WO2008039416A1 - Séparateur résistant aux dendrites destiné à des accumulateurs alcalins - Google Patents

Séparateur résistant aux dendrites destiné à des accumulateurs alcalins Download PDF

Info

Publication number
WO2008039416A1
WO2008039416A1 PCT/US2007/020601 US2007020601W WO2008039416A1 WO 2008039416 A1 WO2008039416 A1 WO 2008039416A1 US 2007020601 W US2007020601 W US 2007020601W WO 2008039416 A1 WO2008039416 A1 WO 2008039416A1
Authority
WO
WIPO (PCT)
Prior art keywords
separator
surfactant
cross
polyvinyl alcohol
battery
Prior art date
Application number
PCT/US2007/020601
Other languages
English (en)
Inventor
George W. Adamson
Hieu M. Duong
Huawen Li
Ladan E. Vajdi
Original Assignee
Zpower Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zpower Inc. filed Critical Zpower Inc.
Publication of WO2008039416A1 publication Critical patent/WO2008039416A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • 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
    • 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
    • H01M50/443—Particulate material
    • 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

Definitions

  • This invention is concerned with electrical storage batteries, and in particular, it is concerned with separators for alkaline storage batteries.
  • An electrical storage battery comprises one electrochemical cell or a plurality of electrochemical cells of the same type, the latter typically being connected in series to provide a higher voltage or in parallel to provide a higher charge capacity than provided by a single cell.
  • An electrochemical cell comprises an electrolyte interposed between and in contact with an anode and a cathode.
  • the anode comprises an active material that is readily oxidized
  • the cathode comprises an active material that is readily reduced.
  • the anode active material is oxidized and the cathode active material is reduced, so that electrons flow from the anode through an external load to the cathode, and ions flow through the electrolyte between the electrodes.
  • Many electrochemical cells used for electrical storage applications also include a separator between the anode and the cathode is required to prevent reactants and reaction products present at one electrode from reacting and/or interfering with reactions at the other electrode.
  • a separator between the anode and the cathode is required to prevent reactants and reaction products present at one electrode from reacting and/or interfering with reactions at the other electrode.
  • An exception is the common lead acid sulfate battery for which the reactants and reaction products for both electrodes are insoluble lead metal or lead oxides and sulfates.
  • a battery separator must be electronically insulating, and remain so during the life of the battery, to avoid battery self-discharge via internal shorting between the electrodes, hi addition, a battery separator must be both an effective electrolyte transport barrier and a sufficiently good ionic conductor to avoid excessive separator resistance that substantially lowers the discharge voltage.
  • the separator must be chemically stable in strongly alkaline solution, resist oxidation in contact with the highly oxidizing cathode, and resist reduction in contact with the highly reducing anode. Since ions, especially metal oxide ions, from the cathode can be somewhat soluble in alkaline solutions and tend to be chemically reduced to metal on separator surfaces, the separator must also inhibit transport and/or chemical reduction of metal ions. Otherwise, a buildup of metal deposits within separator pores may increase the separator resistance in the "k short term and ultimately lead to shorting failure due to formation of a continuous metal path through the separator.
  • the separator must suppress dendritic growth and/or resist dendrite penetration to avoid failure due to formation of a dendritic short between the electrodes.
  • a related issue with anodes is shape change, in which the central part of the electrode tends to thicken during charge-discharge cycling. The causes of shape change are complicated and not well-understood but apparently involve differentials in the current distribution and solution mass transport along the electrode surface.
  • the separator preferably mitigates zinc electrode shape change by exhibiting uniform and stable ionic conductivity and ionic transport properties.
  • a separator stack comprised of a plurality of separator layers that perform specific functions is needed.
  • the key required functions are resistance to electrochemical oxidation and silver ion transport from the cathode, and resistance to electrochemical reduction and dendrite penetration from the anode.
  • Cellophane is an effective separator developed for alkaline batteries; however, this separator material decomposes chemically in alkaline electrolytes, which limits the useful life of the battery. Cellophane is also subject to chemical oxidation by soluble silver ions and electrochemical oxidation in contact with silver electrodes. Furthermore, cellophane exhibits low mechanical strength and poor resistance to penetration by dendrites. [0009] To solve some of the problems caused by the cellophane separators, new separator materials have been developed.
  • the invention provides separators for use in an alkaline battery (e.g., a zinc-silver oxide alkaline battery) comprising an alkaline electrolyte, an anode, and a cathode, wherein the separator comprises a cross-linked polyvinyl alcohol polymer and a zirconium oxide powder.
  • the separators of the present invention can optionally comprise additives such as a conductivity enhancer, a surfactant, a plasticizer, or the like.
  • the separators comprising a cross-linked polyvinyl alcohol polymer and a zirconium oxide powder exhibit a resistance to dendrite formation caused by the migration of cathode and anode metals into the separator.
  • Separators comprising a cross- linked polyvinyl alcohol polymer, a zirconium oxide powder, and a conductivity enhancer formation are resistant to dendrite formation but also exhibits high ionic conductivity which is beneficial for battery discharge performance.
  • Another aspect of the present invention provides batteries that are formed from an anode comprising zinc, a cathode comprising silver oxide, an electrolyte, and a separator comprising a cross-linked polyvinyl alcohol polymer and a zirconium oxide powder.
  • Another aspect of the present invention provides methods of forming a separator comprising providing a mixture of a polyvinyl precursor polymer, a cross-linking agent, and zirconium oxide powder.
  • the mixture also comprises additives such as a surfactant, a conductivity enhancer, a plasticizer, or the like.
  • the mean molecular weight of the polyvinyl precursor polymer is greater than about 5000 amu. In other embodiments, the precursor polymer is at least about 80% hydrolyzed.
  • Some precursor polymers further comprise vinyl acetate, ethylene, vinyl butyral, or any combination thereof.
  • the present invention provides separators useful in alkaline storage batteries, wherein the separator comprises a cross-linked polyvinyl alcohol polymer and zirconium oxide powder.
  • the present invention also provides batteries comprising this novel separator and methods of forming such separators.
  • separators of the present invention reduce the formation of dendrites in zinc-silver oxide batteries under normal operating conditions, i.e., when the batteries are stored and used in temperatures from about -20° C to about 70° C, and are not overcharged or charged above their rated capacity.
  • battery encompasses electrical storage devices comprising one electrochemical cell or a plurality of electrochemical cells.
  • a “secondary battery” is rechargeable, whereas a “primary battery” is not rechargeable.
  • a “battery anode” is designated as the positive electrode during battery discharge, and as the negative electrode during battery charge.
  • M denotes molar concentration
  • batteries and battery electrodes are denoted with respect to the active materials in the fully-charged state.
  • a zinc-silver oxide battery comprises a zinc anode and a silver oxide cathode.
  • a zinc electrode generally comprises zinc metal and zinc oxide (except when fully charged)
  • a silver oxide electrode usually comprises silver oxide
  • oxide applied to alkaline batteries and alkaline battery electrodes encompasses corresponding "hydroxide” species, which are typically present, at least under some conditions.
  • Battery separators may be configured in a variety of ways.
  • a separator for a rectangular battery electrode may be in the form of a sheet or film comparable in size or slightly larger than the electrode, and may simply be placed on the electrode or may be sealed around the edges.
  • the edges of the separator may be sealed to the electrode, an electrode current collector, a battery case, or another separator sheet or film on the backside of the electrode via an adhesive sealant, a gasket, or fusion (heat sealing) of the separator or another material.
  • the separator may also be in the form of a sheet or film wrapped and folded around the electrode to form a single layer (front and back), an overlapping layer, or multiple layers.
  • the separator may be spirally wound with the electrodes in a jellyroll configuration.
  • the separator is included in an electrode stack comprising a plurality of separator layers.
  • the separator of this invention may be incorporated in a battery in any suitable configuration.
  • the present invention provides a separator for use in a zinc-silver oxide storage battery, comprising a cross-linked polyvinyl alcohol polymer, a cross-linking agent, and a zirconium oxide powder.
  • the cross-linked polyvinyl alcohol polymer is a copolymer.
  • the cross-linked PVA polymer is a copolymer comprising a first monomer, PVA, and a second monomer.
  • the PVA polymer is a copolymer comprising at least 60 mole percent of PVA and a second monomer.
  • the second monomer comprises vinyl acetate, ethylene, vinyl butyral, or any combination thereof.
  • the cross-linking agent used in the separators of the present invention comprises a monoaldehyde (e.g., formaldehyde or glyoxilic acid); aliphatic, furyl or aryl dialdehydes (e.g., glutaraldehyde, 2,6 furyldialdehyde or terephthaldehyde); dicarboxylic acids (e.g., oxalic acid or succinic acid); polyisocyanates; methylolmelamine; copolymers of styrene and maleic anhydride; germaic acid and its salts; boron compounds (e.g., boron oxide, boric acid or its salts; or metabolic acid or its salts); or salts of copper, zinc, aluminum or titanium.
  • the cross-linking agent comprises boric acid
  • Separators of the present invention also comprise zirconium oxide powder.
  • the separator comprises from about 1 wt % to about 99 wt % (e.g., from about 2 wt % to about 98 wt %, from about 20 wt % to about 60 wt %, or from about 30 wt % to about 50 wt %).
  • Separators of the present invention also comprise a reduced ionic conductivity.
  • the separator comprises an ionic resistance of less than about 20 m ⁇ /cm 2 , (e.g., less than about 10 m ⁇ /cm 2 , less than about 5 m ⁇ /cm 2 , or less than about 4m ⁇ /cm 2 ).
  • the separators of the present invention can optionally comprise any suitable additives such as a conductivity enhancer, a surfactant, a plasticizer, or the like.
  • the separator further comprises a conductivity enhancer.
  • the separator comprises a cross-linked polyvinyl alcohol polymer, a zirconium oxide powder, and a conductivity enhancer.
  • the conductivity enhancer comprises a copolymer of polyvinyl alcohol and a hydroxyl-conducting polymer. Suitable hydroxyl- conducting polymers have functional groups that facilitate migration of hydroxyl ions.
  • the hydroxyl-conducting polymer comprises polyacrylate, polylactone, polysulfonate, polycarboxylate, polysulfate, polysarconate, polyamide, polyamidosulfonate, or any combination thereof.
  • a solution containing a copolymer of a polyvinyl alcohol and a polylactone is sold commercially under the trade name Vytek ® polymer by Celanese, Inc.
  • the separator comprises from about 1 wt % to about 10 wt % of conductivity enhancer. [0034] In other embodiments, the separator further comprises a surfactant.
  • the separator comprises a cross-linked polyvinyl alcohol polymer, a zirconium oxide powder, and a surfactant.
  • the surfactant comprises one or more surfactants selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an ampholytic surfactant, an amphoteric surfactant, and a zwitterionic surfactant. Such surfactants are commercially available.
  • the separator comprises from about 0.01 wt % to about 1 wt % of surfactant.
  • the separator further comprises a plasticizer.
  • the separator comprises a cross-linked polyvinyl alcohol polymer, a zirconium oxide powder, and a plasticizer.
  • the plasticizer comprises one or more plasticizers selected from glycerin, low-molecular- weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1 ,3 pentanediol branched analogs, 1 ,3 pentanediol, and/or water.
  • the plasticizer comprises greater than about 1 wt % of glycerin, low-molecular-weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1 ,3 pentanediol branched analogs, 1 ,3 pentanediol, or any combination thereof, and less than 99 wt % of water.
  • the plasticizer comprises from about 1 wt % to about 10 wt % of glycerin, low-molecular- weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1 ,3 pentanediol branched analogs, 1,3 pentanediol, or any combination thereof, and from about 99 wt % to about 90 wt % of water.
  • Separators of the present invention can be a free-standing separator or they can optionally further comprise a substrate.
  • the separator comprises a cross-linked polyvinyl alcohol polymer, a zirconium oxide powder, and a porous or nonporous substrate.
  • the substrate can be a porous substrate.
  • the substrate is a porous substrate that comprises a woven or non-woven material.
  • Another aspect of the present invention provides a dendrite-resistant separator comprising a cross-linked polyvinyl alcohol polymer, a cross-linking agent, and a zirconium oxide powder.
  • Such separators can optionally comprise additives such as a conductivity enhancer, a surfactant, a plasticizer, a substrate, or any combination thereof as described above, and in any amounts described above.
  • a battery that comprises an anode comprising zinc, a cathode comprising silver oxide, an electrolyte, and a separator, wherein the separator comprises a cross-linked polyvinyl alcohol polymer, a cross-linking agent, and a zirconium oxide powder.
  • the cross-linked polyvinyl alcohol polymer is a copolymer comprising a first monomer consisting essentially of polyvinyl alcohol, and a second monomer, and the copolymer comprises at least 60 mole percent of the polyvinyl alcohol.
  • the second monomer comprises vinyl acetate, ethylene, vinyl butyral, or any combination thereof.
  • the cross-linked polyvinyl alcohol polymer is cross- linked with a cross-linking agent selected from a monoaldehyde, a dialdehyde, a dicarboxylic acid, a polyisocyanate, a methylolmelamine, a copolymer of styrene, a copolymer of maleic anhydride, germaic acid, a salt of germaic acid, a compound of boron, copper, zinc, aluminum or titanium, or any combination thereof.
  • the cross-linking agent comprises boric acid.
  • the separator of the present battery further comprises a conductivity enhancer comprising a copolymer of polyvinyl alcohol and a hydroxyl- conducting polymer.
  • the hydroxyl-conducting polymer comprises polyacrylate, polylactone, polysulfonate, polycarboxylate, polysulfate, polysarconate, polyamide, or polyamidosulfonate, or combination thereof.
  • the separator of the present invention further comprises a plasticizer.
  • the plasticizer comprises glycerin, a low-molecular-weight polyethylene glycol, an aminoalcohol, a polypropylene glycols, a 1,3 pentanediol branched analog, 1 ,3 pentanediol, or combinations thereof, and/or water.
  • the separator of the present battery further comprises a porous substrate.
  • the substrate comprises a woven material or a nonwoven material.
  • the separator of the present battery further comprises a surfactant.
  • the surfactant comprises an anionic surfactant, a cationic surfactant, a nonionic surfactant, an ampholytic surfactant, an amphoteric surfactant, or a zwitterionic surfactant, or combinations thereof.
  • the separator of the present battery comprises from about 2 wt % to about 98 wt % of zirconium oxide.
  • the separator of the present battery comprises an ionic resistance of less than about 20 m ⁇ /cm2.
  • Another aspect of the present invention provides methods of forming separators comprising providing a mixture comprising a polyvinyl precursor polymer, a cross-linking agent, and zirconium oxide powder and at least partially curing the mixture to form a separator.
  • the PVA precursor polymer has a mean molecular weight of greater than about 5000 amu. In other examples, the PVA precursor polymer is at least partially hydrolyzed (e.g., at least about 70 % hydrolyzed, at least about 75 % hydrolyzed, or at least about 80 % hydrolyzed). In some examples, the PVA precursor polymer has a mean molecular weight greater than about 5000 amu and is at least 80 % hydrolyzed.
  • the polyvinyl alcohol precursor comprises a first monomer, i.e., PVA, and a second monomer.
  • the PVA precursor polymer comprises at least 60 mole percent of PVA and a second monomer comprising vinyl acetate, ethylene, vinyl butyral, or any combination thereof.
  • the mixture comprises an amount of cross-linking agent sufficient to render the separator substantially insoluble in water.
  • the cross-linking agent comprises a monoaldehyde (e.g., formaldehyde or glyoxilic acid); aliphatic, furyl or aryl dialdehydes (e.g., glutaraldehyde, 2,6 furyldialdehyde or terephthaldehyde); dicarboxylic acids (e.g., oxalic acid or succinic acid); polyisocyanates; methylolmelamine; copolymers of styrene and maleic anhydride; germaic acid and its salts; boron compounds (e.g., boron oxide, boric acid or its salts; or metaboric acid or its salts); or salts of copper, zinc, aluminum or titanium.
  • the cross-linking agent comprises boric acid.
  • the mixture also comprises zirconium oxide powder.
  • the separator comprises from about 1 wt % to about 99 wt % (e.g., from about 2 wt % to about 98 wt %) of zirconium oxide powder.
  • additives can be combined with the mixture to form separators of the present invention, such as conductivity enhancers, surfactants, and plasticizers.
  • the mixture further comprises a conductivity enhancer comprising a copolymer of polyvinyl alcohol and a hydroxyl-conducting polymer.
  • Suitable hydroxyl-conducting polymers have functional groups that facilitate migration of hydroxyl ions, hi some examples, the hydroxyl-conducting polymer comprises polyacrylate, polylactone, polysulfonate, polycarboxylate, polysulfate, polysarconate, polyamide, polyamidosulfonate, or any combination thereof.
  • the mixture comprises from about 1 wt % to about 10 wt % of conductivity enhancer.
  • the mixture further comprises a surfactant.
  • the surfactant may be one of many sold commercially as surfactants or dispersion agents. Suitable surfactants include anionic, cationic, nonionic, ampholytic, amphoteric or zwitterionic surfactants, and mixtures thereof. In some examples, the mixture comprises from about 0.01 wt % to about 1 wt % of surfactant.
  • the mixture further comprises a plasticizer.
  • the plasticizer can facilitate removal of a separator layer from a casting tray or mold.
  • the mixture comprises a plasticizer comprising glycerin, low-molecular-weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1,3 pentanediol branched analogs, 1,3 pentanediol, or any combination thereof and/or water.
  • the conductivity enhancer comprises greater than 1 wt % of glycerin, low-molecular-weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1 ,3 pentanediol branched analogs, 1 ,3 pentanediol, or any combination thereof, and less than 99 wt % water.
  • the conductivity enhancer comprises from about 1 wt % to about 10 wt % of glycerin, low-molecular- weight polyethylene glycols, aminoalcohols, polypropylene glycols, 1 ,3 pentanediol branched analogs, 1 ,3 pentanediol, or any combination thereof, and from about 99 wt % to about 90 wt % of water.
  • the mixture can be cast as a free-standing film, or it can be applied to a substrate.
  • the mixture is applied to a substrate.
  • the mixture is applied to the substrate by painting, spraying, dipping, or co-extruding the substrate with the mixture. Any combination of these is also suitable for applying the mixture to a substrate.
  • Other application techniques include without limitation, manual painting, roller painting, spraying, or co-extrusion onto a conveyor belt.
  • the method of the present invention also comprises at least partially curing the mixture.
  • the mixtures of the present invention can be cured using any suitable technique such as exposure to electromagnetic radiation (e.g., UV or X-Ray), heating, air drying, or any combination thereof.
  • the separator formed using the abovementioned methods is a dendrite-resistant separator.
  • the dendrite-resistance of the separator comprising PVA material, a cross-linking agent, and zirconium oxide powder, and any optional additives, as described above, can be demonstrated comparatively against a separator that comprises a cross-linked PVA material and is substantially free of zirconium oxide powder (e.g., the separator comprises less than 1 wt % of zirconium oxide powder (e.g., less than 0.5 wt % of zirconium oxide powder)) using standard testing methods such as those described in "Study to Investigate and Improve the Zinc Electrode for Spacecraft Electrochemical Cells", James McBreen, August 1967 Accession Number N67-38923, Page 6, hereby incorporated in its entirety by reference.
  • EXAMPLE EXAMPLE
  • a mixture according to the invention was prepared by adding 1.8 g of zirconium oxide, 40.0 g of 5% Vytek ® 2012 polymer solution, and 0.006 g of sodium salt of dodecylbenzenesulfonic acid to 60.0 g of 5% aqueous solution of polyvinyl alcohol (Dupont). The mixture was stirred until uniform in appearance, and 1.2 g of 5% solution of boric acid was added as cross-linking agent. This mixture was stirred, placed on a casting tray and dried overnight.
  • the resulting separator layer exhibited an ionic resistance below the detection limit of the measurement apparatus (4 m ⁇ /cm 2 ), whereas a PVA film of comparable thickness but without additives exhibited a high ionic resistance (20 m ⁇ /cm 2 ).
  • the separator layer of the invention was also found to be more resistant to silver and zinc ion migration than a PVA film without additives.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne une couche de séparation résistant aux dendrites, pour une utilisation dans des accumulateurs à oxyde de zinc/argent, comportant un revêtement d'un polymère de polyvinylalcool réticulé chargé de poudre d'oxyde de zircon. La couche de séparation peut être libre ou appliquée à un substrat, et éventuellement contenir des additifs tels qu'un agent améliorateur de conductivité, un agent tensioactif ou un agent plastifiant.
PCT/US2007/020601 2006-09-25 2007-09-24 Séparateur résistant aux dendrites destiné à des accumulateurs alcalins WO2008039416A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82686306P 2006-09-25 2006-09-25
US60/826,863 2006-09-25

Publications (1)

Publication Number Publication Date
WO2008039416A1 true WO2008039416A1 (fr) 2008-04-03

Family

ID=39091875

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/020601 WO2008039416A1 (fr) 2006-09-25 2007-09-24 Séparateur résistant aux dendrites destiné à des accumulateurs alcalins

Country Status (1)

Country Link
WO (1) WO2008039416A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012037426A3 (fr) * 2010-09-16 2012-05-03 Zpower, Llc Séparateur d'électrodes
US9960399B2 (en) 2008-03-27 2018-05-01 Zpower, Llc Electrode separator
CN111697270A (zh) * 2019-03-13 2020-09-22 北京师范大学 一种通过原位转移形成负极保护层的方法
CN113497307A (zh) * 2020-04-02 2021-10-12 时代沃顿科技有限公司 聚烯烃多层复合隔膜的制备方法和由此制备的聚烯烃多层复合隔膜

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951687A (en) * 1973-11-21 1976-04-20 Tokyo Shibaura Electric Co., Ltd. Nickel-zinc storage battery
GB1550038A (en) * 1977-03-16 1979-08-08 Comp Generale Electricite Electric cell with a zinc electrode and method of preparing a separator therefor
WO1999033125A1 (fr) * 1997-12-19 1999-07-01 Moltech Corporation Separateurs pour cellules electrochimiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951687A (en) * 1973-11-21 1976-04-20 Tokyo Shibaura Electric Co., Ltd. Nickel-zinc storage battery
GB1550038A (en) * 1977-03-16 1979-08-08 Comp Generale Electricite Electric cell with a zinc electrode and method of preparing a separator therefor
WO1999033125A1 (fr) * 1997-12-19 1999-07-01 Moltech Corporation Separateurs pour cellules electrochimiques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9960399B2 (en) 2008-03-27 2018-05-01 Zpower, Llc Electrode separator
WO2012037426A3 (fr) * 2010-09-16 2012-05-03 Zpower, Llc Séparateur d'électrodes
CN111697270A (zh) * 2019-03-13 2020-09-22 北京师范大学 一种通过原位转移形成负极保护层的方法
CN111697270B (zh) * 2019-03-13 2022-01-14 北京师范大学 一种通过原位转移形成负极保护层的方法
CN113497307A (zh) * 2020-04-02 2021-10-12 时代沃顿科技有限公司 聚烯烃多层复合隔膜的制备方法和由此制备的聚烯烃多层复合隔膜

Similar Documents

Publication Publication Date Title
US20120189896A1 (en) Electrode separator
US20160301077A1 (en) Electrodes and electrochemical cells employing the same
JP5591220B2 (ja) 電極セパレーター
US7153607B2 (en) Alkaline zinc secondary cell and method for preparation thereof
JP5638058B2 (ja) 改善されたカソード
EP3190652A1 (fr) Ensemble d'électrodes à sécurité améliorée, son procédé de fabrication et élément électrochimique comprenant l'ensemble d'électrodes
JP2011515821A5 (fr)
US9634359B2 (en) Electrolyte for zinc-based rechargeable batteries, method for producing the same and batteries including said electrolyte
DK2901516T3 (en) cathode
KR20090109550A (ko) 금속성 아연-기반의 집전기
US11398660B2 (en) Flame retardant separator having asymmetric structure for secondary batteries
KR102446619B1 (ko) 전고체 전지용 전해질막 및 이를 제조하는 방법
JP7204885B2 (ja) 固体電解質膜及びそれを含む全固体電池
KR20150071453A (ko) 고용량 특성을 갖는 리튬 이온 이차 전지용 음극
KR20190067734A (ko) 리튬 금속 전지용 음극 및 이를 포함하는 전기화학소자
WO2008039419A2 (fr) Séparateur résistant à l'oxydation destiné à des accumulateurs à oxyde de zinc/argent
WO2008039416A1 (fr) Séparateur résistant aux dendrites destiné à des accumulateurs alcalins
WO2008039417A1 (fr) Séparateur résistant à l'oxydation destiné à des accumulateurs alcalins
KR20100056257A (ko) 코팅용 겔 전해액을 사용하여 표면 개질된 음극 및 분리막을 포함하는 알칼리 아연 이차전지
US20110123859A1 (en) Polymer Electrolytes
KR102516551B1 (ko) 아연 이차 전지
KR102572102B1 (ko) 저항개선을 통해 수명 안정성을 향상시킨 전기화학소자용 분리막 및 그 제조 방법과 이를 포함하는 전기화학소자

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07838747

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07838747

Country of ref document: EP

Kind code of ref document: A1