb 7200 microg/L for municipal solid waste incinerator fly ash. After hydrothermal process with experimental condition [Na2CO3 dosage (5 g Na2CO3/50 g fly ash), reaction time = 10 h, L/S ratio = 10/1], the heavy metal removal efficiencies of medical waste incinerator fly ash were 86.2%-97.3%, and 94.7%-99.6% for municipal solid waste incinerator fly ash. The leachabilities of both two kinds of fly ash were lower than that of the Chinese national limit. The mechanism of heavy metal stabilization can be concluded to the chemisorption and physically encapsulation effects of aluminosilicates during its formation, crystallization and aging process, the high pH value has some contribution to the heavy metal removal and stabilization.

  6. Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

    NASA Astrophysics Data System (ADS)

    Xu, Shenzhen

    Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

  7. A theoretical study of the structure and thermochemical properties of alkali metal fluoroplumbates MPbF3.

    PubMed

    Boltalin, A I; Korenev, Yu M; Sipachev, V A

    2007-07-19

    Molecular constants of MPbF3 (M=Li, Na, K, Rb, and Cs) were calculated theoretically at the MP2(full) and B3LYP levels with the SDD (Pb, K, Rb, and Cs) and cc-aug-pVQZ (F, Li, and Na) basis sets to determine the thermochemical characteristics of the substances. Satisfactory agreement with experiment was obtained, including the unexpected nonmonotonic dependence of substance dissociation energies on the alkali metal atomic number. The bond lengths of the theoretical CsPbF3 model were substantially elongated compared with experimental estimates, likely because of errors in both theoretical calculations and electron diffraction data processing.

  8. A binary catalyst system of a cationic Ru-CNC pincer complex with an alkali metal salt for selective hydroboration of carbon dioxide.

    PubMed

    Ng, Chee Koon; Wu, Jie; Hor, T S Andy; Luo, He-Kuan

    2016-09-27

    Binary catalyst systems comprising a cationic Ru-CNC pincer complex and an alkali metal salt were developed for selective hydroboration of CO 2 utilizing pinacolborane at r.t. and 1 atm CO 2 , with the combination of [Ru(CNC Bn )(CO) 2 (H)][PF 6 ] and KOCO 2 t Bu producing formoxyborane in 76% yield. A bicyclic catalytic mechanism was proposed and discussed.

  9. Catalysis using hydrous metal oxide ion exchanges

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

    1985-01-01

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  10. Catalysis using hydrous metal oxide ion exchangers

    DOEpatents

    Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

    1983-07-21

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  11. Spent lithium-ion battery recycling - Reductive ammonia leaching of metals from cathode scrap by sodium sulphite.

    PubMed

    Zheng, Xiaohong; Gao, Wenfang; Zhang, Xihua; He, Mingming; Lin, Xiao; Cao, Hongbin; Zhang, Yi; Sun, Zhi

    2017-02-01

    Recycling of spent lithium-ion batteries has attracted wide attention because of their high content of valuable and hazardous metals. One of the difficulties for effective metal recovery is the separation of different metals from the solution after leaching. In this research, a full hydrometallurgical process is developed to selectively recover valuable metals (Ni, Co and Li) from cathode scrap of spent lithium ion batteries. By introducing ammonia-ammonium sulphate as the leaching solution and sodium sulphite as the reductant, the total selectivity of Ni, Co and Li in the first-step leaching solution is more than 98.6% while it for Mn is only 1.36%. In detail understanding of the selective leaching process is carried out by investigating the effects of parameters such as leaching reagent composition, leaching time (0-480min), agitation speed (200-700rpm), pulp density (10-50g/L) and temperature (323-353K). It was found that Mn is primarily reduced from Mn 4+ into Mn 2+ into the solution as [Formula: see text] while it subsequently precipitates out into the residue in the form of (NH 4 ) 2 Mn(SO 3 ) 2 ·H 2 O. Ni, Co and Li are leached and remain in the solution either as metallic ion or amine complexes. The optimised leaching conditions can be further obtained and the leaching kinetics is found to be chemical reaction control under current leaching conditions. As a result, this research is potentially beneficial for further optimisation of the spent lithium ion battery recycling process after incorporating with metal extraction from the leaching solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. An alkali-metal ion extracted layered compound as a template for a metastable phase synthesis in a low-temperature solid-state reaction: preparation of brookite from K0.8Ti1.73Li0.27O4.

    PubMed

    Ozawa, Tadashi C; Sasaki, Takayoshi

    2010-03-15

    We have designed a new approach to synthesize brookite, i.e., to extract alkali-metal ions from K(0.8)Ti(1.73)Li(0.27)O(4) (KTLO) and to apply simultaneous heat treatment to the remaining lepidocrocite-type layers of TiO(6) octahedra. For the alkali-metal ion extraction and the simultaneous heat treatment, KTLO was heated at 400 degrees C with polytetrafluoroethylene (PTFE) in flowing Ar. PTFE has been found to be an effective agent to extract strongly electropositive alkali-metal ions from KTLO because of the strong electronegativity of F as its component. The product of this reaction consists of a mixture of brookite, K(2)CO(3), LiF, and PTFE derivatives, indicating the complete extraction of K(+) and Li(+) from KTLO and formation of brookite from the lepidocrocite-type layer of TiO(6) octahedra as a template. This brookite has a partial replacement of O(2-) with F(-) and/or slight oxygen deficiency; thus, its color is light-bluish gray. Fully oxidized brookite formation and complete decomposition of PTFE derivatives have been achieved by further heating in flowing air, and coproduced alkali-metal salts have been removed by washing in water. Powder X-ray diffraction, Raman spectroscopy, and chemical analysis results have confirmed that the final brookite product treated at 600 degrees C is single phase, and it is white. The method to extract alkali-metal ions from a crystalline material using PTFE is drastically different from the common methods such as soft-chemical and electrochemical reactions. It is likely that this new synthetic approach is applicable to other layered systems to prepare a diverse family of compounds, including novel metastable ones.

  13. Highly reversible zinc metal anode for aqueous batteries

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Borodin, Oleg; Gao, Tao; Fan, Xiulin; Sun, Wei; Han, Fudong; Faraone, Antonio; Dura, Joseph A.; Xu, Kang; Wang, Chunsheng

    2018-06-01

    Metallic zinc (Zn) has been regarded as an ideal anode material for aqueous batteries because of its high theoretical capacity (820 mA h g-1), low potential (-0.762 V versus the standard hydrogen electrode), high abundance, low toxicity and intrinsic safety. However, aqueous Zn chemistry persistently suffers from irreversibility issues, as exemplified by its low coulombic efficiency (CE) and dendrite growth during plating/ stripping, and sustained water consumption. In this work, we demonstrate that an aqueous electrolyte based on Zn and lithium salts at high concentrations is a very effective way to address these issues. This unique electrolyte not only enables dendrite-free Zn plating/stripping at nearly 100% CE, but also retains water in the open atmosphere, which makes hermetic cell configurations optional. These merits bring unprecedented flexibility and reversibility to Zn batteries using either LiMn2O4 or O2 cathodes—the former deliver 180 W h kg-1 while retaining 80% capacity for >4,000 cycles, and the latter deliver 300 W h kg-1 (1,000 W h kg-1 based on the cathode) for >200 cycles.

  14. Competing forces in liquid metal electrodes and batteries

    NASA Astrophysics Data System (ADS)

    Ashour, Rakan F.; Kelley, Douglas H.; Salas, Alejandro; Starace, Marco; Weber, Norbert; Weier, Tom

    2018-02-01

    Liquid metal batteries are proposed for low-cost grid scale energy storage. During their operation, solid intermetallic phases often form in the cathode and are known to limit the capacity of the cell. Fluid flow in the liquid electrodes can enhance mass transfer and reduce the formation of localized intermetallics, and fluid flow can be promoted by careful choice of the locations and topology of a battery's electrical connections. In this context we study four phenomena that drive flow: Rayleigh-Bénard convection, internally heated convection, electro-vortex flow, and swirl flow, in both experiment and simulation. In experiments, we use ultrasound Doppler velocimetry (UDV) to measure the flow in a eutectic PbBi electrode at 160 °C and subject to all four phenomena. In numerical simulations, we isolate the phenomena and simulate each separately using OpenFOAM. Comparing simulated velocities to experiments via a UDV beam model, we find that all four phenomena can enhance mass transfer in LMBs. We explain the flow direction, describe how the phenomena interact, and propose dimensionless numbers for estimating their mutual relevance. A brief discussion of electrical connections summarizes the engineering implications of our work.

  15. Esr Spectra of Alkali-Metal Atoms on Helium Nanodroplets: a Theoretical Model for the Prediction of Helium Induced Hyperfine Structure Shifts

    NASA Astrophysics Data System (ADS)

    Hauser, Reas W.; Filatov, Michael; Ernst, Wolfgang E.

    2013-06-01

    We predict He-droplet-induced changes of the isotropic HFS constant a_{HFS} of the alkali-metal atoms M = Li, Na, K and Rb on the basis of a model description. Optically detected electron spin resonance spectroscopy has allowed high resolution measurements that show the influence of the helium droplet and its size on the unpaired electron spin density at the alkali nucleus. Our theoretical approach to describe this dependence is based on a combination of two well established techniques: Results of relativistic coupled-cluster calculations on the alkali-He dimers (energy and HFS constant as functions of the binding length) are mapped onto the doped-droplet-situation with the help of helium-density functional theory. We simulate doped droplets He_{N} with N ranging from 50 to 10000, using the diatomic alkali-He-potential energy curves as input. From the obtained density profiles we evaluate average distances between the dopant atom and its direct helium neighborhood. The distances are then set in relation to the variation of the HFS constant with binding length in the simplified alkali-He-dimer model picture. This method yields reliable relative shifts but involves a systematic absolute error. Hence, the absolute values of the shifts are tied to one experimentally determined HFS constant for ^{85}Rb-He_{N = 2000}. With this parameter choice we obtain results in good agreement with the available experimental data for Rb and K^{a,b} confirming the predicted 1/N trend of the functional dependence^{c}. M. Koch, G. Auböck, C. Callegari, and W. E. Ernst, Phys. Rev. Lett. 103, 035302-1-4 (2009) M. Koch, C. Callegari, and W. E. Ernst, Mol. Phys. 108 (7), 1005-1011 (2010) A. W. Hauser, T. Gruber, M. Filatov, and W. E. Ernst, ChemPhysChem (2013) online DOI: 10.1002/cphc.201200697

  16. Monte Carlo simulation of the mixed alkali effect with cooperative jumps

    NASA Astrophysics Data System (ADS)

    Habasaki, Junko; Hiwatari, Yasuaki

    2000-12-01

    In our previous works on molecular dynamics (MD) simulations of lithium metasilicate (Li2SiO3), it has been shown that the long time behavior of the lithium ions in Li2SiO3 has been characterized by the component showing the enhanced diffusion (Lévy flight) due to cooperative jumps. It has also been confirmed that the contribution of such component decreases by interception of the paths in the mixed alkali silicate (LiKSiO3). Namely, cooperative jumps of like ions are much decreased in number owing to the interception of the path for unlike alkali-metal ions. In the present work, we have performed a Monte Carlo simulation using a cubic lattice in order to establish the role of the cooperative jumps in the transport properties in a mixed alkali glass. Fixed particles (blockage) were introduced instead of the interception of the jump paths for unlike alkali-metal ions. Two types of cooperative motions (a pull type and a push type) were taken into account. Low-dimensionality of the jump path caused by blockage resulted in a decrease of a diffusion coefficient of the particles. The effect of blockage is enhanced when the cooperative motions were introduced.

  17. In situ alkali-silica reaction observed by x-ray microscopy

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

    Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.

    1997-04-01

    In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques availablemore » for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.« less

  18. Acquisition of Co metal from spent lithium-ion battery using emulsion liquid membrane technology and emulsion stability test

    NASA Astrophysics Data System (ADS)

    Yuliusman; Wulandari, P. T.; Amiliana, R. A.; Huda, M.; Kusumadewi, F. A.

    2018-03-01

    Lithium-ion batteries are the most common type to be used as energy source in mobile phone. The amount of lithium-ion battery wastes is approximated by 200 – 500 ton/year. In one lithium-ion battery, there are 5 – 20% of cobalt metal, depend on the manufacturer. One of the way to recover a valuable metal from waste is leaching process then continued with extraction, which is the aim of this study. Spent lithium-ion batteries will be characterized with EDX and AAS, the result will show the amount of cobalt metal with form of LiCoO2 in the cathode. Hydrochloric acid concentration used is 4 M, temperature 80°C, and reaction time 1 hour. This study will discuss the emulsion stability test on emulsion liquid membrane. The purpose of emulsion stability test in this study was to determine optimum concentration of surfactant and extractant to produce a stable emulsion. Surfactant and extractant used were SPAN 80 and Cyanex 272 respectively with both concentrations varied. Membrane and feed phase ratios used in this experiment was 1 : 2. The optimum results of this study were SPAN 80 concentrations of 10% w/v and Cyanex 272 0.7 M.

  19. Battery resource assessment. Subtask 2.5: Battery manufacturing capability recycling of battery materials

    NASA Astrophysics Data System (ADS)

    Pemsler, P.

    1981-02-01

    Studies were conducted on the recycling of advanced battery system components for six different battery systems. These include: nickel/zinc, nickel/iron, zinc/chlorine, zinc/bromine, sodium/sulfur, and lithium-aluminum/iron sulfide. For each battery system, one or more processes were developed which would permit recycling of the major or active materials. Each recycle process was designed to produce a product material which can be used directly as a raw material by the battery manufacturer. Metal recoverabilities are in the range of 93 to 95% for all processes. In each case, capital and operating costs were developed for a recycling plant which processes 100,000 electric vehicle batteries per year.

  20. SnO2 promoted by alkali metal oxides for soot combustion: The effects of surface oxygen mobility and abundance on the activity

    NASA Astrophysics Data System (ADS)

    Rao, Cheng; Shen, Jiating; Wang, Fumin; Peng, Honggen; Xu, Xianglan; Zhan, Hangping; Fang, Xiuzhong; Liu, Jianjun; Liu, Wenming; Wang, Xiang

    2018-03-01

    In this study, SnO2-based catalysts promoted by different alkali metal oxides with a Sn/M (M = Li, Na, K, Cs) molar ratio of 9/1 have been prepared for soot combustion. In comparison with the un-modified SnO2 support, the activity of the modified catalysts has been evidently enhanced, following the sequence of CsSn1-9 > KSn1-9 > NaSn1-9 > LiSn1-9 > SnO2. As testified by Raman, H2-TPR, soot-TPR-MS, XPS and O2-TPD results, the incorporation of various alkali metal oxides can induce the formation of more abundant and mobile oxygen species on the surface of the catalysts. Moreover, quantified results have proved that the amount of the surface active oxygen species is nearly proportional to the activity of the catalysts. CsSn1-9, the catalyst promoted by cesium oxide, owns the largest amount of surface mobile oxygen species, thus having the highest activity among all the studied catalysts. It is concluded that the amount of surface active and mobile oxygen species is the major factor determining the activity of the catalysts for soot combustion.