JP2021532531A - リチウムイオン電池及びそれを含む電気機器 - Google Patents
リチウムイオン電池及びそれを含む電気機器 Download PDFInfo
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- JP2021532531A JP2021532531A JP2020564740A JP2020564740A JP2021532531A JP 2021532531 A JP2021532531 A JP 2021532531A JP 2020564740 A JP2020564740 A JP 2020564740A JP 2020564740 A JP2020564740 A JP 2020564740A JP 2021532531 A JP2021532531 A JP 2021532531A
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- Prior art keywords
- group
- positive electrode
- electrolytic solution
- ion battery
- lithium ion
- Prior art date
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 101
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 115
- 239000007774 positive electrode material Substances 0.000 claims abstract description 46
- 238000009792 diffusion process Methods 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- -1 phosphoric acid ester compound Chemical class 0.000 claims description 72
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001764 infiltration Methods 0.000 claims description 14
- 230000008595 infiltration Effects 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 125000004450 alkenylene group Chemical group 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001923 cyclic compounds Chemical class 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- 229910052720 vanadium Inorganic materials 0.000 claims description 6
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- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
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- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 claims description 4
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- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
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- 125000001424 substituent group Chemical group 0.000 claims description 3
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical group FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- ZDCRNXMZSKCKRF-UHFFFAOYSA-N tert-butyl 4-(4-bromoanilino)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1NC1=CC=C(Br)C=C1 ZDCRNXMZSKCKRF-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 238000010586 diagram Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 19
- 239000011572 manganese Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 229910013716 LiNi Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
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- 239000011267 electrode slurry Substances 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 4
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- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 4
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 4
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
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- 230000005484 gravity Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
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- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
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- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-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
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- LTXHKPDRHPMBKA-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2] LTXHKPDRHPMBKA-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000007572 expansion measurement Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 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
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- PIHTXGRVQBTVRE-KFYAXVMHSA-N olivin Chemical group OC1=CC(O)=C2C(O)=C(C(=O)[C@H]([C@H]([C@H](OC)C(=O)[C@@H](O)[C@@H](C)O)C3)O)C3=CC2=C1 PIHTXGRVQBTVRE-KFYAXVMHSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
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Abstract
Description
電極アセンブリと、前記電極アセンブリに浸潤された電解液と、を備え、
前記電極アセンブリは、電極本体、正極タブ、及び負極タブを含み、
前記電極本体は、軸線周りに巻回された正電極シート、負電極シート、及び前記正電極シートと前記負電極シートとの間に設けられたセパレータを含み、前記正電極シートは、正極集電体、及び前記正極集電体の少なくとも一方の表面に設けられた正極材料層を含み、前記正極タブは、前記正電極シートに接続され、前記負極タブは、前記負電極シートに接続され、
前記電極本体は、軸線方向(X)に沿って対向して配置された両側部を有し、前記正極タブ及び前記負極タブは、前記電極本体の両側部からそれぞれ延出しており、
前記電解液は、添加剤Aを含有し、前記添加剤Aは、不飽和結合含有のリン酸エステル化合物、−SO2−結合含有の環状化合物、不飽和結合含有の環状シロキサン化合物のうちの少なくとも1つを含み、前記電極本体における前記電解液の拡散速度vは、0.01μg/s〜5μg/sであり、
前記v=γ×H/Lであり、
前記γは、前記電解液に対する前記正電極シートの吸液速度であり、単位は、μg/sであり、
前記Hは、前記電極本体の幅方向(Z)に沿った側部の最大長さであり、単位は、mmであり、
前記Lは、前記電極本体の前記軸線方向(X)に沿った長さであり、単位は、mmである、
リチウムイオン電池。
リチウムイオン電池を含む電気機器。
本願のリチウムイオン電池は、巻回型リチウムイオン電池であり、正・負極タブをそれぞれ軸線方向に沿った電極本体の両側部に設けることにより、電池セルの内部空間利用率を効果的に向上させることができ、電池の体積エネルギー密度を高めることができる。同時に、正電極シートの表面に緻密なSEI膜を形成することができる添加剤Aを電解液に添加し、電解液の浸潤性を正電極シートのミクロ構造や電極本体の構造に合わせることで、添加剤A含有の電解液の電極本体への拡散速度を0.01μg/s〜5μg/sの範囲に制御でき、よって、電解液がサイクル過程で巻回型コア内部へ速やかに浸潤又は還流できるよう確保し、また、正電極シートの表面に新たなSEI膜を適時に形成でき、そのため、リチウムイオン電池のサイクル性能や安全性を向上でき、高容量リチウムイオン電池のガス生成問題を抑制できる。したがって、本願で提供されるリチウムイオン電池は、高エネルギー密度、高サイクル安定性、及び高安全性の特徴を有する。より好ましくは、リチウムイオン電池は、より高い高温貯蔵性能を有することもできる。本願の電気機器は、上述したリチウムイオン電池を含むので、少なくとも同様の利点を有する。
Li1+XNiaCobM1−a−bO2−yAy 式(1)
Li1+X’Nia’M’2−a’O4−y’A’y’ 式(2)
c[Li2MnO3]・(1−c)[LiM”2O2−y”A”y”] 式(3)
以下の実施例は、本願において開示される内容をより具体的に説明する。これらの実施例は、単に説明のためのものであり、本願の開示の範囲内での様な修正及び変更は、当業者にとっては明らかである。特に明記しない限り、以下の実施例において報告される全ての部、百分率、及び比率は、重量に基づいており、実施例において使用された全ての試薬は市販されているか、又は常法に従って合成されており、さらに処理することなく直接使用することができる。また、実施例で使用される装置は市販されている。
本実施例は、正電極シート、セパレータ、及び負電極シートが順次巻回されてなる電極本体と、前記電極本体の両端にそれぞれ設けられた正極タブ及び負極タブと、前記電極本体に浸潤された電解液と、を備えたリチウムイオン電池である(具体的な構成は、図1を参照)。具体的に、本実施例のリチウムイオン電池の製造工程は、以下の通りである。
(1)正電極シートの製造
正極活物質 LiNi0.8Co0.1Mn0.1O2(NCM811)、導電剤 Super P、接着剤 ポリフッ化ビニリデン(PVDF)を94:3:3の質量百分率で混合して、溶媒 N−メチルピロリドン(NMP)へ添加し、真空攪拌機を用いて系が均一になるまで攪拌して、正極スラリーを取得し、正極スラリーにおける固形分は77wt%である。正極スラリーを厚さ 14μmの正極集電体アルミニウム箔上に均一に塗布し、85℃で乾燥した。その後、冷間プレス、耳切、シートカット、バーカットを経て、最後に85℃の真空条件下で4時間乾燥して、正電極シートを得た。
(2)負電極シートの製造
負極活物質 黒鉛、導電剤 Super P、増粘剤 カルボキシメチルセルロースナトリウム CMC−Na、接着剤 スチレンブタジエンゴムエマルジョン SBRを94:2:2:2の質量百分率で混合し、溶媒 脱イオン水へ添加し、真空攪拌機の作用下で、負極スラリーを取得し、負極スラリーにおける固形分は54wt%である。負極スラリーを厚さ 8μmの負極集電体銅箔上に均一に塗布し、85℃で乾燥した。その後、冷間プレス、耳切、シートカット、バーカットを経て、最後に120℃の真空条件下で12時間乾燥し、負電極シートを得た。
(3)電解液の製造
含水量<10ppmのアルゴン雰囲気グローブボックス内でEC、EMC、EAを30:60:10の質量百分率で混合して有機溶媒とし、次に、十分に乾燥されたリチウム塩LiPF6を混合後の有機溶媒で溶解し、その後、添加剤A トリアリルホスフェートを2wt%添加し、均一に混合して電解液を得た。
当該電解液において、LiPF6の濃度は、1moL/Lである。
(4)セパレータの製造
厚さ 16μmのポリエチレンフィルムPEをベースフィルムとし、PE多孔質フィルムの少なくとも一方の表面にセラミック粒子含有のコーティング層を塗布してセパレータを形成した。
(5)リチウムイオン電池の製造
正電極シート、セパレータ、負電極シートを順次に積層し、セパレータが正電極シートと負電極シートとの間で分離の役割を果たすようにした後、角型の電極本体に巻いて、電極本体の長手方向の両端にタブを溶接し、電極本体を包装材料アルミプラスチックフィルム又はスチールシェルに入れた後、80℃で乾燥して水を除去した後、対応する電解液を注入して密封し、その後、静置、熱冷間プレス、化成、排気、整形、容量テストなどの工程を経て、完成品のリチウムイオン電池を得た。
実施例2〜18及び比較例1〜3は、それぞれリチウムイオン電池であり、実施例1との相違点を表1に示す。表1において、各溶媒及び添加剤Aの添加量は、電解液の全質量を基準として算出した質量百分率である。その他は実施例1と同様である。
次に、各実施例及び比較例のリチウムイオン電池の性能を測定する。
1)電解液に対する正電極シートの吸液速度γの測定方法
実施例及び比較例に記載の正電極シートを十分に乾燥させた後、5cm×5cmの正方形に切断し、試料台に固定する。次に、直径d=0.2mmのキャピラリーを選択して、実施例及び比較例に記載の電解液を一定の高さHまで吸収する。電解液が吸い込まれたキャピラリーを正電極シートに垂直に接触させ、キャピラリーの液面が下がるのをストップウォッチで計時する。液面が全部下がったら、液体吸収時間tを読取る。最後に、式γ=π×(d/2)2×h×ρ/tに従って、吸液速度の値を計算し、ここで、ρは電解液の密度である。
各実施例及び比較例の測定結果を表1に示す。
実施例及び比較例で製造した新品のリチウムイオン二次電池を25℃で5分間放置し、1Cの定電流で4.2Vまで充電し、さらに電流が0.05C以下になるまで定電圧で充電した後、5分間放置し、さらに1Cの定電流で2.8Vまで放電したものを一回の充放電サイクルとし、今回の放電容量をリチウムイオン二次電池の初回目サイクルの放電容量とする。リチウムイオン電池を上記の方法で800回サイクル充放電測定を行い、1回サイクル当たりの放電容量を記録する。各実施例及び比較例の測定結果を表2に示す。
リチウムイオン電池の25℃、1C/1Cで400回サイクル後の容量保持率(%)=800回目サイクルの放電容量/初回目サイクルの放電容量×100%。
25℃で、1Cの定電流で4.2Vの電圧まで充電し、4.2Vの定電圧で0.05Cの電流まで充電した後、リチウムイオン電池の体積を測定し、V2として記録する。次に、満充電のリチウムイオン電池を80℃の恒温槽に入れ、10日間保存し、排水法を用いて体積を測定し、V3として記録する。
リチウムイオン電池の80℃で10日間保存した後の体積膨張率(%)=(V3−V2)/V2×100%。
各実施例及び比較例の測定結果を表2に示す。
Claims (17)
- 電極アセンブリと、前記電極アセンブリに浸潤された電解液と、を備え、
前記電極アセンブリは、電極本体、正極タブ、及び負極タブを含み、
前記電極本体は、軸線周りに巻回された正電極シート、負電極シート、及び前記正電極シートと前記負電極シートとの間に設けられたセパレータを含み、前記正電極シートは、正極集電体、及び前記正極集電体の少なくとも一方の表面に設けられた正極材料層を含み、前記正極タブは、前記正電極シートに接続され、前記負極タブは、前記負電極シートに接続され、
前記電極本体は、軸線方向(X)に沿って対向して配置された両側部を有し、前記正極タブ及び前記負極タブは、前記電極本体の両側部からそれぞれ延出しており、
前記電解液は、添加剤Aを含有し、前記添加剤Aは、不飽和結合含有のリン酸エステル化合物、−SO2−結合含有の環状化合物、不飽和結合含有の環状シロキサン化合物のうちの少なくとも1つを含み、前記電極本体における前記電解液の拡散速度vは、0.01μg/s〜5μg/sであり、
前記v=γ×H/Lであり、
前記γは、前記電解液に対する前記正電極シートの吸液速度であり、単位は、μg/sであり、
前記Hは、前記電極本体の幅方向(Z)に沿った側部の最大長さであり、単位は、mmであり、
前記Lは、前記電極本体の前記軸線方向(X)に沿った長さであり、単位は、mmである、
リチウムイオン電池。 - 前記電極本体における前記電解液の拡散速度vは、0.2μg/s〜2μg/sである、
請求項1に記載のリチウムイオン電池。 - 前記H及び前記Lは、0.05≦H/L≦0.8、好ましくは、0.1≦H/L≦0.6、より好ましくは、0.15≦H/L≦0.5を満たす、
請求項1又は2に記載のリチウムイオン電池。 - 前記電極本体の軸線方向(X)は水平方向である、
請求項1乃至3のいずれか1項に記載のリチウムイオン電池。 - 前記電解液中の前記添加剤Aの質量百分率w(%)及び拡散速度v(μg/s)は、0.1≦w×v≦10、好ましくは、0.4≦w×v≦5を満たす、
請求項1乃至4のいずれか1項に記載のリチウムイオン電池。 - 前記不飽和結合含有のリン酸エステル化合物は、式1の化合物のうちの少なくとも1つであり、
ここで、R1、R2及びR3は、それぞれ独立に、炭素数1〜6のアルキル基、アルケニル基、アルキニル基、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、炭素数6〜10のアリール基、又はハロアリール基から選択される1つであり、R1、R2及びR3のうちの少なくとも1つは、二重結合又は三重結合を含み、
好ましくは、リン−酸素結合含有化合物のR1、R2及びR3の少なくとも1つの分岐鎖の末端は、炭素−炭素不飽和結合であり、
より好ましくは、リン−酸素結合含有化合物のR1、R2及びR3の分岐鎖の末端は、すべてが炭素−炭素不飽和結合である、
請求項1乃至5のいずれか1項に記載のリチウムイオン電池。 - 前記−SO2−結合含有の環状化合物は、式2〜式5の化合物のうちの少なくとも1つを含み、
ここで、R4は、炭素数1〜4のアルキレン基、炭素数1〜4のフルオロアルキレン基、炭素数2〜4のアルケニレン基、炭素数2〜4のフルオロアルケニレン基、炭素数6〜14のアリーレン基、炭素数6〜10のフルオロアリーレン基のうちの1つであり、
R5、R6、R7及びR8は、それぞれ独立に、H、炭素数1〜6のアルキル基、アルケニル基、アルキニル基、ハロアルキル基、ハロアルケニル基、ハロアルキニル基、炭素数6〜10のアリール基、又はハロアリール基のうちの1つであり、nは、1、2又は3であり、
R17及びR18は、それぞれ独立に、炭素数1〜4のアルキレン基、炭素数1〜4のフルオロアルキレン基、炭素数2〜4のアルケニレン基、炭素数2〜4のフルオロアルケニレン基、炭素数6〜14のアリーレン基、炭素数6〜10のフルオロアリーレン基のうちの1つである、
請求項1乃至5のいずれか1項に記載のリチウムイオン電池。 - 前記添加剤Aは、1,3−プロパンスルトン、プロペンスルトン、メタンジスルホン酸メチレン、トリアリルホスフェート、テトラメチルテトラビニルシクロテトラシロキサンのから選択される少なくとも1つであり、
好ましくは、前記添加剤Aは、メタンジスルホン酸メチレン、トリアリルホスフェート、及びテトラメチルテトラビニルシクロテトラシロキサンから選択される少なくとも1つである、
請求項1乃至8のいずれか1項に記載のリチウムイオン電池。 - 前記電解液の25±3℃での粘度は、0.5mPa・s〜5.0mPa・sであり、及び/又は
前記電解液の0℃での粘度は、1mPa・s〜6.0mPa・sである、
請求項1乃至9のいずれか1項に記載のリチウムイオン電池。 - 前記電解液は低粘度溶媒を含み、前記低粘度溶媒の25±3℃での粘度は、0.65mPa・s以下であり、
好ましくは、前記低粘度溶媒は、炭酸ジメチル(DMC)、ギ酸メチル(MF)、ギ酸エチル(EF)、酢酸メチル(MA)、酢酸エチル(EA)、プロピオン酸エチル(EP)、酪酸エチル(EB)、テトラヒドロフラン(THF)、2−メチルテトラヒドロフラン、ジオキソラン(DOL)、1,2−ジメトキシエタン(DME)、アセトニトリル(AN)、メチルノナフルオロブチルエーテル(MFE)及びエチルノナフルオロブチルエーテル(EFE)から選択される少なくとも1つであり、
より好ましくは、低粘度溶媒の電解液中の質量分率は、10%〜80%である、
請求項1乃至10のいずれか1項に記載のリチウムイオン電池。 - 前記電解液は、浸潤剤を含み、前記浸潤剤は、好ましくは、1,1,2,2−テトラフルオロエチル−2,2,3,3−テトラフルオロプロピルエーテル、1H,1H,5H−オクタフルオロペンチル−1,1,2,2テトラフルオロエチルエーテル、又は1,1,2,2−テトラフルオロエチル−2,2,2−トリフルオロエチルエーテルのうちの少なくとも1つを含み、
好ましくは、前記浸潤剤の電解液中の質量分率は、0.1%〜10%である、
請求項1乃至11のいずれか1項に記載のリチウムイオン電池。 - 前記正極材料層の空孔率は、10〜50%、好ましくは、20〜40%である、
請求項1乃至12のいずれか1項に記載のリチウムイオン電池。 - 前記正極材料層の比表面積は、0.5m2/g〜1.5m2/gである、
請求項1乃至13のいずれか1項に記載のリチウムイオン電池。 - 前記正極材料層の結晶方位のOI値は、5〜120、好ましくは、30〜70である、
請求項1乃至14のいずれかに1項記載のリチウムイオン電池。 - 前記正極材料層には、正極活物質が含有され、前記正極活物質は、式(1)〜式(3)に示される化合物のうちの少なくとも1つを含み、
Li1+XNiaCobM1−a−bO2−yAy 式(1)
Li1+X’Nia’M’2−a’O4−y’A’y’ 式(2)
c[Li2MnO3]・(1−c)[LiM”2O2−y”A”y”] 式(3)
式(1)において、−0.1≦x≦0.2、0.5≦a<1、0.02<b<0.3、0.55<a+b<1、0≦y<0.2であり、Mは、Mn、Fe、Cr、Ti、Zn、V、Al、Zr及びCeのうちの1種以上を含み、Aは、S、N、F、Cl、Br及びIのうちの1種以上を含み、
式(2)において、−0.1≦x’≦0.2、0.4≦a’<0.6、0≦y’<0.2であり、M’は、Mnを含むか、或いは、M’は、Mnと、Fe、Cr、Ti、Zn、V、Al、Zr、Mg、Ceのうちの1種以上と、を含み、A’は、S、N、F、Cl、Br及びIのうちの1種以上を含み、
式(3)において、0<c<1、0≦y”<0.2であり、M”は、Ni、Co及びMnを含むか、或いは、M”は、Ni、Co及びMnと、Fe、Cr、Ti、Zn、V、Al、Zr及びCeのうちの1種以上と、を含み、A”は、S、N、F、Cl、Br及びIのうちの1種以上を含む、
請求項1乃至15のいずれかに1項記載のリチウムイオン電池。 - 請求項1乃至16のいずれか1項に記載のリチウムイオン電池を含む、
電気機器。
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EP4087006A1 (en) | 2022-11-09 |
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CN110323487A (zh) | 2019-10-11 |
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EP4087006B1 (en) | 2023-05-24 |
US11329319B2 (en) | 2022-05-10 |
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US20210119258A1 (en) | 2021-04-22 |
CN113690481A (zh) | 2021-11-23 |
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WO2021004151A1 (zh) | 2021-01-14 |
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