WO2018078703A1 - セパレータ、およびセパレータを含む二次電池 - Google Patents
セパレータ、およびセパレータを含む二次電池 Download PDFInfo
- Publication number
- WO2018078703A1 WO2018078703A1 PCT/JP2016/081480 JP2016081480W WO2018078703A1 WO 2018078703 A1 WO2018078703 A1 WO 2018078703A1 JP 2016081480 W JP2016081480 W JP 2016081480W WO 2018078703 A1 WO2018078703 A1 WO 2018078703A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- separator
- layer
- secondary battery
- positive electrode
- negative electrode
- Prior art date
Links
- 229920000098 polyolefin Polymers 0.000 claims abstract description 42
- 238000012360 testing method Methods 0.000 abstract description 31
- 238000005259 measurement Methods 0.000 abstract description 14
- 230000014509 gene expression Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 128
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 26
- 239000000945 filler Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- 238000005096 rolling process Methods 0.000 description 21
- 239000007774 positive electrode material Substances 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 19
- 239000007773 negative electrode material Substances 0.000 description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920005672 polyolefin resin Polymers 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 230000010220 ion permeability Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 230000033001 locomotion Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011086 high cleaning Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- DOMLQXFMDFZAAL-UHFFFAOYSA-N 2-methoxycarbonyloxyethyl methyl carbonate Chemical compound COC(=O)OCCOC(=O)OC DOMLQXFMDFZAAL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- 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
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910017115 AlSb Inorganic materials 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- UKCBKQLNTLMFAA-UHFFFAOYSA-N F.[F] Chemical compound F.[F] UKCBKQLNTLMFAA-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910018122 Li 3-x M Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910005881 NiSi 2 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- GRQJZSJOACLQOV-UHFFFAOYSA-N [Li].[N] Chemical class [Li].[N] GRQJZSJOACLQOV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- JBDAPRHNHMFGAN-UHFFFAOYSA-N carbamic acid N,N-dimethylacetamide Chemical class NC(O)=O.CN(C)C(C)=O JBDAPRHNHMFGAN-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007586 pull-out test Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
-
- 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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/24—Organic non-macromolecular coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/706—Anisotropic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- One embodiment of the present invention relates to a separator and a secondary battery including the separator.
- one embodiment of the present invention relates to a separator that can be used in a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery including the separator.
- a typical example of a non-aqueous electrolyte secondary battery is a lithium ion secondary battery.
- Lithium ion secondary batteries have a high energy density, and are therefore widely used in electronic devices such as personal computers, mobile phones, and portable information terminals.
- the lithium ion secondary battery has a positive electrode, a negative electrode, an electrolytic solution filled between the positive electrode and the negative electrode, and a separator.
- the separator functions as a membrane that separates the positive electrode and the negative electrode and allows the electrolyte and carrier ions to pass therethrough.
- Patent Documents 1 to 5 disclose separators containing polyolefin.
- One of the objects of the present invention is to provide a separator that can be used in a secondary battery such as a non-aqueous electrolyte secondary battery, and a secondary battery including the separator.
- One embodiment of the present invention is a separator having a first layer made of porous polyolefin.
- a parameter X defined by the following formula is 0 or more and 20 or less, and the minimum height of the sphere in the falling ball test for the first layer is 50 cm or more and 150 cm or less.
- MD tan ⁇ and TD tan ⁇ are the loss tangent in the flow direction and the loss tangent in the width direction, respectively, obtained by measuring the viscoelasticity of the first layer at a temperature of 90 ° C. and a frequency of 10 Hz.
- the minimum height is the minimum height at which the first layer tears when a ball of 14.3 mm in diameter and 11.9 g in weight placed on the first layer is dropped freely with respect to the first layer. Value.
- a separator that not only has excellent slipperiness and cutting workability, but also provides a secondary battery capable of suppressing an increase in internal resistance when charging and discharging are repeated.
- a secondary battery including the same can be provided.
- the cross-sectional schematic diagram of the secondary battery of one Embodiment of this invention, and a separator The figure which shows the jig
- the expressions “substantially only contain A” or “consisting of A” refer to states that do not contain substances other than A, states that contain A and impurities, and measurement errors. This includes a state in which a substance other than A is misidentified. When this expression indicates a state containing A and impurities, there is no limitation on the type and concentration of impurities.
- the secondary battery 100 includes a positive electrode 110, a negative electrode 120, and a separator 130 that separates the positive electrode 110 and the negative electrode 120.
- the secondary battery 100 has an electrolytic solution 140.
- the electrolyte solution 140 is present mainly in the gaps between the positive electrode 110, the negative electrode 120, and the separator 130 and in the gaps between the members.
- the positive electrode 110 may include a positive electrode current collector 112 and a positive electrode active material layer 114.
- the negative electrode 120 can include a negative electrode current collector 122 and a negative electrode active material layer 124.
- the secondary battery 100 further includes a housing, and the positive electrode 110, the negative electrode 120, the separator 130, and the electrolytic solution 140 are held by the housing.
- the separator 130 is a film that is provided between the positive electrode 110 and the negative electrode 120, separates the positive electrode 110 and the negative electrode 120, and carries the movement of the electrolyte solution 140 within the secondary battery 100.
- FIG. 1B is a schematic cross-sectional view of the separator 130.
- the separator 130 has the 1st layer 132 containing porous polyolefin, and can further have the porous layer 134 as arbitrary structures. As shown in FIG. 1B, the separator 130 may have a structure in which two porous layers 134 sandwich the first layer 132. However, the separator 130 is porous only on one surface of the first layer 132.
- the layer 134 may be provided, or the porous layer 134 may not be provided.
- the first layer 132 may have a single-layer structure or may include a plurality of layers.
- the first layer 132 has pores connected to the inside. Due to this structure, the electrolyte solution 140 can pass through the first layer 132, and carrier ions such as lithium ions can move through the electrolyte solution 140. At the same time, physical contact between the positive electrode 110 and the negative electrode 120 is prohibited. On the other hand, when the secondary battery 100 reaches a high temperature, the first layer 132 melts and becomes nonporous, thereby stopping the movement of carrier ions. This operation is called shutdown. By this operation, heat generation and ignition due to a short circuit between the positive electrode 110 and the negative electrode 120 are prevented, and high safety can be ensured.
- the first layer 132 includes porous polyolefin.
- the first layer 132 may be made of porous polyolefin. That is, the first layer 132 may be configured to include only porous polyolefin or substantially only porous polyolefin.
- the porous polyolefin can contain an additive.
- the first layer 132 may be composed of only a polyolefin and an additive, or substantially only a polyolefin and an additive.
- the porous polyolefin contains an additive, the polyolefin can be contained in the porous polyolefin with a composition of 95% by weight or more, or 97% by weight or more.
- the polyolefin may be included in the first layer 132 with a composition of 95% by weight or more, or 97% by weight or more.
- the additive include an organic compound (organic additive), and the organic compound may be an antioxidant (organic antioxidant) or a lubricant.
- Examples of the polyolefin constituting the porous polyolefin include homopolymers obtained by polymerizing ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, and copolymers thereof. be able to.
- the first layer 132 may contain a mixture of these homopolymers or copolymers, or may contain a mixture of homopolymers or copolymers having different molecular weights. That is, the molecular weight distribution of polyolefin may have a plurality of peaks.
- the organic additive can have a function of preventing oxidation of the polyolefin.
- phenols and phosphates can be used as the organic additive.
- Phenols having a bulky substituent such as a t-butyl group at the ⁇ -position and / or ⁇ -position of the phenolic hydroxyl group may be used.
- Typical examples of the polyolefin include a polyethylene polymer.
- a polyethylene polymer either low density polyethylene or high density polyethylene may be used.
- a copolymer of ethylene and ⁇ -olefin may be used.
- These polymers or copolymers may be a high molecular weight body having a weight average molecular weight of 100,000 or more, or an ultrahigh molecular weight body having a weight average molecular weight of 1,000,000 or more.
- the shutdown function can be expressed at a lower temperature, and high safety can be imparted to the secondary battery 100.
- the thickness of the first layer 132 can be 4 ⁇ m or more and 40 ⁇ m or less, 5 ⁇ m or more and 30 ⁇ m or less, or 6 ⁇ m or more and 15 ⁇ m or less.
- the basis weight of the first layer 132 may be appropriately determined in consideration of strength, film thickness, weight, and handleability. For example, 4 g / m 2 or more and 20 g / m 2 or less, 4 g / m 2 or more and 12 g / m 2 or less, or 5 g / m 2 or more so that the weight energy density and volume energy density of the secondary battery 100 can be increased. It can be 10 g / m 2 or less.
- the basis weight is the weight per unit area.
- the air permeability of the first layer 132 can be selected from the range of 30 s / 100 mL to 500 s / 100 mL, or 50 s / 100 mL to 300 s / 100 mL in terms of Gurley value. Thereby, sufficient ion permeability can be obtained.
- the porosity of the first layer 132 is in the range of 20% by volume to 80% by volume, or 30% by volume to 75% by volume so that the retention amount of the electrolytic solution 140 can be increased and the shutdown function can be expressed more reliably. You can choose from. Further, the pore diameter (average pore diameter) of the first layer 132 is 0.1 ⁇ m or more and 0.3 ⁇ m or less, or 0.1 ⁇ m or more and 0 so that sufficient ion permeability and a high shutdown function can be obtained. .. Can be selected from a range of 14 ⁇ m or less.
- the parameter X defined by the following formula is 0 or more and 20 or less, or 2 or more and 20 or less, and the minimum height of the sphere in the falling ball test is 50 cm or more and 150 cm or less.
- MD tan ⁇ and TD tan ⁇ are a loss tangent and a width direction (TD: TD) in the flow direction (MD: Machine Direction, also called the machine direction) obtained by measuring the viscoelasticity of the first layer at a temperature of 90 ° C. and a frequency of 10 Hz, respectively.
- Transverse Direction also called the transverse direction
- the anisotropy of tan ⁇ in the in-plane direction of the material is smaller, the deformation follow-up property of the material with respect to a change in external force becomes isotropic, and the material can be uniformly deformed in the surface direction.
- the electrodes (positive electrode 110 and negative electrode 120) expand and contract during charging and discharging, so pressure and shearing force in the surface direction is applied to the separator.
- the separator is also uniformly deformed. Therefore, the anisotropy of stress generated in the first layer 132 with the periodic deformation of the electrode in the charge / discharge cycle is also reduced. This makes it difficult for the positive electrode active material layer 114 and the negative electrode active material layer 124 to drop off, thereby suppressing an increase in internal resistance of the secondary battery and improving cycle characteristics.
- the dynamic viscoelasticity measurement at a frequency of 10 Hz and a temperature of 90 ° C. is performed at 20 to 60 ° C. which is a temperature at which the secondary battery is normally operated.
- the frequency when the temperature range is set as a reference is much lower than 10 Hz, and is close to the time scale of the expansion and contraction motion of the electrode accompanying the charge / discharge cycle of the secondary battery. Therefore, rheological evaluation corresponding to the time scale of the charge / discharge cycle in the operating temperature range of the secondary battery can be performed by measuring the dynamic viscoelasticity at 10 Hz and 90 ° C.
- the anisotropy of tan ⁇ is evaluated by the parameter X defined by the above formula.
- the parameter X is 0 or more and 20 or less, or 2 or more and 20 or less, the internal resistance of the secondary battery in the charge / discharge cycle is increased. Can be suppressed.
- the separator 130 is cut into a predetermined size. If tearing occurs in an unintended direction during cutting, the yield of the secondary battery is reduced. Further, when a wound type secondary battery is manufactured using the separator 130, the separator 130 and the electrode (the positive electrode 110 and the negative electrode 120) are wound around a cylindrical member (hereinafter, referred to as a pin), and then the pin is removed. At this time, if the friction between the separator 130 and the pin is large, the pin cannot be easily pulled out, and the separator 130, the electrode, or the pin is destroyed. As a result, the manufacturing process is adversely affected and the yield of the secondary battery is reduced. To do.
- the separator 130 can be selectively cut only in the intended direction by configuring the first layer 132 so that the minimum height of the ball in the falling ball test is 50 cm or more and 150 cm or less. And it was found that the friction with the pin can be reduced.
- the falling ball test is an evaluation test performed as follows.
- a sphere having a diameter of 14.3 mm, a weight of 11.9 g, and a mirror surface is freely dropped from the height h onto the first layer 132.
- the height h is the distance between the first layer 132 and the sphere immediately before starting free fall.
- the minimum value of the height h at which the first layer 132 is torn is the minimum height of the sphere.
- the first layer 132 is obtained by a rolling process as will be described later.
- a hard and brittle skin layer is formed on the surface during the rolling process.
- a difference in orientation occurs in the rolling direction.
- Rolling only to TD strengthens the orientation of TD
- rolling only to MD strengthens the orientation of MD.
- the ratio of the skin layer and the MD-TD orientation balance are related to the tearing of the first layer 132. That is, the greater the proportion of the fragile skin layer, the weaker the impact and the easier it is to tear in an unintended direction.
- the ratio of the skin layer and the orientation balance of MD and TD affect the cutting processability and frictional force of the first layer 132.
- the minimum height of the ball in the falling ball test the smaller the skin layer ratio and the smaller the orientation difference between MD and TD. And it turned out that generation
- the minimum height is necessary to increase the thickness of the first layer 132 or lower the porosity. However, increasing the thickness decreases the energy density of the secondary battery, and decreasing the porosity decreases the battery characteristics. For this reason, the minimum height is preferably 150 cm or less.
- the puncture strength of the first layer 132 is preferably 3N to 10N, or 3N to 8N. This can prevent the separator 130 including the first layer 132 from being destroyed when external pressure is applied to the secondary battery in the assembly process, and prevent the positive and negative electrodes from being short-circuited. Can do.
- the positive electrode 110 may include the positive electrode current collector 112 and the positive electrode active material layer 114.
- the negative electrode 120 can include a negative electrode current collector 122 and a negative electrode active material layer 124 (see FIG. 1A).
- the positive electrode current collector 112 and the negative electrode current collector 122 have a function of holding the positive electrode active material layer 114 and the negative electrode active material layer 124 and supplying current to the positive electrode active material layer 114 and the negative electrode active material layer 124, respectively.
- the positive electrode current collector 112 and the negative electrode current collector 122 for example, a metal such as nickel, stainless steel, copper, titanium, tantalum, zinc, iron, cobalt, or an alloy containing these metals such as stainless steel can be used. .
- the positive electrode current collector 112 and the negative electrode current collector 122 may have a structure in which a plurality of films containing these metals are stacked.
- the positive electrode active material layer 114 and the negative electrode active material layer 124 each include a positive electrode active material and a negative electrode active material.
- the positive electrode active material and the negative electrode active material are materials responsible for the release and absorption of carrier ions such as lithium ions.
- the positive electrode active material examples include materials that can be doped / undoped with carrier ions.
- a lithium composite oxide containing at least one transition metal such as vanadium, manganese, iron, cobalt, or nickel can be given.
- such composite oxides include lithium composite oxides having an ⁇ -NaFeO 2 type structure such as lithium nickelate and lithium cobaltate, and lithium composite oxides having a spinel type structure such as lithium manganese spinel. These composite oxides have a high average discharge potential.
- the lithium composite oxide may contain other metal elements, for example, titanium, zirconium, cerium, yttrium, vanadium, chromium, manganese, iron, cobalt, copper, silver, magnesium, aluminum, gallium, indium, tin, etc.
- composite lithium nickelate containing aluminum or manganese and having nickel of 85 mol% or more, or 90 mol% or more can be used as the positive electrode active material.
- a material that can be doped / undoped with carrier ions can be used as the negative electrode active material.
- lithium metal or a lithium alloy can be used.
- carbonaceous materials such as graphite such as natural graphite and artificial graphite, coke, carbon black, and burned polymer compound such as carbon fiber; oxide that performs doping and dedoping of lithium ions at a lower potential than the positive electrode, Chalcogen compounds such as sulfides; elements such as aluminum, lead, tin, bismuth and silicon that are alloyed or combined with alkali metals; cubic intermetallic compounds (AlSb, Mg that can insert alkali metals between lattices) 2 Si, NiSi 2); lithium nitrogen compounds (Li 3-x M x N (M: transition metal)) and the like can be used.
- carbonaceous materials mainly composed of graphite such as natural graphite and artificial graphite have high potential flatness and low average discharge potential, and therefore give a large energy density when combined with the positive electrode 110.
- carbonaceous materials mainly composed of graphite such as natural graphite and artificial graphite have high potential flatness and low average discharge potential, and therefore give a large energy density when combined with the positive electrode 110.
- a mixture of graphite and silicon having a silicon to carbon ratio of 5 mol% or more or 10 mol% or more can be used as the negative electrode active material.
- the positive electrode active material layer 114 and the negative electrode active material layer 124 may each include a conductive additive, a binder, and the like in addition to the positive electrode active material and the negative electrode active material.
- Examples of conductive aids include carbonaceous materials. Specific examples include graphite such as natural graphite and artificial graphite, coke, carbon black, pyrolytic carbon, and fired organic polymer compound such as carbon fiber. A plurality of the above materials may be mixed and used as a conductive aid.
- PVDF polyvinylidene fluoride
- vinylidene fluoride-hexafluoropropylene copolymer tetrafluoroethylene-hexafluoropropylene copolymer
- tetrafluoroethylene-perfluoroalkyl vinyl ether Copolymer ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc.
- copolymers using vinylidene fluoride as one of the monomers thermoplastic polyimide
- thermoplastic resins such as polyethylene and polypropylene, acrylic resins, and styrene-butadiene rubber. Note that the binder also has a function as a thickener.
- the positive electrode 110 can be formed, for example, by applying a mixture of a positive electrode active material, a conductive additive, and a binder onto the positive electrode current collector 112. In this case, a solvent may be used to create or apply the mixture. Alternatively, the positive electrode 110 may be formed by pressurizing and molding a mixture of the positive electrode active material, the conductive additive, and the binder, and placing the mixture on the positive electrode 110.
- the negative electrode 120 can also be formed by a similar method.
- the electrolytic solution 140 includes a solvent and an electrolyte, and at least a part of the electrolyte is dissolved in the solvent and ionized.
- the solvent water or an organic solvent can be used.
- an organic solvent is used.
- Organic solvents include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane Ethers such as tetrahydrofuran, 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N, N-dimethylformamide and N, N-dimethylacetamide Carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 1,3-propane sultone; and fluorine is introduced into the organic solvent. Such as fluorine-containing organic solvent and the like. A mixed solvent of these organic solvents may be used
- a typical electrolyte includes a lithium salt.
- a lithium salt For example, LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Li 2 B 10 Cl 10 , carbon number 2 To 6 carboxylic acid lithium salts, LiAlCl 4 and the like. Only one type of lithium salt may be used, or two or more types may be combined.
- the electrolyte sometimes refers to a solution in which the electrolyte is dissolved in a broad sense, but the narrow meaning is adopted in the present specification and claims. That is, the electrolyte is a solid, is ionized by being dissolved in a solvent, and is treated as giving ion conductivity to the resulting solution.
- a negative electrode 120, a separator 130, and a positive electrode 110 are arranged to form a stacked body.
- the laminate is installed in a housing (not shown), and the housing is filled with the electrolyte, and the housing is sealed while reducing the pressure, or the housing is sealed and then the housing is filled with the electrolyte and then sealed.
- the secondary battery 100 can be manufactured.
- the shape of the secondary battery 100 is not particularly limited, and may be a thin plate (paper) type, a disk type, a cylindrical type, a rectangular column type such as a rectangular parallelepiped, or the like.
- One of the methods for forming the first layer 132 is (1) a step of kneading an ultrahigh molecular weight polyethylene, a low molecular weight hydrocarbon, and a pore forming agent to obtain a polyolefin composition, and (2) rolling the polyolefin composition.
- the step of rolling a roll to form a sheet (rolling step), (3) the step of removing the hole forming agent from the sheet obtained in step (2), and (4) the sheet obtained in step (3).
- the process includes drawing and forming into a film.
- Low molecular weight hydrocarbons include low molecular weight polyolefins such as polyolefin waxes and low molecular weight polymethylenes such as Fischer-Tropsch waxes.
- the weight average molecular weight of the low molecular weight polyolefin or the low molecular weight polymethylene is, for example, 200 or more and 3000 or less. Thereby, the volatility of the low molecular weight hydrocarbon can be suppressed, and it can be uniformly mixed with the ultrahigh molecular weight polyolefin.
- polymethylene is also defined as a kind of polyolefin.
- ultra high molecular weight polyolefin and low molecular weight polyolefin may be mixed with a mixer (first stage mixing), and a pore-forming agent may be added to this mixture and mixed again (second stage mixing).
- first stage mixing an organic compound such as an antioxidant may be added.
- second stage mixing an organic compound such as an antioxidant may be added.
- polyolefin, a pore formation agent, and low molecular weight polyolefin are mixed uniformly.
- Uniform mixing in particular, uniform mixing of ultra-high molecular weight polyolefin and low molecular weight polyolefin can be confirmed by increasing the bulk density of the mixture. Uniform crystallization proceeds with uniform mixing. As a result, the crystal distribution becomes uniform and the anisotropy of Tan ⁇ can be reduced. It is preferable that there is an interval of 1 minute or more after the first stage mixing until the pore-forming agent is added.
- Examples of the pore forming agent used in step (1) include organic fillers and inorganic fillers.
- organic filler for example, a plasticizer may be used, and examples of the plasticizer include low molecular weight hydrocarbons such as liquid paraffin.
- inorganic fillers include inorganic materials that are soluble in neutral, acidic, or alkaline solvents, and examples include calcium carbonate, magnesium carbonate, and barium carbonate.
- inorganic compounds such as calcium chloride, sodium chloride, and magnesium sulfate can be used. Only one type of pore-forming agent may be used, or two or more types may be used in combination.
- a typical pore-forming agent is calcium carbonate.
- water or a solution obtained by adding an acid or a base to an organic solvent can be used as the cleaning liquid.
- a surfactant may be added to the cleaning liquid.
- the addition amount of the surfactant can be arbitrarily selected in the range of 0.1 wt% to 15 wt%, or 0.1 wt% to 10 wt%. By selecting the addition amount from this range, it is possible to ensure high cleaning efficiency and prevent the surfactant from remaining.
- the washing temperature may be selected from a temperature range of 25 ° C. to 60 ° C., 30 ° C. to 55 ° C., or 35 ° C. to 50 ° C. Thereby, high cleaning efficiency can be obtained and evaporation of the cleaning liquid can be suppressed.
- the pore-forming agent may be removed using a cleaning solution, and then further washing with water may be performed.
- the temperature at the time of washing with water can be selected from a temperature range of 25 ° C. to 60 ° C., 30 ° C. to 55 ° C., or 35 ° C. to 50 ° C.
- the stretched first layer 132 may be annealed (heat-set).
- a region where orientation crystallization is caused by stretching and an amorphous region are mixed.
- Annealing treatment causes reconstruction (clustering) of amorphous parts, and eliminates mechanical inhomogeneities in the microscopic region.
- the annealing temperature is (Tm ⁇ 30 ° C.) or more and less than Tm, (Tm ⁇ 20 ° C.) or more and less than Tm, where Tm is the melting point of the ultrahigh molecular weight polyolefin, or ( Tm-10 ° C.) or more and less than Tm.
- the porous layer 134 can be provided on one side or both sides of the first layer 132 (see FIG. 1B). When the porous layer 134 is stacked on one surface of the first layer 132, the porous layer 134 may be provided on the positive electrode 110 side or the negative electrode 120 side of the first layer 132.
- the porous layer 134 is preferably insoluble in the electrolytic solution 140 and contains an electrochemically stable material in the usage range of the secondary battery 100.
- materials include polyolefins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer; fluorine-containing polymers such as polyvinylidene fluoride and polytetrafluoroethylene; vinylidene fluoride-hexafluoropropylene copolymer, fluoride Fluorine-containing polymers such as vinylidene-hexafluoropropylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer; aromatic polyamide (aramid); styrene-butadiene copolymer and its hydride, methacrylate ester copolymer Rubbers such as polymers, acrylonitrile-acrylic acid ester copolymers, styrene-acrylic acid ester copolymers,
- Aromatic polyamides include, for example, poly (paraphenylene terephthalamide), poly (metaphenylene isophthalamide), poly (parabenzamide), poly (metabenzamide), poly (4,4′-benzanilide terephthalamide), poly (Paraphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (metaphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide), poly (metaphenylene) -2,6-naphthalenedicarboxylic acid amide), poly (2-chloroparaphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer, metaphenylene terephthalamide / 2,6-dichloroparaphth Such as two-terephthalamide copolymer.
- the porous layer 134 may contain a filler.
- the filler include fillers made of organic or inorganic substances, and fillers made of inorganic substances called fillers are suitable, and silica, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, zeolite, aluminum hydroxide More preferred is a filler made of an inorganic oxide such as boehmite, more preferred is at least one filler selected from the group consisting of silica, magnesium oxide, titanium oxide, aluminum hydroxide, boehmite and alumina, and particularly preferred is alumina.
- Alumina has many crystal forms such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina, and any of them can be suitably used. Among these, ⁇ -alumina is most preferred because of its particularly high thermal stability and chemical stability. Only one type of filler may be used for the porous layer 134, or two or more types of fillers may be used in combination.
- the shape of the filler is not limited, and the filler can take a spherical shape, a cylindrical shape, an elliptical shape, a bowl shape, or the like. Alternatively, a filler in which these shapes are mixed may be used.
- the filler content can be 1% by volume or more and 99% by volume or less, or 5% by volume or more and 95% by volume or less of the porous layer 134.
- the thickness of the porous layer 134 can be selected in the range of 0.5 ⁇ m to 15 ⁇ m, or 2 ⁇ m to 10 ⁇ m. Therefore, when the porous layer 134 is formed on both surfaces of the first layer 132, the total film thickness of the porous layer 134 can be selected from a range of 1.0 ⁇ m to 30 ⁇ m, or 4 ⁇ m to 20 ⁇ m.
- the total film thickness of the porous layer 134 By setting the total film thickness of the porous layer 134 to 1.0 ⁇ m or more, an internal short circuit due to damage of the secondary battery 100 can be more effectively suppressed.
- the total film thickness of the porous layer 134 30 ⁇ m or less, it is possible to prevent an increase in the transmission resistance of carrier ions, and a deterioration of the positive electrode 110 due to an increase in the transmission resistance of carrier ions and a decrease in battery characteristics and cycle characteristics. Can be suppressed. Furthermore, an increase in the distance between the positive electrode 110 and the negative electrode 120 can be avoided, and the secondary battery 100 can be reduced in size.
- the basis weight of the porous layer 134 can be selected from a range of 1 g / m 2 to 20 g / m 2 , or 2 g / m 2 to 10 g / m 2 . Thereby, the weight energy density and volume energy density of the secondary battery 100 can be made high.
- the porosity of the porous layer 134 can be 20% to 90% by volume, or 30% to 80% by volume. Thereby, the porous layer 134 can have sufficient ion permeability.
- the average pore diameter of the pores of the porous layer 134 can be selected from the range of 0.01 ⁇ m or more and 1 ⁇ m or less, or 0.01 ⁇ m or more and 0.5 ⁇ m or less, whereby sufficient ions for the secondary battery 100 can be obtained. Transparency can be imparted and the shutdown function can be improved.
- the air permeability of the separator 130 including the first layer 132 and the porous layer 134 described above can be a Gurley value of 30 s / 100 mL to 1000 s / 100 mL, or 50 s / 100 mL to 800 s / 100 mL.
- the separator 130 can ensure sufficient strength and shape stability at high temperature, and at the same time have sufficient ion permeability.
- a coating solution In the case of forming the porous layer 134 containing a filler, the above-described polymer or resin is dissolved or dispersed in a solvent, and then the filler is dispersed in the mixed solution (hereinafter referred to as a coating solution).
- Create Solvents include water; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and t-butyl alcohol; acetone, toluene, xylene, hexane, N-methylpyrrolidone, N, N-dimethylacetamide, N, And N-dimethylformamide. Only one type of solvent may be used, or two or more types of solvents may be used.
- a mechanical stirring method for example, a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, a media dispersion method, or the like may be applied.
- the filler after the filler is dispersed in the mixed solution, the filler may be wet pulverized using a wet pulverizer.
- additives such as a dispersing agent, a plasticizer, surfactant, and a pH adjuster
- the coating solution is applied onto the first layer 132.
- the coating liquid is directly applied to the first layer 132 by using a dip coating method, a spin coating method, a printing method, a spray method, or the like, and then the porous layer 134 is formed by removing the solvent. 132 can be formed.
- the coating liquid may not be directly formed on the first layer 132 but may be transferred onto the first layer 132 after being formed on another support.
- a resin film, a metal belt, a drum, or the like can be used as the support.
- any of natural drying, air drying, heat drying, and vacuum drying may be used.
- the solvent may be replaced with another solvent (for example, a low boiling point solvent) before drying.
- heating it can be carried out at 10 ° C. or higher and 120 ° C. or lower, or 20 ° C. or higher and 80 ° C. or lower. Thereby, it can avoid that the pore of the 1st layer 132 shrinks and air permeability falls.
- the thickness of the porous layer 134 can be controlled by the thickness of the coating film in a wet state after coating, the filler content, the concentration of polymer or resin, and the like.
- Example 1 68% by weight of ultra high molecular weight polyethylene powder (GUR2024, manufactured by Ticona), 32% by weight of polyethylene wax (FNP-0115, manufactured by Nippon Seiki Co., Ltd.) having a weight average molecular weight of 1000, and the total of the ultra high molecular weight polyethylene and polyethylene wax.
- antioxidant Irg1010, manufactured by Ciba Specialty Chemicals
- P168 manufactured by Ciba Specialty Chemicals
- the sheet was cooled stepwise while being pulled by a take-up roll (draw ratio (winding roll speed / rolling roll speed) 1.4 times) to prepare a sheet having a film thickness of about 64 ⁇ m.
- This sheet was immersed in hydrochloric acid (4 mol / L) containing 0.5% by weight of a nonionic surfactant to remove calcium carbonate, and then stretched in the transverse direction 6.2 times at 100 ° C.
- the separator 130 was obtained by annealing at 126 ° C. (melting point 134 ° C.-8 ° C. of the polyolefin resin composition).
- Example 2> Using ultra-high molecular weight polyethylene powder, 71.5% by weight of Ticona GUR4032, 28.5% by weight of polyethylene wax, three rolling rolls R1, R2 and R3 having a surface temperature of 150 ° C. The same method as in Example 1 except that a sheet having a thickness of about 70 ⁇ m was prepared, the sheet was stretched 7.0 times, and annealed at 123 ° C. (melting point 133 ° C.-10 ° C. of the polyolefin resin composition). Thus, a separator 130 was obtained.
- Example 3 Rolling using a pair of rolling rolls having a surface temperature of 150 ° C., a point using 70% by weight of ultrahigh molecular weight polyethylene powder, a point using 30% by weight of polyethylene wax, a point using calcium carbonate at 37% by volume, Cooling stepwise while pulling with a roll with a different speed ratio (draw ratio (winding roll speed / rolling roll speed) 1.4 times), creating a sheet with a film thickness of about 41 ⁇ m, stretching to 6.2 times A separator 130 was obtained in the same manner as in Example 2 except that the heat setting treatment was performed at 120 ° C. (melting point 133 ° C.-13 ° C. of the polyolefin resin composition).
- Ultra high molecular weight polyethylene powder (GUR4032, manufactured by Ticona) is 70% by weight, polyethylene wax having a weight average molecular weight of 1000 (FNP-0115, manufactured by Nippon Seiki Co., Ltd.), 30% by weight, and the total of the ultra high molecular weight polyethylene and polyethylene wax is As 100 parts by weight, antioxidant (Irg1010, manufactured by Ciba Specialty Chemicals) 0.4% by weight, (P168, manufactured by Ciba Specialty Chemicals) 0.1% by weight, sodium stearate 1.3% by weight Furthermore, calcium carbonate (manufactured by Maruo Calcium Co., Ltd.) having an average pore diameter of 0.1 ⁇ m was added at the same time so as to be 36% by volume with respect to the total volume, and mixed for 150 seconds at a rotation speed of 440 rpm using a Henschel mixer.
- antioxidant Irg1010, manufactured by Ciba Specialty Chemicals
- P168 manufactured by Ciba Specialty Chemicals
- the light bulk density of the powder was about 350 g / L.
- the mixture thus obtained is rolled using a pair of rolling rolls having a surface temperature of 150 ° C., and cooled stepwise while being pulled by a winding roll with a different speed ratio (draw ratio (winding roll speed / rolling roll A sheet having a speed of 1.4 times and a film thickness of about 29 ⁇ m was prepared.
- This sheet was immersed in hydrochloric acid (4 mol / L) containing 0.5% by weight of a nonionic surfactant to remove calcium carbonate, and then stretched in the transverse direction 6.2 times at 100 ° C.
- the first layer 132 was obtained by annealing at 115 ° C. (melting point of polyolefin resin composition 133 ° C.-12 ° C.).
- Comparative Example 2 As the separator of Comparative Example 2, a commercially available polyolefin porous film (polyolefin separator) was used.
- Positive electrode> A commercially available positive electrode manufactured by applying a laminate of LiNi 0.5 Mn 0.3 Co 0.2 O 2 / conductive material / PVDF (weight ratio 92/5/3) to an aluminum foil was processed.
- LiNi 0.5 Mn 0.3 Co 0.2 O 2 is an active material layer.
- the aluminum foil is cut out so that the size of the positive electrode active material layer is 45 mm ⁇ 30 mm and the outer periphery thereof has a width of 13 mm and no positive electrode active material layer is formed. Used as a positive electrode in the process.
- the thickness of the positive electrode active material layer was 58 ⁇ m, the density was 2.50 g / cm 3 , and the positive electrode capacity was 174 mAh / g.
- Negative electrode> A commercial negative electrode manufactured by applying graphite / styrene-1,3-butadiene copolymer / sodium carboxymethylcellulose (weight ratio 98/1/1) to a copper foil was processed.
- graphite functions as a negative electrode active material layer.
- the copper foil is cut out so that the size of the negative electrode active material layer is 50 mm ⁇ 35 mm, the width is 13 mm, and the negative electrode active material layer is not formed, and the assembly described below is performed. Used as a negative electrode in the process.
- the thickness of the negative electrode active material layer was 49 ⁇ m, the density was 1.40 g / cm 3 , and the negative electrode capacity was 372 mAh / g.
- the positive electrode, the separator, and the negative electrode were laminated in this order to obtain a laminate.
- the positive electrode and the negative electrode were arranged so that the entire upper surface of the positive electrode active material layer overlapped with the main surface of the negative electrode active material layer.
- the laminated body was arrange
- electrolytic solution a mixed solution in which LiPF 6 having a concentration of 1.0 mol / L was dissolved in a mixed solvent having a volume ratio of ethyl methyl carbonate, diethyl carbonate, and ethylene carbonate of 50:20:30 was used.
- the secondary battery was produced by heat-sealing a housing
- the design capacity of the secondary battery was 20.5 mAh.
- the film thickness was measured using a high-precision digital length measuring machine manufactured by Mitutoyo Corporation.
- the specific gravity is the specific gravity of the ultra high molecular weight polyethylene powder.
- Dynamic viscoelasticity measurement> The dynamic viscoelasticity of the separator was measured under the conditions of a measurement frequency of 10 Hz and a measurement temperature of 90 ° C. using a dynamic viscoelasticity measuring device itk DVA-225 manufactured by ITK Corporation.
- a tension of 30 cN was applied to a test piece obtained by cutting the separators of Examples 1 to 3 and Comparative Examples 1 and 2 in a strip shape having a width of 5 mm with the flow direction as a longitudinal direction and a distance between chucks of 20 mm.
- the tan ⁇ (MD tan ⁇ ) in the flow direction was measured.
- a test piece cut in a strip shape having a width of 5 mm from the separator in a longitudinal direction was given a tension of 30 cN with a distance between chucks of 20 mm, and tan ⁇ (TD tan ⁇ ) in the longitudinal direction was measured.
- the measurement was performed while increasing the temperature from room temperature at a rate of 20 ° C./min, and the parameter X was calculated using the value of tan ⁇ when the temperature reached 90 ° C.
- FIG. 2A is a top view of the frame 200 on which the separator 130 is placed.
- FIGS. 2B and 2C show a state in which the separator 130 and the SUS plate 204 are installed on the frame 200, respectively. They are a top view and a side view.
- the frame 200 has a 47 mm ⁇ 35 mm hole 202 and has a rectangular shape of 85 mm ⁇ 65 mm.
- a separator 130 cut to a size of 85 mm ⁇ 65 mm was placed on the frame 200 (FIG. 2C). At this time, the separator 130 was placed so that the MD of the separator 130 was parallel to the long side of the hole 202.
- an SUS plate 204 having the same shape as the frame 200 is placed on the separator 130, and the frame 200 and the SUS are placed near the center of each side.
- the plate 204 was fixed with a clamp (non-twist clamp) 206.
- the separator 130 is sandwiched between the frame 200 and the SUS plate 204.
- the height of the sphere to be freely dropped in the first falling ball test that is, the distance between the separator 130 and the sphere immediately before the sphere was freely dropped was h1.
- the height h2 of the ball in the second falling ball test is set to (h1-5 cm), and when the separator 130 is not broken, the second time
- the height h2 of the sphere in the falling ball test was set to (h1 + 5 cm). In this way, the falling ball test was repeated while changing the height of the sphere.
- the separator 130 when the separator 130 is confirmed to be broken as a result of evaluation at the distance hk between the separator 130 and the sphere in the k-th (k is an integer equal to or greater than 1) falling ball test, the height of the sphere in the (k + 1) th falling ball test.
- the height hk + 1 of the sphere in the (k + 1) th falling ball test was set to (hk + 5 cm). Repeat the falling ball test until the number of falling ball tests with confirmed destruction and the number of falling ball tests with no confirmed destruction reached 5 or more. Was the minimum height.
- Cutting workability> 3A and 3B show a method for evaluating cutting workability.
- one side of the long side of the separator 130 cut into MD 10 cm and TD 5 cm was fixed with a tape 210.
- the cutter knife 212 is moved in parallel with TD at a speed of about 8 cm / s while being held at an angle of 80 ° with respect to the horizontal direction, and the separator 130 is cut by 3 cm, The cutting state was confirmed (see dotted arrow in the figure). Evaluation was made with a case where tearing in the unintended direction (MD) was confirmed at the cut site as-, and a case where tearing was not confirmed as +.
- MD unintended direction
- a product number A300 manufactured by NT Cutter was used, and as a cutter table, a product number Mar 44N manufactured by KOKUYO was used.
- the blade was exchanged for each test, and a product number BA-160 manufactured by NT Cutter was used as a replacement blade.
- the separator 130 was cut into a strip of TD 62 mm ⁇ MD 30 cm, and with one end of the MD attached with a 300 g weight, the other end was wound around a stainless ruler (Shinwa Co., Ltd., product number 13131) five times. .
- the stainless ruler has a bending knob at one end in the longitudinal direction, and the separator 130 is wound so that the TD of the separator and the longitudinal direction of the stainless ruler are parallel to each other. Thereafter, the stainless ruler was pulled out to the side where the bending knob was formed at a speed of about 8 cm / s, and the sensitivity (extraction sensitivity) of the ease of removal was evaluated.
- “+” indicates a case where the resistance is smoothly pulled out without feeling resistance
- “ ⁇ ” indicates a case where a slight resistance is felt
- “ ⁇ ” indicates a case where the resistance is felt and it is difficult to pull out.
- the width of TD of the separator 130 at the portion wound five times before and after the stainless ruler was pulled out was measured with a caliper, and the amount of change (mm) was calculated.
- This amount of change is the amount of elongation in the pulling direction when the separator starts to move in the pulling direction of the stainless ruler due to the friction between the stainless ruler and the separator 130 and the separator is deformed in a spiral shape.
- FIGS. 4A and 4B are diagrams showing a sled member 220 for measuring pin pull-out resistance, showing the magnitude of friction between the surface of the separator 130 and other members.
- FIGS. 4A and 4B are a bottom view and a side view of the sled member, respectively.
- the sled member 220 has two protrusions 222 having a tip of 3 mm in curvature on the bottom surface.
- the protrusions 222 are arranged to be parallel to each other with an interval of 28 mm.
- the separator 130 was cut into TD 6 cm and MD 5 cm, and the separator 130 was attached to the ridge 222 with tape so that the TD of the separator 130 and the direction of the ridge 222 coincided.
- the sled member 220 having the separator 130 attached to the lower surface was placed on a plate (silverstone (registered trademark) processed plate) 224 processed with a fluororesin.
- a weight 226 was installed on the sled member 220.
- the total weight of the weight 226 and the sled member 220 was 1800 g.
- the separator 130 was disposed between the sled member 220 and the plate 224.
- Silverstone processing was carried out by Hakusui Sangyo Co., Ltd. on a plate of high-speed tool steel SKH51.
- the thickness of the processed silver stone was 20 to 30 ⁇ m, and the surface roughness Ra measured with a handy surf was 0.8 ⁇ m.
- the voltage range 4.2 ⁇ 2.7V at 55 ° C., the charge current value 1C, a constant current of the discharge current value 10C as one cycle, and 100 cycles of charge and discharge cycles A test was conducted. Thereafter, using an LCR meter (manufactured by Hioki Denki, chemical impedance meter: type 3532-80), a voltage was applied to the secondary battery with an amplitude of 10 mV at a room temperature of 25 ° C., and the AC impedance of the secondary battery was measured.
- LCR meter manufactured by Hioki Denki, chemical impedance meter: type 3532-80
- Table 1 summarizes the characteristics of the separators of Examples 1 to 3, Comparative Examples 1 and 2, and secondary batteries manufactured using these separators.
- the lightly loaded bulk density of the polyolefin resin composition as the raw material of Examples 1 to 3 is as large as 500 g / L. This is because ultra-high molecular weight polyethylene powder, polyethylene wax, and antioxidant were mixed uniformly, then calcium carbonate was added and mixed again, so ultra-high molecular weight polyethylene and calcium carbonate, low molecular weight polyolefin, antioxidant This is probably because the agent was mixed uniformly.
- Comparative Example 1 the lightly loaded bulk density of the polyolefin resin composition is as small as 350 g / L, suggesting that uniform mixing has not been achieved.
- the separator 130 of Examples 1 to 3 has a parameter X of 20 or less and a minimum height of the falling ball test of 50 cm or more and 150 cm or less.
- the parameter X is 20 or more and the minimum height is as low as 40 cm or less.
- the ratio of the skin layer is smaller than those of Comparative Examples 1 and 2 because the film thickness of the first layer 132 during rolling is large.
- the cutting processability and the removal sensitivity were good, and the amount of change in the width before and after drawing was as small as 0.04 mm or less.
- the separator 130 of Examples 1 to 3 has a smaller skin layer ratio than the separators 130 of Comparative Examples 1 and 2, and the MD and TD orientation balance is in an appropriate range. It is done. Further, in Comparative Examples 1 and 2, it was confirmed that the pin pull-out resistance exceeded 0.1.
- the pin pull-out resistance correlates with the frictional force of the separator 130 and indicates the ease of pin pull-out when assembling a wound type secondary battery. For this reason, by reducing the pin pull-out resistance, the slipping property with respect to the pin is improved, which contributes to the reduction of the manufacturing tact time of the secondary battery.
- 100 secondary battery, 110: positive electrode, 112: positive electrode current collector, 114: positive electrode active material layer, 120: negative electrode, 122: negative electrode current collector, 124: negative electrode active material layer, 130: separator, 132: first , 134: porous layer, 140: electrolyte, 200: frame, 202: hole, 204: plate, 206: clamp, 210: tape, 212: cutter knife, 220: sled member, 222: protrusion, 224 : Board, 228: Pulley
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明の実施形態の一つである二次電池100の断面模式図を図1(A)に示す。二次電池100は、正極110、負極120、正極110と負極120を分離するセパレータ130を有する。図示していないが、二次電池100は電解液140を有する。電解液140は主に正極110、負極120、セパレータ130の空隙や各部材間の隙間に存在する。正極110は正極集電体112と正極活物質層114を含むことができる。同様に、負極120は負極集電体122と負極活物質層124を含むことができる。図1(A)では図示していないが、二次電池100はさらに筐体を有し、筐体によって正極110、負極120、セパレータ130、および電解液140が保持される。
<1-1.構成>
セパレータ130は、正極110と負極120の間に設けられ、正極110と負極120を分離するとともに、二次電池100内で電解液140の移動を担うフィルムである。図1(B)にセパレータ130の断面模式図を示す。セパレータ130は多孔質ポリオレフィンを含む第1の層132を有し、さらに任意の構成として、多孔質層134を有することができる。セパレータ130は、図1(B)に示すように、2つの多孔質層134が第1の層132を挟持する構造を有することもできるが、第1の層132の一方の面のみに多孔質層134を設けてもよく、あるいは多孔質層134を設けない構成とすることもできる。第1の層132は単層の構造を有していてもよく、複数の層から構成されていてもよい。
第1の層132は、以下の式で定義されるパラメータXが0以上20以下、あるいは2以上20以下であり、かつ、落球試験における球の最低高さが50cm以上150cm以下である。ここで、MDtanδとTDtanδはそれぞれ、温度90℃、周波数10Hzにおける前記第1の層の粘弾性測定で得られる流れ方向(MD:Machine Direction。機械方向とも呼ばれる)の損失正接、幅方向(TD:Transverse Direction。横方向とも呼ばれる)の損失正接である。
tanδ=E”/E’
の式で示される。損失弾性率は応力に対する不可逆変形性を示しており、貯蔵弾性率は応力に対する可逆変形性を示している。そのため、tanδは、外部からの力の変化に対する物質の変形の追随性を示している。そして、物質の面内方向におけるtanδの異方性が小さいほど、外部からの力の変化に対する物質の変形追随性が等方的となり、面方向に均等に変形することができる。
上述したように、正極110は正極集電体112と正極活物質層114を含むことができる。同様に、負極120は負極集電体122と負極活物質層124を含むことができる(図1(A)参照)。正極集電体112、負極集電体122はそれぞれ、正極活物質層114、負極活物質層124を保持し、電流を正極活物質層114、負極活物質層124へ供給する機能を有する。
電解液140は溶媒と電解質を含み、電解質のうち少なくとも一部は溶媒に溶解し、電離している。溶媒としては水や有機溶媒を用いることができる。二次電池100を非水電解液二次電池として用いる場合には、有機溶媒が用いられる。有機溶媒としては、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、1,2-ジ(メトキシカルボニルオキシ)エタンなどのカーボネート類;1,2-ジメトキシエタン、1,3-ジメトキシプロパン、テトラヒドロフラン、2-メチルテトラヒドロフランなどのエーテル類;ギ酸メチル、酢酸メチル、γ-ブチロラクトンなどのエステル類;アセトニトリル、ブチロニトリルなどのニトリル類;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミドなどのアミド類;3-メチル-2-オキサゾリドンなどのカルバメート類;スルホラン、ジメチルスルホキシド、1,3-プロパンサルトンなどの含硫黄化合物;および上記有機溶媒にフッ素が導入された含フッ素有機溶媒などが挙げられる。これらの有機溶媒の混合溶媒を用いてもよい。
図1(A)に示すように、負極120、セパレータ130、正極110を配置し、積層体を形成する。その後図示しない筐体へ積層体を設置し、筐体内を電解液で満たし、減圧しつつ筐体を密閉することにより、または筐体内を減圧しつつ共体内を電解液で満たしたのちに密閉することにより、二次電池100を作製することができる。二次電池100の形状は特に限定されず、薄板(ペーパー)型、円盤型、円筒型、直方体などの角柱型などであってもよい。
本実施形態では、第1実施形態で述べた第1の層132の作成方法について述べる。第1実施形態と同様の構成に関しては説明を割愛することがある。
本実施形態では、セパレータ130が第1の層132とともに多孔質層134を有する態様を説明する。
第1実施形態で述べたように、多孔質層134は、第1の層132の片面、または両面に設けることができる(図1(B)参照)。第1の層132の片面に多孔質層134が積層される場合には、多孔質層134は、第1の層132の正極110側に設けてもよく、負極120側に設けてもよい。
フィラーを含む多孔質層134を形成する場合、上述した高分子や樹脂を溶媒中に溶解、あるいは分散させたのち、この混合液にフィラーを分散させて分散液(以下、塗工液と記す)を作成する。溶媒としては、水;メチルアルコール、エチルアルコール、n-プロピルアルコール、イソプロピルアルコール、t-ブチルアルコールなどのアルコール;アセトン、トルエン、キシレン、ヘキサン、N-メチルピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミドなどが挙げられる。1種類の溶媒のみを用いてもよく、2種類以上の溶媒を用いてもよい。
セパレータ130の作成例を以下に述べる。以下の実施例では、作成した第1の層132をセパレータ130として用いた。
超高分子量ポリエチレン粉末(GUR2024、ティコナ社製)を68重量%、重量平均分子量1000のポリエチレンワックス(FNP-0115、日本精鑞社製)32重量%、この超高分子量ポリエチレンとポリエチレンワックスの合計を100重量部として、酸化防止剤(Irg1010、チバ・スペシャリティ・ケミカルズ社製)0.4重量%、(P168、チバ・スペシャリティ・ケミカルズ社製)0.1重量%、ステアリン酸ナトリウム1.3重量%を加え、これらを粉末のままヘンシェルミキサーを用いて、回転数440rpmで70秒混合した。次いで全体積に対して38体積%となるように平均孔径0.1μmの炭酸カルシウム(丸尾カルシウム社製)を加え、さらにヘンシェルミキサーを用いて、回転数440rpmで80秒混合した。このとき、粉体の軽装かさ密度は約500g/Lであった。得られた混合物を表面温度が150℃の3本の圧延ロールR1、R2、R3を用い、R1、R2で1回目の圧延、R2、R3で2回目の圧延を行い、速度比を変えた巻取りロールで引張りながら段階的に冷却し(ドロー比(巻取りロール速度/圧延ロール速度)1.4倍)、膜厚約64μmのシートを作成した。このシートを0.5重量%の非イオン系界面活性剤を含む塩酸(4mol/L)に浸漬させることで炭酸カルシウムを除去し、続いて100℃で6.2倍に横方向に延伸したのち、126℃(ポリオレフィン樹脂組成物の融点134℃-8℃)でアニールすることでセパレータ130を得た。
超高分子量ポリエチレン粉末としてティコナ社製GUR4032を71.5重量%用いた点、ポリエチレンワックスを28.5重量%用いた点、表面温度が150℃の3本の圧延ロールR1、R2、R3を用いて膜厚約70μmのシートを作成した点、7.0倍に延伸した点、123℃(ポリオレフィン樹脂組成物の融点133℃-10℃)でアニールした点を除き、実施例1と同様の手法によりセパレータ130を得た。
超高分子量ポリエチレン粉末を70重量%用いた点、ポリエチレンワックスを30重量%用いた点、炭酸カルシウムを37体積%で用いた点、表面温度が150℃の一対の圧延ロールを用いて圧延し、速度比を変えたロールで引張りながら段階的に冷却し(ドロー比(巻取りロール速度/圧延ロール速度)1.4倍)、膜厚約41μmのシートを作成した点、6.2倍に延伸した点、熱固定処理を120℃(ポリオレフィン樹脂組成物の融点133℃-13℃)で行った点を除き、実施例2と同様の手法によりセパレータ130を得た。
超高分子量ポリエチレン粉末(GUR4032、ティコナ社製)を70重量%、重量平均分子量1000のポリエチレンワックス(FNP-0115、日本精鑞社製)30重量%、この超高分子量ポリエチレンとポリエチレンワックスの合計を100重量部として、酸化防止剤(Irg1010、チバ・スペシャリティ・ケミカルズ社製)0.4重量%、(P168、チバ・スペシャリティ・ケミカルズ社製)0.1重量%、ステアリン酸ナトリウム1.3重量%を加え、さらに全体積に対して36体積%となるように平均孔径0.1μmの炭酸カルシウム(丸尾カルシウム社製)を同時に加え、ヘンシェルミキサーを用いて、回転数440rpmで150秒混合した。このとき、粉体の軽装かさ密度は約350g/Lであった。こうして得られた混合物を表面温度が150℃の一対の圧延ロールを用いて圧延を行い、速度比を変えた巻取りロールで引張りながら段階的に冷却し(ドロー比(巻取りロール速度/圧延ロール速度)1.4倍)、膜厚約29μmのシートを作成した。このシートを0.5重量%の非イオン系界面活性剤を含む塩酸(4mol/L)に浸漬させることで炭酸カルシウムを除去し、続いて100℃で6.2倍に横方向に延伸したのち、115℃(ポリオレフィン樹脂組成物の融点133℃-12℃)でアニールすることで第1の層132を得た。
比較例2のセパレータとして、市販品のポリオレフィン多孔質フィルム(ポリオレフィンセパレータ)を用いた。
実施例1から3、および比較例1、2のセパレータを含む二次電池の作製方法を以下に記す。
LiNi0.5Mn0.3Co0.2O2/導電材/PVDF(重量比92/5/3)の積層をアルミニウム箔に塗布することにより製造された市販の正極を加工した。ここで、LiNi0.5Mn0.3Co0.2O2は活物質層である。具体的には、正極活物質層の大きさが45mm×30mmであり、かつその外周に幅13mmで正極活物質層が形成されていない部分が残るように、アルミニウム箔を切り取り、以下に述べる組立工程において正極として用いた。正極活物質層の厚さは58μm、密度は2.50g/cm3、正極容量は174mAh/gであった。
黒鉛/スチレン-1,3-ブタジエン共重合体/カルボキシメチルセルロースナトリウム(重量比98/1/1)を銅箔に塗布することにより製造された市販の負極を加工した。ここで、黒鉛が負極活物質層として機能する。具体的には、負極活物質層の大きさが50mm×35mmであり、かつその外周に幅13mmで負極活物質層が形成されていない部分が残るように、銅箔を切り取り、以下に述べる組立工程において負極として用いた。負極活物質層の厚さは49μm、の密度は1.40g/cm3、負極容量は372mAh/gであった。
ラミネートパウチ内で、正極、セパレータ、および負極をこの順で積層し、積層体を得た。この時、正極活物質層の上面の全てが負極活物質層の主面と重なるように、正極および負極を配置した。
実施例1から3、および比較例1、2のセパレータの各種物性、およびこれらのセパレータを含む二次電池の特性の評価結果を以下に述べる。
膜厚は、株式会社ミツトヨ製の高精度デジタル測長機を用いて測定した。
第1の層132を一辺の長さ10cmの正方形に切り取り、重量W(g)を測定した。以下の式に従い、膜厚D(μm)と重量W(g)から空隙率(体積%)を算出した。
空隙率(体積%)=(1-(W/比重)/(10×10×D/10000))×100
ここで、比重は超高分子量ポリエチレン粉末の比重である。
JIS R9301-2-3に準拠して測定した。
セパレータ約50mgをアルミニウム製パンに詰め、セイコーインスツルメンツ製示差走査熱量計EXSTAR6000を用いて、昇温速度20℃/minでDSC(Differencial Scanning Calorimetry)サーモグラムを測定した。140℃付近の融解ピークの頂点をセパレータの融点Tmとして得た。
アイティーケー株式会社製動的粘弾性測定装置itk DVA-225を使用し、測定周波数10Hz、測定温度90℃の条件で、セパレータの動的粘弾性の測定を行った。
図2(A)から図2(C)に落球試験で用いる治具を示す。図2(A)は、セパレータ130が載置される枠200の上面図であり、図2(B)と図2(C)はそれぞれ、枠200上にセパレータ130とSUSプレート204を設置した状態の上面図と側面図である。枠200は47mm×35mmの穴202を有し、85mm×65mmの矩形状である。枠200の上に85mm×65mmのサイズに切り取られたセパレータ130を載置した(図2(C))。このとき、セパレータ130のMDが穴202の長辺と平行になるようにセパレータ130を載置した。次に、図2(B)、図2(C)に示されるように、枠200と同形状のSUSプレート204をセパレータ130の上に載置し、各辺の中央付近において、枠200とSUSプレート204とをクランプ(ノンツイストクランプ)206で固定した。図2(C)に示されるように、セパレータ130が枠200とSUSプレート204とで挟持される。
対物レンズ:5倍(マイケルソン型)、中間レンズ:1倍、波長フィルター:530nm、CCDカメラ:1/3インチ、測定モード:Wave、データの補正:半径 7.15mmの球面近似。
図3(A)、図3(B)に切断加工性の評価方法を示す。図3(A)に示すように、MD10cm、TD5cmに切断したセパレータ130の長辺の一辺をテープ210で固定した。そして、図3(B)に示すように、カッターナイフ212を水平方向に対して80°の角度で保持した状態で約8cm/sの速度でTDに平行に動かし、セパレータ130を3cm切断し、切断状態を確認した(図中、点線矢印参照)。切断箇所において意図しない方向(MD)への裂けが確認されたものを-、裂けが確認されなかったものを+として評価を行った。カッターナイフ212はNTカッター製の品番A300を、カッター台はコクヨ製の品番マ-44Nを用いた。刃は試験ごとに交換し、替刃としてNTカッター製の品番BA-160を使用した。
セパレータ130をTD62mm×MD30cmの短冊状に切断し、MDの一方の端部に300gの重りを付けた状態で、他方の端部をステンレス定規(シン
ワ株式会社製 品番13131)に5回巻きつけた。ステンレス定規は長手方向の一端に曲げつまみを有しており、セパレータのTDとステンレス定規の長手方向とが平行となるようにセパレータ130を巻いた。その後、ステンレス定規を約8cm/sの速度で曲げつまみが形成されている側に引き抜き、抜けやすさの感度(抜け感度)を評価した。具体的には、抵抗を感じることなくスムーズに引き抜けた場合を+、わずかな抵抗を感じた場合を±、抵抗があり、引き抜きにくい感覚があった場合を-とした。
図4(A)、図4(B)は、セパレータ130の表面と他の部材との摩擦の大きさを示す、ピン抜け抵抗を測定するためのそり部材220を示す図である。図4(A)、図4(B)はそれぞれ、そり部材の底面図、側面図である。図4(A)に示すように、そり部材220は、先端が曲率3mmの2つの突条222を底面に有している。突条222は、28mmの間隔を空けて、互いに平行になるように配置されている。
ピン抜け抵抗=F×1000/(9.80665/1800)
上述した方法で作製された二次電池の充放電サイクル前後の内部抵抗の増加量は、以下の要領で求めた。温度25℃において、電圧範囲4.1~2.7V、電流値0.2C(1時間率の放電容量による定格容量を1時間で放電する電流値を1Cとする、以下も同様)を1サイクルとする充放電を二次電池に対して4サイクル行った。こののち、LCRメーター(日置電気製、ケミカルインピーダンスメーター:形式3532-80)を用い、室温25℃において、電圧を振幅10mVで二次電池に印加し、二次電池の交流インピーダンスを測定した。
R1(Ω)=Rs1-Rs2
ここで、Rs1は、主に、セパレータをLi+イオンが透過する際の抵抗(液抵抗)、正負極内の導電抵抗、および正極と電解液との界面を移動するイオンの抵抗の合計抵抗を示している。Rs2は、主に液抵抗を示している。そのため、R1は、正負極内内の導電抵抗、および正負極と電解液との界面を移動するイオンの抵抗との合計を示す。
R2(Ω)=Rs3-Rs4
充放電サイクル前後の内部抵抗の増加量[Ω]=R2-R1
実施例1から3、比較例1、2のセパレータ、およびこれらのセパレータを用いて作製された二次電池の特性を表1にまとめる。表1に示されるように、実施例1から3の原料となるポリオレフィン樹脂組成物の軽装かさ密度は500g/Lと大きい。これは、超高分子量ポリエチレン粉末、ポリエチレンワックス、および酸化防止剤を均一に混合した後に、炭酸カルシウムを添加して再度混合を行ったために、超高分子量ポリエチレンや炭酸カルシウム、低分子量ポリオレフィン、酸化防止剤が均一に混合されたためと考えられる。これに対し比較例1では、ポリオレフィン樹脂組成物の軽装かさ密度が350g/Lと小さく、均一な混合が達成されていないことが示唆される。均一に混合されたポリオレフィン樹脂組成物を用いて成形されたシートを延伸した後アニールすることで、ポリエチレンの結晶がミクロレベルで等方的に発達するものと考えられる。そのため、実施例1から3のセパレータでは、tanδの異方性を示すパラメータXが20以下と小さくなっていることがわかる。なお、比較例2は市販品であるため、ポリオレフィン樹脂組成物の軽装かさ密度は不明である。
Claims (7)
- 前記パラメータXが2以上20以下である、請求項1に記載のセパレータ。
- 前記セパレータの厚さが4μm以上20μm以下である、請求項1に記載のセパレータ。
- 前記セパレータの空隙率が20%以上55%以下である、請求項1に記載のセパレータ。
- 前記第1の層上に多孔質層をさらに含む、請求項1に記載のセパレータ。
- 前記第1の層を挟持する一対の多孔質層をさらに含む、請求項1に記載のセパレータ。
- 請求項1に記載の前記セパレータを有する二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/344,104 US20200067139A1 (en) | 2016-10-24 | 2016-10-24 | Separator and secondary battery including the separator |
JP2018546954A JP6588171B2 (ja) | 2016-10-24 | 2016-10-24 | セパレータ、およびセパレータを含む二次電池 |
KR1020197013296A KR20190062539A (ko) | 2016-10-24 | 2016-10-24 | 세퍼레이터 및 세퍼레이터를 포함하는 이차 전지 |
PCT/JP2016/081480 WO2018078703A1 (ja) | 2016-10-24 | 2016-10-24 | セパレータ、およびセパレータを含む二次電池 |
CN201680090377.8A CN109906525B (zh) | 2016-10-24 | 2016-10-24 | 间隔件和包含间隔件的二次电池 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2016/081480 WO2018078703A1 (ja) | 2016-10-24 | 2016-10-24 | セパレータ、およびセパレータを含む二次電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018078703A1 true WO2018078703A1 (ja) | 2018-05-03 |
Family
ID=62024475
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/081480 WO2018078703A1 (ja) | 2016-10-24 | 2016-10-24 | セパレータ、およびセパレータを含む二次電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20200067139A1 (ja) |
JP (1) | JP6588171B2 (ja) |
KR (1) | KR20190062539A (ja) |
CN (1) | CN109906525B (ja) |
WO (1) | WO2018078703A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111199935A (zh) * | 2018-11-20 | 2020-05-26 | 奥特斯奥地利科技与系统技术有限公司 | 电子封装件和生产电子封装件的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10298325A (ja) * | 1997-04-23 | 1998-11-10 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2012227066A (ja) * | 2011-04-21 | 2012-11-15 | Sony Corp | セパレータおよび非水電解質電池、ならびに電池パック、電子機器、電動車両、蓄電装置および電力システム |
JP6025957B1 (ja) * | 2015-11-30 | 2016-11-16 | 住友化学株式会社 | 非水電解液二次電池用セパレータ、非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材、非水電解液二次電池および非水電解液二次電池用セパレータの製造方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2543697B1 (en) * | 2010-03-02 | 2017-01-04 | Mitsubishi Plastics, Inc. | Method of producing a porous polypropylene resin film, cell separator, and cell |
JP4868556B2 (ja) | 2010-04-23 | 2012-02-01 | 日立マクセルエナジー株式会社 | リチウム二次電池 |
JP5835211B2 (ja) * | 2011-01-20 | 2015-12-24 | 東レ株式会社 | 多孔質積層フィルム、蓄電デバイス用セパレータ、および蓄電デバイス |
JP5767202B2 (ja) | 2012-12-18 | 2015-08-19 | 旭化成ケミカルズ株式会社 | エチレン重合体並びに延伸成形体、微多孔膜、及び電池用セパレータ |
JP2014182875A (ja) | 2013-03-18 | 2014-09-29 | Toray Ind Inc | 二次電池用セパレータおよび二次電池 |
JP2015065153A (ja) * | 2013-08-30 | 2015-04-09 | 三菱製紙株式会社 | 電気化学素子用セパレータ、電気化学素子用セパレータの製造方法及び電気化学素子 |
JP5840743B2 (ja) * | 2013-09-05 | 2016-01-06 | 旭化成ケミカルズ株式会社 | ポリエチレン樹脂組成物、微多孔性フィルム及びその製造方法、並びに、電池用セパレーター |
TWI501452B (zh) * | 2014-07-03 | 2015-09-21 | Benq Materials Corp | 耐熱多孔隔離膜及其製造方法 |
-
2016
- 2016-10-24 KR KR1020197013296A patent/KR20190062539A/ko not_active IP Right Cessation
- 2016-10-24 CN CN201680090377.8A patent/CN109906525B/zh active Active
- 2016-10-24 US US16/344,104 patent/US20200067139A1/en not_active Abandoned
- 2016-10-24 JP JP2018546954A patent/JP6588171B2/ja active Active
- 2016-10-24 WO PCT/JP2016/081480 patent/WO2018078703A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10298325A (ja) * | 1997-04-23 | 1998-11-10 | Tonen Chem Corp | ポリオレフィン微多孔膜及びその製造方法 |
JP2012227066A (ja) * | 2011-04-21 | 2012-11-15 | Sony Corp | セパレータおよび非水電解質電池、ならびに電池パック、電子機器、電動車両、蓄電装置および電力システム |
JP6025957B1 (ja) * | 2015-11-30 | 2016-11-16 | 住友化学株式会社 | 非水電解液二次電池用セパレータ、非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材、非水電解液二次電池および非水電解液二次電池用セパレータの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN109906525B (zh) | 2020-05-01 |
US20200067139A1 (en) | 2020-02-27 |
JP6588171B2 (ja) | 2019-10-09 |
JPWO2018078703A1 (ja) | 2019-06-27 |
CN109906525A (zh) | 2019-06-18 |
KR20190062539A (ko) | 2019-06-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6580798B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6025957B1 (ja) | 非水電解液二次電池用セパレータ、非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材、非水電解液二次電池および非水電解液二次電池用セパレータの製造方法 | |
KR101745283B1 (ko) | 비수 전해액 이차 전지용 세퍼레이터, 비수 전해액 이차 전지용 적층 세퍼레이터, 비수 전해액 이차 전지용 부재 및 비수 전해액 이차 전지 | |
US20170155114A1 (en) | Nonaqueous electrolyte secondary battery separator | |
JP2017103209A (ja) | 非水電解液二次電池用セパレータ、非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材、非水電解液二次電池および非水電解液二次電池用セパレータの製造方法 | |
JP6605753B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6595725B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6588171B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
WO2018078710A1 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6647418B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6569013B2 (ja) | セパレータ、およびセパレータを含む二次電池 | |
WO2018078702A1 (ja) | セパレータ、およびセパレータを含む二次電池 | |
JP6634364B2 (ja) | 非水電解液二次電池用セパレータ、非水電解液二次電池用積層セパレータ、非水電解液二次電池用部材および非水電解液二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16920283 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018546954 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197013296 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16920283 Country of ref document: EP Kind code of ref document: A1 |