JP4807538B2 - 電気化学セル用セパレーターのための保護コーティング - Google Patents
電気化学セル用セパレーターのための保護コーティング Download PDFInfo
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- JP4807538B2 JP4807538B2 JP2000588826A JP2000588826A JP4807538B2 JP 4807538 B2 JP4807538 B2 JP 4807538B2 JP 2000588826 A JP2000588826 A JP 2000588826A JP 2000588826 A JP2000588826 A JP 2000588826A JP 4807538 B2 JP4807538 B2 JP 4807538B2
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- separator
- layer
- protective coating
- coating layer
- polymer
- Prior art date
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- Expired - Lifetime
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- 239000011253 protective coating Substances 0.000 title claims abstract description 274
- 239000010410 layer Substances 0.000 claims abstract description 630
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 226
- 229920000642 polymer Polymers 0.000 claims abstract description 194
- 239000003792 electrolyte Substances 0.000 claims abstract description 155
- 238000000034 method Methods 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims description 112
- 239000007788 liquid Substances 0.000 claims description 88
- 239000011148 porous material Substances 0.000 claims description 87
- -1 poly (p-phenylene) Polymers 0.000 claims description 80
- 239000011247 coating layer Substances 0.000 claims description 73
- 239000000463 material Substances 0.000 claims description 61
- 239000000178 monomer Substances 0.000 claims description 58
- 238000000576 coating method Methods 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 42
- 229910052744 lithium Inorganic materials 0.000 claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 33
- 150000002500 ions Chemical class 0.000 claims description 32
- 239000005518 polymer electrolyte Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 229920000098 polyolefin Polymers 0.000 claims description 20
- 229910001593 boehmite Inorganic materials 0.000 claims description 19
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 229920001940 conductive polymer Polymers 0.000 claims description 18
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- 230000008569 process Effects 0.000 claims description 16
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- 239000011244 liquid electrolyte Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 9
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 125000004386 diacrylate group Chemical group 0.000 claims description 8
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical class C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 6
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- 229920002635 polyurethane Polymers 0.000 claims description 6
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000002200 LIPON - lithium phosphorus oxynitride Substances 0.000 claims description 5
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 5
- GLVGLXXAZUYQQV-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[La+3] GLVGLXXAZUYQQV-UHFFFAOYSA-N 0.000 claims description 5
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 5
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 5
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- 150000003440 styrenes Chemical class 0.000 claims description 5
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 4
- 229920003026 Acene Polymers 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- PMNLZQYZDPTDNF-UHFFFAOYSA-N P(=O)(=O)SP(=O)=O.[Li] Chemical compound P(=O)(=O)SP(=O)=O.[Li] PMNLZQYZDPTDNF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- H01G11/52—Separators
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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
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- 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
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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
- 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
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- H—ELECTRICITY
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- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- H—ELECTRICITY
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- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/215,029 | 1998-12-17 | ||
| US09/215,029 US6194098B1 (en) | 1998-12-17 | 1998-12-17 | Protective coating for separators for electrochemical cells |
| US09/399,967 | 1999-09-21 | ||
| US09/399,967 US6183901B1 (en) | 1998-12-17 | 1999-09-21 | Protective coating for separators for electrochemical cells |
| US09/447,901 | 1999-11-23 | ||
| US09/447,901 US6277514B1 (en) | 1998-12-17 | 1999-11-23 | Protective coating for separators for electrochemical cells |
| PCT/US1999/030214 WO2000036671A1 (en) | 1998-12-17 | 1999-12-16 | Protective coating for separators for electrochemical cells |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2002532852A JP2002532852A (ja) | 2002-10-02 |
| JP2002532852A5 JP2002532852A5 (cg-RX-API-DMAC7.html) | 2007-02-08 |
| JP4807538B2 true JP4807538B2 (ja) | 2011-11-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000588826A Expired - Lifetime JP4807538B2 (ja) | 1998-12-17 | 1999-12-16 | 電気化学セル用セパレーターのための保護コーティング |
Country Status (2)
| Country | Link |
|---|---|
| US (4) | US6194098B1 (cg-RX-API-DMAC7.html) |
| JP (1) | JP4807538B2 (cg-RX-API-DMAC7.html) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013541168A (ja) * | 2010-10-29 | 2013-11-07 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | リチウムアノードの保護層のエクスサイチュー製造 |
Families Citing this family (210)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6232010B1 (en) * | 1999-05-08 | 2001-05-15 | Lynn Tech Power Systems, Ltd. | Unitized barrier and flow control device for electrochemical reactors |
| US6355379B1 (en) * | 1999-02-03 | 2002-03-12 | Sanyo Electric Co., Ltd. | Polymer electrolyte batteries having improved electrode/electrolyte interface |
| EP1214748A2 (en) * | 1999-06-09 | 2002-06-19 | Moltech Corporation | Methods of preparing electrochemical cells |
| WO2000079618A1 (fr) * | 1999-06-22 | 2000-12-28 | Mitsubishi Denki Kabushiki Kaisha | Separateur de cellule, cellule, et procede de production dudit separateur |
| US6413284B1 (en) * | 1999-11-01 | 2002-07-02 | Polyplus Battery Company | Encapsulated lithium alloy electrodes having barrier layers |
| US6797428B1 (en) * | 1999-11-23 | 2004-09-28 | Moltech Corporation | Lithium anodes for electrochemical cells |
| US7081142B1 (en) | 1999-11-23 | 2006-07-25 | Sion Power Corporation | Methods of preparing electrochemical cells |
| US6733924B1 (en) | 1999-11-23 | 2004-05-11 | Moltech Corporation | Lithium anodes for electrochemical cells |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20010000485A1 (en) | 2001-04-26 |
| JP2002532852A (ja) | 2002-10-02 |
| US6423444B1 (en) | 2002-07-23 |
| US6183901B1 (en) | 2001-02-06 |
| US6194098B1 (en) | 2001-02-27 |
| US6410182B1 (en) | 2002-06-25 |
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