CN115832640A - Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device - Google Patents
Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device Download PDFInfo
- Publication number
- CN115832640A CN115832640A CN202111385349.8A CN202111385349A CN115832640A CN 115832640 A CN115832640 A CN 115832640A CN 202111385349 A CN202111385349 A CN 202111385349A CN 115832640 A CN115832640 A CN 115832640A
- Authority
- CN
- China
- Prior art keywords
- lithium
- layer
- secondary battery
- insulating
- lithium intercalation
- 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.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 335
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 335
- 239000000463 material Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011135 tin Substances 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 11
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 11
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 238000009830 intercalation Methods 0.000 claims description 153
- 230000002687 intercalation Effects 0.000 claims description 149
- 238000000576 coating method Methods 0.000 claims description 78
- 239000011248 coating agent Substances 0.000 claims description 77
- -1 polyethylene Polymers 0.000 claims description 64
- 239000007773 negative electrode material Substances 0.000 claims description 63
- 239000011810 insulating material Substances 0.000 claims description 34
- 239000004743 Polypropylene Substances 0.000 claims description 32
- 229920001155 polypropylene Polymers 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 31
- 239000006258 conductive agent Substances 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 24
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 24
- 239000002562 thickening agent Substances 0.000 claims description 24
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 22
- 229920000573 polyethylene Polymers 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 21
- 229920002125 Sokalan® Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 16
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 16
- 239000004954 Polyphthalamide Substances 0.000 claims description 15
- 229910001593 boehmite Inorganic materials 0.000 claims description 15
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 15
- 239000004584 polyacrylic acid Substances 0.000 claims description 15
- 229920006375 polyphtalamide Polymers 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920001568 phenolic resin Polymers 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 9
- 238000003780 insertion Methods 0.000 claims description 8
- 230000037431 insertion Effects 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000012774 insulation material Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 210000001787 dendrite Anatomy 0.000 abstract description 73
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 220
- 239000003792 electrolyte Substances 0.000 description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 26
- 229910001416 lithium ion Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 239000002131 composite material Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 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 7
- 239000000654 additive Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002134 carbon nanofiber Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 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 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 239000000661 sodium alginate Substances 0.000 description 4
- 235000010413 sodium alginate Nutrition 0.000 description 4
- 229940005550 sodium alginate Drugs 0.000 description 4
- 239000011366 tin-based material Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000004308 accommodation Effects 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000003475 lamination Methods 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
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- 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
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910015643 LiMn 2 O 4 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
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 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
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical class [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 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
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a negative pole piece and a preparation method thereof, a secondary battery and a preparation method thereof, a battery module, a battery pack and an electric device; a negative pole piece comprises a negative pole active material layer, an insulating layer and a lithium embedding layer, wherein the insulating layer is arranged on the negative pole active material layer, the lithium embedding layer is arranged on the insulating layer, the lithium embedding layer comprises a lithium embedding material, and the lithium embedding material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate. This application negative pole piece has restrained lithium dendrite's degree of depth growth at secondary battery operation in-process, has improved secondary battery's first coulomb effect and cycle performance, has improved secondary battery operational security and stability, has avoided lithium dendrite degree of depth growth to pierce through the inside short circuit problem of secondary battery that the barrier film causes.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a negative pole piece and a preparation method thereof, a secondary battery and a preparation method thereof, a battery module, a battery pack and an electric device.
Background
In recent years, with the wider application range of secondary batteries, 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, electric automobiles, military equipment, and aerospace. As the development of secondary batteries has been greatly advanced, higher requirements are also placed on energy density, cycle performance, safety performance, and the like.
When the conventional secondary battery is used, when the charging current exceeds a lithium precipitation window or is overcharged, lithium dendrite is generated on the surface of a negative pole piece, and the lithium dendrite continuously grows to cause consumption of active lithium, so that the first coulombic efficiency and the cycle performance of the secondary battery are reduced, and the lithium dendrite grows to a certain degree to pierce through a diaphragm, so that short circuit in a battery core is caused, and thermal runaway of the battery core is caused.
Therefore, it is highly desirable to suppress the growth of lithium dendrites in a secondary battery, thereby solving the problems of the first coulomb efficiency reduction and the cycle performance reduction of the secondary battery caused by lithium precipitation, while improving the safety and stability of the secondary battery.
Disclosure of Invention
The present invention has been made in view of the above problems, and it is an object of the present invention to provide a negative electrode sheet and a method for manufacturing the same, a secondary battery and a method for manufacturing the same, a battery module, a battery pack, and an electric device, which are capable of suppressing the growth of lithium dendrites during the operation of the secondary battery, thereby solving the problems of the first coulomb efficiency reduction and the cycle performance reduction of the secondary battery due to the precipitation of lithium, improving the safety and stability of the operation of the secondary battery, and solving the problem of the internal short circuit of the secondary battery due to the penetration of the separator due to the excessive growth of lithium dendrites.
In order to achieve the above object, a first aspect of the present application provides a negative electrode plate, including a negative electrode active material layer, an insulating layer, and a lithium intercalation layer, the insulating layer being disposed on the negative electrode active material layer, the lithium intercalation layer being disposed on the insulating layer, and the lithium intercalation layer including a lithium intercalation material selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin, and iron phosphate;
therefore, in the negative pole piece, the insulating layer is a substance which is not conductive to conduct ions, and the lithium intercalation layer is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that the charging current exceeds a lithium analysis window or overcharge, the lithium dendrite penetrates through the insulating layer to contact with the lithium embedding layer, and the lithium dendrite and the lithium embedding layer form a lithium embedding loop under the action of electrolyte, so that lithium embedding reaction occurs, further growth of the lithium dendrite is inhibited, when the secondary battery discharges, electrons of the lithium dendrite in the lithium embedding layer are lost to be changed into lithium ions to return to the electrolyte again, the problem that the lithium dendrite continuously grows to consume active lithium ions is solved, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the operation of the secondary battery are improved; meanwhile, the insulating layer and the lithium embedding layer are sequentially arranged on the negative electrode active material layer, so that a space is reserved between the lithium embedding layer and the isolating membrane of the secondary battery, and therefore, even if the volume of the secondary battery suddenly shrinks in the using process, the phenomenon that the lithium dendrite punctures the isolating membrane due to the sudden shrinkage of the battery volume cannot occur.
In any embodiment, the insulating layer has a thickness of 0.03 to 8 μm, optionally 0.03 to 4 μm. If the insulating layer is too thin, the contact between the negative active material layer and the lithium intercalation layer cannot be effectively isolated, so that the lithium intercalation layer fails and the further growth of lithium dendrites cannot be inhibited; if the insulating layer is too thick, the internal space of the battery cell is occupied, and the energy density of the battery is reduced.
In any embodiment, the thickness of the lithium intercalation layer is 0.05 to 10 μm, optionally 0.05 to 5 μm. If the lithium intercalation layer is too thin, lithium intercalation reaction can not be effectively carried out on the top of the lithium dendrite, and further growth of the lithium dendrite can not be effectively inhibited; the lithium intercalation layer is too thick, and occupies the internal space of the battery cell, resulting in a decrease in energy density of the secondary battery.
In any embodiment, the insulating layer comprises an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid. The insulating material is conductive to ions but not conductive to ions, and can effectively block the contact between the negative electrode active material layer and the lithium intercalation layer.
In any embodiment, the lithium intercalation material is present in the lithium intercalation layer in an amount of 93% to 98%, for example 97%, by weight. The lithium intercalation material is a substance capable of reversibly deintercalating lithium ions, and when deep lithium precipitation occurs, the lithium dendrite, the lithium intercalation material and the electrolyte form a lithium intercalation circuit to generate a lithium intercalation reaction, so that the further growth of the lithium dendrite is inhibited.
In any embodiment, the lithium insertion layer further comprises an adjuvant.
In any embodiment, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener. The addition of the auxiliary agent is beneficial to the formation of the lithium intercalation layer and the smooth proceeding of the lithium intercalation reaction.
A second aspect of the present application provides a secondary battery, including a negative electrode plate, a lithium intercalation layer and a separator, wherein the lithium intercalation layer is disposed on one surface of the separator facing the negative electrode plate; the negative pole piece comprises a negative active material layer and an insulating layer, wherein the insulating layer is arranged on the negative active material layer; and the lithium intercalation layer contains a lithium intercalation material selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
Therefore, in the secondary battery, the insulating layer is a substance which conducts ions without conducting electrons, and the lithium intercalation layer is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that the charging current exceeds a lithium analysis window or the secondary battery is overcharged, lithium dendrite firstly penetrates through an insulating layer and then contacts a lithium embedding layer on an isolating membrane along with growth, the lithium dendrite and the lithium embedding layer form a lithium embedding loop under the action of electrolyte, lithium embedding reaction is generated, further growth of the lithium dendrite is inhibited, when the secondary battery discharges, lithium losing electrons in the lithium embedding layer are changed into lithium ions and then return to the electrolyte, the problem that the lithium dendrite continuously grows to consume active lithium and the problem that the lithium dendrite continuously grows to pierce the isolating membrane to cause short circuit in the battery are avoided, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the secondary battery in operation are improved.
In any embodiment, the insulating layer has a thickness of 0.03 to 8 μm, optionally 0.03 to 4 μm.
In any embodiment, the thickness of the lithium intercalation layer is 0.05 to 10 μm, optionally 0.05 to 5 μm.
In any embodiment, the insulating layer comprises an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid.
In any embodiment, the lithium intercalation material is present in the lithium intercalation layer in an amount of 93% to 98%, for example 97%, by weight.
In any embodiment, the lithium insertion layer further comprises an adjuvant.
In any embodiment, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
A third aspect of the present application provides a method for preparing a negative electrode sheet, comprising the steps of:
coating an insulating coating on the negative electrode active material layer, drying, and forming an insulating layer on the negative electrode active material layer;
coating lithium embedding paint on the insulating layer, and drying to obtain a negative pole piece;
therefore, in the negative pole piece, the insulating layer is a substance which is not conductive and conducts ions, and the lithium intercalation layer formed by the lithium intercalation coating is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that charging current exceeds a lithium analysis window or overcharge, lithium dendrite penetrates through an insulating layer to contact a lithium embedding layer, the lithium dendrite and the lithium embedding layer form a lithium embedding loop under the action of electrolyte, lithium embedding reaction occurs, growth of the lithium dendrite is inhibited, when the secondary battery discharges, metal lithium in the lithium embedding layer loses electrons and becomes lithium ions to be returned to the electrolyte again, the problem that the lithium dendrite continuously increases and consumes active lithium ions is solved, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure state is improved, and the safety and the stability of operation of the secondary battery are improved; and the insulating layer and the lithium embedding layer are sequentially arranged on the negative electrode active material layer, so that a space is reserved between the lithium embedding layer and the isolating membrane of the secondary battery, and therefore, even if the volume of the secondary battery suddenly shrinks in the using process, lithium dendrites cannot penetrate through the isolating membrane due to the sudden shrinkage of the volume of the secondary battery, and the occurrence of short circuit inside the secondary battery is avoided.
A fourth aspect of the present application provides a method of manufacturing a secondary battery, comprising the steps of:
coating an insulating coating on the negative active material layer, and drying to obtain a negative pole piece;
coating a lithium-intercalation coating on one surface of the isolating membrane facing the negative pole piece, and drying to obtain the isolating membrane provided with a lithium-intercalation layer;
and assembling the secondary battery by using the negative pole piece and the isolating membrane provided with the lithium-embedded layer.
Therefore, in the secondary battery, the insulating layer formed by the insulating coating is a substance which is not conductive to conduct ions, and the lithium intercalation layer is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that the charging current exceeds a lithium analysis window or the secondary battery is overcharged, lithium dendrite firstly penetrates through an insulating layer, then the lithium dendrite and the lithium intercalation layer on an isolating membrane form a lithium intercalation loop under the action of electrolyte, lithium intercalation reaction is generated, growth of the lithium dendrite is restrained, when the secondary battery discharges, metal lithium in the lithium intercalation layer loses electrons and becomes lithium ions to return to the electrolyte again, the problem that the lithium dendrite continuously grows to consume active lithium ions and the problem that the lithium dendrite pierces the isolating membrane to cause short circuit in the secondary battery are solved, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the secondary battery in operation are improved.
In any embodiment, the lithium insertion coating is prepared by the steps of:
mixing a lithium intercalation material, water and an optional auxiliary agent to obtain a lithium intercalation coating; wherein, the lithium embedding material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
In any embodiment, the lithium intercalation material is present in the lithium intercalation coating in an amount of 93% to 98% by weight, for example 97%.
In any embodiment, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
In any embodiment, the insulating coating is prepared by the steps of:
mixing an insulating material with a solvent to obtain an insulating coating; wherein the insulating material is selected from at least one of boehmite, aluminum oxide, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose and polyacrylic acid;
alternatively, the insulating paint is prepared by the following steps:
mixing the first insulating material with a solvent, crushing, and then mixing with a second insulating material to obtain an insulating coating; wherein the first insulating material is selected from at least one of boehmite and alumina, and the second insulating material is selected from at least one of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene and polyacrylic acid.
In any embodiment, the solvent is selected from the group consisting of water, ethanol, and solutions thereof.
In any embodiment, the weight of the solvent is 90 to 110 times, for example 100 times, the total weight of the insulation material.
In any embodiment, the mixing is at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃).
A fifth aspect of the present application provides a further secondary battery comprising the negative electrode tab of the first aspect of the present application or the negative electrode tab produced by the method of the third aspect of the present application.
A sixth aspect of the present application provides a battery module comprising the secondary battery of the second aspect of the present application, the secondary battery produced by the method of the fourth aspect of the present application, or the secondary battery of the fifth aspect of the present application.
A seventh aspect of the present application provides a battery pack including the battery module of the sixth aspect of the present application.
An eighth aspect of the present application provides an electric device including at least one selected from the group consisting of the secondary battery of the second aspect of the present application, the secondary battery produced by the method of the fourth aspect of the present application, the secondary battery of the fifth aspect of the present application, the battery module of the sixth aspect of the present application, and the battery pack of the seventh aspect of the present application.
Drawings
Fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 4 is a schematic diagram of a battery pack according to an embodiment of the present application.
Fig. 5 is an exploded view of the battery pack according to the embodiment of the present application shown in fig. 4.
Fig. 6 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Fig. 7 is a schematic structural view of the negative electrode tab 3.
Fig. 8 is a schematic structural view of a secondary battery employing the negative electrode tab 2 and the separator 2.
Fig. 9 is a capacity-cycle graph of the secondary batteries of examples 1 to 3 and comparative examples 1 to 3.
Description of reference numerals:
1, a battery pack; 2, putting the box body on the box body; 3, a lower box body; 4 a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 a top cover assembly; 71 a negative electrode current collector; 72 a negative electrode active material layer; 73 an insulating layer; 74 embedding lithium layer; 75 lithium dendrites; 81 a negative current collector; 82 a negative electrode active material layer; 83 an insulating layer; 84 embedding a lithium layer; 85 polypropylene film; 86 lithium dendrites.
Detailed Description
Hereinafter, embodiments of the negative electrode sheet and the method for producing the same, the secondary battery and the method for producing the same, the battery module, the battery pack, and the electric device according to the present application are specifically disclosed in detail with reference to the drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may 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 this application, unless otherwise stated, 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, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is simply an abbreviated representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose 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 and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, a method comprising steps (a) and (b) means that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to a process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not 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 not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
[ Secondary Battery ]
A secondary battery is also called a rechargeable battery or a secondary battery, and refers to a battery that can be continuously used by activating an active material by means of charging after the battery is discharged.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. In the process of charging and discharging the battery, active ions (such as lithium ions) are inserted and extracted back and forth between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable active ions to pass through. The electrolyte is arranged between the positive pole piece and the negative pole piece and mainly plays a role in conducting active ions.
Negative pole piece
One embodiment of the present application provides a negative electrode sheet including a negative electrode active material layer, an insulating layer, and a lithium intercalation layer, the insulating layer being disposed on the negative electrode active material layer, the lithium intercalation layer being disposed on the insulating layer, and the lithium intercalation layer including a lithium intercalation material selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin, and iron phosphate.
Although the mechanism is not clear, the applicant has surprisingly found that: in the negative pole piece, the insulating layer is a substance which does not conduct electrons and conducts ions, and the lithium intercalation layer is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that charging current exceeds a lithium analysis window or overcharge, lithium dendrite penetrates through the insulating layer to contact the lithium embedding layer, and the lithium dendrite and the lithium embedding layer form a lithium embedding loop under the action of electrolyte, so that lithium embedding reaction is generated, further growth of the lithium dendrite is inhibited, when the secondary battery discharges, electrons of the lithium dendrite in the lithium embedding layer are lost to be changed into lithium ions to return to the electrolyte again, the problem that the lithium dendrite continuously grows to consume active lithium ions is avoided, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the operation of the secondary battery are improved; meanwhile, the insulating layer and the lithium embedding layer are sequentially arranged on the negative electrode active material layer, so that a space is reserved between the lithium embedding layer and the isolating membrane of the secondary battery, and therefore, even if the volume of the secondary battery suddenly shrinks in the using process, the phenomenon that the lithium dendrite punctures the isolating membrane due to the sudden shrinkage of the volume of the secondary battery can not occur.
In some embodiments, the insulating layer has a thickness of 0.03 to 8 μm, optionally 0.03 to 4 μm, for example 0.05 to 2 μm. If the insulating layer is too thin, the contact between the negative active material layer and the lithium intercalation layer cannot be effectively isolated, so that the lithium intercalation layer fails and the further growth of lithium dendrites cannot be inhibited; if the insulating layer is too thick, the internal space of the battery cell is occupied, and the energy density of the secondary battery is reduced.
In some embodiments, the thickness of the lithium intercalation layer is from 0.05 to 10 μm, optionally from 0.05 to 5 μm, for example from 1 to 3 μm. If the lithium intercalation layer is too thin, lithium intercalation reaction can not be effectively carried out on the top of the lithium dendrite, and further growth of the lithium dendrite can not be effectively inhibited; if the lithium intercalation layer is too thick, the lithium intercalation layer occupies the internal space of the cell, resulting in a decrease in the energy density of the battery.
In some embodiments, the insulating layer comprises an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid. The insulating material can conduct ions but not electrons, and can effectively prevent the contact between the negative electrode active material layer and the lithium intercalation layer.
In some embodiments, the polyvinylidene fluoride, polyphthalamide, polyethylene, polypropylene, and polyacrylic acid all have a weight average molecular weight greater than 10000 and less than 100000.
In some embodiments, the lithium intercalation material is present in the lithium intercalation layer in an amount of 93% to 98%, for example 97%, by weight. The lithium intercalation material is a substance capable of reversibly deintercalating lithium ions, and when deep lithium precipitation occurs, the lithium dendrite, the lithium intercalation material and the electrolyte form a lithium intercalation circuit to generate a lithium intercalation reaction, so that the further growth of the lithium dendrite is inhibited.
In some embodiments, the lithium intercalation layer further comprises an adjuvant.
In some embodiments, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener. The addition of the auxiliary agent is beneficial to the formation of the lithium intercalation layer and the smooth proceeding of the lithium intercalation reaction.
In some embodiments, the conductive agent is selected from carbon black, carbon nanotubes, carbon fibers, carbon nanofibers, and graphene.
In some embodiments, the binder is selected from styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, and polyalkenoate.
In some embodiments, the thickening agent may be sodium carboxymethyl cellulose.
In some embodiments, the weight ratio of the conductive agent, the binder, and the thickener is 1 (0.7-1.3) to (1-2), optionally 1 (1-2), such as 1.
The addition of the auxiliary agent in the lithium intercalation coating is beneficial to the formation of a lithium intercalation layer and the proceeding of lithium intercalation reaction; wherein, the conductive agent is added to improve the conduction of electrons; the binder can prevent the lithium-embedded layer from falling off in the battery cycle process; the thickener may increase the viscosity or consistency of the lithium intercalation materials for ease of application.
In some embodiments, the negative electrode tab further comprises a negative electrode current collector, a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode active material layer is disposed on either or both of the two surfaces opposite to the negative electrode 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 can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative active material may employ a negative active material for a battery known in the art. As an example, the anode active material 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 selected from at least one of elemental silicon, silicon oxy-compounds, silicon-carbon compounds, silicon-nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative active material layer further optionally includes a binder. As an example, the binder may be selected from at least one of 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).
In some embodiments, the negative active material layer further optionally includes a conductive agent. As an example, the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode active material layer may further optionally include other auxiliaries, such as a thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
Method for preparing negative pole piece
One embodiment of the present application provides a method for preparing a negative electrode sheet, comprising the steps of:
coating an insulating coating on the negative electrode active material layer, drying, and forming an insulating layer on the negative electrode active material layer;
coating lithium embedding paint on the insulating layer, and drying to obtain a negative pole piece;
therefore, in the negative pole piece, the insulating layer is a substance which is not conductive and conducts ions, and the lithium intercalation layer formed by the lithium intercalation coating is a substance which can reversibly deintercalate lithium ions; when the charging current of the battery exceeds a lithium separation window or overcharge causes deep lithium separation, the lithium dendrite penetrates through the insulating layer to contact the lithium intercalation layer, the lithium dendrite and the lithium intercalation layer form a lithium intercalation loop under the action of electrolyte, lithium intercalation reaction occurs, the growth of the lithium dendrite is inhibited, when the secondary battery discharges, metal lithium in the lithium intercalation layer loses electrons and becomes lithium ions to be returned to the electrolyte again, the problem that the lithium dendrite continuously increases and consumes active lithium is solved, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the operation of the secondary battery are improved; and the insulating layer and the lithium embedding layer are sequentially arranged on the negative electrode active material layer, so that a space is reserved between the lithium embedding layer and the isolating membrane of the secondary battery, and therefore, even if the volume of the secondary battery suddenly shrinks in the using process, lithium dendrites cannot penetrate through the isolating membrane due to the sudden shrinkage of the volume of the secondary battery, and the occurrence of short circuit inside the secondary battery is avoided.
In some embodiments, the lithium insertion coating is prepared by the steps of:
mixing a lithium intercalation material, water and an optional auxiliary agent to obtain a lithium intercalation coating; wherein, the lithium embedding material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
In some embodiments, the lithium intercalation coatings are continuously stirred (optionally at a speed of 10 to 30rpm, e.g., 20 rpm) at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃) to prevent settling.
In some embodiments, the lithium intercalation materials are present in the lithium intercalation coating in an amount of 93% to 98%, for example 97%, by weight.
In some embodiments, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
In some embodiments, the conductive agent is selected from carbon black, carbon nanotubes, carbon fibers, carbon nanofibers, and graphene.
In some embodiments, the binder is selected from styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, and polyalkenoate.
In some embodiments, the thickener may be sodium carboxymethylcellulose.
In some embodiments, the weight ratio of the conductive agent, the binder, and the thickener is 1 (0.7-1.3) to (1-2), optionally 1 (1-2), such as 1.
The addition of the auxiliary agent in the lithium intercalation coating is beneficial to the formation of a lithium intercalation layer and the proceeding of a lithium intercalation reaction; wherein, the conductive agent is added to improve the conduction of electrons; the binder can prevent the lithium-embedded layer from falling off in the battery cycle process; the thickener may increase the viscosity or consistency of the lithium intercalation materials for ease of application.
In some embodiments, the insulating coating is prepared by the steps of:
mixing an insulating material with a solvent to obtain an insulating coating; wherein the insulating material is selected from at least one of boehmite, aluminum oxide, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose and polyacrylic acid;
alternatively, the insulating paint is prepared by the following steps:
mixing the first insulating material with a solvent, crushing, volatilizing the solvent, and then mixing the remainder with the second insulating material to obtain an insulating coating; wherein the first insulating material is selected from at least one of boehmite and alumina, and the second insulating material is selected from at least one of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene and polyacrylic acid.
In some embodiments, the solvent is selected from water, ethanol, and solutions thereof. In some embodiments, the weight of the solvent is 90 to 110 times, for example 100 times, the total weight of the insulation material. .
In some embodiments, the mixing is at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃).
In some embodiments, mixing is carried out under stirring conditions (optionally at a stirring speed of 700 to 900 rpm) for 15 to 45 minutes.
In some embodiments, the insulating coating is continuously stirred (optionally at a stirring speed of 10 to 30rpm, for example 20 rpm) at ambient temperature (optionally 20 ℃ to 35 ℃, for example 25 ℃) to prevent sedimentation.
In some embodiments, the disruption is performed by ball milling for 2 to 7 hours (e.g., 4 hours); optionally, ball milling at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃).
In some embodiments, the solvent is volatilized at 70 ℃ to 90 ℃ (e.g., 80 ℃).
In some embodiments, the method of making a negative electrode sheet further comprises: dispersing a negative electrode active material, a conductive agent, a binder, and any other components in a solvent (e.g., deionized water) to form a negative electrode slurry; coating the negative electrode slurry on a negative electrode current collector, and performing the working procedures of drying, cold pressing and the like.
The negative pole piece is prepared by the method for preparing the negative pole piece.
Secondary battery
One embodiment of the present application provides a secondary battery, including a negative electrode plate, a lithium intercalation layer and a separator, wherein the lithium intercalation layer is disposed on one side of the separator facing the negative electrode plate; the negative pole piece comprises a negative active material layer and an insulating layer, wherein the insulating layer is arranged on the negative active material layer; and the lithium intercalation layer contains a lithium intercalation material selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
Therefore, in the secondary battery, the insulating layer is a substance which conducts ions without conducting electrons, and the lithium intercalation layer is a substance which can reversibly intercalate lithium ions; when the charging current of the battery exceeds a lithium separation window or overcharge causes deep lithium separation, the lithium dendrite firstly penetrates through the insulating layer and then contacts with a lithium embedding layer on the isolating membrane along with growth, the lithium dendrite and the lithium embedding layer form a lithium embedding loop under the action of electrolyte, so that lithium embedding reaction occurs, further growth of the lithium dendrite is inhibited, when the secondary battery discharges, metal lithium in the lithium embedding layer loses electrons and becomes lithium ions to return to the electrolyte again, the problem that the lithium dendrite continuously grows to consume active lithium ions and the problem that the lithium dendrite punctures the isolating membrane to cause short circuit in the battery are avoided, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the secondary battery in operation are improved.
In some embodiments, the insulating layer has a thickness of 0.03 to 8 μm, optionally 0.03 to 4 μm, for example 0.05 to 2 μm. If the insulating layer is too thin, the contact between the negative active material layer and the lithium intercalation layer cannot be effectively isolated, so that the lithium intercalation layer fails and the further growth of lithium dendrites cannot be inhibited; if the insulating layer is too thick, the internal space of the cell is occupied, resulting in a decrease in energy density of the secondary battery.
In some embodiments, the lithium insertion layer has a thickness of 0.05 to 10 μm, optionally 0.05 to 5 μm, for example 1 to 3 μm. If the lithium intercalation layer is too thin, lithium intercalation reaction can not be effectively carried out on the top of the lithium dendrite, and further growth of the lithium dendrite can not be effectively inhibited; if the lithium intercalation layer is too thick, the lithium intercalation layer occupies the internal space of the cell, resulting in a decrease in the energy density of the battery.
In some embodiments, the insulating layer comprises an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid. The insulating material can conduct ions but not electrons, and can effectively prevent the contact between the negative electrode active material layer and the lithium intercalation layer.
In some embodiments, the lithium intercalation material is present in the lithium intercalation layer in an amount of 93% to 98%, for example 97%, by weight. The lithium intercalation material is a substance capable of reversibly deintercalating lithium ions, and when deep lithium precipitation occurs, the lithium dendrite, the lithium intercalation material and the electrolyte form a lithium intercalation circuit to generate a lithium intercalation reaction, so that the further growth of the lithium dendrite is inhibited.
In some embodiments, the lithium intercalation layer further comprises an adjuvant.
In some embodiments, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
The addition of the auxiliary agent in the lithium intercalation coating is beneficial to the formation of a lithium intercalation layer and the proceeding of a lithium intercalation reaction; wherein, the conductive agent is added to improve the conduction of electrons; the binder can prevent the lithium-embedded layer from falling off in the battery cycle process; the thickener may increase the viscosity or consistency of the lithium intercalation materials for ease of application.
In some embodiments, the negative electrode tab further comprises a negative electrode current collector, a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode active material layer is disposed on either or both of the two surfaces opposite to the negative electrode 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 can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative active material may employ a negative active material for a battery known in the art. As an example, the anode active material 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 selected from at least one of elemental silicon, silicon oxy-compounds, silicon-carbon compounds, silicon-nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative active material layer further optionally includes a binder. As an example, the binder may be selected from at least one of 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).
In some embodiments, the negative active material layer further optionally includes a conductive agent. As an example, the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode active material layer may further optionally include other auxiliaries, such as a thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
Method for manufacturing secondary battery
One embodiment of the present application provides a method of manufacturing a secondary battery, including the steps of:
coating an insulating coating on the negative active material layer, and drying to obtain a negative pole piece;
coating a lithium-intercalation coating on one surface of the isolating membrane facing the negative pole piece, and drying to obtain the isolating membrane provided with a lithium-intercalation layer;
and assembling the secondary battery by using the negative pole piece and the isolating membrane provided with the lithium-embedded layer.
Therefore, in the secondary battery, the insulating layer formed by the insulating coating is a substance which is not conductive to conduct ions, and the lithium intercalation layer is a substance which can reversibly deintercalate lithium ions; when the secondary battery deeply analyzes lithium due to the fact that the charging current exceeds a lithium analysis window or the secondary battery is overcharged, lithium dendrite firstly penetrates through an insulating layer, then the lithium dendrite and the lithium intercalation layer on an isolating membrane form a lithium intercalation loop under the action of electrolyte, lithium intercalation reaction is generated, growth of the lithium dendrite is restrained, when the secondary battery discharges, lithium losing electrons in the lithium intercalation layer are changed into lithium ions and then return to the electrolyte, the problem that the lithium dendrite continuously grows to consume active lithium and the problem that the lithium dendrite pierces the isolating membrane to cause short circuit in the battery are solved, the first coulomb effect and the cycle performance of the secondary battery are improved, the capacity of the secondary battery in a critical failure charge state is improved, and the safety and the stability of the secondary battery in operation are improved.
In some embodiments, the lithium insertion coating is prepared by the steps of:
mixing a lithium intercalation material, water and an optional auxiliary agent to obtain a lithium intercalation coating; wherein, the lithium-embedded material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
In some embodiments, the lithium intercalation materials are continuously stirred (optionally at 10-30 rpm, e.g., 20 rpm) at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃) to prevent settling.
In some embodiments, the lithium intercalation materials are present in the lithium intercalation coating in an amount of 93% to 98%, for example 97%, by weight. The lithium intercalation material is a substance capable of reversibly deintercalating lithium ions, and when deep lithium precipitation occurs, the lithium dendrite, the lithium intercalation material and the electrolyte form a lithium intercalation circuit to generate a lithium intercalation reaction, so that the further growth of the lithium dendrite is inhibited.
In some embodiments, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
In some embodiments, the conductive agent is selected from carbon black, carbon nanotubes, carbon fibers, carbon nanofibers, and graphene.
In some embodiments, the binder is selected from styrene butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, and polyalkenoate.
In some embodiments, the thickening agent may be sodium carboxymethyl cellulose. In some embodiments, the weight ratio of the conductive agent, the binder, and the thickener is 1 (0.7-1.3) to (1-2), optionally 1 (1-2), such as 1.
The addition of the auxiliary agent in the lithium intercalation coating is beneficial to the formation of a lithium intercalation layer and the proceeding of lithium intercalation reaction; wherein, the conductive agent is added to improve the conduction of electrons; the binder can prevent the lithium-embedded layer from falling off in the battery cycle process; the thickener may increase the viscosity or consistency of the lithium intercalation materials for ease of application.
In some embodiments, the insulating coating is prepared by the steps of:
mixing an insulating material with a solvent to obtain an insulating coating; wherein the insulating material is selected from at least one of boehmite, aluminum oxide, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose and polyacrylic acid;
alternatively, the insulating paint is prepared by the following steps:
mixing the first insulating material with a solvent, crushing, volatilizing the solvent, and then mixing the remainder with the second insulating material to obtain an insulating coating; wherein the first insulating material is selected from at least one of boehmite and alumina, and the second insulating material is selected from at least one of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene and polyacrylic acid.
The insulating layer formed after the insulating coating is coated can conduct ions but not conduct electrons, and can effectively prevent the contact between the negative electrode active material layer and the lithium intercalation layer.
In some embodiments, the solvent is selected from water, ethanol, and solutions thereof.
In some embodiments, the solvent is present in an amount of 90 to 110 times, for example 100 times, the total weight of the insulation material. In some embodiments, mixing is at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃).
In some embodiments, mixing is carried out under stirring conditions (optionally at a stirring speed of 700 to 900 rpm) for 15 to 45 minutes.
In some embodiments, the insulating coating is continuously stirred (optionally at a stirring speed of 10 to 30rpm, for example 20 rpm) at ambient temperature (optionally 20 ℃ to 35 ℃, for example 25 ℃) to prevent settling.
In some embodiments, the disruption is performed by ball milling for 2 to 7 hours (e.g., 4 hours); optionally, ball milling at ambient temperature (optionally 20 ℃ to 35 ℃, e.g., 25 ℃). The fineness of the first insulating material particles in the insulating coating can be ensured by crushing through ball milling treatment so as to ensure the quality of the insulating layer.
In some embodiments, the solvent is volatilized at 70 ℃ to 90 ℃ (e.g., 80 ℃).
The above-described secondary battery is manufactured by the method of manufacturing a secondary battery according to the present application.
[ Positive electrode sheet ]
The positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, and the positive electrode film layer includes a positive electrode active material.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, an aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive active material may employ a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material 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 positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide 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 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, 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 referred to as LFP for short)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
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), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
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.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ electrolyte ]
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethylsulfone, methylethylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. By way of example, the additives may include a negative electrode film-forming additive, a positive electrode film-forming additive, and may further include additives capable of improving certain properties of the battery, such as additives that improve the overcharge properties of the battery, additives that improve the high-or low-temperature properties of the battery, and the like.
[ isolation film ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator as described above may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and electrolyte.
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 outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other arbitrary shape. For example, fig. 1 is a secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 2, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodation chamber, and a cover plate 53 can 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 within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to the actual needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries included in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
Fig. 3 is a battery module 4 as an example. Referring to fig. 3, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other manner. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack 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 pack.
Fig. 4 and 5 are a battery pack 1 as an example. Referring to fig. 4 and 5, a battery pack 1 may include a battery case and a plurality of battery modules 4 disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. A plurality of battery modules 4 may be arranged in any manner in the battery box.
In addition, this application still provides an electric installation, and electric installation includes at least one in secondary battery, battery module or the battery package that this application provided. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The powered device may include, but is not limited to, a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, and a satellite, an energy storage system, etc.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to its use requirement.
Fig. 6 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle and the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
[ examples ]
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Examples 1 to 3 and comparative examples 1 to 3
Preparation of (I) insulating coating
1. Preparation of insulating coating 1:
dissolving 68g of polyacrylic acid (PAA) in 6800g of deionized water, stirring at 25 ℃ and 800rpm for 30 minutes to obtain a uniform colloidal solution, and continuously stirring at 25 ℃ and 20rpm to prevent gel sedimentation to obtain an insulating coating 1;
2. preparation of insulating paint 2:
mixing 54g of aluminum oxide, 36g of boehmite powder and 1000g of absolute ethyl alcohol, ball-milling for 4 hours at 25 ℃, standing for 30min in a high-temperature oven at 80 ℃ to obtain particles with the size of 0.5-2 mu m, mixing the particles with 10g of PVDF, and continuously stirring at 20rpm at 25 ℃ to obtain the insulating coating 2;
preparation of lithium-insertion coating
Preparation of lithium intercalation coating 1:
dissolving an active material lithium titanate, a conductive agent carbon black, a binder Styrene Butadiene Rubber (SBR) and a thickening agent sodium carboxymethyl cellulose (CMC) in deionized water according to a weight ratio of 96.2;
(III) preparation of negative pole piece
1. Preparing a negative pole piece 1:
dissolving active substance artificial graphite, a conductive agent carbon black, a binder Styrene Butadiene Rubber (SBR) and a thickening agent sodium carboxymethyl cellulose (CMC) in deionized water according to a weight ratio of 96.2; uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector for one time or multiple times, and drying and cold pressing to obtain a negative electrode plate 1 which comprises a negative electrode current collector and a negative electrode active material layer loaded on the negative electrode current collector;
2. preparing a negative pole piece 2:
coating insulating paint on a negative active material layer by adopting a negative pole piece 1 through a transfer coating machine, drying to obtain a negative pole piece 2, and performing die cutting for later use; the negative pole piece 2 comprises a negative pole current collector, a negative pole active material layer loaded on the negative pole current collector and an insulating layer loaded on the negative pole active material layer;
3. preparing a negative pole piece 3:
coating the lithium-embedded coating on the insulating layer by a coating machine by adopting a negative pole piece 2, drying to obtain a negative pole piece 3, and performing die cutting for later use; the negative electrode tab 3 includes a negative electrode collector 71, a negative electrode active material layer 72 supported on the negative electrode collector 71, an insulating layer 73 supported on the negative electrode active material layer 72, and a lithium intercalation layer 74 supported on the insulating layer 73, and the structure is shown in fig. 7.
(IV) preparation of isolation Membrane
1. Preparation of the separator 1:
taking a polypropylene film as a separation film 1;
2. preparation of the separator 2:
coating a lithium embedding coating on one surface of the polypropylene film, and drying to obtain a separation film 2 which comprises the polypropylene film and a lithium embedding layer loaded on the polypropylene film;
3. preparation of the separator 3:
coating an insulating coating on the lithium intercalation layer by a transfer coating machine by adopting a separation film 2, and drying to obtain a separation film 3, wherein the separation film 3 comprises a polypropylene film, a lithium intercalation layer loaded on the polypropylene film and an insulating layer loaded on the lithium intercalation layer;
(V) preparation of positive pole piece
Uniformly mixing a nickel-cobalt-manganese (NCM) ternary material, a conductive agent carbon black, a binder polyvinylidene fluoride (PVDF), and N-methylpyrrolidone (NMP) according to a weight ratio of 97.5; uniformly coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and slitting to obtain a positive electrode piece;
(VI) preparation of electrolyte
In a glove box under argon atmosphere (water content)<0.1ppm, oxygen content<0.1 ppm), mixing uniformly organic solvent Ethylene Carbonate (EC)/Ethyl Methyl Carbonate (EMC) at a volume ratio of 3/7, adding 12.5% of LiPF 6 Dissolving lithium salt and uniformly stirring to obtain electrolyte;
(VII) Battery Assembly
The battery core is assembled by adopting the positive pole piece, the negative pole piece, the isolating membrane and the electrolyte, and is injected with liquid, and the secondary battery is obtained through procedures of formation, aging, K measurement, capacity test and the like.
The structure of the secondary battery adopting the negative electrode plate 2 and the isolating membrane 2 is shown in fig. 8: the negative electrode tab 2 includes a negative electrode current collector 81, a negative electrode active material layer 82 supported on the negative electrode current collector 81, and an insulating layer 83 supported on the negative electrode active material layer 82; the separator 2 includes a polypropylene film 85 and a lithium intercalation layer 84 supported on the polypropylene film 85.
The parameters of examples 1 to 3 and comparative examples 1 to 3 are detailed in Table 1.
TABLE 1 parameters of examples 1-3 and comparative examples 1-3
Battery testing
(1) The secondary batteries of examples 1 to 3 and comparative examples 1 to 3 were charged and discharged at 25 ℃ at a rate of 1.5C for 500 cycles, the charging and discharging depths were all 100%, and the results of capacity retention rates of the secondary batteries after the cycles are shown in table 2, in which the capacity-cycle curves of the secondary batteries of examples 1 to 3 and comparative examples 1 to 3 are shown in fig. 9.
(2) The secondary batteries of examples 1 to 3 and comparative examples 1 to 3 were charged at a constant current of 1/3C times, and were overcharged until the electric quantity charged in the battery cell could not be charged or the battery capacity rapidly decayed, and the potential of the negative electrode plate with respect to elemental lithium was less than 0, and the battery capacity measured at this time was taken as the critical failure state of charge, and the results are shown in table 2.
(3) The secondary batteries of examples 1 to 3 and comparative examples 1 to 3 were subjected to 100% deep charge-discharge cycling at-30 ℃ to 0 ℃ for 100 times, and then to a self-discharge rate test for full charge (100% soc) of the secondary battery, in general, the separator was penetrated by lithium dendrite to cause internal short circuit of the battery, which caused self-discharge of the secondary battery, and the self-discharge rate of the secondary battery was 0.04mV/h or more, which was generally considered to have caused internal short circuit of the battery, and the results of the measured self-discharge rate were shown in table 2.
TABLE 2 results of Performance test of examples 1 to 3 and comparative examples 1 to 3
As can be seen from table 2 and fig. 9, compared with comparative examples 1 to 3, the cycle capacity retention rate of the battery of the embodiment of the present application is higher, and the battery capacity in the critical failure state of charge is higher, which indicates that the deep growth of lithium dendrite in the secondary battery of the embodiment of the present application is effectively inhibited, so that the first coulombic efficiency and the cycle capacity retention rate of the battery are improved, and the safety and the stability of the battery use are improved. Moreover, the self-discharge rate of the secondary batteries of comparative examples 1 to 3 after 100 cycles of 100% deep charge and discharge at low temperature was 0.097 to 0.139mV/h, which indicates that the batteries of comparative examples 1 to 3 had short circuits in the batteries caused by the penetration of lithium dendrites into the separator, while the self-discharge rate of the secondary batteries of the embodiments of the present application after 100 cycles of 100% deep charge and discharge at low temperature was much less than 0.04mV/h, indicating that the secondary batteries of the embodiments of the present application can effectively avoid the problem of short circuits in the batteries caused by the penetration of lithium dendrites into the separator.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (18)
1. A negative electrode plate comprises a negative electrode active material layer, an insulating layer and a lithium intercalation layer, wherein the insulating layer is arranged on the negative electrode active material layer, the lithium intercalation layer is arranged on the insulating layer, the lithium intercalation layer contains a lithium intercalation material, and the lithium intercalation material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
2. The negative electrode tab of claim 1, wherein the insulating layer has a thickness of 0.03 to 8 μm.
3. The negative electrode tab according to claim 1 or 2, wherein the thickness of the lithium intercalation layer is 0.05-10 μm.
4. The negative electrode tab of any one of claims 1 to 3, wherein the insulating layer contains an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenol resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid.
5. The negative electrode plate as claimed in any one of claims 1 to 4, wherein the weight content of the lithium intercalation material in the lithium intercalation layer is 93-98%;
optionally, the lithium intercalation layer further comprises a promoter;
optionally, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
6. A secondary battery comprises a negative pole piece, a lithium embedding layer and a separation film, wherein the lithium embedding layer is arranged on one surface of the separation film facing the negative pole piece; the negative pole piece comprises a negative active material layer and an insulating layer, wherein the insulating layer is arranged on the negative active material layer; and the lithium intercalation layer contains a lithium intercalation material selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate.
7. The secondary battery according to claim 6, wherein the insulating layer has a thickness of 0.03 to 8 μm.
8. The secondary battery according to claim 6 or 7, wherein the thickness of the lithium intercalation layer is 0.05-10 μm.
9. The secondary battery according to any one of claims 6 to 8, wherein the insulating layer contains an insulating material selected from at least one of boehmite, alumina, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenol resin, polyethylene, polypropylene, carboxymethyl cellulose, and polyacrylic acid.
10. The secondary battery according to any one of claims 6 to 9, wherein the lithium intercalation material is present in an amount of 93-98% by weight in the lithium intercalation layer;
optionally, the lithium intercalation layer further comprises an auxiliary agent;
optionally, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
11. A method for preparing a negative pole piece comprises the following steps:
coating an insulating coating on the negative electrode active material layer, and drying to form an insulating layer on the negative electrode active material layer;
and coating a lithium embedding coating on the insulating layer, and drying to obtain the negative pole piece.
12. A method of manufacturing a secondary battery, comprising the steps of:
coating an insulating coating on the negative active material layer, and drying to obtain a negative pole piece;
coating a lithium-embedded coating on one surface of the isolating membrane facing to the negative pole piece, and drying to obtain the isolating membrane provided with the lithium-embedded layer;
and assembling the secondary battery by using the negative pole piece and the isolating membrane provided with the lithium-embedded layer.
13. The method of claim 11 or 12, wherein the lithium insertion coating is prepared by:
mixing a lithium intercalation material, water and an optional auxiliary agent to obtain a lithium intercalation coating; wherein the lithium intercalation material is selected from at least one of lithium titanate, titanium niobate, lithium niobate, graphite, silicon, tin and iron phosphate;
optionally, the weight content of the lithium intercalation material in the lithium intercalation coating is 93-98%;
optionally, the auxiliary agent is selected from at least one of a conductive agent, a binder, and a thickener.
14. The method according to claim 11 or 12, wherein the insulating paint is prepared by:
mixing an insulating material with a solvent to obtain an insulating coating; wherein the insulating material is selected from at least one of boehmite, aluminum oxide, polyvinylidene fluoride, styrene butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene, carboxymethyl cellulose and polyacrylic acid;
alternatively, the insulating paint is prepared by the following steps:
mixing the first insulating material with a solvent, crushing, volatilizing the solvent, and then mixing the remainder with the second insulating material to obtain an insulating coating; wherein the first insulating material is selected from at least one of boehmite and alumina, and the second insulating material is selected from at least one of carboxymethyl cellulose, polyvinylidene fluoride, styrene-butadiene rubber, polyphthalamide, phenolic resin, polyethylene, polypropylene and polyacrylic acid;
optionally, the solvent is selected from water, ethanol, and solutions thereof;
optionally, the weight of the solvent is 90 to 110 times, for example 100 times, the total weight of the insulation material;
alternatively, mixing is performed at normal temperature.
15. A secondary battery comprising the negative electrode tab of any one of claims 1 to 5 or the negative electrode tab made by the method of claim 11 or 13 or 14.
16. A battery module comprising the secondary battery of any one of claims 6 to 10, the secondary battery produced by the method of any one of claims 12 to 14, or the secondary battery of claim 15.
17. A battery pack comprising the battery module of claim 16.
18. An electric device comprising at least one selected from the group consisting of the secondary battery according to any one of claims 6 to 10, the secondary battery produced by the method according to any one of claims 12 to 14, the secondary battery according to claim 15, the battery module according to claim 16, and the battery pack according to claim 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111385349.8A CN115832640A (en) | 2021-11-22 | 2021-11-22 | Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111385349.8A CN115832640A (en) | 2021-11-22 | 2021-11-22 | Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115832640A true CN115832640A (en) | 2023-03-21 |
Family
ID=85515470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111385349.8A Pending CN115832640A (en) | 2021-11-22 | 2021-11-22 | Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115832640A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116526069A (en) * | 2023-07-04 | 2023-08-01 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery and electricity utilization device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| CN108448160A (en) * | 2017-02-16 | 2018-08-24 | 宁德新能源科技有限公司 | Safe floor and lithium secondary battery |
| CN111354904A (en) * | 2018-12-21 | 2020-06-30 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery diaphragm, lithium ion battery electrode and lithium ion battery |
-
2021
- 2021-11-22 CN CN202111385349.8A patent/CN115832640A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| CN108448160A (en) * | 2017-02-16 | 2018-08-24 | 宁德新能源科技有限公司 | Safe floor and lithium secondary battery |
| CN111354904A (en) * | 2018-12-21 | 2020-06-30 | 深圳市比亚迪锂电池有限公司 | Lithium ion battery diaphragm, lithium ion battery electrode and lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116526069A (en) * | 2023-07-04 | 2023-08-01 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery and electricity utilization device |
| CN116526069B (en) * | 2023-07-04 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery and electricity utilization device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115810796B (en) | Electrolyte, secondary battery comprising same and preparation method of secondary battery | |
| CN115832184A (en) | Lithium-free negative pole piece and preparation method thereof, secondary battery, battery module, battery pack and electric device | |
| CN115832290A (en) | Negative electrode active material, preparation method thereof, negative electrode plate, secondary battery, battery module, battery pack and electric device | |
| CN117747952A (en) | Lithium ion battery, battery module, battery pack and electricity utilization device | |
| CN116526069B (en) | Separator, battery cell, battery and electricity utilization device | |
| CN115832640A (en) | Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device | |
| CN116670846A (en) | Secondary battery and electricity device comprising same | |
| CN115810863A (en) | Separator, method for producing same, secondary battery, battery module, battery pack, and electric device | |
| CN116941091A (en) | Negative electrode plate, preparation method thereof, secondary battery, battery module, battery pack and power utilization device | |
| CN116897442A (en) | Positive pole piece and lithium ion battery comprising same | |
| CN115133030A (en) | Anode piece of lithium ion battery and application thereof | |
| CN116053469B (en) | Positive electrode active material, positive electrode sheet, secondary battery, and electricity device | |
| WO2023141954A1 (en) | Lithium-ion battery, battery module, battery pack, and electric apparatus | |
| WO2024000102A1 (en) | Negative electrode sheet and preparation method therefor, secondary battery, battery module, battery pack, and electric device | |
| WO2023133833A1 (en) | Secondary battery, battery module, battery pack and electric apparatus | |
| US20230112421A1 (en) | Electrode assembly, secondary battery, battery module, battery pack and electrical device | |
| WO2023082039A1 (en) | Negative electrode sheet, secondary battery, battery module, battery pack, and electric device | |
| CN116470047A (en) | Negative electrode sheet, secondary battery, battery module, battery pack, and electricity-using device | |
| CN115832240A (en) | Positive electrode active material, method for producing same, secondary battery, battery module, battery pack, and electric device | |
| CN115832462A (en) | Core-shell material, coating, secondary battery, battery module, battery pack, and electric device | |
| CN118213597A (en) | Battery monomer, battery and power consumption device | |
| CN117044005A (en) | Electrolyte, and secondary battery, battery module, battery pack, and electricity device using same | |
| CN117239212A (en) | Secondary battery, manufacturing method thereof, battery module, battery pack and power utilization device | |
| CN116941084A (en) | Secondary battery | |
| CN116979020A (en) | Negative electrode plate, secondary battery, battery module, battery pack and power utilization device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |