WO1998049737A1 - Vinylidene fluoride polymer-based binder solution and electrode-forming composition - Google Patents
Vinylidene fluoride polymer-based binder solution and electrode-forming composition Download PDFInfo
- Publication number
- WO1998049737A1 WO1998049737A1 PCT/JP1998/001930 JP9801930W WO9849737A1 WO 1998049737 A1 WO1998049737 A1 WO 1998049737A1 JP 9801930 W JP9801930 W JP 9801930W WO 9849737 A1 WO9849737 A1 WO 9849737A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinylidene fluoride
- electrode
- fluoride polymer
- polymer
- binder solution
- Prior art date
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims abstract description 77
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- 235000011837 pasties Nutrition 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920006366 Foraflon Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
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- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 101100454869 Rattus norvegicus Lhx5 gene Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
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- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/225—Vinylidene fluoride with non-fluorinated comonomers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
-
- 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
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a binder solution and an electrode-forming composition for forming an electrode suitable for use in a non-aqueous electrolytic solution within a non-aqueous electrochemical device, such as a non-aqueous (secondary) battery, particularly a lithium ion battery, or an electric double layer capacitor; and an electrode structure, and further a non-aqueous battery, respectively obtained therefrom.
- a non-aqueous electrochemical device such as a non-aqueous (secondary) battery, particularly a lithium ion battery, or an electric double layer capacitor
- an electrode structure and further a non-aqueous battery, respectively obtained therefrom.
- the non-aqueous electrolytic solution shows only a low ionic conductivity on the order of 10 " ⁇ - 10 ⁇ ⁇ S/cm compared with an ordinary level ionic conductivity of ca. 10 -1 S/cm in an aqueous electrolytic solution, so that it becomes essential to use an electrode (layer) in a small thickness of several ⁇ m to several hundred ⁇ m and in a large area.
- a powdery electrode material comprising an electrode active substance in a binder solution which is obtained by dissolving an organic polymer functioning as a binder for the powdery electrode material to form an electrode-forming composition and applying the composition onto an electroconductive substrate, such as a metal foil or a metal net, followed by drying to form a composite electrode layer.
- Such a structure comprising a thin electrode layer of a powdery electrode material and a resinous binder on an electroconductive substrate is similarly used as an electrode structure for an electric double layer capacitor (e.g., as disclosed in Japanese Laid-Open Patent Application (JP-A) 7-82450).
- JP-A Japanese Laid-Open Patent Application
- a binder solution for forming electrodes used in non-aqueous electro-chemical devices such as a non-aqueous battery and an electric double layer capacitor
- polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, N,N-dimethylacetamide
- a vinylidene fluoride polymer is stable against a non-aqueous electrolytic solution while it is swollen to some extent within such a non- aqueous electrolytic solution. Further, a vinylidene fluoride polymer can retain a good adhesion onto a substrate of metal, etc., by copolymerization or modification.
- the binder is swollen to some extent in the non-aqueous electrolytic solution since the vinylidene fluoride polymer principally comprising polar monomer units has a good affinity with a polar solvent constituting the electrolytic solution. If the binder is swollen when the electrode structure is soaked in the electrolytic solution, the contact resistance between the powdery electrode materials, and between the electroconductive substrate and the powdery electrode materials, is increased, thereby lowering the discharge capacity of the battery with time and deteriorating the charge-discharge cycle performance.
- An object of the present invention is to provide a vinylidene fluoride polymer-based binder solution capable of reducing the swellability of the binder constituting the electrode structure and preventing the peeling of the composite electrode layer, thereby allowing the production of a battery which is safe and excellent in cycle performance.
- Another object of the present invention is provide an electrode-forming composition containing the binder solution, and an electrode structure and a battery formed by using the electrode-forming composition.
- a major linkage (portion) of the resultant polymer chain may comprise hydrogen- attached carbons and fluorine-attached carbons arranged alternately ( ... -CH2-CF2-CH2-CF2- ... ) , but some linkage (portion) can comprise hydrogen-attached carbons and fluorine-attached carbons in a different arrangement ( ... -CH2-CF2-CF2-CH2 ... , or ...
- abnormal linkage comprising non-alternately arranged hydrogen-attached carbons and fluorine-attached carbons is called an abnormal linkage (portion) .
- abnormal linkage content refers to a percentage of the abnormal linkage to the whole vinylidene fluoride monomer linkages in the vinylidene fluoride polymer. There is no substantial difference in atomic size between a hydrogen atom and a fluorine atom by nature, so that the abnormal linkage portion is also incorporated in the crystalline portion of a vinylidene fluoride polymer.
- the crystalline portion is caused to have a lower packing density and a reduced interaction between molecular chains to provide a lower crystalline melting point, leading to a lower resistance to a non-aqueous electrolytic solution and a lower swelling resistance in the electrolytic solution of the resultant vinylidene fluoride polymer.
- This is assumed to be a reason why a lower abnormal linkage content provides a better resistance to and a lower swellability in an electrolytic solution.
- Such a vinylidene fluoride polymer having a lower abnormal linkage content can be produced by polymerization at a temperature (around or lower than room temperature) which is lower than a polymerization temperature adopted for producing conventional vinylidene fluoride polymers for binders.
- a method for measuring the abnormal linkage content of a vinylidene fluoride polymer will be described later.
- a binder solution for forming an electrode suitable for use in a non-aqueous electrolytic solution comprising a solution of a vinylidene fluoride polymer having an abnormal linkage content of below 4.0 % in an organic solvent.
- an electrode-forming composition comprising a mixture of a powdery electrode material with the above-mentioned binder solution.
- the present invention further provides an electrode structure suitable for use in a non-aqueous electrolytic solution, comprising: an electroconductive substrate, and a composite electrode layer formed on at least one surface of the electroconductive substrate; said composite electrode layer comprising a powdery electrode material and a binder comprising a vinylidene fluoride polymer having an abnormal linkage content of below 4 %.
- the present invention further provides a non- aqueous battery, comprising: a positive electrode, a negative electrode, and a non-aqueous electrolytic solution disposed between the positive and negative electrodes; wherein at least one of the positive and negative electrodes comprises an electrode structure as described above.
- Figures 1 and 2 are each a partial sectional view of an embodiment of the electrode structure according to the invention.
- Figure 3 is a partial sectional view schematically showing a laminate structure of an electric double layer capacitor which can be constituted according to the invention.
- Figure 4 is a partially exploded perspective view of a non-aqueous secondary battery which can be constituted according to the invention.
- Figure 5 is a graph showing cycle characteristics of lithium secondary batteries (Cells 1 - 5) including negative electrodes formed by using electrode-forming compositions according to Examples 4 - 6 and Comparative Examples 3 and 4. [DETAILED DESCRIPTION OF THE INVENTION]
- the vinylidene fluoride polymer used in the present invention may include vinylidene fluoride homopolymer, vinylidene fluoride copolymer and modified products of these. Vinylidene fluoride homopolymer is preferred in view of resistance to a non-aqueous electrolytic solution, particularly anti- swelling property.
- the homopolymer is liable to exhibit a somewhat low adhesion onto an electroconductive substrate, e.g., metal, so that it is preferred to use a copolymer of vinylidene fluoride with another monomer, particularly an unsaturated dibasic acid monoester, a vinylene carbonate, an epoxy group-containing vinyl monomer, etc., to obtain a copolymer having a polar group, such as a carboxyl group, a carbonate group or an epoxy group (similar to those disclosed in U.S. Patent No. 5,415,958 except for the abnormal linkage content).
- a modified vinylidene fluoride polymer obtained by treating such a vinylidene fluoride homopolymer or copolymer in a solvent capable of dissolving or swelling such a vinylidene fluoride polymer with a silane coupling agent or titanate coupling agent having a group reactive with the vinylidene fluoride polymer, such as an amino group or a mercapto group, and a hydrolyzable group in combination.
- the vinylidene fluoride polymer may preferably retain at least 90 mol. %, particularly at least 95 mol. %, of untreated vinylidene fluoride units.
- vinylidene fluoride polymer it is possible to admix an organic acid, such as acrylic acid, maleic acid, maleic anhydride or fumaric acid, or a low-molecular weight compound or polymer having a good miscibility with the vinylidene fluoride polymer, such as an acrylic polymer. It is also possible to improve the adhesiveness onto a metal electrode by heating or addition of an alkaline substance to the vinylidene fluoride polymer to generate hydrofluoric acid in an amount of 400 - 20,000 ppm of the vinylidene fluoride polymer and also by adding an acid, such as an organic acid.
- an organic acid such as acrylic acid, maleic acid, maleic anhydride or fumaric acid
- a low-molecular weight compound or polymer having a good miscibility with the vinylidene fluoride polymer, such as an acrylic polymer.
- the vinylidene fluoride polymer used in the present invention is characterized by an abnormal linkage content of below 4 %, but may preferably have an abnormal linkage content of at most 3.5 %, particularly at most 3.0 %.
- the vinylidene fluoride polymer may preferably have a crystalline melting peak temperature (melting point) of at least 173 °C, more preferably at least 175 °C, as measured by differential scanning calorimetry (DSC) on heating at a temperature-raising rate of 10 °C/min. Accordingly, it is preferred that the vinylidene fluoride polymer has a abnormal linkage content of below 4 % and a melting point of at least 173 °C, more preferably an abnormal linkage content of at most 3.5 % and a melting point of at least 175 °C.
- the vinylidene fluoride polymer may preferably have an inherent viscosity (i.e., a logarithmic viscosity number as measured at a concentration of 4 g-resin in 1 liter of N,N- dimethylformamide at 30 °C) of 0.5 - 15 dl/g, more preferably 1.0 - 10 dl/g, further preferably 1.3 - 5.0 dl/g.
- an inherent viscosity i.e., a logarithmic viscosity number as measured at a concentration of 4 g-resin in 1 liter of N,N- dimethylformamide at 30 °C
- the vinylidene fluoride polymer has an inherent viscosity of below 0.5 dl/g, the polymer is liable to be swollen in the electrolytic solution and only have a low effect of binding the powdery electrode material, so that it is difficult to obtain the effect of the present invention.
- a vinylidene fluoride polymer having an inherent viscosity in excess of 15 dl/g causes not only a difficulty in dissolution thereof in a solvent but also a difficulty in suppressing the gelation of a resultant binder solution, thus being liable to fail in application of an electrode-forming composition obtained therefrom.
- the vinylidene fluoride polymer used in the present invention may be prepared by polymerization of vinylidene fluoride or copolymerization of vinylidene fluoride with a comonomer copolymerizable therewith.
- the polymerization or copolymerization may be performed by suspension polymerization, emulsion polymerization, solution polymerization, etc. From the easiness of post treatment, it is particularly preferred to perform suspension polymerization in an aqueous medium. However, in the case of performing the polymerization at a temperature of 0 °C or below, it is particularly preferred to effect emulsion polymerization in a mixture medium of water and alcohol .
- suspension aid such as methyl cellulose, methoxylated methyl cellulose, propoxidized methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide or gelatin.
- fluorine-containing surfactant such as sodium perfluorooctanoate.
- a polymerization initiator in the suspension polymerization it is possible to use, e.g., diisopropylperoxydicarbonate, dinormal peroxydicarbonate or isobutyl peroxide, soluble in the vinylidene fluoride monomer.
- a polymerization initiator in the emulsion polymerization it is possible to use a redox catalyst system including an oxidizing agent (e.g., hydrogen peroxide, ammonium persulfate or potassium persulfate), a reducing agent (e.g., sodium sulfite), and a transition metal compound (e.g., ferrous nitrate) .
- an oxidizing agent e.g., hydrogen peroxide, ammonium persulfate or potassium persulfate
- a reducing agent e.g., sodium sulfite
- a transition metal compound e.g., ferrous nitrate
- a chain transfer agent such as ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetaldehyde, propylaldehyde, ethyl propionate, or carbon tetrachloride, so as to control the polymerization degree of the resultant copolymer.
- a chain transfer agent may be used as desired in an amount of 0.1 - 5 wt. % of the total monomer amount.
- the binder solution according to the present invention may be prepared by dissolving the above- mentioned vinylidene fluoride polymer in an organic solvent.
- the organic solvent used for this purpose may preferably be a polar one, whose examples may include: N-methyl-2-pyrrolidone, dimethylformamide, N,N-dimethylacetamide, N,N-dimethylsulfoxide, hexamethylphosphamide, dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate, and trimethyl phosphate.
- the vinylidene fluoride polymer used in the present invention has a much higher crystallinity than a conventional one and is difficult to dissolve in an ordinary organic solvent, it is further preferred to use a nitrogen-containing organic solvent having a larger dissolving power, such as N-methyl-2- pyrrolidone, dimethylformamide or N,N- dimethylacetamide among the above-mentioned organic solvents.
- a nitrogen-containing organic solvent having a larger dissolving power such as N-methyl-2- pyrrolidone, dimethylformamide or N,N- dimethylacetamide.
- the binder solution it is preferred to dissolve 0.1 - 15 wt. parts, particularly 1 - 10 wt. parts, of the above-mentioned vinylidene fluoride polymer in 100 wt. parts of such an organic solvent.
- the polymer occupies too small a proportion in the solution, thus being liable to fail in exhibiting its performance of binding the powdery electrode material.
- the solution is liable to have an abnormally high viscosity, so that not only the preparation of the electrode-forming composition becomes difficult but also the suppression of gelation of the electrode-forming composition becomes difficult, thus being liable to fail in uniform application thereof onto an electroconductive substrate, in extreme cases.
- the vinylidene fluoride polymer binder solution it is preferred to dissolve the vinylidene fluoride polymer in an organic solvent at a temperature of 20 - 200 °C, more preferably at an elevated temperature of 30 - 120 °C.
- An electrode-forming composition may be obtained by adding and dispersing a powdery electrode material (an active substance for a battery or an electric double layer capacitor, and optional additives, such as an electroconductivity-imparting additive) into the thus-obtained vinylidene fluoride polymer binder solution according to the present invention.
- a powdery electrode material an active substance for a battery or an electric double layer capacitor, and optional additives, such as an electroconductivity-imparting additive
- the active substance may comprise a composite metal chalcogenide represented by a general formula of LiM_2, wherein M denotes at least one species of transition metals such as Co, Ni, Fe, Mn, Cr and V; and Y denotes a chalcogen, such as O or S.
- M denotes at least one species of transition metals such as Co, Ni, Fe, Mn, Cr and V
- Y denotes a chalcogen, such as O or S.
- Preferred examples thereof may include: LiCo ⁇ 2 » LiNi0 2 , LiNi ⁇ Co 1 _ ⁇ 0 2 (0 ⁇ x ⁇ 1), and spinel- structured LiM ⁇ O ⁇
- the active substance may preferably comprise a carbonaceous material, such as graphite, activated carbon or a carbonaceous material obtained by carbonization of phenolic resin, pitch. etc.
- the carbonaceous material may preferably be used in the form of particles having an average diameter of ca. 0.5 - 100 ⁇ m.
- An electroconductivity-imparting additive may be added in order to improve the conductivity of a resultant composite electrode layer formed by applying and drying of the electrode-forming composition of the present invention, particularly in case of using an active substance, such as LiCo ⁇ 2, showing a small electron-conductivity.
- an active substance such as LiCo ⁇ 2 showing a small electron-conductivity.
- examples thereof may include: carbonaceous materials, such as carbon black, graphite fine powder and fiber, and fine powder and fiber of metals, such as nickel and aluminum. In the case of using a carbonaceous material having a large electroconductivity as an electrode material, it is unnecessary to add such an electroconductivity- imparting additive.
- the active substance for an electric double layer capacitor may preferably comprise fine particles or fiber, such as activated carbon, activated carbon fiber, silica or alumina particles, having an average particle (or fiber) diameter of 0.5 - 100 ⁇ m and a
- the electrode-forming composition according to the present invention may preferably be formed by mixing 100 wt. parts of the powdery electrode material with the binder solution containing 0.1 - 50 wt. parts, particularly 1 - 20 wt. parts of the vinylidene fluoride polymer.
- the thus-prepared electrode-forming composition may be used for forming electrode structures having partial sectional structures as shown in Figure 1 and Figure 2. More specifically, the electrode-forming composition may be applied onto both surfaces ( Figure 1) or one surface ( Figure 2) of an electroconductive substrate 11 comprising a foil or wire net of a metal, such as iron, stainless steel, steel, copper, aluminum, nickel or titanium and having a thickness of, e.g., 5 - 100 ⁇ m, or 5 - 20 ⁇ m for a small-sized device, and dried at, e.g., 50 - 170 °C to form a composite electrode layer (12a, 12b or 12) of, e.g., 10 - 1000 ⁇ m in thickness for a small-sized device, thereby providing an electrode structure (10 or 20).
- a metal such as iron, stainless steel, steel, copper, aluminum, nickel or titanium
- an electrode structure similar to the one shown in Figure 1 or Figure 2 by once forming a composite electrode layer 12 as shown in Figure 2 on an electroconductive substrate 11 or an arbitrary substrate having a better releasability by application and drying, then peeling only the composite electrode layer 12 apart from the substrate to obtain an electrode sheet, and then applying the electrode sheet onto an electroconductive substrate 11 with an electroconductive adhesive by a manufacturer of an electrochemical device, such as a battery.
- the thus-formed electrode structure 10 or 20 may preferably be used as an electrode for a battery or an electric double layer capacitor wherein it is used in the state of being dipped in a non-aqueous electrolytic solution.
- a laminate structure as shown in Figure 3 may be formed by disposing a pair of electrode structures 20 shown in Figure 2 so that their composite electrode layers 12 are disposed on inner sides and opposite to each other, disposing a liquid permeable separator 13 so as to be sandwiched between the composite electrode layers 12, and impregnating the composite electrode layers 12 and the separator 13 with a non-aqueous electrolytic solution.
- Such a laminate structure as shown in Figure 3 may constitute a battery or an electric double layer capacitor.
- the electrode structure according to the present invention preferably in the form of an electrodes structure 10 ( Figure 1) having composite electrode layers 12a and 12b on both sides, may be used as a positive electrode or a negative electrode of a non-aqueous battery, particularly a lithium ion battery .
- Figure 4 is a partially exploded perspective view of a lithium secondary battery as an embodiment of a non-aqueous battery according to the present invention, including an electrode structure prepared in the above-described manner.
- the secondary battery basically includes a laminate structure including a positive electrode 1, a negative electrode 2 and a separator 3 disposed between the positive and negative electrodes 1 and 2 and comprising a fine porous film of a polymeric material, such as polyethylene or polypropylene, impregnated with an electrolytic solution.
- the laminate structure is wound in a vortex shape to form an electricity-generating element which is housed within a metal casing 5 having a bottom constituting a negative electrode terminal 5a.
- the negative electrode 2 is electrically connected to the negative electrode terminal 5a, and the uppermost portion of the battery is constituted by disposing a gasket 6 and a safety valve 7 covered with a top plate 8 having a projection constituting a positive electrode terminal 8a electrically connected to the positive electrode. Further, the uppermost rim 5b of the casing 5 is crimped toward the inner side to form an entirely sealed cell structure enclosing the electricity- generating element.
- the positive electrode 1 and the negative electrode 2 may have a structure of the electrode structure 10 or 20 shown in Figure 1 or 2.
- the composite electrode layer (12a, 12b or 12) may be formed in the above-described manner, i.e., by forming a layer of a composite electrode material comprising a powdery electrode material (a fine powdery or fibrous active substance, and optionally added electroconductivity-imparting additive, such as carbon) and a vinylidene fluoride polymer binder, applied onto an electroconductive substrate (11) as described above.
- a powdery electrode material a fine powdery or fibrous active substance, and optionally added electroconductivity-imparting additive, such as carbon
- a vinylidene fluoride polymer binder a vinylidene fluoride polymer binder
- the non-aqueous electrolyte solution impregnating the separator 3 may comprise a solution of an electrolyte, such as a lithium salt, in a non- aqueous solvent (organic solvent).
- an electrolyte such as a lithium salt
- Examples of the electrolyte may include: LiPF 6 , LiAsF 6 , LiC10 3 , LiBF 4 , CH 3 S0 3 Li, CF 3 S0 3 Li, LiN(S0 2 CF 3 ) 2 , LiC(S0 2 CF 3 ) 3 , LiCl, and LiBr.
- Examples of the organic solvent for such an electrolyte may include: propylene carbonate, ethylene carbonate, 1,2- dimethoxyethane, 1,2-diethoxyethane, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ⁇ f-butyrolactone, methyl propionate, ethyl propionate, and mixtures of these, but they are not exhaustive.
- the non-aqueous battery according to the present invention can basically have any other shapes, such as those of a coin, a rectangular parallelepiped, or a paper or sheet.
- Example 1 the present invention will be described more specifically based on Examples and Comparative Examples.
- Example 1 the present invention will be described more specifically based on Examples and Comparative Examples.
- a vinylidene fluoride polymer (“KYNAR731", available from Penwalt Co.) was used, which exhibited an inherent viscosity of 1.0 (dl/g). Comparative Example 2 A vinylidene fluoride polymer ("FORAFLON
- the abnormal linkage content of a vinylidene fluoride polymer is determined from diffraction peaks of its 1 Q 3 F-NMR spectrum. More specifically, ca. 5 mg of a vinylidene fluoride polymer sample is dissolved in a solvent mixture of 0.4 ml of dimethylformamide (DMF) and 0.1 ml of deuterium dimethylformamide (DMF-dy) as a solvent for NMR measurement, and the resultant solution is subjected to the ⁇ 1 QF-NMR measurement at room temperature.
- DMF dimethylformamide
- DMF-dy deuterium dimethylformamide
- a resultant X ⁇ F-NMR spectrum generally exhibits 5 major peaks, which appear at -91.6 ppm, -92.1 ppm, -94.7 ppm, -113.5 ppm and -115.9 ppm, respectively, with reference to CFC1 3 .
- peaks at -113.5 ppm and -115.9 ppm are identified as peaks attributable to the abnormal linkage.
- a press sheet of a vinylidene fluoride polymer sample is stamped to provide 5 mg of a sample, which is charged in an aluminum pan and subjected to differential scanning calorimetry at a temperature- raising rate of 10 °C/min by using an apparatus ("TCIOA-Type Processor", available from Mettler Instrumente A.G.).
- Tmp melting point
- a sample polymer solution in N-methyl-2- pyrrolidone at a concentration of 10 wt. % is cast onto a glass sheet and dried for 5 hours at 130 °C.
- the cast film is peeled apart from the glass sheet and then further dried at 80 °C under a reduced pressure to prepare a ca. 200 ⁇ m- hick film.
- the thus-obtained cast film in a size of 17 mm x 35 mm is dipped for 6 days at 70 °C in an electrolytic solution having the following composition, and the percentage weight increase of the dipped film was measured as a swellability. (Electrolytic solution)
- NMP N-methyl-2-pyrrolidone
- the electrode-forming composition had a weight percentage of the polymer with respect to the total weight of the polymer and the powdery carbonaceous material of 10 wt. %.
- the pasty electrode-forming composition was uniformly applied onto an aluminum foil, dried and peeled apart from the aluminum foil to be stamped into a 15 mm-dia. disk.
- the stamped composite layer was pressure-bonded onto a 17 mm-dia. stainless steel net disk by means of a press, to form a negative electrode having a ca. 130 ⁇ m-thick composite electrode layer.
- the composition was uniformly applied onto an aluminum foil and dried. Then, the dried composition layer was peeled apart from the aluminum foil and stamped into a 14 mm-dia. disk. The disk was press-bonded onto a 16 mm-dia. stainless steel mesh disk to form a positive electrode having a ca. 100 ⁇ m-thick composite electrode layer.
- the thus-formed positive electrode was used for preparation of a battery (cell) in combination with the negative electrode prepared in the above- described manner.
- An electrolytic solution was prepared by adding LiPFg (electrolyte) at a rate of 1 mol/1 in a 1:1 (by volume) mixture solvent of ethylene carbonate and diethyl carbonate.
- a 25 ⁇ m-thick separator of porous polypropylene membrane was impregnated with the electrolytic solution and sandwiched between the positive electrode and the negative electrode to form a coin-shaped non-aqueous lithium secondary battery (Cell 1).
- Example 5 A non-aqueous lithium secondary battery (Cell
- Example 6 was prepared in the same manner as in Example 4 except for using the vinylidene fluoride polymer having an abnormal linkage content of 3.7 % of Example 1.
- Example 6 was prepared in the same manner as in Example 4 except for using the vinylidene fluoride polymer having an abnormal linkage content of 3.7 % of Example 1.
- Example 3 was prepared in the same manner as in Example 4 except for using the vinylidene fluoride polymer having an abnormal linkage content of 3.9 % of Example 3.
- Example 4 was prepared in the same manner as in Example 4 except for using the vinylidene fluoride polymer having an abnormal linkage content of 4.9 % of Comparative Example 1. Comparative Example 4
- Example 5 was prepared in the same manner as in Example 4 except for using the vinylidene fluoride polymer having an abnormal linkage content of 5.1 % of Comparative Example 2. [Battery cycle performance test]
- Each battery was subjected to repetition of a charge-discharge cycle including charging at a constant current of 2.5 mA up to 4.2 volts and holding at 4.2 volts so that the total charging time did not exceed 2.5 hours (a constant current-constant voltage charging process), followed by discharging at a constant current of 2.5 mA down to 2.5 volts where the discharging was immediately interrupted (a constant current discharge process).
- the charge-discharge cycle was repeated while measuring a discharge capacity of the battery at each cycle. For each battery, a capacity retention ratio was measured for each of second and subsequent cycles by dividing the discharge capacity at these cycles with the discharge capacity at the second cycle and expressed in the unit of percentage (%) by multiplying the quotient with 100.
- the present invention provides a binder solution for providing electrodes for non-aqueous batteries and electric double layer capacitors by dissolving a vinylidene fluoride polymer having an abnormal linkage content of below 4 % in an organic solvent, whereby the stability of the electrode-forming binder against an electrolytic solution is improved, thereby providing a secondary battery or an electric double layer capacitor having an improved charge-discharge cycle performance.
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Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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DE69803684T DE69803684T2 (en) | 1997-04-28 | 1998-04-27 | BINDER SOLUTION CONTAINING POLYVINYLIDEN FLUORIDE AND COMPOSITION FOR PRODUCING ELECTRODES |
CA002288157A CA2288157A1 (en) | 1997-04-28 | 1998-04-27 | Vinylidene fluoride polymer-based binder solution and electrode-forming composition |
EP98917700A EP1016151B1 (en) | 1997-04-28 | 1998-04-27 | Vinylidene fluoride polymer-based binder solution and electrode-forming composition |
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JP9122862A JPH10302800A (en) | 1997-04-28 | 1997-04-28 | Battery binder solution, electrode mix containing the same and electrode body structure and battery using mix |
JP9/122862 | 1997-04-28 |
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WO1998049737A1 true WO1998049737A1 (en) | 1998-11-05 |
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JP (1) | JPH10302800A (en) |
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EP2196479A1 (en) * | 2007-10-11 | 2010-06-16 | Kureha Corporation | Vinylidene fluoride polymer powder and use thereof |
DE102013106021A1 (en) | 2013-06-10 | 2014-12-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting compound, in particular for producing coated metal foils, and their use for electrodes or separators in accumulators |
WO2016041808A1 (en) * | 2014-09-17 | 2016-03-24 | Solvay Specialty Polymers Italy S.P.A. | Vinylidene fluoride polymers |
CN109314276A (en) * | 2016-06-20 | 2019-02-05 | 索尔维公司 | Fluoropolymer film |
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JP2002141060A (en) * | 2000-11-02 | 2002-05-17 | Matsushita Electric Ind Co Ltd | Manufacturing method of negative electrode mixture and non-aqueous system secondary battery using the same |
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EP2196479A1 (en) * | 2007-10-11 | 2010-06-16 | Kureha Corporation | Vinylidene fluoride polymer powder and use thereof |
EP2196479A4 (en) * | 2007-10-11 | 2010-11-24 | Kureha Corp | Vinylidene fluoride polymer powder and use thereof |
US8298446B2 (en) | 2007-10-11 | 2012-10-30 | Kureha Corporation | Vinylidene fluoride based polymer powder and use thereof |
DE102013106021A1 (en) | 2013-06-10 | 2014-12-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting compound, in particular for producing coated metal foils, and their use for electrodes or separators in accumulators |
EP2819213A2 (en) | 2013-06-10 | 2014-12-31 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting material, in particular for producing coated metal films, and their use for electrodes or separators in batteries |
WO2016041808A1 (en) * | 2014-09-17 | 2016-03-24 | Solvay Specialty Polymers Italy S.P.A. | Vinylidene fluoride polymers |
CN107075021A (en) * | 2014-09-17 | 2017-08-18 | 索尔维特殊聚合物意大利有限公司 | Vinylidene fluoride polymer |
US10676549B2 (en) | 2014-09-17 | 2020-06-09 | Solvay Specialty Polymers Italy S.P.A. | Vinylidene fluoride polymers |
CN107075021B (en) * | 2014-09-17 | 2020-06-30 | 索尔维特殊聚合物意大利有限公司 | Vinylidene fluoride polymer |
CN109314276A (en) * | 2016-06-20 | 2019-02-05 | 索尔维公司 | Fluoropolymer film |
CN109314276B (en) * | 2016-06-20 | 2022-10-04 | 索尔维公司 | Fluoropolymer films |
Also Published As
Publication number | Publication date |
---|---|
DE69803684T2 (en) | 2002-10-31 |
DE69803684D1 (en) | 2002-03-14 |
EP1016151B1 (en) | 2002-01-30 |
EP1016151A1 (en) | 2000-07-05 |
CA2288157A1 (en) | 1998-11-05 |
JPH10302800A (en) | 1998-11-13 |
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