JP2023539963A - リチウムイオン二次電池、電池モジュール、電池パック及び電力消費装置 - Google Patents
リチウムイオン二次電池、電池モジュール、電池パック及び電力消費装置 Download PDFInfo
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- JP2023539963A JP2023539963A JP2022548240A JP2022548240A JP2023539963A JP 2023539963 A JP2023539963 A JP 2023539963A JP 2022548240 A JP2022548240 A JP 2022548240A JP 2022548240 A JP2022548240 A JP 2022548240A JP 2023539963 A JP2023539963 A JP 2023539963A
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- Prior art keywords
- ion secondary
- lithium ion
- negative electrode
- secondary battery
- compound
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 74
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003792 electrolyte Substances 0.000 claims abstract description 63
- 239000000126 substance Substances 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 239000007773 negative electrode material Substances 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 10
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 229910013100 LiNix Inorganic materials 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 2
- 239000006182 cathode active material Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- -1 and M is Co Substances 0.000 description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 239000010410 layer Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 11
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- 239000011267 electrode slurry Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
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- 230000007423 decrease Effects 0.000 description 7
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
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- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
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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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- 239000001257 hydrogen Substances 0.000 description 3
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- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 3
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- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 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
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 229910012423 LiSO3F Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 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
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 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
- 230000002159 abnormal effect Effects 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012948 isocyanate 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
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000002441 reversible effect Effects 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
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Abstract
Description
前記正極活物質は、LiNixCoyNzM1-x-y-zO2を含み、そのうち、Nは、Mn及びAlから選択され、Mは、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V及びTiのうちのいずれかの一つから選択され、0.5≦x<1、0≦y≦1、0≦z≦1、x+y+z≦1であり、
前記電解液は、化学式(1)の化合物と、化学式(2)の化合物と、化学式(3)の化合物とを含み、
また、化学式(1)の化合物の含有量は、W1%であり、化学式(2)の化合物の含有量は、W2%であり、化学式(3)の化合物の含有量は、W3%であり、いずれも電解液の総重量に対する重量%含有量であり、W1、W2及びW3は、1≦W3/W2≦4かつ0.5≦W1/W2≦1を満たす。
W3=25x2という条件(a)と、
W2=10xという条件(b)とのうちの少なくとも一つを満たす。
一般的には、リチウムイオン二次電池は、正極極板、負極極板、セパレータ及び電解液を含む。電池の充放電過程において、活性イオンは、正極極板と負極極板との間で往復して吸蔵し放出する。セパレータは、正極極板と負極極板との間に設けられ、隔離の作用を奏する。電解液は、正極極板と負極極板との間でイオンを伝導する作用を奏する。
前記正極活物質は、LiNixCoyNzM1-x-y-zO2を含み、そのうち、Nは、Mn及びAlから選択され、Mは、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V及びTiのうちのいずれかの一つから選択され、0.5≦x<1、0≦y≦1、0≦z≦1、x+y+z≦1であり、
前記電解液は、化学式(1)の化合物と、化学式(2)の化合物と、化学式(3)の化合物とを含み、
また、化学式(1)の化合物の含有量は、W1%であり、化学式(2)の化合物の含有量は、W2%であり、化学式(3)の化合物の含有量は、W3%であり、いずれも電解液の総重量に対する重量%含有量であり、W1、W2及びW3は、1≦W3/W2≦4かつ0.5≦W1/W2≦1を満たす。
W3=25x2という条件(a)と、
W2=10xという条件(b)とのうちの少なくとも一つを満たす。
電解液は、正極極板と負極極板との間でイオンを伝導する作用を奏する。電解液は、電解質塩と、溶媒とを含む。
正極極板は、正極集電体と、正極集電体の少なくとも一つの表面に設けられる正極材料層とを含み、前記正極材料層は、正極活物質と、炭素とを含む。
負極極板は、負極集電体と、負極集電体の少なくとも一つの表面に設けられる負極材料層とを含み、前記負極材料層は、負極活物質を含む。
電解液を採用するリチウムイオン二次電池には、セパレータがさらに含まれる。セパレータは、正極極板と負極極板との間に設けれ、隔離作用を奏する。本出願では、セパレータの種類に対して特に限定されなく、良好な化学的安定性と機械的安定性を有する任意のよく知られている多孔質構造のセパレータを選択してもよい。いくつかの実施形態では、セパレータの材質は、ガラス繊維、不織布、ポリエチレン、ポリプロピレン及びポリフッ化ビニリデンのうちの一つ以上から選択されてもよい。セパレータは、単層フィルムであってもよく、多層複合フィルムであってもよく、特に制限はない。セパレータが多層複合フィルムである場合、各層の材料は同じであってもよく、異なってもよく、特に制限はない。
いくつかの実施形態では、リチウムイオン二次電池は、電池モジュールに組み立てることができ、電池モジュールに含まれるリチウムイオン二次電池の数は、一つ又は複数であってもよく、具体的な数は、当業者が電池モジュールの用途と容量に基づいて選択してもよい。
以下では、本出願の実施例を説明する。以下に記述されている実施例は、例示的なもので、本出願を解釈することのみに用いられ、本出願を制限するものとして理解すべきではない。実施例において具体的な技術又は条件が明記されていないものは、当分野の文献に記述されている技術若しくは条件、又は製品説明書に従って実行する。使用する試薬又は機器について、製造メーカーが明記されていないものは、いずれも市販で購入できる一般的な製品である。
1.リチウムイオン二次電池の製造
(1)電解液の製造
アルゴンガスが充足されたグローブボックス(水含有量<10ppm、酸素ガス含有量<1ppm)内において、化学式(1)の化合物としてフルオロベンゼンと、化学式(2)の化合物としてエトキシペンタフルオロシクロトリホスファゼンをECとDECとの混合溶媒(質量比EC:DEC=3:5)に添加し、ビニレンカーボネート1重量%及び1,3-プロペンスルトン1重量%を添加する。均一混合した後、リチウム塩LiPF6及び化学式(3)の化合物としてリチウムビス(フルオロスルホニル)イミドを徐々に溶解し、得られた溶液におけるリチウム塩総濃度を1mol/Lとし、溶液の総重量に対して、フルオロベンゼン含有量を5重量%、エトキシペンタフルオロシクロトリホスファゼン含有量を5重量%、リチウムビス(フルオロスルホニル)イミド含有量を5重量%とし、電解液を得る。
正極活物質LiNi0.8Co0.1Mn0.1O2、導電剤Super P、接着剤ポリフッ化ビニリデン(PVDF)を質量比8:1:1でN-メチルピロリドン(NMP)において正極スラリーとして製造する。正極スラリーにおける固体含有量は、50重量%とする。正極スラリーを集電体アルミニウム箔(正極活物質のアルミニウム箔への塗布質量は0.14mg/mm2とする)に塗布し、85℃で乾燥させた後冷間プレスを行い、その後、エッジカット、切断、ストリップを経た後、85℃の真空条件で4時間乾燥させ、正極極板を製造する。
負極活物質としての黒鉛(ここで、OI≧8の黒鉛は、全黒鉛において10%質量比を占める)、導電剤Super P、増稠剤CMC、結着剤スチレンブタジエンゴム(SBR)を質量比80:15:3:2で脱イオン水に均一に混合し、負極スラリーとして製造する。負極スラリーにおける固体含有量は、30重量%とする。負極スラリーを集電体銅箔(負極活物質の銅箔への塗布重量は、0.08mg/mm2とする)に塗布し、85℃で乾燥させた後、冷間プレス、エッジカット、切断、ストリップを行い、120℃の真空条件で12時間乾燥させ、負極極板を製造する。
16μmのポリエチレンフィルム(PE)をセパレータとし、作製された正極極板、セパレータ、負極極板を順に積層し、セパレータを正負極極板の中央に位置させて正負極を隔離する作用を奏し、巻回してベアセルを得る。タブを溶接し、ベアセルを外装に配置し、上記で製造された電解液を乾燥した電池コアに注入し、パッケージ、静置、化成、整形を経て、リチウムイオン二次電池の製造を完成する。電池の厚さ4.0mm、幅60mm、長さ140mmである。
(1)リチウムイオン電池高温貯蔵性能試験
25℃で、リチウムイオン電池を1Cで4.2Vまで定電流充電し、そして4.2Vの電圧で電流が0.05Cになるまで定電圧充電し、さらに0.5Cで2.8Vまで放電し、放電容量D0を得る。電池を60℃の恒温槽に入れて保管し、30日後取り出し、室温に冷却した後、1Cで2.8Vまで定電流放電し、5分静置し、さらに1Cで4.2Vまで定電流充電し、そして4.2Vの電圧で電流が0.05Cになるまで定電圧充電し、さらに0.5Cで2.8Vまで放電し、このときの放電容量をD1とし、電池の高温貯蔵可逆容量維持率=D1/D0*100%である。
環境温度を25℃に調節し、リチウムイオン電池を1Cで4.2Vまで定電流充電し、そして4.2Vの電圧で電流が0.05Cになるまで定電圧充電する。感温線を電池コア表面の中心位置に貼り付ける。そして電池を加熱炉に入れ、炉を10℃/分で昇温させ、10℃昇温するごとに30分保温し、感温線の温度が瞬間的に急激に増加し、炉温度よりもはるかに高くなると、このときの電池コアが熱暴走していると考えられる。電池が熱暴走したときの炉の温度を記録する。
25℃で、リチウムイオン電池を1Cで4.2Vまで定電流充電し、そして4.2Vの電圧で電流が0.05Cになるまで定電圧充電し、そして1Cで30分放電する。電池コアを0℃で2時間放置し、このときの電圧V1を記録し、そして0.36Cで10秒定電流放電し、このときの電圧V2を記録し、DCR=(V1-V2)/0.36Cである。DCRが低いほど、低温放電パワー値が高くなる。
実施例1-1と同様である方式で行われるが、実施例1-1との相違点は、表1に示すように、W1、W2及びW3を変更したことである。
実施例1-1と同様である方式で行われるが、実施例1-1との相違点は、フルオロベンゼンを使用しないこと、エトキシペンタフルオロシクロトリホスファゼンを使用しないこと又はリチウムビス(フルオロスルホニル)イミドを使用しないことである。
実施例1-1と同様である方式で行われるが、実施例1-1との相違点は、W1、W2及びW3を変更したことである。
実施例1-1と同様である方式で行われるが、実施例1-1との相違点は、正極活物質の種類、W1、W2及びW3を変更したことである。
実施例1-1と同様である方式で行われるが、実施例1-1との相違点は、化学式(1)の化合物としてトリフルオロメチルベンゼンを用い、化学式(2)の化合物としてメトキシペンタフルオロシクロトリホスファゼンを用い、化学式(3)の化合物として(フルオロスルホニル)(トリフルオロメチル)スルホイミドリチウムを用い、そして表4に示されるW1、W2及びW3値を用いたことである。
2 上ケース
3 下ケース
4 電池モジュール
5 リチウムイオン二次電池
51 ケース
52 電極コンポーネント
53 蓋板
Claims (13)
- リチウムイオン二次電池であって、正極極板、負極極板、セパレータ及び電解液を有し、前記正極極板は、正極集電体と、正極集電体の少なくとも一つの表面に設けられる正極材料層とを含み、前記正極材料層は、正極活物質を含み、
前記正極活物質は、LiNixCoyNzM1-x-y-zO2を含み、Nは、Mn及びAlから選択され、Mは、Co、Ni、Mn、Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V及びTiのうちのいずれかの一つから選択され、0.5≦x<1、0≦y≦1、0≦z≦1、x+y+z≦1であり、
前記電解液は、化学式(1)の化合物と、化学式(2)の化合物と、化学式(3)の化合物とを含み、
また、前記化学式(1)の化合物の含有量は、W1%であり、前記化学式(2)の化合物の含有量は、W2%であり、前記化学式(3)の化合物の含有量は、W3%であり、いずれも電解液の総重量に対する重量%含有量であり、W1、W2及びW3は、1≦W3/W2≦4かつ0.5≦W1/W2≦1を満たす、リチウムイオン二次電池。 - W1%は、1%~15%範囲、選択的に、3%~10%範囲である、請求項1に記載のリチウムイオン二次電池。
- W2%は、1%~20%範囲、選択的に、5%~15%範囲である、請求項1に記載のリチウムイオン二次電池。
- W3%は、5%~20%範囲、選択的に、5%~16%範囲である、請求項1に記載のリチウムイオン二次電池。
- 前記化学式(2)において、R1~R6は、それぞれ独立して、ハロゲン及びC1-C6アルコキシ基から選択され、選択的に、R1~R5は、いずれもフッ素原子であり、かつR6は、C1-C6アルコキシ基である、請求項1に記載のリチウムイオン二次電池。
- 前記化学式(3)の化合物は、リチウムビス(フルオロスルホニル)イミドである、請求項1に記載のリチウムイオン二次電池。
- W3=25x2という条件(a)と、
W2=10xという条件(b)とのうちの少なくとも一方を満たす、請求項1に記載のリチウムイオン二次電池。 - 0.65≦x≦0.9、選択的に、x=0.8である、請求項1に記載のリチウムイオン二次電池。
- 前記電解液に含まれるリチウム塩の総濃度は、0.8M~1.5Mであり、選択的に、0.8M~1.2Mである、請求項1に記載のリチウムイオン二次電池。
- 前記負極極板は、負極集電体と、負極集電体の少なくとも一つの表面に設けられる負極材料層とを含み、前記負極材料層は、負極活物質を含み、前記負極活物質は、負極活物質の総重量に対して、含有量≦20重量%のOI≧8の黒鉛を含み、選択的に、前記OI≧8の黒鉛の含有量は、負極活物質の総重量に対して、10重量%~20重量%である、請求項1に記載のリチウムイオン二次電池。
- 請求項1~10のいずれか1項に記載のリチウムイオン二次電池を含む、電池モジュール。
- 請求項11に記載の電池モジュールを含む、電池パック。
- 請求項1~10のいずれか1項に記載のリチウムイオン二次電池、請求項11に記載の電池モジュール又は請求項12に記載の電池パックのうちの一つ以上を含む、電力消費装置。
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