WO1993006626A1 - Separateurs selectifs a permeation et leurs procedes de fabrication - Google Patents

Separateurs selectifs a permeation et leurs procedes de fabrication Download PDF

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Publication number
WO1993006626A1
WO1993006626A1 PCT/AU1992/000491 AU9200491W WO9306626A1 WO 1993006626 A1 WO1993006626 A1 WO 1993006626A1 AU 9200491 W AU9200491 W AU 9200491W WO 9306626 A1 WO9306626 A1 WO 9306626A1
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Prior art keywords
polystyrene
separator
ion exchange
cross
duolite
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PCT/AU1992/000491
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English (en)
Inventor
Sie Chung Chieng
Michael Kazacos
Maria Kazacos
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Unisearch Limited
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Publication of WO1993006626A1 publication Critical patent/WO1993006626A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to a permeation selective separators and a process for 5 making such a separator and an all-vanadium cell including such a separator.
  • Vanadium redox batteries require a 10 membrane or separator to prevent cross-mixing of the electrolytes from the negative and the positive half-cell while still permitting the transport of hydrogen ions to complete the circuit during the passage of current.
  • the ideal membrane should be permselective to the hydrogen ions for high ionic conductance.
  • Cation and anion exchange membranes have been used in the past as separators in the vanadium redox battery.
  • Anion exchange 15 membranes can successfully suppress the diffusion of positive vanadium ions across the membrane in both half-cells but the transport of hydrogen ions are also impeded.
  • the cation exchange membrane Selemion CMVTM [ s 0 ne of the preferred membranes which has been used in the research and development of the vanadium redox battery.
  • the Selemion CMVTM membrane has shown chemical instability in 20 long term cycle testing and the performance of the battery drops to unacceptable levels in long term cycle testing. Much higher stabilities are currently being demonstrated by anion exchange membranes but the long term testing of these membranes in large battery stacks has still to be undertaken.
  • the NafionTM N324, NE112 and N423 membranes and the new Selmion membrane (Asahi Glass, Japan, 1992) meet the necessary 25 requirements of chemical stability and low permeation rates.
  • OBJECTS OF INVENTION Objects of this invention are to provide a permeation selective separator and a process for making such a separator and an all-vanadium cell including such a separator.
  • ; dilemma selective separator comprising a microporous separator having at least one ion exchange material crosslinked with the separator.
  • a microporous separator with a solvent comprising, at least partially dissolved therein, at least one ion exchange material and at least one crosslinker, for a period sufficient to permit the ion exchange material and the crosslinker to be taken up by the pores of the microporous separator; crosslinking the ion exchange material with the microporous separator to form the permeation selective separator, wherein the permeation selective separator has greater permeation selectivity than the permeation selectivity of the uncrosslinked microporous separator.
  • Permeation selective separator may be fabricated in accordance with the invention that are suitable for use in a redox battery, in particular an all-vanadium redox battery-
  • the ion exchange material is selected from the group consisting of an ion exchange resin, a polyelectrolyte, and an ion exchange resin cross linked with a polyelectrolyte.
  • the ion exchange material is adsorbed on and/or absorbed on and/or derivatized to the microporous separator before it is cross-linked with the separator.
  • the polyelectrolyte when crosslinked with the ion exchange resin, may be crosslinked with the ion exchange resin with a different crosslinker than the crosslinker used to crosslink the ion exchange material and the microporous separator.
  • a permeation selective separator when prepared by the process of the second embodiment.
  • a redox battery having a positive compartment containing a catholyte in electrical contact with a positive electrode, the catholyte comprising an electrolyte containing a cationic redox couple, a negative compartment containing an anolyte in electrical contact with a negative electrode, the anolyte comprising an electrolyte containing a cationic redox couple, and a permeation selective separator of the first or third embodiments disposed between the positive and negative compartments and in contact with the catholyte and anolyte to provide ionic communication and permeation selectivity therebetween.
  • the ion exchange material is cross linked with the microporous separator in a solvent which includes a polymerization initiator to initiate polymerization (and thus cross-linking) between the ion exchange material and the microporous separator.
  • the microporous separator may be a membrane of polystyrene, C2-CI6 polyolefin such as polyethylene or polypropylene material including a polyethylene material such as Daramic (Daramic is a polyethylene-silica based material) or other microporous polyethylene.
  • the separator may be of polyvinyl chloride, polyvinylidene chloride, natural or synthetic rubbers. Homogeneous membranes prepared by the graft polymerization of polyethylene and styrene following the soaking of a film of polyethylene in styrene monomer may be used.
  • Selective membranes which preferentially allow the passage of cations or ⁇ anions may have enhanced selectivity after treatment via a process of the invention.
  • Nonionic membranes such as Acropor
  • An anion or cation ion exchange resin may be used depending on what ions are
  • anion ion exchange resins include Dowex 1 (tri ethyl benzyl ammonium/polystyrene), Dowex 21K (trimethyl benzyl ammonium/polystyrene, Duolite A-101 D (quaternary ammonium/polystyrene), lonac A-540 (quaternary ammonium/polystyrene), Dowex 2 (dimethyl ethanol benzyl ammonium/polystyrene), Duolite A-102 D (quaternary
  • Amberlite IR-45 (aminated chloromethylated cross linked polystyrene).
  • cation exchange resins include Amberlite CG400, Amberlite IR-120 (sulphonated cross linked polystyrene), Dowex 50 (sulphonated cross linked polystyrene), Permutit Q (sulphonated cross linked polystyrene), polysulphone, Duolite C-20 (sulphonated cross «t linked polystyrene), Amberlite IRC-50 (cross linked polymethacrylic acid), Duolite C-3
  • polyelectrolytes examples include polystyrene sulphonated (PSS), carboxy methyl cellulose sodium, poly(styrene-co-maleic acid), poly(metaphosphoric acid), poly(4-vinylpyridine), poly(vinylsulphonic acid), poly(vinyl methyl ether-co-maleic acid), polyethyleneimine, poly (acrylic acid), poly(p-styrenesulphonic acid), poIy(methacrylic acid) and polyvinylamine.
  • PSS polystyrene sulphonated
  • carboxy methyl cellulose sodium examples include poly(styrene-co-maleic acid), poly(metaphosphoric acid), poly(4-vinylpyridine), poly(vinylsulphonic acid), poly(vinyl methyl ether-co-maleic acid), polyethyleneimine, poly (acrylic acid), poly(p-styrenesulphonic acid), poIy(methacrylic acid) and polyvinylamine
  • An appropriate solvent for dissolving the polyelectrolyte/ion exchange resin may be selected depending on the nature of the polyelectrolyte and the ion exchange resin chosen.
  • the polyelectrolytes chosen are polystyrene sulphonated and carboxy methyl cellulose sodium and the ion exchange resin is Amberlite CG400
  • an appropriate solvent was dimethyl formamide, 1M H2SO4 and 50% ethanol/H ⁇ O mixture.
  • solvents for polymers are given in J. Brandup and E. H. Immergut, "Polymer Handbook", 3rd Edition, John Wiley and Sons, New York, 1989, the contents of which are incorporated herein by cross reference.
  • the cross linking agent is generally chosen depending on the nature of the polyelectrolyte, ion exchange resin and/or microporous separator.
  • the microporous separator comprises poly(vinyl alcohol) a monomer including vinylidene chloride, vinyl acetate, styrene, acrylamide, 1 ,3 butadiene, methacrylic acid, vinyl chloride, acrylonitrile, 2-hydroxyethyl methacrylate, methyl methacrylate, may be chosen depending on the polyelectrolyte and ion exchange resin.
  • esters of acrylic and methacrylic acid such as methyl, ethyl, propyl, isobutyl, isopropyl, butyl, tert-butyl, sec- butyl, ethylhexyl, amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, isobornyl, benzyl, phenyl, alkylphenyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl, ethoxyphenyl, ethoxybenzyl, ethoxycyclohexyl, hydroxyethyl, hydroxypropyl, ethylene, propylene, isobutylene, diisobutylene, styrene, ethylvinylbenzen
  • polyethylenically unsaturated monomers include: divinylbenzene, divinylpyridine, divinylnaphthalenes, diallylphthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropanetri methacrylate, divinylsulfone, polyvinyl or polyallyl ethers of glycol, of glycerol, of pentaerythritol, of diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, divinyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, diethyleneglycol, of monothio-derivatives of glycols, and of resorcinol divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinate, diallyl carbonate, diallyl mal
  • aromatic diacids and their derivatives including phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, dimethylphthalate, aliphatic dibasic acids such as maleic acid, fumaric acid, itaconic acid, 1 , 1-cyclobutane- dicarboxylic acid, aliphatic diamines such as piperazine, 2-methylpiperazine, cis, cis-bis (4-aminocyclohexyl) methane, metaxylylenediamine, glycols such as diethylene glycol, triethylene glycol, 1,2-butanediol, neopentyl glycol, bischloro-formates such as cis and trans-1 ,4-cyclohexylbis-cbloroformate, 2,2,2,4-tetra-methyl-l ,3-cyclobutyl bischloroformate and bischloroformate and bischloroformate
  • cross linking agents examples include J. Brandup and E. H. Immergut, "Polymer Handbook", 3rd Edition, John Wiley and Sons, New York, 1989, the contents of which are incorporated herein by cross reference.
  • the amount of cross-linking agent used depends on the ions that are required to be selectively permeated or substantially excluded through the permeation selective separator, as well as the type of ion exchange material and the type of microporous separator and in particular the initial pore size of the microporous separator. For given set of circumstances, the amount of cross-linking agent to be used may be readily determined by trial an error without undue experimentation.
  • a divinyl benzene (DVB):organic solvent (eg methanol or ethanol) ratio of 25:75 to 75:25, more typically, 30:70 to 60:40 and even more typically, 40:60, may be used to cross-link Daramic.
  • the polymer initiator is generally chosen depending on the nature of the cross linking agent, polyelectrolyte, ion exchange resin and/or microporous separator. Examples of polymer initiators are given in J. Brandup and E. H. Immergut, "Polymer Handbook", 3rd Edition, John Wiley and Sons, New York, 1989, the contents of which are incorporated herein by cross reference.
  • the permeation selective separator of the invention may be readily tailored to selectively permeate diferent type of ions by choosing the appropriate ion exchange material, microporous separator and in particular the initial pore size of the microporous separator and cross-linking agent for the particular ions required to be separated.
  • Examples of possible ions for selective peremation include halogen, H, OH", Na, K, phosphate or sulphate, whilst substantially excluding ions such as Li, Au, Mn, Pt, Ir, Ru, Os, Re, Rh, Sb, Te, Pb, Fe, Co, Ni, Cu, Ce, La, V, Ag, Mo, Cr, Al, Pb, Bi, Tl, Hg, Cd, In, Ag, Be, Ga, Sb, As, Zn, Ca and/or Mg ions.
  • ions for selective peremation include halogen, H, OH", Na, K, phosphate or sulphate, whilst substantially excluding ions such as Li, Au, Mn, Pt, Ir, Ru, Os, Re, Rh, Sb, Te, Pb, Fe, Co, Ni, Cu, Ce, La, V, Ag, Mo, Cr, Al, Pb, Bi, Tl, Hg, Cd, In, Ag, Be, Ga, Sb
  • an all- vanadium redox battery having a positive compartment containing a catholyte in electrical contact with a positive electrode, the catholyte comprising an electrolyte containing tetravalent vanadium ions or pentavalent vanadium ions, a negative compartment containing an anolyte in electrical contact with a negative electrode, the anolyte comprising an electrolyte containing tetravalent vanadium ions, trivalent vanadium ions or divalent vanadium ions, and a permeation selective separator of the first or third embodiments disposed between the positive and negative compartments and in contact with the catholyte and anolyte to provide ionic communication and permeation selectivity therebetween and wherein the catholyte includes a salt selected from the group consisting of a salt of the formula VO(X) v where y is 2 and X is F, Br or Cl, a salt of the formula VO
  • the electrochemical reactions of the redox cell can be conducted in any electrochemical cell which has an anode compartment and a cathode compartment through which the appropriate fluids can be transported.
  • a particular redox cell in which the permeation selective membranes may be used to advantage is an all-vanadium battery described in United States Patent No. 4,786,567, the contents of which are incorporated herein by cross reference.
  • the design of the electrode and cathode compartments of the redox cell are not critical to the practice of this invention, certain embodiments are preferred.
  • a parallel plate electrochemical cell in which anode and cathode compartments alternate in order to increase voltage and decrease current is a preferred embodiment.
  • the electrode material will depend on the nature and composition of the anolytes and catholytes in the redox cell and are typically chosen on efficiency and stability grounds, i.e. the higher the efficiency and the greater stability in the particular anolyte and catholyte used in the redox battery, then generally the more it is favoured.
  • Typical positive and negative electrodes may be selected from metal or a carbon/graphite, with suitable metals including transition metals such as titanium, iron, nickel, copper, silver, platinum, gold, palladium, tin, tantalum, cobalt, cadmium, lead, ruthenium oxide, and alloys and mixtures thereof.
  • Suitable carbon/graphite electrodes include glassy (amorphous) carbons, reticulated vitreous carbons, pyrolytic carbons, carbon and graphite felt, mat, plate, rod, knit, fibre, and cloth; carbon impregnated teflon; carbon impregnated polyethylene; carbon impregnated polypropylene; carbon impregnated polystyrene; carbon impregnated polyvinylchloride; carbon impregnated polyvinylidenechloride; glassy carbon; non-woven carbon fibre material; cellulose; carbon and graphite felt, mat, plate, rod, knit, fibre, and cloth, carbon impregnated teflon, carbon impregnated polyethylene, carbon impregnated polypropylene, carbon impregnated polystyrene, carbon impregnated polyvinylchloride and carbon impregnated polyvinylidenechloride, impregnated with and/or coated with Au, Pt, Ir, Ru, Os, Re,
  • carbon/graphite electrodes such as glassy (amorphous) carbons, reticulated vitreous carbons, pyrolytic carbons, carbon and graphite felt, mat, plate, rod, knit, fibre, and cloth; are bonded onto a conducting substrate such as carbon impregnated teflon, carbon impregnated polyethylene, carbon impregnated polypropylene, carbon impregnated polystyrene, carbon impregnated polyvinylchloride and carbon impregnated polyvinylidenechloride, etc.
  • typical anode stable materials include graphite/carbon based electrodes, Dimensionally Stable Anodes i.e.
  • metal oxides such as Ti ⁇ 2, Ir 2C*3 > Pt O > Mn ⁇ 2 or mixtures of these coated onto a titanium substrate.
  • coatings of anion activated polypyrrole on conducting plastic where the conducting plastic can be graphite impregnated polyethylene/ polypropylene or polyethylene/polypropylene impregnated with a mixture of 5-50% polypyrrole powder plus 5-20% graphite fibres.
  • conducting plastics can be used as substrates for coating polypyrrole electroactive films.
  • typical cathode stable materials include graphite, carbon, graphite filled conducting plastics, Pb, Pt, Au, nickel, steel, etc.
  • the construction of the electrode will depend on the material type, with metal electrodes generally being in the form of plates, bars, and screens, or being sintered to form a highly porous structure.
  • the positive and negative electrodes can be any shape desired. It is preferred that the positive and negative electrodes are rectangular-plate shaped.
  • Metal electrodes may also be formed by depositing a film or layer of the metal on a nonconductive substrate, such as glass.
  • the structure of carbon/graphite electrodes will depend upon the type of carbon. Glassy carbon electrodes are generally flat, polished surfaces while reticulated vitreous carbons are glass-like porous structures, typically pyrolyzed polyacrylonitriles.
  • Pyrolytic carbons are produced by vapour phase deposition of carbon on a substrate, resulting in a polycrystalline structure with a high degree of atomic orientation.
  • Preferred is the use of graphite, carbon/graphite or carbon felt electrodes which have been found to provide particularly effective catalytic sites after an oxidation pretreatment.
  • the graphite, carbon/graphite or carbon felt electrodes are generally bonded onto a conducting carbon or graphite filled plastic electrode to form the final electrode configuration.
  • Carbon felts are generally woven from yarns which are bundles of individual carbon monofilaments generally having a diameter in the range from about 1 to 50 ⁇ m, usually in the range from about 5 to 10 ⁇ m.
  • the yarns will typically include from aoout 100 to 20,000 monofilaments, usually having from about 3,000 to 6,000 filaments.
  • the denier of the yarns used as in fabricating the carbon felts will typically be in the range from about 500 to 5,000 mg/m, usually being in the range from about 1,000 to 2,000 mg/m. Denier is equal to the number of grams which yield 9,000 meters of the yarn or filament.
  • the yarns are woven by conventional weaving machines yielding large fabrics which may be cut into the desired dimensions for the electrode. Each electrode may employ a plurality of layers of the fabric, so that the final dimensions of the electrode may vary widely.
  • the electrodes will have a height in the range from about 0.5 cm to 600 cm, more typically, 5 to 250cm, a width in the range from about 0.1 cm to 600 cm, more typically, 5 to 250cm, and a thickness in the range from about 0.1 cm to 1.0 cm.
  • the particular dimensions chosen will depend primarily on the capacity of the electrochemical cell.
  • Carbon felts suitable for use in the present invention may be obtained commercially from suppliers such as FMI Fibre Materials, Inc., Biddleford, Maine; Hercules, Inc., Wilmington, Delaware; Celanese Engineering, Chatham, New Jersey; Ultra Carbon Corp. , Bay City, Michigan; and Union Carbide Corp., Mitsubishi, Japan, Toray, Japan, Kureha, Japan, Sigri, Germany, Specialty Polymers and Composites Division, Danbury, Connecticut.
  • a separator of the invention comprises a microporous membrane an example of which is DaramicTM which has been treated with a basic anion exchange resin, a cross-linking agent and initiator.
  • the basic anion exchange resin is typically a polystyrene based polymer.
  • the cross-linking agent is typically divinyl benzene (DVB) and the polymerization initiator is typically sodium persulphate.
  • the separator comprises a 40x60 cm ⁇ DaramicTM separator which has been treated with a polystyrene based basic anion exchange resin, AmberliteTM CG400, and cross linked with a solution of 40% divinyl benzene (DVB) and methanol. Polymerization is then facilitated by the addition of the polymerization initiator sodium persulphate.
  • the DaramicTM separator is soaked in a solution of AmberliteTM CG400 and DVB methanol for a period of approximately 1-6 hours and up to 24 hours and more (eg 300 hours).
  • the separator is then placed in an aqueous solution of a polymerization initiator, preferably sodium persulphate, and heated to facilitate polymerization.
  • a polymerization initiator preferably sodium persulphate
  • the separator comprises a 0.23 mm thick DaramicTM separator which has been treated with a solution of AmberliteTM CG400 and treated with divinylbenzene via soaking in a solution of 30 vol% DVB and methanol at 20-25 °C for greater than 2 hours, generally up to 6 hours and even up to 24 hours. Polymerization is then facilitated by removing the soaked membrane from the solution and placing it in a hot (80-90°C) aqueous solution of the initiator sodium persulphate (0.5wt%) for 0.5-3hours or more and then heating the auqeous solution to 93-98 °C and holding the temperature for a further 0.5-3hours or more. The treated separator is then removed from the aqueous solution and rinsed with water.
  • DaramicTM separator which has been treated with a solution of AmberliteTM CG400 and treated with divinylbenzene via soaking in a solution of 30 vol% DVB and methanol at 20-25 °C for greater than 2 hours,
  • a DaramicTM separator is soaked in a solution of Amberlite M CG400 and 50% ethanol. The separator is then placed in a solution of 30 vol % DVB and methanol for 2 hours. The membrane is then transferred to a hot aqueous solution containing 2 g of a polymerization initiator, sodium persulphate, to facilitate polymerization.
  • a polymerization initiator sodium persulphate
  • Fig. 1 schematically depicts a side on exploded view of the experimental cell used for comparative in situ treatment of a microporous separator, where A is the membrane to be treated in situ, B is a graphite plate electrode, C is nitrogen gas and D is a DC power source;
  • Fig. 2 schematically depicts a side on exploded view of the experimental cell used for testing a microporous separator, where A is the membrane to be tested, B is a graphite current collector, C is a connecting copper rod and D is a graphite felt electrode;
  • Fig. 3 is a graph of the long term cycling test data for a 0.23 mm thick, 10x12 cm2 DaramicTM separator, designated X3, treated with polystyrene sulphonated and cycled in a vanadium redox cell at a current density of 40 mA/cm ⁇ .
  • Fig. 4. is a graph of the cell efficiencies of a charge/discharge test for a 0.23 mm thick, 10x12 cm ⁇ DaramicTM separator, designated Y3, treated with carboxy methyl cellulose sodium and 30 vol. % DVB and cycled in a vanadium redox cell at a current density of 40 mA/cra ⁇ .
  • Fig. 5 is a graph of the cell efficiencies at various current densities with a DaramicTM separator (0.15mm) treated with AmberliteTM CG400 and 40 vol. % of DVB;
  • Fig. 6 is a graph of the long term cycling test data for a Daramic ⁇ M separator, designated X3, (0.15 mm) treated with AmberliteTM CG400 and 40 vol. % DVB and cycled in a vanadium redox cell at a current density of 40 mA/cm ⁇ ; and
  • Fig. 7 is an all vanadium battery having a permeation selective separator.
  • BEST MODE AND OTHER MODES FOR CARRYING OUT THE INVENTION A permeation selective membrane for use in an all vanadium battery, of the type described in United States Patent No. 4,786,567, is prepared by immersing a 0.15mm thick, 12 x 14 cm ⁇ sheet of Daramic (W.R. Grace), in a mixture of divinylbenzene (DVB) and methanol (50ml) containing lg of Amberlite 400CG (Rohm & Haas), for typically 1-6 hours and up to 24 hours and more.
  • DVD divinylbenzene
  • methanol 50ml
  • Amberlite 400CG Amberlite 400CG
  • the soaked membrane is then transferred to a polymerization reactor to which lg of sodium persulphate (Sigma Chemical Co.) is added to 200 ml of distilled water at 80° C. Polymerization is continued for 1 hour at 90° C and 1 hour at 95 °C to produce the permeation selective membrane.
  • the ratio of DVB: methanol (vol. %), is about 40%. Methanol is used to facilitate the penetration of the initiator, sodium persulphate, into the membrane. This is subsequently exchanged with water during polymerisation, since water and DVB do not mutually dissolve.
  • an all-vanadium redox battery 70 includes redox cell 71 which has a negative compartment 72 having negative electrode 73 and positive compartment 74 having positive electrode 75.
  • Negative compartment 72 contains anolyte 99 in electrical contact with negative electrode 73 and positive compartment 74 contains catholyte 98 in electrical contact with positive electrode 75.
  • Cell 71 includes permeation selective electrode 76, of the type described immediately above, disposed between positive and negative compartments 72, 74 and in contact with catholyte 98 and anolyte 99 to provide permeation selective ionic communication therebetween.
  • Anolyte 99 and catholyte 98 are prepared by leaching V2O5, V2O4, V2O3, or NH4VO3 with a solution containing V ⁇ + and/or V ⁇ + to produce a mixture of V ⁇ + and/or V ⁇ + and/or VO ⁇ + and/or VO + 2 i° ns at a tota ' vanadium concentration of 0.1M to 2.5M in 0.1M to 6M H2SO4 and this solution is loaded into anolyte reservoir 77 and negative compartment 72 and catholyte reservoir 78 and positive compartment 74.
  • Anolyte 99 is then pumped through negative compartment 72 and anolyte reservoir 77 via anolyte recirculation lines 89, 80 and 79 by anolyte pump 81 and simultaneously catholyte 98 is pumped through positive compartment 74 and catholyte reservoir 78 via catholyte recirculation lines 90, 83 and 82 by catholyte pump 84.
  • Cell 71 is then charged by providing electrical energy from power source 85, which is electrically connected to positive electrode 75 via lines 93 and 91, to positive and negative electrodes 75 and 73 by closing switch 86, which is electrically connected to source 85 via line 97 and to negative electrode 73 via lines 95 and 94, and opening switch 87 which is electrically connected to negative electrode 73 via line 94 and to load 88 via line 96, to derive divalent vanadium ions in anolyte 99 and pentavalent vanadium ions in catholyte 98 . Electricity is produced from cell 71 by opening switch 86, closing switch 87 and withdrawing electrical energy via load 88, which is electrically connected to positive electrode 75 via line 91.
  • Cell 71 is re-charged by opening switch 87, closing switch 86 and providing electrical energy from power source 85 to derive divalent vanadium ions in anolyte 99 and quinvalent vanadium ions in catholyte 98.
  • the following examples are provided by way of illustration and are not intended to limit the invention in any way.
  • Example 1 The in-situ treatment of microporous separator, Daramic is described in Grimes P. G . and Bellows R. J., "Method of improving the ion selectivity of membranes", U.S.Patent 4,365,009, 1982. With this method, the polyelectrolytes disposed in the cell fluid would migrate to the membrane surface under the influence of an ionic field and formed an ionic barrier to enhance the selectivity of the membrane. Experimental Materials and Reagents Microporous separator, Daramic (W.R Grace) of thicknesses 0.15 and 0.23mm were used for the study.
  • the polyelectrolytes used were polystyrene sulphonated (PSS), M.W 500,000, supplied by National Starch & Co. and carboxy methyl cellulose sodium (CMCS), M.W 120,000, supplied by Tokyo Kasei Kogyo Co..
  • PSS polystyrene sulphonated
  • CMCS carboxy methyl cellulose sodium
  • ion-exchange resin used was Amberlite 400CG (Amb) supplied by Rohm & Haas Co.. All other reagents used were analytical grade.
  • Fig.l For the in-situ treatment, the set up of the experiment is shown in Fig.l.
  • Daramic to be treated (0.15mm size: 10xl2cm2) was pressed between the two half cells. Each half-cell was filled with 70ml 2M V3.5+ (i.e. IM V(III) + IM V(IV)) in 2.5M H2SO4 solutions.
  • the electrodes used were graphite blocks, connected to the positive and the negative terminal of the power supply.
  • 0.5g of the polyelectrolytes, PSS was added to the negative half-cell. Nitrogen gas was bubbled continuously through the negative half- cell to provide stirring.
  • the cell was charged and discharged at a constant current of 1 Amp and 0.3 Amp respectively, for 48 hours.
  • the treated Daramic was removed and washed with distilled water before being put together for the charge/discharge test with the cell shown in Fig. 2.
  • the temperatures at which the membranes immersed in the polyelectrolytes solutions/mixtures were at 20° C and 60° C for 24 hours.
  • the resulting membranes were washed with distilled water and dried in vacuum oven at 50° C for 2 hours.
  • the polyelectrolytes solutions/mixtures were prepared by dissolving 0.25g of polyelectrolytes in 50ml of solvents.
  • MgSO4 was used to equalise the ionic strengths of the two solutions and minimise osmotic pressure effects.
  • a 3ml sample of the initial vanadium-free solution was withdrawn and its absorbance was measured at the appropriate wavelength using a Varian Super Scan 3 U.V visible spectrograph. The sample was then returned to the cell and the procedure was discontinued when the absorbance was greater than one.
  • the area resistivity was determined by measuring conductance with a Radiometer conductivity meter.
  • the membrane was glued between two rubber gaskets with 1 cm hole diameter in the centre and was mounted between two halves of the cell containing 2M VOSO4 in 3M H2SO4 and graphite plate electrodes.
  • Membrane resistance was obtained by subtracting the cell resistance without the membrane from the cell resistance with the membrane present.
  • the redox flow cell used was constructed from PVC sheet with graphite felt electrodes and graphite plates as current collector as shown in Fig.2.
  • the electrode and the membrane area were 25cm 2 and 30cm 2 respectively while the volume of the electrolytes was 65ml for each side of the cell.
  • the cell was charged and discharged at the constant current density of 40 mA/cm 2 .
  • the state-of-charge (SOC) of the electrolytes in both half cells was balanced at the end of the first charging cycle to bring the electrolytes of the two half cells to the same SOC. This was done by exchanging an appropriate volume of the charged positive V(V) solution with an equivalent volume of the V(IV) solution.
  • the adsorption of polyelectrolytes is shown to depend strongly on the charge of the polyelectrolytes and on the difference between the dielectric constants of the solution and the substrate.
  • the charge of the substrate also influenced the adsorption affinity of the polyelectrolytes.
  • the surface charges of the microporous membrane, Daramic were not determined.
  • the effects of using different solvents to dissolve the polyelectrolytes/ion-exchange resins for the treatments did not show any definite trends based on the resistivity and the diffusivity measurements. The small difference in the measured parameters were not conclusive indication of the effects of the different solvents used.
  • the treatment did not produce membranes with uniform properties throughout the whole sheet and the resistivity of the samples varied quite significantly (30-50%).
  • the original material, Daramic have uniform properties based on the resistivity and the diffusivity measurement over the whole sheet.
  • the non-uniformity of the treatment could cause high permeation of vanadium ions at some spots.
  • Table 3 shows the cell efficiencies of the second cycle charge/discharge test at a constant current density of 40 mA/cm 2 for both treated sample XI -XI 4 and untreated Daramic. Table 3. Cell efficiencies of the second cycle charge/discharge test for sample XI to X14 and untreated Daramic at a current density of 40 mA/cm .
  • the average pore sizes of Daramic provided by the manufacturer was lOOnm compared with the ion-exchange membrane with a typical value of ⁇ 20nm. With the large initial pore sizes, the adsorbed/absorbed/derivatized polyelectrolytes/ion exchange resins on the Daramic produced a significant reduction in the hydraulic permeability. Comparing the results obtained for the diffusivity measurement and the charge/discharge test, the effects of the adsorbed/absorbed/derivatized polyelectrolytes on the diffusional permeability was substantially less than the reduction in hydraulic permeability.
  • the diffusivity values of the samples were based on the diffusion measurement of
  • V(IV) species In the charge/discharge test, the presence of high concentrations of different vanadium species on both sides of the membrane could present a different diffusion phenomena and this could also produced an osmotic pressure effect.
  • Treatment method for sample X3 shows the largest improvement in terms of cell efficiencies from the charge/discharge test.
  • the stability and the irreversibility of the adsorbed/absorbed/derivatized polyelectrolytes from the treatment was tested with sample, X3 in the cycle charge/discharge testing.
  • the number of hours tested was 160 hours for 34 cycles.
  • the cell efficiencies versus the cycle number is shown in Fig.3.
  • the coulombic efficiency was still maintained at the initial value after 160 hours indicating that the adsorbed/absorbed/derivatized polyelectrolytes did not redissolve in the vanadium electrolytes.
  • the solutions from the anolyte and the catholyte were rebalanced to restore the capacity of the redox cell and the performance of the cell recovered to its initial value.
  • the diffusivity of the samples, Y 1 -Y3 were lower compared to those treated with the polyelectrolytes/ion-exchange resins only. Quite significant improvement in the selectivity was achieved by the treatment using Amb in 50% ethanol with crosslinking using DVB.
  • the increase in selectivity for treated Daramic with crosslinking could be attributed to the decreased in swelling due to the more rigid physical structure of the membrane and the ion-exchange sites incorporated into the crosslinking element.
  • the pore sizes of the treated Daramic could also be reduced.
  • the improvement in selectivity was negligible.
  • the all-vanadium redox battery requires a membrane or separator to prevent cross-mixing of the electrolytes from the negative and the positive half-cell and whilst still permitting the transport of hydrogen ions to complete the circuit during the passage of current.
  • the ideal membrane should be permselective to the hydrogen ions for high ionic conductance.
  • anion exchange membrane can successfully suppress the diffusion of positive vanadium ions across the membrane in both of the half-cell but the transport of hydrogen ions are also impeded. Both cation and anion exchange membranes have been tested and found to be satisfactory for application as separator in the vanadium redox battery.
  • selemion CMV Asahi Glass Co.
  • selemion CMV membrane has shown chemical instability in long term cycle testing and the performance of the battery drops to unacceptable level. Much higher stabilities are currently being demonstrated by the types of anion exchange membranes, and long term testing in large battery stacks will soon be undertaken with these materials.
  • these membranes are relatively inexpensive when compared with the highly stable teflon-based membranes, the availability of an even lower cost chemical inert separator material can lead to significant cost reductions in the development of commercial redox battery systems.
  • Example 1 significant improvements in selectivity was observed for Daramic after treatment with Amberlite CG400 which were further crosslinked using divinyl benzene.
  • the treatment produced Daramic with ion selective capability.
  • the pore sizes of Daramic were also reduced with the treatment.
  • the membrane diffusivity and resistivity were evaluated by the methods described in Example 1.
  • the ion-exchange capacity of the membrane was determined by the method of S. Fisher and R.Kunin, Anal. Chem 27, (1955) 1191. The composite membrane was converted to Cl" formed by soaking the membrane in 0. IM sodium chloride solution for 24 hours.
  • the excess chloride ions in the membrane were leached out by washing with ultra pure water until the chloride concentration was less than 1 ppm.
  • the resulting membrane was immersed in 0.05M Na2S04 solution for 5 days to ensure equilibrium was reached.
  • the amount of Cl exchanged was analysed using ion- exchange chromatography (Waters ion-chromatography with IC-Pak column).
  • the average pore size distribution of the membrane was determined using bubble point technique with a Coulter porometer (Coulter Electronics Limited).
  • the membrane was cut into discs to size.
  • the fluid used to wet the membrane is Porofils supplied by Coulter Electronics Limited. Membrane stability and performance in charge/discharge test.
  • Example 1 The redox flow cell and the set-up for the charge/discharge test are described in Example 1.
  • the cell was charged/discharged at various current densities from 20 to 80 mA/cm 2 .
  • the long term cyclic charge/discharge test was conducted at a constant current density of 40 mA/cm ⁇ .
  • the state-of-charge (SOC) of the electrolytes in both half cells was balanced periodically when the performance of the cell dropped to an undesirable level. An imbalance in the SOC of the two half-cells can occur when air penetrates the unsealed negative half-cell causing oxidization of V(II) to V(III). No effort was made to seal the cell nor was nitrogen used to maintain an inert atmosphere in the negative half- cell.
  • the resistivity and diffusivity (K s ) of the composite membrane modified with different degree of cross-linking are shown in Table 1A.
  • the degree of crosslinking refers to the vol. of DVB used in the treatment.
  • the actual percentage of crosslinking of the composite membrane was not determined since the base material was not soluble in any of the solvents tried. This could be due to the silica which was incorporated in the base material.
  • Table 1A Resistivity and diffusivity of composite membrane with different degree of cross-linking.
  • the resistivity of the composite membrane was seen to rise sharply when more than 40 vol. % DVB was used in the treatment of the membrane.
  • the diffusion coefficient (K s ) of the composite membrane is lowered by a factor of 10 with the 40-50 vol. % DVB used in cross linking.
  • the swelling of the membrane is reduced by crosslinking using DVB.
  • the degrees of swelling decreases with increased crosslink density. The more highly cross linked membranes would be less permeable because of reduced internal volume of the network.
  • the composite membrane produced with 40 vol. % DVB thus shows a six-fold increase in area resistivity while the diffusivity is reduced by 8 times.
  • the average pore sizes for Daramic determined using the bubble point technique was 0.095 ⁇ m corresponding to the manufacturer's specification of O. l ⁇ m.
  • the average pore sizes for all the 3 different thicknesses of Daramic 0.15, 0.20 and 0.23mm were 0.095 ⁇ m.
  • Fig. l shows the differential pore number distribution of Daramic (0.15mm).
  • the pore size distribution of Daramic fall in a very narrow range.
  • the composite membrane had pore sizes ⁇ 0.06 ⁇ m and the pore sizes were beyond the limit detectable by the Coulter porometer.
  • Mercury intrusion technique was employed to determine the pore size distribution of both the composite and the untreated Daramic. Summary of the results from mercury intrusion obtained for both the composite and the untreated Daramic are shown in Table 3B.
  • Table 3B Summary of the results from mercmy intrusion obtained for both the composite and the untreated Daramic.
  • Ion-exchange capacity (IEC) of the composite membrane was 0.4meq/dg and was low compared to the ion-exchange membranes of typical values in the range of 1-5 meq/dg. However, the incorporation of even a very small quantity of IEC could affect the transport property of the membrane quite significantly.
  • the electrolyte uptake of the membrane was tested by soaking in 2M V 3 -5 + in 2.5M H2SO4, since in the all vanadium redox battery application, the predominant ions in the pores of the membrane are V(III) and V(IV). The electrolyte uptake of the composite membrane shows a mark decrease by about 80% .
  • Tortuosity is defined as the effective path length of the migrating ions through the membrane which is made of a network of interlocking pores. These networks act as physical barrier to the migrating ions and ions mobility is effectively reduced with increase in tortuosity. With the decrease in pore sizes, the ion exchange sites incorporate into the crosslinking element would be more effective in excluding the co-ions (Vanadium ions).
  • the increase in resistance of the composite membrane can be attributed by the decrease in the percentage of electrolyte uptake.
  • the electrical conductivity is directly proportional to the concentration of the current carrying species in the membrane which is predominantly H + ions in the all-vanadium redox cell.
  • the composite membrane (0.15mm) produced with 40 vol. % of the DVB used was chosen for this studies.
  • the efficiencies of the cell at various densities are shown in Fig. 5.
  • the efficiencies obtained for the composite membrane were comparable to the cation-exchange membrane, selemion CMV (Asahi Glass Co.).
  • the coulombic efficiency remains fairly constant with the range of current densities investigated, while the voltage efficiency drops with increasing current density due to increase iR losses, the overall energy efficiency thus drops off with increasing current density, a maximum of 84% being observed at 20 mA/cm-.
  • Fig.6 The long term cycling test data for this membrane are shown in Fig.6.
  • the average current, voltage and energy efficiencies over 700 cycles (4000 hours) were 95, 79 and 75% respectively.
  • the highest cell efficiencies obtained at the 550th cycle were 96, 85 and 83% for current, voltage and energy respectively.
  • the coulombic efficiency fluctuates between 93% and 100%.
  • the fluctuation in coulombic efficiency was due to the air oxidation of the negative half-cell electrolytes and the imbalance in the SOC of the electrolytes.
  • the imbalance in the SOC of the electrolytes in the two half-cells was caused by the volumetric crossover of the electrolytes across the membrane in either direction during cycling.
  • the cell resistivity measured at 50% SOC was 2.65 ⁇ cm 2 for charging and 2.75 ⁇ cm 2 for discharging.
  • the cell resistivity at 50% SOC was 2.33 ⁇ cm 2 and 2.54 ⁇ cm 2 for charging and discharging respectively. The decrease in the cell resistivity during cycling could be due to the activation of the graphite felt electrodes.
  • the composite membrane is shown to be chemically stable and resistant to fouling.
  • the composite membrane produced posses the properties required as separator for the redox battery application.
  • Scale-up of membrane size The treatment process of the invnetion was scaled up in the laboratory to prepare a 2400 cm 2 (effective area 1500 cm 2 ) Daramic/Amberlite/DVB membrane sheets. The manufacturer (W.R.Grace) was not able to supply the size of the Daramic membrane required. However, an alternative Daramic membrane with the required size was provided. This Daramic membrane, according to the manufacturer is similar in all properties to the previous samples of Daramic membrane provided by them except the colouring pigment. Previous samples were grey coloured, while this batch of samples was white in colour.
  • Table 4A shows the area resistance and the diffusion coefficient prepared with different degree of cross-linking using 1 g of Amberlite CG400 for 50 cm 3 of the solution mixture and the corresponding properties extracted from these samples produced are shown in Table 5A.
  • Table 6A shows the area resistance and the diffusion coefficient of the samples prepared using different amount of Amberlite CG400 in the 50 cm 3 of the solution mixture. Results obtained with xylene extraction using a soxhlet extractor are included in Table 7A for the different ratio of methanol and DVB used for the cross-linking with varying amount of Amberlite. Other properties of the composite membrane related to the samples are also presented in Table 7A.
  • Table 4A Properties of composite membrane prepared by different degree of cross ⁇ linking.
  • Amberlite DVB Methanol Area resistance Diffusion coefficient Sample ratio ⁇ cm 2 x 10" 4 (cm/min)
  • Table 7A Properties of the composite membrane treated using different amount of Amberlite CG400.
  • Example 2 a composite membrane has been developed using Daramic as substrate and Amberlite. Further cross-linking using DVB has resulted in properties which are suitable for application in redox batteries.
  • the performance of the membrane in the charge/discharge testing of a vanadium redox cell is comparable with that observed with ion-exchange membranes available commercially.
  • the chemical stability of the membrane was found to be excellent and the membrane was not susceptible to fouling.
  • the composite membrane was fabricated from the microporous separator, Daramic, treated with ion-exchange resin, Amberlite 400CG and crosslinked using DVB.
  • the membrane tested in charge/discharge with Vanadium redox cell gave average coulombic, voltage and energy efficiencies of 95, 79, 75 % respectively.

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Abstract

On décrit un séparateur sélectif à perméation et son procédé de fabrication. Le séparateur sélectif à perméation comprend un séparateur microporeux comportant au moins un matériau échangeur d'ions réticulé avec le séparateur. Le procédé de fabrication du séparateur sélectif à perméation consiste à mettre en contact le séparateur microporeux avec un solvant comprenant, au moins partiellement dissous, au moins un matériau échangeur d'ions ainsi qu'au moins un agent de réticulation, pendant une période suffisante pour permettre au matériau échangeur d'ions et à l'agent de réticulation de pénétrer dans les pores du séparateur microporeux. Le matériau échangeur d'ions est ensuite réticulé avec le séparateur microporeux pour former le séparateur sélectif à perméation, celui-ci présentant une sélectivité de perméation supérieure à celle du séparateur microporeux non-réticulé.
PCT/AU1992/000491 1991-09-17 1992-09-17 Separateurs selectifs a permeation et leurs procedes de fabrication WO1993006626A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2122727A1 (fr) * 2007-02-12 2009-11-25 Deeya Energy, Inc. Appareil et procédés de détermination de l'état de charge dans une batterie à oxydoréduction
WO2009125985A3 (fr) * 2008-04-08 2010-01-14 Sk Energy Co., Ltd. Procédé de fabrication de film composite polyoléfinique microporeux avec une couche thermiquement stable à haute température
EP2301098A1 (fr) * 2008-07-01 2011-03-30 Deeya Energy, Inc. Cuve de circulation redox
CN103140978A (zh) * 2010-09-28 2013-06-05 巴特尔纪念研究院 Fe-V氧化还原液流电池
JP2014514717A (ja) * 2011-04-11 2014-06-19 ユナイテッド テクノロジーズ コーポレイション 複数の異なる細孔径および／または異なる層を備えた電極を有するフロー電池
US8883297B2 (en) 2008-10-10 2014-11-11 Imergy Power Systems, Inc. Methods for bonding porous flexible membranes using solvent
WO2014200324A2 (fr) * 2013-12-23 2014-12-18 Oci Company Ltd. Batterie redox au vanadium
US9077011B2 (en) 2010-09-28 2015-07-07 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
WO2017147568A1 (fr) * 2016-02-26 2017-08-31 Case Western Reserve University Membranes composites pour batteries à circulation
US10673090B2 (en) 2014-10-06 2020-06-02 Battelle Memorial Institute All-vanadium sulfate acid redox flow battery system
CN112652784A (zh) * 2019-10-11 2021-04-13 中国科学院大连化学物理研究所 一种Daramic复合离子传导膜及制备和应用

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2122727A1 (fr) * 2007-02-12 2009-11-25 Deeya Energy, Inc. Appareil et procédés de détermination de l'état de charge dans une batterie à oxydoréduction
EP2122727A4 (fr) * 2007-02-12 2014-03-19 Deeya Energy Inc Appareil et procédés de détermination de l'état de charge dans une batterie à oxydoréduction
WO2009125985A3 (fr) * 2008-04-08 2010-01-14 Sk Energy Co., Ltd. Procédé de fabrication de film composite polyoléfinique microporeux avec une couche thermiquement stable à haute température
EP2301098A4 (fr) * 2008-07-01 2014-04-09 Deeya Energy Inc Cuve de circulation redox
EP2301098A1 (fr) * 2008-07-01 2011-03-30 Deeya Energy, Inc. Cuve de circulation redox
US8883297B2 (en) 2008-10-10 2014-11-11 Imergy Power Systems, Inc. Methods for bonding porous flexible membranes using solvent
US9819039B2 (en) 2010-09-28 2017-11-14 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
US9123931B2 (en) 2010-09-28 2015-09-01 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
EP2622674A1 (fr) * 2010-09-28 2013-08-07 Battelle Memorial Institute Batteries redox fe-v
EP2622674A4 (fr) * 2010-09-28 2014-06-18 Battelle Memorial Institute Batteries redox fe-v
CN103140978A (zh) * 2010-09-28 2013-06-05 巴特尔纪念研究院 Fe-V氧化还原液流电池
US9077011B2 (en) 2010-09-28 2015-07-07 Battelle Memorial Institute Redox flow batteries based on supporting solutions containing chloride
JP2014514717A (ja) * 2011-04-11 2014-06-19 ユナイテッド テクノロジーズ コーポレイション 複数の異なる細孔径および／または異なる層を備えた電極を有するフロー電池
WO2014200324A2 (fr) * 2013-12-23 2014-12-18 Oci Company Ltd. Batterie redox au vanadium
WO2014200324A3 (fr) * 2013-12-23 2015-03-05 Oci Company Ltd. Batterie redox au vanadium
US10673090B2 (en) 2014-10-06 2020-06-02 Battelle Memorial Institute All-vanadium sulfate acid redox flow battery system
US11532832B2 (en) 2014-10-06 2022-12-20 Battelle Memorial Institute All-vanadium sulfate acid redox flow battery system
WO2017147568A1 (fr) * 2016-02-26 2017-08-31 Case Western Reserve University Membranes composites pour batteries à circulation
US11444306B2 (en) 2016-02-26 2022-09-13 Case Western Reserve University Composite membranes for flow batteries
CN112652784A (zh) * 2019-10-11 2021-04-13 中国科学院大连化学物理研究所 一种Daramic复合离子传导膜及制备和应用
CN112652784B (zh) * 2019-10-11 2022-05-06 中国科学院大连化学物理研究所 一种Daramic复合离子传导膜及制备和应用

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