JP2008266593A - 多孔質フィルム - Google Patents
多孔質フィルム Download PDFInfo
- Publication number
- JP2008266593A JP2008266593A JP2008062268A JP2008062268A JP2008266593A JP 2008266593 A JP2008266593 A JP 2008266593A JP 2008062268 A JP2008062268 A JP 2008062268A JP 2008062268 A JP2008062268 A JP 2008062268A JP 2008266593 A JP2008266593 A JP 2008266593A
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- JP
- Japan
- Prior art keywords
- porous film
- filler
- particles
- less
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000002245 particle Substances 0.000 claims abstract description 92
- 239000000945 filler Substances 0.000 claims abstract description 65
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000012798 spherical particle Substances 0.000 claims description 5
- 230000035699 permeability Effects 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 37
- -1 cyclic olefin Chemical class 0.000 description 23
- 239000000843 powder Substances 0.000 description 22
- 229920003235 aromatic polyamide Polymers 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 239000003990 capacitor Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 16
- 239000011255 nonaqueous electrolyte Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
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- 229910052744 lithium Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
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- 239000000243 solution Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 6
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- 229910002804 graphite Inorganic materials 0.000 description 6
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- 230000005484 gravity Effects 0.000 description 6
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- 229910052759 nickel Inorganic materials 0.000 description 6
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- 238000012643 polycondensation polymerization Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 150000002892 organic cations Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001786 chalcogen compounds Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical group [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- ZYAMKYAPIQPWQR-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-3-methoxypropane Chemical compound COCC(F)(F)C(F)(F)F ZYAMKYAPIQPWQR-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- PCTQNZRJAGLDPD-UHFFFAOYSA-N 3-(difluoromethoxy)-1,1,2,2-tetrafluoropropane Chemical compound FC(F)OCC(F)(F)C(F)F PCTQNZRJAGLDPD-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017008 AsF 6 Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
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- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- FZXVVMPYCPCKGU-UHFFFAOYSA-N 4-(3-chloro-7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2Cl FZXVVMPYCPCKGU-UHFFFAOYSA-N 0.000 description 1
- GKZFQPGIDVGTLZ-UHFFFAOYSA-N 4-(trifluoromethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)C1COC(=O)O1 GKZFQPGIDVGTLZ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
【解決手段】耐熱樹脂と2種以上のフィラーとを含有してなり、該2種以上のフィラーのそれぞれにつき構成する粒子の平均粒子径を測定して得られる値のうち、1番目に大きい値をD1、2番目に大きい値をD2としたとき、D2/D1の値が0.15以下である多孔質フィルム。D1が0.1μm以上1μm以下であり、D2が0.01μm以上0.1μm未満である前記の多孔質フィルム。フィラーを構成する粒子のすべてがアルミナ粒子である前記の多孔質フィルム。
【選択図】なし
Description
<1>耐熱樹脂と2種以上のフィラーとを含有してなり、該2種以上のフィラーのそれぞれにつき構成する粒子の平均粒子径を測定して得られる値のうち、1番目に大きい値をD1、2番目に大きい値をD2としたとき、D2/D1の値が0.15以下である多孔質フィルム。
<2>厚みが1μm以上50μm以下である前記<1>記載の多孔質フィルム。
<3>全フィラーの重量を100としたとき、構成する粒子の平均粒子径がD1であるフィラーの重量および構成する粒子の平均粒子径がD2のフィラーの重量が90以上である前記<1>または<2>記載の多孔質フィルム。
<4>D1が0.1μm以上であり、D2が0.1μm未満である前記<1>〜<3>のいずれかに記載の多孔質フィルム。
<5>D1が10μm以下である前記<1>〜<4>のいずれかに記載の多孔質フィルム。
<6>D1が0.1μm以上1μm以下であり、D2が0.01μm以上0.1μm未満である前記<4>または<5>記載の多孔質フィルム。
<7>フィラーを構成する粒子のすべてがアルミナ粒子である前記<1>〜<6>のいずれかに記載の多孔質フィルム。
<8>フィラーを構成する粒子の一部または全部が略球状粒子である前記<1>〜<7>のいずれかに記載の多孔質フィルム。
<9>多孔質フィルムの総重量を100としたとき、前記フィラーの重量が20以上95以下である前記<7>または<8>記載の多孔質フィルム。
<10>耐熱樹脂が含窒素芳香族重合体である前記<1>〜<9>のいずれかに記載の多孔質フィルム。
<11>前記<1>〜<10>のいずれかに記載の多孔質フィルムからなるセパレータ。
多孔質フィルムを作製する方法としては、耐熱樹脂とフィラーとを含有する塗工液を板状またはフィルム状の基材に塗工して多孔質フィルムを形成する方法等が挙げられ、具体的には以下のような工程を含む方法が挙げられる。
(a)耐熱樹脂100重量部を含む極性有機溶媒溶液に、該耐熱樹脂100重量部に対しフィラーを1〜1500重量部分散したスラリー状塗工液を調製する。
(b)該塗工液を基材に塗工し、塗工膜を形成する。
(c)加湿、溶媒除去あるいは耐熱樹脂を溶解しない溶媒への浸漬等の手段で、前記塗工膜から耐熱樹脂を析出し、多孔質フィルムを形成させた後、必要に応じて乾燥後、必要に応じて基材から多孔質フィルムを剥離する。
正極集電体に前記の正極用電極合剤を塗布する方法としては、加圧成型による方法、溶媒などを用いて正極用電極合剤をペースト化し正極集電体上に塗布、乾燥後プレスし圧着する方法等が挙げられる。
前記の電解液が後述のエチレンカーボネートを含有しない場合において、ポリエチレンカーボネートを含有した負極用電極合剤を用いると、得られる電池のサイクル特性と大電流放電特性が向上することがあり好ましい。
また、アルカリ金属及びアルカリ土類金属の金属分がほとんど含まれていない、すなわち、該金属分の含有量100ppm以下であるような活性炭は、該金属分による分極がなく、多くの電気二重層を与えることから、電極として好適に用いられる。通常、電極として成形しやすいように、電極には、さらに結合剤、導電剤などが含有される。
(1)厚み測定
多孔質フィルムの厚みは、JIS規格(K7130−1992)に従い、測定した。
(2)ガーレー法による透気度の測定
多孔質フィルムの透気度は、JIS P8117に基づいて、株式会社安田精機製作所製のデジタルタイマー式ガーレー式デンソメータで測定した。
(3)空孔率
多孔質フィルムのサンプルを一辺の長さ10cmの正方形に切り取り、重量W(g)と厚みD(cm)を測定した。サンプルを構成する材料の重量(Wi)を計算し、Wiとサンプルを構成する材料の真比重(g/cm3)とから、次式より空孔率(体積%)を求めた。
空孔率(体積%)=100×{1−(W1/真比重1+W2/真比重2+・・+Wn/真比重n)/(10×10×D)}
(1)正極シートの作製
カルボキシメチルセルロース、ポリテトラフルオロエチレン、アセチレンブラック、正極活物質であるコバルト酸リチウム粉末および水を分散混練し、正極用電極合剤のペーストを得た。このペーストに含有される各成分の重量比としては、カルボキシメチルセルロース:ポリテトラフルオロエチレン:アセチレンブラック:コバルト酸リチウム粉末:水の重量比で0.75:4.55:2.7:92:45であった。該ペーストを正極集電体である厚さ40μmAl箔に塗布し、乾燥、ロールプレスし、正極シートを得た。
多孔質フィルムからなるセパレータと、正極シート、負極としての金属リチウムとを、正極シート、セパレータ、金属リチウムの順になるように重ねてコインセル容器内に入れ、電解液として、エチレンカーボネートとジメチルカーボネートとエチルメチルカーボネートの体積比16:10:74混合液にLiPF6を1モル/リットルとなるように溶解した電解液を含浸した後、フタをかしめてコインセルを得た。コインセルの作製は、アルゴン置換したグローブボックス内で実施した。
上記のようにして得られたコインセルを用いて、充放電試験を実施し、電池のレート特性(大電流放電特性)の評価を行った。
<レート特性評価>
充電条件としては、充電最大電圧4.3V、充電時間8時間、充電電流0.2Cの条件で行い、放電条件としては、放電最小電圧3.0V、放電電流0.2C、2Cの条件で行った。
(1)塗工液の製造
NMP4200gに塩化カルシウム272.7gを溶解した後、パラフェニレンジアミン132.9gを添加して完全に溶解させた。得られた溶液に、テレフタル酸ジクロライド(以下、TPCと略す)243.3gを徐々に添加して重合し、パラアラミドを得て、さらにNMPで希釈して、濃度2.0重量%のパラアラミド溶液(A)を得た。得られたパラアラミド溶液100gに、アルミナ粉末(a)2g(日本アエロジル社製、アルミナC、数平均粒径0.02μm(D2に相当)、粒子は略球状で、粒子のアスペクト比は1)とアルミナ粉末(b)2g(住友化学株式会社製スミコランダム、AA03、数平均粒径0.3μm(D1に相当)、粒子は略球状で、粒子のアスペクト比は1)とをフィラーとして計4g添加して混合し、ナノマイザーで3回処理し、さらに1000メッシュの金網で濾過、減圧下で脱泡して、スラリー状塗工液(B)を製造した。パラアラミドおよびアルミナ粉末の合計重量に対するアルミナ粉末(フィラー)の重量は、67重量%となる。また、D2/D1は0.07となる。
厚み100μmのPETフィルムの上に、テスター産業株式会社製バーコーターにより、該PETフィルムの上にスラリー状塗工液(B)を塗工した。PETフィルム上の塗工された塗工膜を一体にしたまま、貧溶媒である水中に浸漬させ、パラアラミド多孔質膜を析出させた後、溶媒を乾燥させた後、PETフィルムより剥離させて、多孔質フィルム1を得た。多孔質フィルム1の厚みは25μmであった。多孔質フィルム1の透気度は300秒/100cc、空孔率は60%であった。多孔質フィルム1の断面を走査型電子顕微鏡(SEM)により観察をしたところ、0.03μm〜0.06μm程度の微細孔と0.1μm〜1μm程度の微細孔を有することがわかった。
多孔質フィルム1を用いて、上記のようにして得たコインセルにつき、レート特性を評価したところ、0.2C放電時における容量に対する2C放電時における容量の比(2C/0.2C)は70%であった。
実施例1におけるフィラーを、アルミナ粉末(a)4g(日本アエロジル社製、アルミナC、平均粒子径0.02μm)のみを用いて添加した以外は、実施例1と同様にして、多孔質フィルム2を得た。多孔質フィルム2の厚みは20μmであった。多孔質フィルム2の透気度は500秒/100cc、空孔率は60%であった。多孔質フィルム2における耐熱層の表面を走査型電子顕微鏡(SEM)により観察をしたところ、0.03μm〜0.06μm程度の孔であった。
Claims (11)
- 耐熱樹脂と2種以上のフィラーとを含有してなり、該2種以上のフィラーのそれぞれにつき構成する粒子の平均粒子径を測定して得られる値のうち、1番目に大きい値をD1、2番目に大きい値をD2としたとき、D2/D1の値が0.15以下である多孔質フィルム。
- 厚みが1μm以上50μm以下である請求項1記載の多孔質フィルム。
- 全フィラーの重量を100としたとき、構成する粒子の平均粒子径がD1であるフィラーの重量および構成する粒子の平均粒子径がD2のフィラーの重量が90以上である請求項1または2記載の多孔質フィルム。
- D1が0.1μm以上であり、D2が0.1μm未満である請求項1〜3のいずれかに記載の多孔質フィルム。
- D1が10μm以下である請求項1〜4のいずれかに記載の多孔質フィルム。
- D1が0.1μm以上1μm以下であり、D2が0.01μm以上0.1μm未満である請求項4または5記載の多孔質フィルム。
- フィラーを構成する粒子のすべてがアルミナ粒子である請求項1〜6のいずれかに記載の多孔質フィルム。
- フィラーを構成する粒子の一部または全部が略球状粒子である請求項1〜7のいずれかに記載の多孔質フィルム。
- 多孔質フィルムの総重量を100としたとき、前記フィラーの重量が20以上95以下である請求項7または8記載の多孔質フィルム。
- 耐熱樹脂が含窒素芳香族重合体である請求項1〜9のいずれかに記載の多孔質フィルム。
- 請求項1〜10のいずれかに記載の多孔質フィルムからなるセパレータ。
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JP7126281B2 (ja) | 2013-04-29 | 2022-08-26 | オプトドット コーポレイション | 熱伝導率を高めたナノ多孔質複合セパレータ |
JP2021122026A (ja) * | 2013-04-29 | 2021-08-26 | オプトドット コーポレイションOptodot Corporation | 熱伝導率を高めたナノ多孔質複合セパレータ |
WO2015083790A1 (ja) | 2013-12-06 | 2015-06-11 | ダイキン工業株式会社 | 二次電池用セパレータ及び二次電池 |
KR20160071440A (ko) | 2013-12-06 | 2016-06-21 | 다이킨 고교 가부시키가이샤 | 이차 전지용 세퍼레이터 및 이차 전지 |
JP2019079807A (ja) * | 2017-10-24 | 2019-05-23 | 住友化学株式会社 | 非水電解液二次電池用多孔質層 |
JPWO2019187130A1 (ja) * | 2018-03-30 | 2021-01-07 | 株式会社東芝 | 電極群、電池、及び電池パック |
WO2019187130A1 (ja) * | 2018-03-30 | 2019-10-03 | 株式会社 東芝 | 電極群、電池、及び電池パック |
Also Published As
Publication number | Publication date |
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WO2008117840A1 (ja) | 2008-10-02 |
TW200902610A (en) | 2009-01-16 |
EP2133387A4 (en) | 2011-10-19 |
KR20100015445A (ko) | 2010-02-12 |
KR101460827B1 (ko) | 2014-11-11 |
CN101657497B (zh) | 2012-11-14 |
EP2133387A1 (en) | 2009-12-16 |
JP5309628B2 (ja) | 2013-10-09 |
US8323837B2 (en) | 2012-12-04 |
CN101657497A (zh) | 2010-02-24 |
US20100092754A1 (en) | 2010-04-15 |
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