CN116706436A - Separator, method for producing separator, secondary battery, and electric device - Google Patents
Separator, method for producing separator, secondary battery, and electric device Download PDFInfo
- Publication number
- CN116706436A CN116706436A CN202310974157.3A CN202310974157A CN116706436A CN 116706436 A CN116706436 A CN 116706436A CN 202310974157 A CN202310974157 A CN 202310974157A CN 116706436 A CN116706436 A CN 116706436A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- modified polyester
- separator
- fibers
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920001225 polyester resin Polymers 0.000 claims abstract description 116
- 239000004645 polyester resin Substances 0.000 claims abstract description 116
- 238000000576 coating method Methods 0.000 claims abstract description 94
- 239000011248 coating agent Substances 0.000 claims abstract description 93
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 238000004132 cross linking Methods 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 58
- 229910052710 silicon Inorganic materials 0.000 claims description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 53
- 239000010703 silicon Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 49
- 239000000835 fiber Substances 0.000 claims description 43
- -1 aliphatic isocyanate Chemical class 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000000945 filler Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 229920002748 Basalt fiber Polymers 0.000 claims description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 11
- 229920006231 aramid fiber Polymers 0.000 claims description 11
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004760 aramid Substances 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 6
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 6
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
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- 239000012528 membrane Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
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- 239000002562 thickening agent Substances 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
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- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000004308 accommodation Effects 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
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- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
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- 238000003475 lamination Methods 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
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- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000289517 Colletotrichum lini Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910012619 LiNi0.5Co0.25Mn0.25O2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015717 LiNi0.85Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 description 1
- KAEZJNCYNQVWRB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)F)(=O)F.[Li+].[Li+] KAEZJNCYNQVWRB-UHFFFAOYSA-K 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 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 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BVWQQMASDVGFGI-UHFFFAOYSA-N ethene propyl hydrogen carbonate Chemical compound C(CC)OC(O)=O.C=C BVWQQMASDVGFGI-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 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
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
Abstract
The application provides a separation film, a preparation method thereof, a secondary battery and an electric device. The isolating film comprises a diaphragm substrate and a heat-resistant coating arranged on at least one side surface of the diaphragm substrate, wherein the heat-resistant coating comprises a polymer obtained by crosslinking an organosilicon modified polyester resin and a crosslinking curing agent, and the organosilicon modified polyester resin comprises a structural unit shown in a formula I. The isolating film has good high temperature resistance and can improve the safety performance of the battery.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a separation film, a preparation method thereof, a secondary battery and an electric device.
Background
In recent years, as the application range of secondary batteries is becoming wider, secondary batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power and solar power stations, and in various fields such as electric tools, electric bicycles, electric motorcycles and electric automobiles.
As secondary batteries have been greatly developed, higher demands are also being made on their safety performance. Batteries excellent in safety performance have high requirements for separator films. For example, a battery separator having excellent safety performance should have good high temperature resistance, so that thermal runaway can be prevented from occurring when the battery is short-circuited or the temperature inside the battery cell is increased due to other abnormalities, and high safety performance of the battery is ensured.
Therefore, the search for a separator film having more excellent high temperature resistance is one of the important directions of those skilled in the art.
Disclosure of Invention
The present application has been made in view of the above problems, and an object thereof is to provide a separator having excellent high temperature resistance.
In order to achieve the above object, a first aspect of the present application provides a separator comprising a separator substrate and a heat-resistant coating layer provided on at least one side surface of the separator substrate, the heat-resistant coating layer comprising a polymer obtained by crosslinking a silicone-modified polyester resin and a crosslinking curing agent, the silicone-modified polyester resin comprising a structural unit represented by formula I;
a formula I;
wherein R is 1 、R 2 At least one of which is selected from the group consisting of groups reactive with the crosslinking curing agentA bolus;
R 3 selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms;
R 4 selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms;
n is a natural number greater than 0, and m is a natural number greater than 0.
According to the isolating film disclosed by the application, the heat-resistant coating is arranged on the diaphragm substrate, the heat-resistant coating comprises the polymer, and the polymer is obtained by crosslinking the organosilicon modified polyester resin and the crosslinking curing agent, wherein the organosilicon modified polyester resin comprises the structural unit shown in the formula I, so that the isolating film has good high temperature resistance, and the safety performance of a battery can be improved.
In any embodiment, R in the structural unit represented by formula I 1 、R 2 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an aromatic group, a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and R 1 、R 2 At least one of which is selected from a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms. Thus, R in the structural unit 1 、R 2 Can well carry out cross-linking curing reaction with a cross-linking curing agent, and improves the high temperature resistance of the isolating film.
In any embodiment, the silicone-modified polyester resin has a weight average molecular weight of 5000 to 20000.
In any embodiment, the cross-linking curing agent comprises at least one of an aliphatic isocyanate or an open aromatic isocyanate.
In any embodiment, the crosslinking curing agent comprises at least one of hexamethylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 6-toluene diisocyanate, 1, 5-naphthalene diisocyanate, or terephthal-ene diisocyanate.
In any embodiment, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin is (0.05 to 0.3): 1. therefore, the polymer has proper curing degree, and the heat-resistant coating formed after curing has better toughness and strength.
In any embodiment, the mass fraction of silicon element in the organic silicon modified polyester resin is 0.01% -0.52%. Therefore, the heat-resistant coating has better flexibility and better temperature resistance, so that the isolating film has better flexibility and high temperature resistance.
In any embodiment, the heat-resistant coating further comprises a filler, wherein the filler comprises at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles. Thus, the fibrous filler not only can disperse the cracking of the heat-resistant coating caused by the stress shrinkage generated by the curing reaction; the deformation such as heat shrinkage, wrinkling and the like generated when the coating is cured of the isolating film can be improved, and the risk of thermal runaway of the battery is reduced; the puncture strength of the isolating membrane can also be obviously improved. The silicon dioxide particles can be used as a thickener of coating slurry, so that the sedimentation problem of the slurry can be improved; the silicon dioxide can also react with lithium dendrites generated in the battery cycle process, so that the risk of internal short circuit caused by lithium precipitation of the battery can be reduced. The alumina particles can further improve the mechanical strength of the barrier film.
In any embodiment, the alumina fibers, the alkali-free glass fibers, the basalt fibers, the silicon carbide fibers, the silicon nitride fibers, the aramid fibers or the potassium titanate whiskers have an average length of 0.007 mm to 1 mm, and further an average length of 0.05 mm to 0.3 mm; the average diameter is 0.4 μm to 1 μm.
In any embodiment, the silica particles have an average particle diameter Dv50 of 7 nm to 40 nm.
In any embodiment, the silica particles have a specific surface area of 120 m 2 /g~150 m 2 /g。
In any embodiment, the thickness of the heat-resistant coating is 1 μm to 3 μm. Thus, the high temperature resistance of the isolation film can be further improved.
In any embodiment, the porosity of the isolating film is 35% -45%. Therefore, lithium ions can better pass through the isolating membrane, and the dynamics of the battery is improved.
A second aspect of the present application provides a method for producing the release film of the first aspect of the present application, comprising the steps of:
providing a separator substrate;
mixing a solvent, an organosilicon modified polyester resin, a crosslinking curing agent and an initiator to obtain slurry;
setting the slurry on at least one side surface of the diaphragm matrix, and curing to obtain a separation film;
Wherein the organosilicon modified polyester resin comprises a structural unit shown in a formula I;
a formula I;
wherein R is 1 、R 2 At least one of which is selected from the group consisting of groups reactive with the crosslinking curing agent;
R 3 selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms;
R 4 selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms;
n is a natural number greater than 0, and m is a natural number greater than 0.
The preparation method of the application adopts the organic silicon modified polyester resin comprising the structural unit shown in the formula I to react with the crosslinking curing agent to form the heat-resistant coating, so that the isolating film has better high temperature resistance, thereby improving the safety performance of the battery.
In any embodiment, the slurry further comprises a pore-forming agent, wherein the pore-forming agent comprises an ester organic compound.
In any embodiment, the ester-based organic compound includes at least one of ethyl formate, butyl formate, ethyl acetate, vinyl acetate, methacrylate, methyl acrylate, dimethyl carbonate, or hydroxyethyl methacrylate. Thus, by adding the pore-forming agent into the slurry, the boiling point of the pore-forming agent is close to the curing temperature of the heat-resistant coating, the uniformity of the pores of the heat-resistant coating can be improved, and the surface smoothness of the heat-resistant coating can be improved.
In any embodiment, the slurry further comprises a filler, wherein the filler comprises at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles. Based on the total mass of the slurry, the total mass percentage content of the alumina fiber, the alkali-free glass fiber, the basalt fiber, the silicon carbide fiber, the silicon nitride fiber, the aramid fiber and the potassium titanate whisker is 1% -10%; the mass percentage of the silicon dioxide particles is 1% -5%; the mass percentage of the alumina particles is 10% -30%.
In any embodiment, the temperature of the heating and curing is 60-80 ℃. In the temperature range, the organosilicon modified polyester resin can be fully cured, so that the polymerization degree of the polymer is improved, and the high temperature resistance of the heat-resistant coating is improved.
In any embodiment, the initiator comprises dibenzoyl peroxide; based on the total mass of the slurry, the mass fraction of the initiator is 0.05% -0.3%. In this way, dibenzoyl peroxide can be used as an initiator and can oxidize the diaphragm substrate, so that the surface of the diaphragm substrate is hydroxylated, the compatibility between the diaphragm substrate and the heat-resistant coating is increased, the combination between the heat-resistant coating cured in situ and the diaphragm substrate is firmer, and the heat shrinkage resistance of the isolating film can be improved.
A third aspect of the application provides a secondary battery comprising the separator of the first aspect of the application, or comprising the separator produced by the production method of the second aspect of the application.
A fourth aspect of the application provides an electric device comprising the secondary battery of the third aspect of the application.
According to the isolating film disclosed by the application, the heat-resistant coating is arranged on the diaphragm substrate, the heat-resistant coating comprises the polymer, the polymer is obtained by crosslinking the organosilicon modified polyester resin and the crosslinking curing agent, and the organosilicon modified polyester resin comprises the specific structural unit shown in the formula I, so that the isolating film has good high temperature resistance, and the safety performance of a battery can be improved.
Drawings
For a better description and illustration of embodiments or examples provided by the present application, reference may be made to one or more of the accompanying drawings. Additional details or examples used to describe the drawings should not be construed as limiting the scope of any of the disclosed applications, the presently described embodiments or examples, and the presently understood best mode of carrying out these applications. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
FIG. 1 is a schematic view of a separator according to an embodiment of the present application;
FIG. 2 is a schematic diagram showing the composition of a coating slurry in a separator according to an embodiment of the present application;
fig. 3 is a schematic view of a battery cell according to an embodiment of the present application;
fig. 4 is an exploded view of a battery cell according to an embodiment of the present application shown in fig. 3;
fig. 5 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1. a separation film; 11. a separator base; 12. a heat-resistant coating; 13. fibrous filler; 14. silica particles; 2. a silicone modified polyester resin; 5. a battery cell; 51. a housing; 52. an electrode assembly; 53. a cover plate; 6. and (5) an electric device.
Detailed Description
Hereinafter, embodiments of the separator, the secondary battery, and the electrical device of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed throughout, and "0-5" is a shorthand representation of only a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
References to "comprising" and "including" in this disclosure mean open ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
The weight described in the specification of the embodiment of the application can be the weight unit which is well known in the chemical industry field such as mu g, mg, g, kg.
At present, as secondary batteries have been greatly developed, higher requirements are also being made on the safety performance of the secondary batteries. Batteries excellent in safety performance have high requirements for separator films. For example, a battery separator having excellent safety performance should have good high temperature resistance so that the battery cells do not thermally run away when a short circuit or other abnormal increase in the internal temperature of the battery occurs. Therefore, the search for a separator film having better high temperature resistance is one of the important directions of those skilled in the art. In this regard, the application provides a separator which has better high temperature resistance by improving the coating on the separator substrate, thereby improving the safety performance of the corresponding battery.
Referring to fig. 1 and 2, an embodiment of the present application provides a separator 1 including a separator substrate 11 and a heat-resistant coating layer 12 provided on at least one side surface of the separator substrate 11; the heat-resistant coating 12 comprises a polymer obtained by crosslinking a silicone-modified polyester resin and a crosslinking curing agent, and the silicone-modified polyester resin 2 comprises a structural unit shown in a formula I;
a formula I;
wherein R is 1 、R 2 At least one of which is selected from the group consisting of groups reactive with the crosslinking curing agent;
R 3 selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms;
R 4 selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms;
n is a natural number greater than 0, and m is a natural number greater than 0.
The heat-resistant coating 12 of the isolating film 1 comprises a polymer, the polymer is obtained by crosslinking the organosilicon modified polyester resin 2 and the crosslinking curing agent, the organosilicon modified polyester resin 2 comprises a specific structural unit shown in the formula I, the polymer can enable the isolating film 1 to have good high temperature resistance, and when the battery is short-circuited or the temperature inside the battery is increased due to other anomalies, the isolating film 1 with good high temperature resistance can avoid thermal runaway of the battery core to a certain extent, so that the safety performance of the battery can be improved.
It is understood that the silicone-modified polyester resin 2 may be formed by joining structural units represented by the above formula I as repeating structural units; r is R 1 、R 2 At least one of which is capable of reacting with a crosslinking curing agent to link a plurality of molecules of the silicone-modified polyester resin 2 to form a polymer with an interpenetrating network structure.
The silicone-modified polyester resin 2 may be a commercially available product. In one specific example, the silicone modified polyester resin 2 may be a product of the type CPJ-3601 manufactured by Zhongshan chemical materials technology Co., ltd.
It is understood that n in the structural unit of the silicone-modified polyester resin 2 may be a natural number of 1, 2, 3, 4, 5 or the like greater than 0, or m may be a natural number of 1, 2, 3, 4, 5 or the like greater than 0.
In some of these embodiments, the silicone modified polyester treeIn the structural unit of lipid 2 represented by formula I, R 1 、R 2 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an aromatic group, a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and R 1 、R 2 At least one of which is selected from a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms. Thus, R in the above-mentioned structural unit 1 、R 2 The hydroxyl, epoxy and alkoxy in the (B) can be used as a group which is reactive with the crosslinking curing agent, so that the (B) can be well crosslinked with the crosslinking curing agent to form the required polymer.
In some of these embodiments, the silicone-modified polyester resin 2 has a weight average molecular weight of 5000 to 20000. It is understood that the weight average molecular weight of the silicone-modified polyester resin 2 may be, but is not limited to, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000.
In some of these embodiments, the crosslinking curing agent includes at least one of an aliphatic isocyanate and an open aromatic isocyanate. Specifically, the crosslinking curing agent may be at least one of HDI (hexamethylene diisocyanate), MDI (4, 4' -diphenylmethane diisocyanate), TDI (2, 6-toluene diisocyanate), NDI (1, 5-naphthalene diisocyanate), or PPDI (p-phenylene diisocyanate). The open type aromatic isocyanate means an aromatic isocyanate in which the isocyanate is not deactivated with a blocking agent; aliphatic isocyanate refers to isocyanate which does not contain benzene rings in the molecular structure and contains alkyl chains in the molecular structure, wherein the alkyl chains can be cyclic alkyl chains, straight-chain alkyl chains or branched-chain alkyl chains.
In some embodiments, the mass ratio of the crosslinking curing agent to the silicone modified polyester resin 2 is (0.05 to 0.3): 1. controlling the mass ratio of the crosslinking curing agent forming the polymer to the organosilicon modified polyester resin 2 to be (0.05-0.3): within the range of 1, the polymer formed after curing can have proper curing degree, so that the heat-resistant coating after curing has better toughness and strength.
It is understood that the mass ratio of the cross-linking curing agent forming the polymer to the silicone modified polyester resin 2 may be, but is not limited to, 0.05:1, 0.07:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2:1, 0.22:1, 0.24:1, 0.26:1, 0.28:1, 0.3:1.
In some embodiments, the mass fraction of silicon element in the organic silicon modified polyester resin 2 is 0.01% -0.52%. Thus, the heat-resistant coating 12 can have better flexibility and better temperature resistance, so that the isolating film 1 has certain flexibility and better temperature resistance. It is understood that the mass fraction of silicon element in the silicone-modified polyester resin 2 may be, but is not limited to, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.52%.
In some of these embodiments, the heat resistant coating further includes a filler comprising at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles.
In the preparation process of the isolating membrane 1, in-situ curing reaction of the coating needs to be carried out on the membrane substrate 11, and in the curing process of the coating, the membrane substrate 11 can form certain shrinkage due to stress generated by the curing reaction, so that the isolating membrane 1 is shrunk and deformed to generate wrinkles and moire patterns. In the conventional preparation process of the isolating membrane 1, the filler is extremely easy to be settled in the slurry system due to the low viscosity of the coating slurry system, so that the process difficulty is increased. According to the heat-resistant coating 12, the silicon dioxide particles 14 are used as the filler, and the silicon dioxide can be used as a thickener of coating slurry, so that the sedimentation problem of the slurry can be effectively improved; meanwhile, silicon dioxide can also react with lithium dendrites generated in the battery cycle process, so that the risk of internal short circuit caused by lithium precipitation of the battery can be effectively reduced. By using alumina particles as the inorganic filler in the heat-resistant coating layer 12, the mechanical strength of the separator 1 can be further improved and the coating cost can be reduced.
In order to solve the problems, the fibrous filler 13 is added into the heat-resistant coating 12 to enable the polymer and the diaphragm matrix 11 to be combined in a chemical or physical mode, so that on one hand, the stress shrinkage of the diaphragm matrix 11 caused by the curing reaction can be reduced, and the deformation of the isolating film 1 such as shrinkage, wrinkling and the like can be improved when the coating is cured; on the other hand, the thermal shrinkage of the isolating film 1 can be improved, and the risk of thermal runaway of the battery is reduced; on the other hand, the puncture strength of the barrier film 1 can be significantly improved.
In some of these embodiments, the fibrous filler 13 has an average length of 0.007 mm to 0.1 mm. In this way, the deformation of the separator 1 such as shrinkage and wrinkling during curing of the coating can be further improved. Further, the average length of the fibrous filler 13 may be 0.05 mm to 0.1 mm. It is understood that the average length of the fibrous filler 13 may be, but is not limited to, 0.007 mm, 0.01 mm, 0.03 mm, 0.05 mm, 0.1 mm.
In some of these embodiments, the fibrous filler 13 has an average diameter of 0.4 μm to 1 μm. In this way, the deformation of the separator 1 such as shrinkage and wrinkling during curing of the coating can be further improved. If the fiber is too large directly, the thickness of the coating layer is too thick. For example, if the fiber diameter is greater than 1 μm, the thickness of the coating is at least greater than 2 μm. It is understood that the average diameter of the fibrous filler 13 may be, but is not limited to, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm.
The filler of the heat-resistant coating layer 12 may be any one of the fibrous filler 13, the silica particles 14, and the alumina particles described above, and two or more of the fibrous filler 13, the silica particles 14, and the alumina particles may be used. In some embodiments, alumina fibers, silica particles 14, and alumina particles are employed as fillers in the heat resistant coating 12.
In some embodiments, the silica particles 14 in the heat-resistant coating 12 are fumed silica particles, and the average particle diameter Dv50 of the silica particles 14 is 7 nm to 40 nm; the specific surface area of the silica particles 14 was 120 m 2 /g~150 m 2 And/g. In this way,the sedimentation problem of the slurry can be further improved, and the risk of internal short circuit of the battery caused by lithium precipitation of the battery is further reduced.
It is understood that the average particle size Dv50 of the silica particles 14 may be, but is not limited to, 7 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, 22 nm, 24 nm, 26 nm, 28 nm, 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, 40 nm; the specific surface area of the silica particles 14 may be, but is not limited to 120 m 2 /g、122 m 2 /g、125 m 2 /g、128 m 2 /g、130 m 2 /g、132 m 2 /g、135 m 2 /g、138 m 2 /g、140 m 2 /g、142 m 2 /g、145 m 2 /g、148 m 2 /g、150 m 2 /g。
In some of these embodiments, the silica particles 14 are 1% -5% by mass based on the total mass of the heat resistant coating 12. It is understood that the mass percent of silica particles 14 in the heat resistant coating 12 can be, but is not limited to, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
In some of these embodiments, the thickness of the heat resistant coating 12 on one side of the separator substrate 11 is 1 μm to 3 μm. Thus, the isolating membrane 1 can have better high-temperature resistance and higher mechanical strength. It is understood that the thickness of the heat-resistant coating 12 on one side of the separator substrate 11 may be, but is not limited to, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm, 2.8 μm, 3 μm.
An embodiment of the present application provides a method for producing a separator 1, comprising the steps of: providing a diaphragm base 11; mixing a solvent, an organosilicon modified polyester resin 2, a crosslinking curing agent and an initiator to obtain slurry; disposing the slurry on at least one side surface of the separator substrate 11, and heat-curing to form a heat-resistant coating layer 12, thereby obtaining the separator 1; wherein the organosilicon modified polyester resin 2 comprises a structural unit shown in a formula I;
a formula I;
wherein R is 1 、R 2 Middle toAt least one group selected from groups reactive with the crosslinking curing agent; r is R 3 Selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms; r is R 4 Selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms; n is a natural number greater than 0, and m is a natural number greater than 0.
According to the application, the heat-resistant coating 12 is formed on the diaphragm substrate 11 in an in-situ crosslinking and curing mode of the organosilicon modified polyester resin 2 and the crosslinking curing agent, and the organosilicon modified polyester resin 2 is provided with the specific structural unit shown in the formula I, so that the heat-resistant coating 12 has good high temperature resistance; when the battery is short-circuited or the temperature inside the battery cell is increased due to other abnormalities, the prepared isolating film 1 can prevent the battery cell from thermal runaway to a certain extent, so that the safety performance of the battery can be improved.
In some of these embodiments, R in the structural unit of the silicone-modified polyester resin 2 represented by formula I above 1 、R 2 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an aromatic group, a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and R 1 、R 2 At least one of which is selected from a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.
In some of these embodiments, the silicone-modified polyester resin has a weight average molecular weight of 5000 to 20000. It is understood that the weight average molecular weight of the silicone modified polyester resin 2 may be, but is not limited to, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000.
In some of these embodiments, the crosslinking curing agent includes at least one of an aliphatic isocyanate or an open-type aromatic isocyanate. Specifically, the crosslinking curing agent may be at least one of HDI (hexamethylene diisocyanate), MDI (4, 4' -diphenylmethane diisocyanate), TDI (2, 6-toluene diisocyanate), NDI (1, 5-naphthalene diisocyanate), or PPDI (p-phenylene diisocyanate).
In some embodiments, the mass ratio of the crosslinking curing agent to the silicone modified polyester resin 2 is (0.05 to 0.3): 1. in some embodiments, the mass fraction of silicon element in the organic silicon modified polyester resin 2 is 0.01% -0.52%.
In some of these embodiments, the slurry further includes a filler comprising at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles.
Wherein, fibrous filler 13 is added in the slurry to combine the heat-resistant coating 12 and the diaphragm matrix 11 in a chemical or physical mode, so that the stress shrinkage of the diaphragm matrix 11 caused by curing reaction can be reduced, and the deformation of the isolating film 1 such as shrinkage, wrinkling and the like during curing of the coating can be improved; but also can improve the thermal shrinkage of the separator 1 and reduce the risk of thermal runaway of the battery; the puncture strength of the barrier film 1 can also be significantly improved.
Fumed silica particles are added into the slurry and can be used as a thickening agent to improve the sedimentation problem of the slurry. Specifically, the three-dimensional dendritic structure of fumed silica particles and the silicon hydroxyl groups on the surface can play a role in thickening and maintaining the stability of the slurry. The action mechanism of the medicine has the following two points: firstly, the three-dimensional dendritic structure of the fumed silica can lead the silica to form hydrogen bonding action to be connected together so as to form a silica network; secondly, the silicon hydroxyl groups form hydrogen bonding with molecules such as resin, curing agent and the like in the slurry. Thus forming an interpenetrating network between molecules such as silicon dioxide and resin in a slurry system, and leading the slurry to have good thickening and stabilizing effects. In addition, the fumed silica particles can also react with lithium dendrites generated in the battery circulation process, so that the risk of internal short circuit caused by battery lithium precipitation can be effectively reduced, and the use safety of the battery is improved. The addition of alumina particles to the slurry can further improve the mechanical strength of the barrier film 1 and reduce the coating cost.
In some of these embodiments, fibrous filler 13 is added to the slurry in an amount of slurry1% -10% of the total mass. Further, the fibrous filler 13 may be added in an amount of 3% to 5%. The average length of the fibrous filler 13 is 0.007 mm to 0.1mm, and further, the average length of the fibrous filler 13 may be 0.05 mm to 0.1mm. The average diameter of the fibrous filler 13 is 0.4 μm to 1 μm. The average particle diameter Dv50 of the fumed silica particles in the coating slurry is 7 nm-40 nm; the specific surface area of the fumed silica particles was 120 m 2 /g~150 m 2 /g。
In some of these embodiments, a pore former is also included in the slurry, the pore former comprising an ester organic compound. Specifically, the ester organic compound pore-forming agent comprises at least one of ethyl formate, butyl formate, ethyl acetate, vinyl acetate, methyl methacrylate, methyl acrylate, dimethyl carbonate or hydroxyethyl methacrylate.
In the traditional preparation method of the diaphragm coating, water is generally used as a foaming agent of a slurry system, the foaming pore diameter of the diaphragm coating is poor in regulation and control, the mechanical strength of the foam is low, and the diaphragm coating is easy to crack in the respiratory expansion process of the battery cell, so that the porosity of the coating is influenced.
According to the pore-forming agent, the pore-forming method of volatilizing the low-boiling-point solvent is adopted, the boiling point of the pore-forming agent is close to the curing temperature of the coating, the curing temperature of the coating is about 60-80 ℃, the pore diameter in the coating can be effectively regulated and controlled, the consistency of pores is ensured, and meanwhile, the surface flatness of the coating can be ensured.
In some of these embodiments, the slurry further includes a filler comprising at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles. Based on the total mass of the slurry, the total mass percentage of the alumina fiber, the alkali-free glass fiber, the basalt fiber, the silicon carbide fiber, the silicon nitride fiber, the aramid fiber and the potassium titanate whisker is 1% -10%; the mass percentage of the silicon dioxide particles is 1% -5%; the mass percentage of the alumina particles is 10% -30%. The mass percentage of the alumina particles in the slurry is controlled within the range of 10% -30%, so that the viscosity of the slurry is moderate, the dispersion uniformity is better, and the uniformity of the heat-resistant coating is improved.
In some of these embodiments, the solvent used in the coating slurry may be N-methylpyrrolidone (NMP). N-methyl pyrrolidone is used as a solvent of the coating slurry, has a certain pore-forming function, and can better regulate and control the pore diameter, the porosity and the pore distribution consistency of the coating by being matched with a pore-forming agent.
It will be appreciated that by adjusting the amount of solvent in the coating slurry, the solids content of the coating slurry is controlled so that the coating slurry has a suitable viscosity. In some embodiments, the viscosity of the coating slurry is maintained at 5000 CP-8000 CP-s by adjusting the amount of solvent used.
In some of these embodiments, the separator substrate 11 coated with the coating slurry is placed in a vacuum environment and cured by heating at a temperature of 60 ℃ to 80 ℃ for 2 hours to 24 hours, thereby in situ curing the separator substrate 11 to form the heat-resistant coating 12. It is understood that the temperature of the heat cure may be, but is not limited to, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃; the time of heat curing may be, but is not limited to, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22 h, 24 h.
In some of these embodiments, the initiator comprises dibenzoyl peroxide; and the mass fraction of dibenzoyl peroxide in the coating slurry is 0.05% -0.3% based on the total mass of the slurry. The dibenzoyl peroxide can be used as an initiator and oxidize the diaphragm substrate 11 by adding the dibenzoyl peroxide into the coating slurry, so that the surface of the diaphragm substrate 11 is hydroxylated, the compatibility of the diaphragm substrate 11 and the organosilicon modified polyester resin 2 is increased, the combination between the in-situ cured coating and the diaphragm substrate 11 is firmer, and the heat shrinkage resistance of the isolating film 1 can be effectively improved. It is understood that the mass fraction of dibenzoyl peroxide in the slurry may be, but is not limited to, 0.05%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.22%, 0.24%, 0.26%, 0.28%, 0.3%.
In some of these embodiments, the separator substrate 11 includes at least one of a PE (polyethylene) separator and a PP (polypropylene) separator.
An embodiment of the present application provides a secondary battery including the separator 1 described above according to the present application or including the separator 1 manufactured by the manufacturing method described above according to the present application. The secondary battery can improve the safety of the battery by adopting the separator 1 of the present application.
An embodiment of the present application also provides an electric device, which includes the secondary battery of the present application.
The secondary battery and the power consumption device according to the present application will be described below with reference to the drawings.
Unless otherwise specified, the components, material types, or contents of the mentioned batteries are applicable to both lithium ion secondary batteries and sodium ion secondary batteries.
In one embodiment of the present application, a secondary battery is provided.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
Positive electrode plate
The positive pole piece comprises a positive current collector and a positive film layer arranged on at least one surface of the positive current collector.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material on a polymeric material substrate. Wherein the metal material includes, but is not limited to, aluminum alloy, nickel alloy, titanium alloy, silver alloy, and the like. Polymeric substrates (such as polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.)
In some embodiments, the positive electrode active material may comprise a positive electrode active material for a battery as known in the art.
As an example, the positive electrode active material of the lithium ion secondary battery may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery positive electrode active material may be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g. LiNiO) 2 ) Lithium manganese oxide (e.g. LiMnO 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM) 333 ）、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM) 523 ）、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM) 211 ）、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM) 622 ）、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM) 811 ) Lithium nickel cobalt aluminum oxide (e.g. LiNi 0.85 Co 0.15 Al 0.05 O 2 ) And at least one of its modified compounds and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO 4 (also abbreviated as LFP)), composite material of lithium iron phosphate and carbon, and manganese lithium phosphate (such as LiMn) PO 4 ) At least one of a composite material of lithium manganese phosphate and carbon, and a composite material of lithium manganese phosphate and carbon.
As an example, the positive electrode active material of the sodium ion secondary battery may include at least one of the following materials: at least one of sodium transition metal oxide, polyanion compound and Prussian blue compound. However, the present application is not limited to these materials, and other conventionally known materials that can be used as a positive electrode active material of a sodium ion battery may be used.
As an alternative embodiment of the present application, the transition metal in the sodium transition metal oxide may be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce. Sodium transition metal oxides such as Na x MO 2 Wherein M is one or more of Ti, V, mn, co, ni, fe, cr and Cu, and x is more than 0 and less than or equal to 1.
As an alternative embodiment of the present application, the polyanionic compound may be a compound having sodium ion, transition metal ion and tetrahedral (YO 4 ) n- A class of compounds of anionic units. The transition metal can be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce; y can be at least one of P, S and Si; n represents (YO) 4 ) n- Is a valence state of (2).
The polyanionic compound may also be a compound having sodium ion, transition metal ion, tetrahedral (YO 4 ) n- A class of compounds of anionic units and halogen anions. The transition metal can be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce; y may be at least one of P, S and Si, and n represents (YO 4 ) n- The valence state of (2); halogen may be at least one of F, cl and Br.
The polyanionic compound may also be a compound having sodium ions, tetrahedra (YO 4 ) n- Anion unit, polyhedral unit (ZO y ) m+ And optionally a halogen anion. Y may be at least one of P, S and Si, and n represents (YO 4 ) n- The valence state of (2); z represents a transition metal, which may be MnAt least one of Fe, ni, co, cr, cu, ti, zn, V, zr and Ce, m represents (ZO y ) m+ The valence state of (2); halogen may be at least one of F, cl and Br.
Polyanionic compounds, e.g. NaFePO 4 、Na 3 V 2 (PO 4 ) 3 (sodium vanadium phosphate, NVP for short), na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )、NaM’PO 4 F (M' is one or more of V, fe, mn and Ni) and Na 3 (VO y ) 2 (PO 4 ) 2 F 3-2y At least one of (0.ltoreq.y.ltoreq.1).
Prussian blue compounds may be sodium ion, transition metal ion and cyanide ion (CN) - ) Is a compound of the formula (I). The transition metal may be at least one of Mn, fe, ni, co, cr, cu, ti, zn, V, zr and Ce. Prussian blue compounds, e.g. Na a Me b Me’ c (CN) 6 Wherein Me and Me' are at least one of Ni, cu, fe, mn, co and Zn respectively, a is more than 0 and less than or equal to 2, b is more than 0 and less than 1, and c is more than 0 and less than 1.
The weight ratio of the positive electrode active material in the positive electrode film layer is 80-100% by weight, based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin. The weight ratio of the binder in the positive electrode film layer is 0-20% by weight based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. The weight ratio of the conductive agent in the positive electrode film layer is 0-20% based on the total weight of the positive electrode film layer.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the components for preparing the positive electrode plate, such as the positive electrode active material, the conductive agent, the binder and any other components, in a solvent (such as N-methyl pyrrolidone) to form positive electrode slurry, wherein the solid content of the positive electrode slurry is 40-80 wt%, the viscosity of the positive electrode slurry at room temperature is adjusted to 5000-25000 mPa.s, the positive electrode slurry is coated on the surface of a positive electrode current collector, and the positive electrode slurry is formed after being dried and cold-pressed by a cold rolling mill; the unit area density of the positive electrode powder coating is 150 mg/m 2 ~350 mg/m 2 The compacted density of the positive pole piece is 3.0 g/cm 3 ~3.6 g/cm 3 Optionally 3.3 g/cm 3 ~3.5 g/cm 3 。
The calculation formula of the compaction density is as follows:
compacted density = coated area density/(post-extrusion pole piece thickness-current collector thickness).
The mass M of the positive electrode active material in the positive electrode sheet per unit area can be weighed using a standard balance.
The thickness T of the positive electrode diaphragm can be measured by a ten-thousandth ruler, for example, the thickness T can be measured by a ten-thousandth ruler with the model of Mitutoyo293-100 and the precision of 0.1 mu m. The thickness of the positive electrode membrane refers to the thickness of the positive electrode membrane used in the positive electrode sheet of the assembled battery after cold pressing and compaction.
Negative pole piece
The negative electrode plate comprises a negative electrode current collector and a negative electrode film layer arranged on at least one surface of the negative electrode current collector, wherein the negative electrode film layer comprises a negative electrode active material.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material on a polymeric material substrate. The metal material includes, but is not limited to, copper alloy, nickel alloy, titanium alloy, silver alloy, etc., and the polymer material substrate includes, but is not limited to, polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art.
As an example, the anode active material of the lithium ion secondary battery may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
As an example, the negative electrode active material of a sodium ion secondary battery is generally a hard carbon material, a two-dimensional metal carbide or nitride. The negative electrode active material of the sodium ion secondary battery is preferably generally a hard carbon material.
The weight ratio of the negative electrode active material in the negative electrode film layer is 70-100% by weight, based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). The weight ratio of the binder in the negative electrode film layer is 0-30% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers. The weight ratio of the conductive agent in the negative electrode film layer is 0-20% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like. The weight ratio of the other auxiliary agents in the negative electrode film layer is 0-15% by weight based on the total weight of the negative electrode film layer.
In some embodiments, the negative electrode sheet may be prepared by: dispersing the components for preparing the negative electrode plate, such as the negative electrode active material, the conductive agent, the binder and any other components, in a solvent (such as deionized water) to form a negative electrode slurry, wherein the solid content of the negative electrode slurry is 30-70wt%, and the viscosity of the negative electrode slurry at room temperature is adjusted to 2000-10000 mPa.s; and (3) coating the obtained negative electrode slurry on a negative electrode current collector, and performing a drying procedure, cold pressing, such as a pair roller, to obtain a negative electrode plate. The unit area density of the negative electrode powder coating is 75 mg/m 2 ~220 mg/m 2 The compacted density of the negative electrode plate is 1.2 g/m 3 ~2.0 g/m 3 。
The mass M of the anode active material in the anode membrane per unit area can be weighed using a standard balance.
The thickness T of the negative electrode diaphragm can be measured by a ten-thousandth ruler, for example, the thickness T can be measured by a ten-thousandth ruler with the model of Mitutoyo293-100 and the precision of 0.1 mu m. The thickness of the negative electrode membrane refers to the thickness of the negative electrode membrane used in the negative electrode plate of the assembled battery after cold pressing and compaction.
Electrolyte composition
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt of the lithium ion secondary battery may be selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalato borate (LiDFOB), lithium difluorooxalato borate (LiBOB), lithium difluorophosphate (LiPO) 2 F 2 ) One or more of lithium difluorooxalate phosphate (LiDFOP) and lithium tetrafluorooxalate phosphate (LiTFOP).
The electrolyte salt of the sodium ion secondary battery can be selected from one or more of sodium hexafluorophosphate, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, sodium trifluoromethanesulfonate, sodium tetrafluoroborate, sodium difluorophosphate, sodium perchlorate and sodium chloride.
The concentration of the electrolyte salt is usually 0.5 mol/L to 5 mol/L.
In some embodiments, the solvent may be selected from one or more of fluoroethylene carbonate (FEC), ethylene Carbonate (EC), propylene Carbonate (PC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl Propyl Carbonate (MPC), ethylene Propyl Carbonate (EPC), butylene Carbonate (BC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS), and diethyl sulfone (ESE).
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
Isolation film
In some embodiments, a separator is further included in the secondary battery. The isolating film adopts the isolating film disclosed by the application or the isolating film prepared by the preparation method.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The secondary battery includes at least one battery cell therein. The secondary battery may include 1 or more battery cells.
In the present application, unless otherwise indicated, "battery cell" refers to a basic unit capable of achieving mutual conversion of chemical energy and electric energy, and further, generally includes at least a positive electrode sheet, a negative electrode sheet, and an electrolyte. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in conducting active ions between the positive electrode plate and the negative electrode plate.
The shape of the battery cell is not particularly limited in the present application, and may be cylindrical, square or any other shape. For example, fig. 3 is a square-structured battery cell 5 as one example.
In some embodiments, referring to fig. 4, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of the electrode assemblies 52 included in the battery cell 5 may be one or more, and those skilled in the art may select the number according to specific practical requirements.
In some embodiments, the battery cells 5 may be assembled into a battery module, and the number of battery cells 5 included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
In the battery module, the plurality of battery cells 5 may be sequentially arranged in the longitudinal direction of the battery module. Of course, the arrangement may be performed in any other way. The plurality of battery cells 5 may be further fixed by fasteners.
Alternatively, the battery module may further include a housing having an accommodating space in which the plurality of battery cells 5 are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
A battery case and a plurality of battery modules disposed in the battery case may be included in the battery pack. The battery box comprises an upper box body and a lower box body, wherein the upper box body can be covered on the lower box body, and a closed space for accommodating the battery module is formed. The plurality of battery modules may be arranged in the battery case in any manner.
In addition, the application also provides an electric device which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 5 shows an electric device 6 in which a secondary battery according to an embodiment of the present application is used as a power source. The electric device 6 is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery of the power consuming device 6, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
The following are some examples.
In order to make the technical problems, technical schemes and beneficial effects solved by the application more clear, the application will be further described in detail below with reference to the embodiments and the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by a person skilled in the art based on the embodiments of the application without any inventive effort, are intended to fall within the scope of the application.
The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Preparation example of the release film
Example 1:
1) Preparation of coating slurry
Adding average particle size to NMP (N-methylpyrrolidone)Dv50 of 20 nm to 40 nm and specific surface area of 150 m 2 Fumed silica/g, alumina fiber with the length of 0.01 mm-0.05 mm and the diameter of 0.4 mu m-1 mu m, and alumina particles with the average particle diameter Dv50 of 20 nm-40 nm are fully and uniformly mixed; and then adding organosilicon modified polyester resin and a crosslinking curing agent MDI (4, 4' -diphenylmethane diisocyanate) into the slurry, initiating agent dibenzoyl peroxide and pore-forming agent ethyl acetate, and fully and uniformly mixing to obtain the coating slurry. The viscosity of the slurry is regulated to be 5000 CP ∙ s-8000 CP ∙ s by controlling the amount of NMP.
Wherein R in structural units of the organosilicon modified polyester resin in the coating slurry 1 Is methoxy, R 2 Is methoxy, R 3 is-CH 2 C（CH 3 ） 2 CH 2 –、R 4 The weight average molecular weight of the silicone-modified polyester resin was 13368 as a benzene ring. The structural unit of the organosilicon modified polyester resin is A1:
A1
the coating slurry comprises 5% of alumina fiber, 2.5% of fumed silica, 20% of alumina particles, 20% of organosilicon modified polyester resin, 4% of cross-linking curing agent, 0.1% of initiator, 3% of pore-forming agent and the balance of solvent NMP.
The mass ratio of the crosslinking curing agent to the organosilicon modified polyester resin is 0.2:1, a step of; the mass fraction of silicon element in the organic silicon modified polyester resin is 0.12%.
2) Preparation of release film with surface in-situ cured coating
The coating paste prepared above was coated on one side surface of a PE separator having a thickness of 9 μm by a coating method. And (3) placing the obtained diaphragm coated with the coating slurry in a vacuum environment at 60-80 ℃ for drying and curing for 2-24 hours to obtain the battery isolating film with the surface in-situ cured heat-resistant coating, wherein the thickness of the PE diaphragm surface coating is 3 mu m. Specific parameters of the release film are shown in table 1.
Example 2:
this embodiment is substantially the same as embodiment 1, except that: the types of silicone-modified polyester resins vary. In the structural unit of the silicone-modified polyester resin in this example, R 1 Is methoxy, R 2 Is methoxy, R 3 is-CH 2 CH 2 –、R 4 Is benzene ring; the weight average molecular weight of the organic silicon modified polyester resin is 10274, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.09%. The structural unit of the organosilicon modified polyester resin is A2:
A2
example 3:
this embodiment is substantially the same as embodiment 1, except that: the types of silicone-modified polyester resins vary. In the structural unit of the silicone-modified polyester resin in this example, R 1 Is methoxy, R 2 Is methoxy, R 3 is-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 –、R 4 Is benzene ring; the molecular weight of the organic silicon modified polyester resin is 8513, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.1%. The structural unit of the organic silicon modified polyester resin is A3:
A3
example 4:
this embodiment is substantially the same as embodiment 1, except that: the types of silicone-modified polyester resins vary. In the structural unit of the silicone-modified polyester resin in this example, R 1 Is methyl, R 2 Is methoxy, R 3 is-CH 2 CH 2 –、R 4 Is benzene ring; the weight average molecular weight of the organic silicon modified polyester resin is 10729, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.13%. The structural unit of the organosilicon modified polyester resin is A4:
A4
example 5:
this embodiment is substantially the same as embodiment 1, except that: the types of silicone-modified polyester resins vary. In the structural unit of the silicone-modified polyester resin in this example, R 1 Is methoxy, R 2 Is (2, 3-epoxypropoxy) propyl, R 3 is-CH 2 CH 2 –、R 4 Is benzene ring; the weight average molecular weight of the organosilicon modified polyester resin is 14827, and the mass fraction of silicon element in the organosilicon modified polyester resin is 0.06%. The structural unit of the organic silicon modified polyester resin is A5:
A5
Example 6:
this embodiment is substantially the same as embodiment 1, except that: the structural unit of the organic silicon modified polyester resin is A1, the weight average molecular weight is 12266, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.01%.
Example 7:
this embodiment is substantially the same as embodiment 1, except that: the structural unit of the organic silicon modified polyester resin is A1, the weight average molecular weight is 9837, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.08%.
Example 8:
this embodiment is substantially the same as embodiment 1, except that: the structural unit of the organosilicon modified polyester resin is A1, and the weight average molecular weight is 11255. The mass fraction of silicon element in the organic silicon modified polyester resin is 0.17%.
Example 9:
this embodiment is substantially the same as embodiment 1, except that: the structural unit of the organic silicon modified polyester resin is A1, the weight average molecular weight is 13012, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.26%.
Example 10:
this embodiment is substantially the same as embodiment 1, except that: the structural unit of the organic silicon modified polyester resin is A1, the weight average molecular weight is 15629, and the mass fraction of silicon element in the organic silicon modified polyester resin is 0.52%.
Example 11:
this embodiment is substantially the same as embodiment 1, except that: the dosage ratio of the crosslinking curing agent to the organosilicon modified polyester resin in the coating slurry is different. In this example, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin in the coating paste was 0.05:1, and the content of the silicone-modified polyester resin in the coating paste was the same as in example 1.
Example 12:
this embodiment is substantially the same as embodiment 1, except that: the dosage ratio of the crosslinking curing agent to the organosilicon modified polyester resin in the coating slurry is different. In this example, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin in the coating paste was 0.1:1, and the content of the silicone-modified polyester resin in the coating paste was the same as in example 1.
Example 13:
this embodiment is substantially the same as embodiment 1, except that: the dosage ratio of the crosslinking curing agent to the organosilicon modified polyester resin in the coating slurry is different. In this example, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin in the coating paste was 0.15:1, and the content of the silicone-modified polyester resin in the coating paste was the same as in example 1.
Example 14:
this embodiment is substantially the same as embodiment 1, except that: the dosage ratio of the crosslinking curing agent to the organosilicon modified polyester resin in the coating slurry is different. In this example, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin in the coating paste was 0.25:1, and the content of the silicone-modified polyester resin in the coating paste was the same as in example 1.
Example 15:
this embodiment is substantially the same as embodiment 1, except that: the dosage ratio of the crosslinking curing agent to the organosilicon modified polyester resin in the coating slurry is different. In this example, the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin in the coating paste was 0.3:1, and the content of the silicone-modified polyester resin in the coating paste was the same as in example 1.
Example 16:
this embodiment is substantially the same as embodiment 1, except that: the filler of the coating slurry does not contain fumed silica; accordingly, the content of alumina particles in the filler is different, but the total amount of filler is unchanged. The mass fraction of alumina particles in the coating paste in this example was 22.5%, and the mass fraction of alumina fibers was 5%.
Example 17:
this embodiment is substantially the same as embodiment 1, except that: the alumina fiber content in the filler of the coating slurry is different; accordingly, the content of alumina particles in the filler is different, but the total amount of filler is unchanged. In this example, the mass content of the alumina fiber in the coating paste was 1%, the mass content of the alumina particles was 24%, and the total filler content was unchanged.
Example 18:
this embodiment is substantially the same as embodiment 1, except that: the alumina fiber content in the coating slurry is different; accordingly, the content of alumina particles in the filler is different, but the total amount of filler is unchanged. In this example, the mass content of alumina fibers in the coating paste was 10%, the mass content of alumina particles was 15%, and the total filler content was unchanged.
Example 19:
this embodiment is substantially the same as embodiment 1, except that: the fumed silica content in the coating slurry varies; accordingly, the content of alumina particles in the filler is different, but the total amount of filler is unchanged. In this example, the mass content of fumed silica in the coating slurry was 1%, the mass content of alumina particles was 21.5%, and the total filler content was unchanged.
Example 20:
this embodiment is substantially the same as embodiment 1, except that: the fumed silica content in the coating slurry varies; accordingly, the content of alumina particles in the filler is different, but the total amount of filler is unchanged. In this example, the mass content of fumed silica in the coating slurry was 5%, the mass content of alumina particles was 17.5%, and the total filler content was unchanged.
Example 21:
this embodiment is substantially the same as embodiment 1, except that: the thickness of the heat resistant coating varies. The thickness of the heat-resistant coating layer on one side surface of the PE separator in this example was 2. Mu.m.
Comparative example 1:
a PE film having a thickness of 9 μm was used as the separator.
Comparative example 2:
this comparative example is substantially identical to example 1, except that: the type of coating varies. The coating on the separator substrate in this comparative example was an alumina ceramic coating bonded with PVDF. Specifically, the coating slurry thereof had a composition of 5 parts by mass of PVDF, 20 parts by mass of alumina nanoparticles, and 55 parts by mass of solvent NMP.
Comparative example 3:
this comparative example is substantially identical to example 1, except that: the type of coating varies. The polymer in the heat-resistant coating in comparative example 3 was a polyester, i.e., the base polyester resin was not modified with a silicone. Specifically, the raw material polyester resin in comparative example 3 was polyethylene terephthalate resin.
Comparative example 4:
this comparative example is substantially identical to example 1, except that: the type of coating varies. The polymer in the heat-resistant coating layer in this comparative example was formed from a silicone-modified polyester resin, but the silicone-modified polyester resin did not include the specific structural unit in the present application. In comparative example 4, R in the structural unit of the silicone-modified polyester resin 1 Is methyl, R 2 Is methyl, R 3 is-CH 2 CH 2 –、R 4 is-CH 2 CH 2 -. The weight average molecular weight of the silicone modified polyester resin was 10189. The structural unit of the organosilicon modified polyester resin is A6:
A6
2. test method
1) Resin weight average molecular weight test
The test was performed using gel permeation chromatography. Specifically, the resin is diluted and fixed in volume by using NMP as a solvent, chloroform is used as a eluent, the flow rate is 1mL/min, the column temperature is kept at 40 ℃, the relation between the column system molecular weight and the elution volume or the elution time is calibrated by using polystyrene as a standard sample, GPC data processing is performed by using Empower software, and the Mw is quantitatively determined by the relative polystyrene molecular weight scale.
2) Diaphragm porosity test
The test is carried out according to the standard GB/T24586-2009. The method comprises the specific process that > 20 wafers with good appearance and no powder falling at the edge are selected by forceps and are filled into a sample cup. Recording the number of sheets, calculating the apparent volume, placing a sample cup filled with a sample in a true density tester, sealing a test system, introducing helium according to a program, detecting the pressure of the gas in a sample chamber and an expansion chamber, and calculating the real volume according to Bohr's law (PV=nRT), thereby obtaining the porosity of the sample to be tested. Notably, the porosity results of the pole piece samples output were not subtracted from the substrate.
3) Diaphragm air permeability test
The test is performed with reference to standard GB/T458-2008. The specific process is that the diaphragm is flattened, a flat and oil-free position is selected, the diaphragm is placed at the air outlet of the air compression cylinder, the diaphragm is screwed and fixed, and after the diaphragm is fixed at a station, the air in the cylinder is compressed by the self gravity of the cylinder floating on the liquid. As air passes through the sample, the cylinder will drop smoothly. The time required for a volume of air to pass through the sample is measured and the air permeability calculated therefrom.
4) Diaphragm tensile Strength test
The test is carried out according to GB/T1040 [1]. 3-2006. The specific process is that the diaphragm is cut into regular strips with the width of 15mm and the length of 90mm along the axial direction or the radial direction, the diaphragm is clamped on a universal testing machine, and the tensile strength of the diaphragm is obtained by carrying out tensile test at the tensile rate of 50 mm/min.
5) Diaphragm puncture strength test
The test was carried out according to GB/T36363-2018. The specific process is that the diaphragm is cut into regular square samples with 60mm by 60mm, the regular square samples are placed on a puncture tester, a needle with the diameter of 1mm is used for testing the puncture strength of the diaphragm at the speed of 50 mm/min.
6) Testing of thermal shrinkage performance of diaphragm
The test was carried out according to GB/T36363-2018. The specific process is that a diaphragm sample with the size of 100Mm (MD) by 50mm (TD) is cut and placed in a blast drying box to be heated for 1h at the constant temperature of 105 ℃, and the shrinkage rate is calculated according to the length changes of the diaphragm in the length direction (MD) and the width direction (TD) before and after the constant temperature.
7) High temperature resistance (rupture temperature) test
The resistance mutation method is adopted to test the temperature resistance of the diaphragm, and the specific test method is as follows: a 50mm by 50mm membrane was immersed in 1M LiPF 6 And ensures that sufficient electrolyte is absorbed. And placing the three layers of diaphragms filled with electrolyte between two copper plates to form a simple battery, and clamping and fixing the simple battery through two pieces of glass. The simple cell was placed in a continuously heatable vacuum oven at a rate of 5 ℃ per minute from 25 ℃ to 300 ℃ during which the ac impedance (at 1 kHz) of the simple cell was measured continuously and the impedance-temperature profile was recorded. The temperature corresponding to the temperature when the battery impedance is greatly increased and then is reduced and approaches zero is taken as the rupture temperature of the diaphragm.
8) Average particle size Dv50 test
The test was carried out in accordance with GB/T19077-2016. The specific process is that alumina powder with proper mass is added into water solution containing surfactant, the alumina suspension is obtained by ultrasonic dispersion, the obtained alumina suspension is led into a liquid tank of a laser particle size analyzer, the shading value is adjusted to be 10% -15% by adding the alumina suspension, measurement is started, and the instrument automatically obtains the particle size test result.
9) Specific surface area test
The test was performed according to GB/T19587-2004. The specific surface area is measured by a nitrogen adsorption method, vacuum degassing is carried out at 200 ℃ for 1h during the test, and the sample is mounted to an equipment analysis station for analysis after cooling and weighing.
10 Silicon element mass fraction test in organic silicon modified polyester resin
The mass fraction of silicon element is tested by inductively coupled plasma atomic emission spectrometry. Dispersing resin with proper mass in a mixed solution of concentrated nitric acid and hydrofluoric acid with a certain volume, then carrying out microwave digestion, and fixing the digestion solution. And (3) analyzing the element content of the solution with the constant volume, so as to calculate and obtain the mass fraction test of the silicon element in the organic silicon modified polyester resin.
The parameters of the release films in the above examples and comparative examples are shown in table 1, and the performance test data of the release films are shown in table 2.
TABLE 1
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TABLE 2
From the above data, it can be seen that:
in embodiments of the present application, by providing a heat-resistant coating layer on a separator substrate, the heat-resistant coating layer includes a polymer, and a raw material silicone-modified polyester resin forming the polymer includes a specific structural unit; the isolating film of each embodiment of the application has higher film breaking temperature, which indicates that the isolating film has better high temperature resistance.
As can be seen from comparative examples 1 and 1 to 4, the barrier film of the present application has higher mechanical strength and more excellent high temperature resistance than the ceramic separator of bare film and conventional PVDF. Compared with the organic silicon modified polyester resin adopted in the application, if the polyester resin is not subjected to organic silicon modification or does not adopt the organic silicon modified polyester resin with the specific structure, the final prepared isolating film has poorer comprehensive performance. In particular, the high temperature resistance of the isolating film is relatively poor without modifying by adopting organic silicon; the organic silicon modified polyester resin with a specific structure is not adopted, namely groups such as methyl, benzene ring and the like are connected to silicon atoms, and the mechanical strength and the high temperature resistance of the isolating film are slightly poor, and the reason is mainly that the resin lacks reaction sites for crosslinking with a crosslinking curing agent, and the coating cannot form an interpenetrating crosslinked network.
Comparing examples 1 and 6-10, it can be found that the high temperature resistance of the barrier film is gradually improved with the increase of the silicon element content ratio in the organic silicon modified polyester resin, because the silicon-oxygen bond energy is higher and the energy required for breaking bond decomposition is larger. The more reactive alkoxy groups are simultaneously connected with silicon atoms, the more chemical crosslinking bonds are formed between the reactive alkoxy groups and the curing agent, and the higher the coating strength is.
In comparative examples 1 and 11-15, it can be found that the addition of the crosslinking curing agent can effectively improve the mechanical properties and high temperature resistance of the isolating film, the film breaking temperature of the isolating film can be increased to 242 ℃, and the puncture strength can also be increased to 723.1 gf, because the isocyanate curing agent can realize reactive crosslinking with the carboxyl end groups of the resin and the alkoxy groups connected to the silicon atoms, an interpenetrating crosslinked coating structure is formed, and further the hardness and the temperature resistance of the coating are improved.
In comparative examples 1 and 16, fumed silica did not affect the properties of the coating much, but during the preparation of the slurry, it was found that the slurry had a low viscosity and was prone to delamination in the rest state.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (16)
1. The isolating film is characterized by comprising a diaphragm substrate and a heat-resistant coating arranged on at least one side surface of the diaphragm substrate, wherein the heat-resistant coating comprises a polymer obtained by crosslinking an organosilicon modified polyester resin and a crosslinking curing agent, and the organosilicon modified polyester resin comprises a structural unit shown in a formula I;
a formula I;
wherein R is 1 、R 2 At least one of which is selected from the group consisting of groups reactive with the crosslinking curing agent;
R 3 selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms;
R 4 selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms;
n is a natural number greater than 0, and m is a natural number greater than 0.
2. The separator according to claim 1, wherein R in the structural unit represented by formula I 1 、R 2 Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, an aromatic group, a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms, and R 1 、R 2 At least one of which is selected from a hydroxyl group, a substituted or unsubstituted epoxy group having 3 to 6 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 3 carbon atoms.
3. The separator according to claim 1, wherein the silicone-modified polyester resin has a weight average molecular weight of 5000-20000.
4. The isolating film according to claim 1, wherein the mass fraction of silicon element in the organic silicon modified polyester resin is 0.01% -0.52%.
5. The release film of claim 1, wherein the cross-linking curing agent comprises at least one of an aliphatic isocyanate or an open aromatic isocyanate.
6. The release film of claim 5, wherein the cross-linking curing agent comprises at least one of hexamethylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 6-toluene diisocyanate, 1, 5-naphthalene diisocyanate, or p-phenylene diisocyanate.
7. The separator according to claim 1, wherein the mass ratio of the crosslinking curing agent to the silicone-modified polyester resin is (0.05 to 0.3): 1.
8. the barrier film of claim 1, wherein the heat resistant coating further comprises a filler comprising at least one of alumina fibers, alkali free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles.
9. The separator according to claim 8, wherein the separator satisfies at least one of the following (1) to (3):
(1) The average length of the alumina fiber, the alkali-free glass fiber, the basalt fiber, the silicon carbide fiber, the silicon nitride fiber, the aramid fiber or the potassium titanate whisker is 0.007-1 mm, and the average diameter is 0.4-1 mu m;
(2) The average particle diameter Dv50 of the silicon dioxide particles is 7 nm-40 nm;
(3) The two partsThe specific surface area of the silica particles was 120 m 2 /g~150 m 2 /g。
10. The separator according to any one of claims 1 to 9, wherein the thickness of the heat-resistant coating is 1-3 μm.
11. The separator according to any one of claims 1 to 9, wherein the separator has a porosity of 35% -45%.
12. The preparation method of the isolating film is characterized by comprising the following steps:
providing a separator substrate;
mixing a solvent, an organosilicon modified polyester resin, a crosslinking curing agent and an initiator to obtain slurry;
setting the slurry on at least one side surface of the diaphragm matrix, and curing to obtain a separation film;
wherein the organosilicon modified polyester resin comprises a structural unit shown in a formula I;
A formula I;
wherein R is 1 、R 2 At least one of which is selected from the group consisting of groups reactive with the crosslinking curing agent;
R 3 selected from triazine ring, phenyl or substituted or unsubstituted hydrocarbon group with 1-8 carbon atoms;
R 4 selected from phenyl or substituted or unsubstituted hydrocarbon groups having 1 to 4 carbon atoms;
n is a natural number greater than 0, and m is a natural number greater than 0.
13. The method of producing a release film according to claim 12, wherein the slurry further comprises a pore-forming agent comprising an ester-type organic compound.
14. The method of producing a separator according to claim 12 or 13, wherein the slurry further comprises a filler comprising at least one of alumina fibers, alkali-free glass fibers, basalt fibers, silicon carbide fibers, silicon nitride fibers, aramid fibers, potassium titanate whiskers, silica particles, or alumina particles.
15. A secondary battery comprising the separator according to any one of claims 1 to 11, or comprising the separator produced by the separator production method according to any one of claims 12 to 14.
16. An electric device comprising the secondary battery according to claim 15.
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