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WO1998038687A1 - Copolymeres de fluorure de vinylidene et d'hexafluoropropylene presentant une teneur en constituants extractibles reduite et une transparence de solution amelioree - Google Patents

Copolymeres de fluorure de vinylidene et d'hexafluoropropylene presentant une teneur en constituants extractibles reduite et une transparence de solution amelioree Download PDF

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Publication number
WO1998038687A1
WO1998038687A1 PCT/US1998/004071 US9804071W WO9838687A1 WO 1998038687 A1 WO1998038687 A1 WO 1998038687A1 US 9804071 W US9804071 W US 9804071W WO 9838687 A1 WO9838687 A1 WO 9838687A1
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WIPO (PCT)
Prior art keywords
vinylidene fluoride
copolymers
hfp
vdf
hexafluoropropylene
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PCT/US1998/004071
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English (en)
Inventor
Roice Andrus Wille
Michael T. Burchill
Original Assignee
Elf Atochem North America, Inc.
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Publication date
Application filed by Elf Atochem North America, Inc. filed Critical Elf Atochem North America, Inc.
Priority to EP98908864A priority Critical patent/EP0907976A4/fr
Priority to KR1019980708803A priority patent/KR100537303B1/ko
Priority to HU9903748A priority patent/HUP9903748A3/hu
Priority to JP53795098A priority patent/JP2002513506A/ja
Priority to CNB988002078A priority patent/CN1311577C/zh
Publication of WO1998038687A1 publication Critical patent/WO1998038687A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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 relates to compositions of matter classified in the art of chemistry as fluoropolymers, more specifically as copolymers of vinylidene fluoride (VDF) , more specifically as copolymers of vinylidene fluoride and hexafluoropropylene (HFP) , still more specifically as copolymers of VDF and HFP having reduced extractable content, longer gel times and improved solution clarity, to novel compositions of matter and articles of manufacture containing such copolymers, as well as to processes for the preparation and use of the copolymers, of compositions of manufacture containing such copolymers and of the articles of manufacture containing such copolymers.
  • VDF vinylidene fluoride
  • HFP hexafluoropropylene
  • VDF/HFP copolymers are well known and are used for their thermoplastic engineering properties, chemical resistance and inertness toward degradation. They may be found in applications such as chemically resistant piping, gasketing, plenum cable jacketing, filtration and extraction membranes and in the construction of lithium batteries.
  • the present invention provides VDF/HFP copolymers containing up to about 24 weight % (12 mole%) HFP having among other improved properties, substantially improved solution clarity, longer gel times and reduced extractables as these terms are defined hereinafter.
  • the process used to make the instant copolymers requires one ratio of VDF and HFP for the initial fill of the reactor, and a different ratio of VDF and HFP during a subsequent continuous feed of the monomers.
  • Any particular desired average HFP content in the copolymer product has corresponding particular initial fill and subsequent feed ratios.
  • the uniformity of compositions prepared this way provide unique and useful properties in comparison to VDF/HFP copolymers described in the prior art.
  • the present invention also provides lithium batteries fabricated from the VDF/HFP copolymers of the present invention and lithium batteries from other homo and copolymers more specifically described hereinbelow prepared by known processes having analogous structure and which the present inventors have recognized as processing properties analogous to those of the VDF/HFP copolymers of the invention which makes them uniquely suitable for lithium battery construction.
  • VDF/HFP copolymers of HFP content 30 to 70 wt% (15 to 50 mol%) which showed utility as elastomers.
  • a batch process with certain initial ratios of VDF and HFP, and a continuous process with fixed ratios of VDF and HFP throughout the process were described. The processes described were such that polymers lacking the improved solution clarity, longer gel times and low extractables of the present invention were made.
  • Lo in U.S. Pat. No. 3,178,399 described VDF/HFP copolymers of HFP content of 2 to 26 wt% (1 to 13 mol%) which showed a numerical value for the product of the tensile strength (psig) and percent reversible elongation of at least 1,000,000.
  • a batch process with certain initial ratios of VDF and HFP, or, alternately, a semicontinuous process with fixed ratios of VDF and HFP throughout the process were used to make the copolymers.
  • the processes discussed were such that copolymers lacking the improved solution clarity, longer gel times and low extractables of the present invention copolymers were made.
  • TFE/HFP copolymers uniform tetrafluoroethylene/hexafluoropropylene copolymers made by a semicontinuous emulsion process. Uniformity was simply defined as there being a low proportion of adjacent HFP units in the polymer chains; there was no disclosure of the disposition of TFE and HFP units otherwise, and there was no discussion of VDF/HFP copolymers or the properties to be expected therefrom.
  • VDF polymer may be used in forming a solid electrolyte for use in secondary battery manufacture. No particular type of polyvinylidene fluoride is identified and no copolymers thereof of any type are suggested.
  • a DSC differential
  • the tangible embodiments of this first composition aspect of the invention are straw colored to colorless semi crystalline solids having melting points, as determined by differential scanning calorimetry (DSC) , lower than VDF/HFP copolymers having the same nominal HFP percentage content prepared by processes reported in detail in the prior art .
  • tangible embodiments of this first composition aspect of the invention also possess longer gelation times from solution than VDF/HFP copolymers having the same nominal HFP content prepared by processes reported in detail in the prior art .
  • the tangible embodiments of the first composition aspect of the invention have the inherent applied use characteristics of being suitable for paint and powder coating vehicles and as chemically resistant shaped objects and films both supported and unsupported. Particular mention is made of copolymers of the first composition aspect of the present invention having from about 2 weight% HFP content to about 8 weight%
  • HFP still more particularly copolymers having about 3 to 6 weight% HFP which possess the inherent applied use characteristics of being particularly suitable as polymeric separators and polymeric electrode matrices for batteries, particularly lithium batteries.
  • copolymers of the first composition aspect of the invention having from about 7 weight percent HFP content to about 15 weight percent HFP content, more particularly copolymers having about 10 weight percent HFP content which possess the inherent applied use characteristic of being suitable as flame resistant insulation for wire and cable .
  • copolymers of the first composition aspect of the invention having greater than about 15 weight percent HFP content, still more particularly of copolymers having about 16% by weight or greater HFP content which have the inherent applied use characteristic as clear, flexible, chemically resistant films.
  • the invention provides in a second composition of matter aspect, an improved article of manufacture comprising an electrochemical cell having a positive electrode, an absorber separator and a negative electrode wherein at least either one of the electrodes comprises a vinylidene fluoride polymer having an electrolyte material combined therewith and/or said absorber separator comprises a vinylidene fluoride polymer having an electrolyte material combined therewith wherein the improvement comprises the polyvinylidene fluoride polymer consisting essentially of a vinylidene fluoride polymer selected from the group consisting of vinylidene fluoride homopolymer having bimodal molecular weight distribution, vinylidene fluoride/chlorotrifluoroethylene copolymer having a substantially homogeneous monomer distribution and a vinylidene fluoride/hexafluoropropylene copolymer as defined in the first composition aspect of the invention.
  • VDF/HFP copolymer has a hexafluoropropylene content of from about 2 wt % up to about 8 wt % hexafluoropropylene, particularly those having from about 3 weight % to about 6 weight % hexafluoropropylene, still more particularly, those having about 3 weight % hexafluoropropylene.
  • Vinylidene fluoride homopolymer having bimodal molecular weight distribution means vinylidene fluoride homopolymer prepared as described in U.S. Patent 4,076,729.
  • Vinylidene fluoride/chlorotrifluoroethylene copolymer having substantially homogeneous monomer distribution means vinylidene fluoride/chlorotrifluoroethylene copolymer prepared as described in U.S. Patent 2,752,331.
  • VDF/CTFE copolymers having from about 2 wt . % up to about 8 wt % CTFE content, more particularly such VDF/CTFE copolymers having about 3 to about 6 weight percent CTFE content.
  • vinylidene fluoride polymers (or VDF polymers) of the present invention means the polyvinylidene fluoride homopolymer having bimodal molecular weight distribution as defined above, the VDF/CTFE copolymers having substantially uniform monomer distribution as defined above and/or the VDF/HFP copolymers which are the first composition aspect of the invention.
  • VDF-HFP copolymers of the present invention have better adhesion of the polymers to metallic portions of electrodes and higher use temperatures than batteries fabricated from VDF-HFP copolymers of the prior art. It has also been observed that VDF-HFP copolymers of the present invention provide batteries having improved electrical properties including the capability of higher discharge rates than batteries fabricated from VDF-HFP copolymers of the prior art. It is expected by the present inventors that in general batteries fabricated according to the present invention will possess such higher temperature use and higher discharge rate capabilities.
  • the invention provides in a third composition aspect, a solution of a composition of the first composition aspect of the invention having improved solution clarity and fluidity.
  • Copolymers of vinylidene fluoride and hexafluoropropylene of up to about 24 wt% hexafluoropropylene are useful semicrystalline thermoplastics. As the HFP content increases in the materials, the crystallinity decreases, and, correspondingly, the flexibility and solvent sensitivity increase. Other properties change as well, such as the final melting point, which decreases with increasing HFP content .
  • VDF/HFP copolymers show lower extractables , improved solution properties, improved clarity and fluidity, and lower melting points in comparison to the nonuniform VDF/HFP copolymers of otherwise similar HFP content and manufacture known in the prior art .
  • Figure 1 is a comparison of the final differential scanning colorimeter/ (DSC) melting point of copolymers of the invention with DSC melting points of prior art compounds whose synthesis is described in detail .
  • Figure 2 shows the effect on HFP level on polymer extractibles in dimethyl carbonate (DMC) at 40°C for copolymers of the invention and copolymers of the prior art whose synthesis is described in detail.
  • Figure 3 shows the relationship between HFP content and log of gelation time from solution (20 wt% in propylene carbonate) of copolymers of the present invention and of copolymers of the prior art having sufficient synthesis detail for reproduction.
  • DMC dimethyl carbonate
  • Figure 4 is a cross section of an electrochemical cell in accord with the present invention.
  • the invention provides copolymers of vinylidene fluoride and hexafluoropropylene having hexafluoropropylene content of up to about 24 wt% and having improved solution clarity and fluidity and reduced extractables.
  • the copolymers are conveniently made by an emulsion polymerization process, but suspension and solution processes may also be used.
  • a reactor is charged with deionized water, water-soluble surfactant capable of emulsifying the reaction mass during polymerization, paraffin antifoulant, vinylidene fluoride, hexafluoropropylene, chain-transfer agent to control copolymer molecular weight, and initiator to start and maintain the polymerization.
  • the initial charge of VDF and HFP monomers is such that the amount of HFP is up to 48% of the combined weight of the monomers initially charged, and then VDF and HFP are fed continuously throughout the reaction such that the amount of the HFP is up to 24% of the combined weight of the monomers fed continuously.
  • VDF/HFP ratios are different in the initial charge and during the continuous feed, and each final polymer composition has definite and related ratios for the initial charge and continuous feed.
  • the process uses total amounts of VDF and HFP monomers such that the amount of HFP used is up to about 24% of the combined total weight of the monomers .
  • the reactor is a pressurized polymerization reactor equipped with a stirrer and heat control means.
  • the temperature of the polymerization can vary depending on the characteristics of the initiator used, but it is typically between 65° and 105°C, and most conveniently it is between 75° and 95°C. The temperature is not limited to this range, however, and might be higher or lower if a high-temperature or low- temperature initiator is used.
  • the VDF/HFP ratios used in the polymerization will be dependent on the temperature chosen for reaction.
  • the pressure of the polymerization is typically between 2750 and 6900 kPa, but it can be higher if the equipment permits operation at higher pressure. The pressure is most conveniently between 3790 and 5860 kPa .
  • Surfactants used in the polymerization are water- soluble, halogenated surfactants, especially fluorinated surfactants such as the ammonium, substituted ammonium, quaternary ammonium, or alkali metal salts of perfluorinated or partially fluorinated alkyl carboxylates, the perfluorinated or partially fluorinated monoalkyl phosphate esters, the perfluorinated or partially fluorinated alkyl ether or polyether carboxylates, the perfluorinated or partially fluorinated alkyl sulfonates, and the perfluorinated or partially fluorinated alkyl sulfates.
  • fluorinated surfactants such as the ammonium, substituted ammonium, quaternary ammonium, or alkali metal salts of perfluorinated or partially fluorinated alkyl carboxylates, the perfluorinated or partially fluorinated monoalkyl phosphate esters, the perfluorin
  • X is hydrogen or fluorine
  • M is an alkali metal, ammonium, substituted ammonium (e.g., alkylamine of 1 to 4 carbon atoms) , or quaternary ammonium ion
  • n is an integer from 6 to 20
  • the surfactant charge is from 0.05% to 2% by weight on the total monomer weight used, and most preferably the surfactant charge
  • the paraffin antifoulant is conventional, and any long-chain, saturated, hydrocarbon wax or oil may be used. Reactor loadings of the paraffin are from 0.01% to 0.3% by weight on the total monomer weight used.
  • the reactor After the reactor has been charged with deionized water, surfactant, and paraffin antifoulant, the reactor is either purged with nitrogen or evacuated to remove oxygen. The reactor is brought to temperature, and chain-transfer agent may optionally be added. The reactor is then pressurized with a mixture of vinylidene fluoride and hexafluoropropylene.
  • Chain-transfer agents which may be used are well- known in the polymerization of fluorinated monomers . Alcohols, carbonates, ketones, esters, and ethers are oxygenated compounds which serve as chain-transfer agents. Specific, but not limiting examples, are isopropyl alcohol, such as described in U.S. Pat. No. 4,360,652, acetone, such as described in U.S.
  • Chain-transfer agents may be added all at once at the beginning of the reaction, in portions throughout the reaction, or continuously as the reaction progresses.
  • the amount of chain-transfer agent and mode of addition which is used depends on the activity of the agent and the desired molecular weight characteristics of the product.
  • the amount of chain-transfer agent used is from 0.05% to 5% by weight on the total monomer weight used, and preferably it is from 0.1 to 2% by weight .
  • the reactor is pressurized by adding vinylidene fluoride and hexafluoropropylene monomers in a definite ratio (first effective ratio) such that the hexafluoropropylene ranges up to 48% of the combined weight of the monomers initially charged.
  • first effective ratio used will depend on the relative reactivity of the two monomers at the polymerization temperature chosen. The reactivity of vinylidene fluoride and hexafluoropropylene has been reported in Bonardelli et al . , Polymer, vol. 27, 905-909 (June 1986) .
  • the relative reactivity is such that to obtain a particular uniform copolymer composition, more hexafluoropropylene has to be charged to the reactor in the initial fill than will be incorporated into the copolymer.
  • the convenient polymerization temperature range of this invention about twice as much hexafluoropropylene has to be charged to the reactor in the initial fill as will appear in the polymer.
  • the reaction can be started and maintained by the addition of any suitable initiator known for the polymerization of fluorinated monomers including inorganic peroxides, "redox" combinations of oxidizing and reducing agents, and organic peroxides.
  • suitable initiator known for the polymerization of fluorinated monomers
  • inorganic peroxides include inorganic peroxides, "redox" combinations of oxidizing and reducing agents, and organic peroxides.
  • typical inorganic peroxides are the ammonium or alkali metal salts of persulfates, which have useful activity in the 65°C to 105°C temperature range.
  • Redox systems can operate at even lower temperatures and examples include combinations of oxidants such as hydrogen peroxide, t-butyl hydroperoxide , cumene hydroperoxide , or persulfate, and reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • oxidants such as hydrogen peroxide, t-butyl hydroperoxide , cumene hydroperoxide , or persulfate
  • reductants such as reduced metal salts, iron (II) salts being a particular example, optionally combined with activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • activators such as sodium formaldehyde sulfoxylate or ascorbic acid.
  • organic peroxides which can be used for the polymerization are the classes of dialkyl peroxides, peroxyesters, and peroxydi
  • dialkyl peroxides is di-t- butyl peroxide
  • peroxyesters are -butyl peroxypivalate and t-amyl peroxypivalate
  • peroxydicarbonates are di(n-propyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di (sec-butyl) peroxydicarbonate, and di (2-ethylhexyl) peroxydi- carbonate.
  • diisopropyl peroxydicarbonate for vinylidene fluoride polymerization and copolymerization with other fluorinated monomers is taught in U.S. Pat. No. 3,475,396, and its use in making vinylidene fluoride/hexafluoropropylene copolymers is further illustrated in U.S. Pat. No.
  • di(n-propyl) peroxydicarbonate in vinylidene fluoride polymerizations is described in the Published Unexamined Application (Kokai) JP 58065711.
  • the quantity of an initiator required for a polymerization is related to its activity and the temperature used for the polymerization.
  • the total amount of initiator used is generally between 0.05% to 2.5% by weight on the total monomer weight used.
  • sufficient initiator is added at the beginning to start the reaction and then additional initiator may be optionally added to maintain the polymerization at a convenient rate.
  • the initiator may be added in pure form, in solution, in suspension, or in emulsion, depending upon the initiator chosen.
  • peroxydicarbonates are conveniently added in the form of an aqueous emulsion.
  • a mixture of vinylidene fluoride and hexafluoropropylene monomers is fed in a definite ratio (second effective ratio) so as to maintain reaction pressure.
  • the second effective ratio used corresponds to the monomer unit ratio desired in the final composition of the copolymer, and it can range up to 24% of the combined weight of the monomers being fed continuously throughout the reaction.
  • the feed of vinylidene fluoride, hexafluoropropylene, and optionally initiator and chain-transfer agent is continued until the desired reactor fill is obtained.
  • the monomer feeds are terminated.
  • all other feeds are stopped at the same time as the monomer feeds, and the reactor is vented as soon as is practicable.
  • a react-out period to consume residual monomer is used with optional continuation of initiator feed.
  • the reaction temperature and agitation are maintained for a period of 20 to 30 minutes, but a longer period can be used if required in order to consume monomer to the point where the reactor pressure is no longer falling to any significant degree.
  • a settling period typically 10 to 40 minutes may be used following the react-out period. During the settling period, temperature is maintained but no initiator feed is used. The reactor is then cooled and vented.
  • the product is recovered as a latex.
  • the latex is coagulated, the coagulum is separated and the separated coagulum may be washed.
  • the coagulum is dried.
  • coagulation step For the coagulation step, several well-known methods can be used including freezing, the addition of acids or salts, or mechanical shear with optional heating.
  • the powder if desired, can be further processed into pellets or other convenient resin forms .
  • the electrochemical cells of the present invention are based on a positive electrode, an absorber-separator sometimes referred as a solid electrolyte and negative electrode operatively associated with one another wherein at least one of the electrodes or the absorber-separator, and preferably both electrodes and the absorber-separator comprise a vinylidene fluoride polymer of the present invention and wherein the vinylidene fluoride polymer of the present invention electrodes have an electrode material combined therewith and the vinylidene fluoride polymer of the present invention absorber- separator has an electrolyte material combined therewith.
  • a plurality of electrodes and absorber- separator elements can be used in the cell structure in order to increase the voltage, and/or amperage of the combined elements in a manner well known to the art.
  • Vinylidene fluoride polymer of the present invention is not required to have an open or closed porous structure for operability. It provides enhanced electrolyte mobility in combination with the intrinsic ionic conductivity effects of the polymer regardless of its initial porous or non porous state. Vinylidene fluoride electrode or separator-absorber combined with electrode or electrolyte materials at the surface of the pores of the porous polymer was previously believed to make the utilization of the active material, whether electrode material or electrolyte material more efficient and provide a method for the easy manufacture of the efficient electrodes and separator-absorber structures. There are, however, other advantages to use of porous polymer structures even for the polyvinylidene fluoride polymers of the present invention.
  • the segregation of the active materials on the surface of active pores will allow for varying the amount of binder in the electrode of the separator-absorber to enhance strength with minimum effect on cell performance.
  • the electrochemical cells formed in this way therefore will have improved mechanical properties and can be made to be self-supporting i.e., secondary reinforcing structures do not have to be employed such as a metal or other conventional battery casing material.
  • the electrochemical cell is enveloped or enclosed in a vinylidene fluoride homopolymer which will adhere to the porous electrodes and/or the absorber-separator structures.
  • Adhesion can be obtained by simple heat bonding or radio frequency (rf) welding or other similar processes well known in the art.
  • Adhesives are not required, but importantly, the exterior part of the electrochemical cell (i.e., the envelope) is of the same type or a substantially similar type of material as the electrodes and absorber-separator and is more compatible therewith and adherent thereto, thereby simplifying and reducing the cost of manufacture in that only one type of material is used for the structural components of the cell as compared to either conventional dry cell or secondary cell construction.
  • vinylidene fluoride polymers of the present invention for electrodes and such polymers or conventional VDF polymer for cladding that are either extremely flexible or somewhat rigid, structures can be fabricated that are in turn either flexible or somewhat rigid. Further in this regard, enhanced rigidity can be obtained by cross-linking the vinylidene fluoride homo- or copolymers in general either chemically, but preferably by employing high energy radiation such as high energy (about 10 to about 20 Mrad) electron beam radiation, with some attendant dehydrofluorination.
  • high energy radiation such as high energy (about 10 to about 20 Mrad) electron beam radiation
  • One potential benefit is the further stabilization of the amorphous regions in the vinylidene fluoride polymers, i.e., inhibitions of crystallization over time which is important since ionic conductivity of the electrolyte is believed to occur primarily in the amorphous or open regions.
  • vinylidene fluoride polymers in general affect ionic conductivity in a manner that makes them suitable for the fabrication of electrochemical cells. Since mobility of charged species is required in electrochemical cells, it is believed that the migration of charged species in polyvinylidene fluoride polymers will be through the amorphous phase.
  • the vinylidene fluoride polymers of the present invention have been recognized by the invention as having enhanced amorphous phases which are more stable and particularly for the HFP and CTFE copolymers provide this benefit to conductivity and the like at lower comonomer levels, thus, providing solubility and temperature advantages approaching that of homopolymers .
  • Vinylidene fluoride polymers are unique in stabilizing positive holes and are one of the most effective media in this regard, presumably due to the highly negative grem- difluorocarbon group.
  • lithium ion batteries such as the rocking-chair batteries described herein
  • the high specific charge and small ionic size of the lithium ion may lead to specific interactions in the host vinylidene fluoride polymer environment, considering the extent of the non-polarizable, negative gem-difluorocarbon groups available.
  • plasticizers such as organic carbonates (e.g., ethylene carbonate, propylene carbonate, dimethylcarbonate and the like) are utilized in order to minimize the effect of the crystalline structure and promote ionic conductivity.
  • organic carbonates e.g., ethylene carbonate, propylene carbonate, dimethylcarbonate and the like
  • Other solvents or plasticizers may also be employed including diethoxyethane, diethylcarbonate, dimethoxyethane , dipropyl carbonate and mixtures thereof especially the two or three component mixtures .
  • the various porous or non-porous structures can be mechanically oriented by stretching or the application of tensile forces in order to enhance the amount of beta conformation within the polymer structure and thereby possibly promote ionic conductivity depending upon the electrolyte and polyvinylidene fluoride composition.
  • polyvinylidene fluoride polymers of the present invention are cast in thin membranes. This method is described by Benzinger et al. in U.S. Patent No. 4,384,047 which is incorporated herein by reference.
  • the electrode materials or the electrolyte materials as described herein can be incorporated into polyvinylidene fluoride solution prior to casting it into a film or sheet, after which the solution may, if desired, be converted to a porous polyvinylidene fluoride membrane combined with the electrode of electrolyte materials.
  • These films or sheets, either with or without the electrode or electrolyte materials can be any where from about 0.25 to about 100, particularly from about 0.5 to about 10, and especially from about 1 to about 8 mils thick, and are especially suitable for further treatment by stretching or the application of tensile forces in order to promote the beta conformation necessary to achieve ferroelectric properties in polyvinylidene fluoride .
  • Active solvents are those organic liquids that dissolve or swell vinylidene fluoride polymers at room temperature and typically consist of lower alkyl ketones, esters and amides.
  • Latent solvents are those organic liquids that do not dissolve vinylidene fluoride homo- or copolymers at room temperature; however, will dissolve polyvinylidene fluoride at elevated temperatures and typically are medium chain length alkyl ketones, esters, glycol ethers and organic carbonates.
  • Non- solvents are organic liquids that do not dissolve or swell vinylidene fluoride polymers up to the boiling point of the liquid or the crystalline melting point of the vinylidene fluoride polymer, whichever condition is met first. These liquids typically are aromatic hydrocarbons, aliphatic hydro-carbons and chlorinated hydrocarbons or other chlorinated organic liquids.
  • the solvents and latent solvents are used in the manufacture of the polyvinylidene fluoride films or sheets of the present invention.
  • polyvinylidene fluoride powders can be sintered to form a porous structure by heating the powders in a non-solvent slurry, or under pressure between opposed platens, until the individual particles sufficiently melt flow into one another to form the desired open cell structure.
  • sintering powder polymers such as PTFE for forming open cell porous structures as described by Menassen et al . "A Polymer Chemist ' s View on Fuel Cell Electrodes, " Proceeding of the 34th International
  • a porous film made by casting polyvinylidene provide polymers of the present invention from a mixture of solvents and non-solvents as described by Benzinger et al . in U.S. Patent 4,383,047, which is about 10 mils thick after formation from the casting solution, may be utilized for the manufacture of an electrochemical cell.
  • the polymer comprises a copolymer of Example 1 herein below.
  • This film is used in fabricating an absorber-separator of solid electrolyte by making a solution of LiPFg in 1:1 mixture by weight of ethylene carbonate :propylene carbonate which is heated to about 125°C and the porous copolymer film immersed in the solution until it is combined with the film.
  • a positive electrode is made from the same porous copolymer.
  • a dispersion of LiMn 2 0 4 , SS carbon black and LiPFg in a 1:1 mixture of ethylene carbonate and propylene carbonate along with tetrahydrofuran (THF) was combined with the porous film by soaking the film in the suspension which is agitated in a vibrating beaker in order to keep solid material in suspension until adequately combined with the film. The film is then placed on an aluminum foil.
  • a negative electrode is prepared by making a dispersion or suspension of petroleum coke, SS carbon black and LiPFg in a 1:1 ethylene carbonate propylene carbonate solution in the same manner as was done for the preparation of the positive electrode and after combining the suspension with the porous film, a copper foil was placed on the film.
  • the electrodes and electrolyte can also be made from sintered polyvinylidene fluoride by forming a dry blend of the electrode or electrolyte materials with powdered polyvinylidene fluoride. Dry mixing techniques, known in the art may be employed, such as tumbler type mixing. For example, the mixture of polyvinylidene fluoride powder and the electrode or electrolyte materials can be subjected to tumbling or ball milling for a time to sufficiently ensure that a good mixture is obtained. A steel or other metal vessel, or ceramic vessel is employed, especially where either is lined with a polyvinylidene fluoride or PTFE layer.
  • Solvents such as ethylene carbonate and propylene carbonate, and their equivalents, especially as noted herein, including mixtures thereof, which are employed in the electrode or electrolyte can be added afterwards by soaking the electrodes and electrolyte structures in such solvents .
  • the soaking can be carried out at room temperature or above to maximize the solvating effect of these materials and to produce optimum ionic conductivity n the electrodes or electrolyte.
  • the positive electrode and the negative electrode thus prepared, are then placed on opposite sides of the absorber-separator prepared as described above with the copper and aluminum surfaces facing outwardly to form a cell as illustrated in Fig.
  • Envelope 12 may be a single film or a plurality of films e.g., two or three films and extends around all sides and completely envelops cell 10. Copper and aluminum leads (not shown) are passed through envelope 10 to make electrical contact with films 14 and 22, respectively and are connected to a load (not shown) to form an electric circuit.
  • the vinylidene fluoride polymers of the present invention may also be employed in cells having a lithium organic electrolyte where the polymer is used either as a binder for particular electrode active materials, as a solid electrolyte for polymeric cells, a porous mesh supporting a quasi-solid state gel electrolyte and as the cell base material.
  • the vinylidene fluoride polymers of the present invention as described herein can also be used in lithium/oxyhalide cells as a bottom insulator. They may also be used in zinc bromide cells as a binder for bipolar electrodes or in nickel -metal hydride cells as a binder for the hydride electrode or for the nickel electrode .
  • the vinylidene fluoride polymers of the present invention are also suitable for use in a silver- zinc cell where the vinylidene fluoride polymers are used as a binder for the zinc electrode or in a lead-acid cell as a spacer between the electrodes and as a separator.
  • the vinylidene fluoride polymers may also be used in thermal batteries for cathode active materials.
  • the vinylidene fluoride polymers may also be used in other alkaline cells such as nickel -cadmium cells, and zinc-air cells, especially where a buffered electrolyte is employed to counteract the dehydrohalogenation effect of the alkali medium of these cells.
  • HFP content was determined by - ⁇ F NMR according to the signal assignments and method described in
  • the reaction conditions were stabilized at 80 degrees Celsius and 4480 kPa, and then the polymerization was begun by introducing 0.026 kg of an initiator emulsion consisting of 2 wt% di-n- propyl peroxydicarbonate and 0.15 wt% mixed perfluoroalkanoate salts dispersed in deionized water.
  • the pressure rose to 4550 kPa with the addition of the initiator emulsion.
  • the polymerization was maintained by the addition of the initiator emulsion at the rate of 0.112 kg per hour, and by the addition of a mixture of vinylidene fluoride/hexafluoropropylene in the ratio 95 vinylidene fluoride/5 hexafluoropropylene so as to maintain pressure.
  • a mixture of vinylidene fluoride/hexafluoropropylene in the ratio 95 vinylidene fluoride/5 hexafluoropropylene so as to maintain pressure.
  • totals of 1.890 kg of vinylidene fluoride and 0.140 kg of hexafluoropropylene had been charged to the reactor. All feeds were stopped, and the reactor was cooled. After 5 minutes of cooling, agitation speed was reduced by 78% and surplus gases were vented. Agitation was stopped, the reactor was further cooled, and then it was emptied of latex.
  • Polymer resin was isolated by coagulating the latex, washing the resulting solids with boiling water, and drying the solids at 110 degrees Celsius to yield fine powder.
  • the resin so made had a melt viscosity of 2770 Pa.s, had a DSC melting point of 152 degrees Celsius, and had a hexafluoropropylene content as measured by NMR of 5.4 wt%.
  • the reaction conditions were stabilized at 80 degrees Celsius, and then the polymerization was begun by introducing 0.040 kg of an initiator emulsion consisting of 2 wt% di-n-propyl peroxydicarbonate and 0.15 wt% mixed perfluoroalkanoate salts dispersed in deionized water.
  • the pressure dropped upon initiation and it was then maintained at 4825 kPa.
  • the polymerization was maintained by the addition of the initiator emulsion at the rate of 0.176 kg per hour, and by the addition of a mixture of vinylidene fluoride/hexafluoropropylene in the ratio 84 vinylidene fluoride/16 hexafluoropropylene so as to maintain pressure.
  • the reaction conditions were stabilized at 80 degrees Celsius and 4480 kPa, and then the polymerization was begun by introducing 0.026 kg of an initiator emulsion consisting of 2 wt% di-n- propyl peroxydicarbonate and 0.15 wt% mixed perfluoroalkanoate salts dispersed in deionized water.
  • the polymerization was maintained by the addition of the initiator emulsion at the rate of 0.112 kg per hour, and by the addition of a mixture of vinylidene fluoride/hexafluoropropylene in the ratio 93 vinylidene fluoride/7 hexafluoropropylene so as to maintain pressure.
  • the resin so made had a melt viscosity of 2550 Pa.s, had a DSC melting point of 154 degrees Celsius, and had a hexafluoropropylene content as measured by NMR of 6.0 wt.%.
  • EXAMPLE 4 Into a 293 liter stainless steel reactor were charged 200.0 kg of deionized water, 1.00 kg of a 10 wt% solution of a mixture of perfluoroalkanoate salts, and 0.015 kg of paraffin oil. The reactor was evacuated and heated to a temperature of 91 degrees Celsius during the charging, and agitation was used.
  • the rate of further initiator emulsion addition was adjusted so as to maintain a total monomer feed rate of 27.0 kg/h.
  • a monomer mixture in the ratio 94 vinylidene fluoride/6 hexafluoropropylene was fed to the reactor so as to maintain pressure at 4480 kPa until the totals of 85.3 kg of vinylidene fluoride and 5.4 kg of hexafluoropropylene had been charged to the reactor. All feeds were stopped, and residual monomer was consumed by maintaining 91° Celsius and agitation for 20 minutes and then by maintaining 91° C for 35 minutes. The reactor was cooled, vented, and emptied of latex.
  • Polymer resin was isolated by coagulating the latex, washing the resulting solids with water, and drying the solids to yield fine powder.
  • the resin so made had a melt viscosity of 1740 Pa.s, had a DSC melting point of 155 degrees Celsius, and had a hexafluoropropylene content as measured by NMR of 4.7 wt.%.
  • EXAMPLES 5 to 12 Copolymers of examples 5 to 8 are made similarly to copolymers of Examples 1 or 2 , and copolymers of examples 9 to 12 are made similarly to copolymers of Examples 3 or 4 and are shown in Table I .
  • solutio (s) having improved clarity and fluidity means that the solution (s) of any particular copolymer of this invention having a particular nominal HFP content will provide solution (s) having descriptive properties analogous to those shown by Example 2 in Table II when dissolved in any of the solvents listed at the same concentration levels at which a copolymer having about the same particular nominal HFP content made by a typical process described in detail in the prior art provides solution descriptive properties analogous to those shown in Table II for Example 12.
  • examples 2 and 12 are shown in Table II. Mixtures of the indicated weight percent were prepared, using heat when necessary to dissolve the polymer completely and form a clear solution. Solutions were then allowed to cool and observed daily over a period of two weeks . The copolymer 2 showed a reduced tendency to gel and to be clearer than the copolymer 12. The retention of fluidity and clarity by the copolymer 2 is advantageous in applications which rely on polymer solutions, such as in the production of cast films and membranes.
  • the reduction in tendency toward gelation by the copolymers of the present invention is further shown in Table II A.
  • the gelation times of propylene carbonate solutions of some of the examples are shown in the table .
  • a Rheometrics dynamic stress rheometer DSR-200 was used to measure the gelation times of 20 wt% solutions of the polymers in propylene carbonate (the propylene carbonate was of nominal 99.7% purity) .
  • the rheometer was fitted with a Peltier fixture and solvent trap.
  • a 40 mm parallel plate geometry was used with a gap of 1 mm.
  • Solid copolymer was mixed with propylene carbonate at room temperature on the day of measurement, the container was sealed, and the solution was formed by heating and stirring the mixture in the sealed container for 1.0 hour in a Pierce Reacti-Therm Heating/Stirring Module set at 120°C.
  • the solutions were quickly loaded at the end of the dissolution period into the test fixture, which was preset at 100°C.
  • a temperature cooling ramp in dynamic oscillatory mode at 1 Hz was begun as soon as the fixture temperature re-equilibrated at 100°C; re-equilibration typically required a minute or less.
  • the cooling ramp was from 100°C to 15°C at a rate of 30°C/m.
  • the final melting point is an important parameter in the use and processing of semicrystalline polymers. It is known that the final melting point of VDF/HFP copolymers is related to the HFP content in the copolymers. The relation between HFP content and final melting point of the VDF/HFP copolymer examples is shown in Figure 1.
  • the copolymers of the present invention and the copolymers prepared according to the prior art synthesis which details are available can be seen to fall on different melting point curves, indicating that they are different materials, with the prior art copolymers having a higher melting point at a given HFP content.
  • the lower melting point property of the copolymers of the present invention can allow lower processing temperatures than for the prior art synthesis copolymers.
  • FIG. 1 shows a plot of the extractables as a function of HFP content (mole%) .
  • Two distinct curves are outlined for the two classes of materials.
  • the upper curve (N samples) shows significantly higher levels of extractables for a given level of HFP compared to the U curve .
  • Measured slopes for these curves are 3% extractables/mole % HFP for the N polymers and 1.7% extractables/mole % HFP for the U polymers.
  • the observed and calculated % extractables under both the single and dual functional model are shown for the N polymers in Table VI and for the U polymers in Table VII.
  • Example 13 Polyvinylidene Fluoride/ Chlorotri- fluorethylene Copolymer Having Substantially Homogeneous Monomer Distribution
  • Example 2 Following a procedure analogous to that of Example 1 provide an initial charge containing 0.40 kg of vinylidene fluoride and 0.0124 kg of chlorotrifluorethylene (97 VDF/3 CTFE) and maintain the reaction by a continuous feed of 96 VDF to 4 CTFE together with initiator emulsion for a total feed convenient for the reactor size of about 1.9525 kg of VDF and 0.0775 kg CTFE to obtain the title copolymer having about 4.0% CTFE content.
  • 97 VDF/3 CTFE chlorotrifluorethylene

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Abstract

La présente invention concerne de nouveaux copolymères de fluorure de vinylidène et d'hexafluoropropylène (HFP) contenant jusqu'à environ 24 % en poids d'héxafluoropropylène présentant une fluidité et une transparence de solution améliorées, des temps de gélification plus longs et une teneur en constituants extractibles inférieure à celle des copolymères de fluorure de vinylidène et d'héxafluoropropylène existants, à teneur en HFP comparable dont les synthèses sont décrites de manière suffisamment détaillée de façon à être dupliquées. La présente invention concerne également de nouvelles compositions et des articles manufacturés contenant les dits copolymères, des procédés de préparation et d'utilisation des copolymères, des compositions de matière contenant les dits copolymères et des articles manufacturés contenant les dits copolymères. La présente invention concerne également de nouvelles constructions de batteries à base de nouveaux copolymères de fluorure de vinylidène et d'héxafluoropropylène de l'invention, d'homopolymères présentant une distribution bimodale des poids moléculaires et de copolymères de fluorure de vinylidène/héxafluoropropylène et de chlorotrifluoroéthylène présentant une distribution monomère sensiblement homogène.
PCT/US1998/004071 1997-02-28 1998-02-27 Copolymeres de fluorure de vinylidene et d'hexafluoropropylene presentant une teneur en constituants extractibles reduite et une transparence de solution amelioree WO1998038687A1 (fr)

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EP98908864A EP0907976A4 (fr) 1997-02-28 1998-02-27 Copolymeres de fluorure de vinylidene et d'hexafluoropropylene presentant une teneur en constituants extractibles reduite et une transparence de solution amelioree
KR1019980708803A KR100537303B1 (ko) 1997-02-28 1998-02-27 비닐리덴 플루오라이드와 헥사플루오로프로필렌과의공중합체 및 이를 포함하는 전기화학전지
HU9903748A HUP9903748A3 (en) 1997-02-28 1998-02-27 Improved batteries containing copolymers of vinylidene fluoride
JP53795098A JP2002513506A (ja) 1997-02-28 1998-02-27 低減された抽出分含有率及び改善された溶液清澄性を有する、弗化ビニリデンとヘキサフルオルプロピレンとのコポリマー
CNB988002078A CN1311577C (zh) 1997-02-28 1998-02-27 电化学电池

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EP1028479A2 (fr) * 1999-02-05 2000-08-16 Ausimont S.p.A. Electrolytes polymères pour générateurs rechargeables au lithium
GB2346729A (en) * 1999-02-10 2000-08-16 Aea Technology Plc Polymer electrolyte
WO2002011230A1 (fr) * 2000-07-31 2002-02-07 Accentus Plc Electrolyte polymere
EP1229597A2 (fr) * 2001-02-03 2002-08-07 Microbatterie GmbH Procédé de fabrication de feuilles d'électrodes
US6506523B1 (en) * 1998-04-27 2003-01-14 Sony Corporation Solid electrolyte secondary battery
WO2004019344A1 (fr) * 2002-08-26 2004-03-04 Nippon Oil Corporation Film conducteur d'ions
US6824927B1 (en) * 1997-12-26 2004-11-30 Kureha Kagaku Kogyo Kabushiki Kaisha Polymer electrolyte containing a vinylidene fluoride copolymer and a nonaqueous electrolytic solution, and nonaqueous battery containing the polymer electrolyte
WO2006001788A1 (fr) * 2004-06-09 2006-01-05 The Gillette Company Cellules electrochimiques
US7066970B2 (en) 2003-05-09 2006-06-27 The Gillette Company Electrochemical cells
US8303609B2 (en) 2000-09-29 2012-11-06 Cordis Corporation Coated medical devices
US9114198B2 (en) 2003-11-19 2015-08-25 Advanced Cardiovascular Systems, Inc. Biologically beneficial coatings for implantable devices containing fluorinated polymers and methods for fabricating the same
USRE45744E1 (en) 2003-12-01 2015-10-13 Abbott Cardiovascular Systems Inc. Temperature controlled crimping
US9175162B2 (en) 2003-05-08 2015-11-03 Advanced Cardiovascular Systems, Inc. Methods for forming stent coatings comprising hydrophilic additives
US20160126600A1 (en) * 2004-12-01 2016-05-05 Sony Corporation Battery
EP3694020A4 (fr) * 2018-06-20 2021-04-14 Lg Chem, Ltd. Séparateur pour dispositif électrochimique, son procédé de fabrication et dispositif électrochimique le comprenant
US20220102756A1 (en) * 2020-09-30 2022-03-31 GM Global Technology Operations LLC Methods for forming solid gel electrolyte membranes and batteries incorporating the same

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CN112585795B (zh) * 2018-09-14 2022-03-29 株式会社吴羽 树脂分散电解液、聚合物凝胶电解质及其制造方法以及二次电池及其制造方法
KR102715482B1 (ko) * 2019-01-04 2024-10-08 주식회사 엘지화학 리튬이차전지용 가교 폴리올레핀 분리막을 제조하기 위한 조성물, 이로부터 제조된 분리막, 및 상기 분리막의 제조방법
FR3106703B1 (fr) * 2020-01-29 2022-07-22 Arkema France Formulation d’electrode pour batterie li-ion et procede de fabrication d’electrode sans solvant

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US8574770B2 (en) 1997-12-26 2013-11-05 Kureha Corporation Vinylidene fluoride copolymer-based polymer electrolyte for nonaqueous battery retaining large proportion of electrolytic solution
US8043386B2 (en) 1997-12-26 2011-10-25 Kureha Corporation Process for producing polymer electrolyte
US6824927B1 (en) * 1997-12-26 2004-11-30 Kureha Kagaku Kogyo Kabushiki Kaisha Polymer electrolyte containing a vinylidene fluoride copolymer and a nonaqueous electrolytic solution, and nonaqueous battery containing the polymer electrolyte
US7452387B2 (en) 1997-12-26 2008-11-18 Kureha Corporation Process for producing a polymer electrolyte of a vinylidene fluoride copolymer for a nonaqueous battery
US6506523B1 (en) * 1998-04-27 2003-01-14 Sony Corporation Solid electrolyte secondary battery
EP1028479A2 (fr) * 1999-02-05 2000-08-16 Ausimont S.p.A. Electrolytes polymères pour générateurs rechargeables au lithium
JP2000231936A (ja) * 1999-02-05 2000-08-22 Ausimont Spa 再充電性リチウム電池用電解質ポリマー
EP1028479A3 (fr) * 1999-02-05 2005-07-27 Solvay Solexis S.p.A. Electrolytes polymères pour générateurs rechargeables au lithium
GB2346729A (en) * 1999-02-10 2000-08-16 Aea Technology Plc Polymer electrolyte
GB2346729B (en) * 1999-02-10 2003-01-15 Aea Technology Plc Polymer electrolyte
WO2002011230A1 (fr) * 2000-07-31 2002-02-07 Accentus Plc Electrolyte polymere
US8303609B2 (en) 2000-09-29 2012-11-06 Cordis Corporation Coated medical devices
EP1229597A2 (fr) * 2001-02-03 2002-08-07 Microbatterie GmbH Procédé de fabrication de feuilles d'électrodes
EP1229597A3 (fr) * 2001-02-03 2004-04-28 VARTA Microbattery GmbH Procédé de fabrication de feuilles d'électrodes
WO2004019344A1 (fr) * 2002-08-26 2004-03-04 Nippon Oil Corporation Film conducteur d'ions
US9175162B2 (en) 2003-05-08 2015-11-03 Advanced Cardiovascular Systems, Inc. Methods for forming stent coatings comprising hydrophilic additives
US7066970B2 (en) 2003-05-09 2006-06-27 The Gillette Company Electrochemical cells
US9114198B2 (en) 2003-11-19 2015-08-25 Advanced Cardiovascular Systems, Inc. Biologically beneficial coatings for implantable devices containing fluorinated polymers and methods for fabricating the same
USRE45744E1 (en) 2003-12-01 2015-10-13 Abbott Cardiovascular Systems Inc. Temperature controlled crimping
WO2006001788A1 (fr) * 2004-06-09 2006-01-05 The Gillette Company Cellules electrochimiques
US20160126600A1 (en) * 2004-12-01 2016-05-05 Sony Corporation Battery
EP3694020A4 (fr) * 2018-06-20 2021-04-14 Lg Chem, Ltd. Séparateur pour dispositif électrochimique, son procédé de fabrication et dispositif électrochimique le comprenant
US11657984B2 (en) 2018-06-20 2023-05-23 Lg Chem, Ltd. Separator for electrochemical device, method for manufacturing same, and electrochemical device comprising same
US20220102756A1 (en) * 2020-09-30 2022-03-31 GM Global Technology Operations LLC Methods for forming solid gel electrolyte membranes and batteries incorporating the same

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EP0907976A1 (fr) 1999-04-14
CN1217824A (zh) 1999-05-26
HUP9903748A3 (en) 2000-06-28
CA2251648A1 (fr) 1998-09-03
EP0907976A4 (fr) 2005-11-02
KR20000065176A (ko) 2000-11-06
CN1311577C (zh) 2007-04-18
ID20294A (id) 1998-11-26
JP2002513506A (ja) 2002-05-08
KR100537303B1 (ko) 2006-07-14
HUP9903748A2 (hu) 2000-03-28

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