CN117894993A - 一种高电压电池 - Google Patents
一种高电压电池 Download PDFInfo
- Publication number
- CN117894993A CN117894993A CN202211223494.0A CN202211223494A CN117894993A CN 117894993 A CN117894993 A CN 117894993A CN 202211223494 A CN202211223494 A CN 202211223494A CN 117894993 A CN117894993 A CN 117894993A
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- China
- Prior art keywords
- battery
- lithium
- protective layer
- equal
- active material
- 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
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- 239000011241 protective layer Substances 0.000 claims abstract description 25
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000010405 anode material Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000006183 anode active material Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N Heptanedioic acid Natural products OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 2
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 11
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 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 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011888 foil Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 238000007600 charging Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 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
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- CMBZEFASPGWDEN-UHFFFAOYSA-N argon;hydrate Chemical compound O.[Ar] CMBZEFASPGWDEN-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-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
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 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
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-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
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
本发明提供了一种高电压电池。本发明的电池是在正极集流体上涂覆一定厚度的保护层,可以解决双氟磺酰亚胺锂和/或双三氟甲基磺酰亚胺锂对正极集流体的腐蚀,同时相比于六氟磷酸锂,电解液中包括双氟磺酰亚胺锂和/或双三氟甲基磺酰亚胺锂时,不产生氢氟酸,从而不会对正极表面腐蚀,不会导致过渡金属离子溶出,此外还可以减少正极表面的副反应及发生副反应带来的产气和界面保护层被破坏等问题,故通过两者的上述的协同效应,解决了高电压电池常温循环性能、高温循环性能、高温存储性能和45℃间隔循环差性能差的问题。
Description
技术领域
本发明属于电池技术领域,具体涉及一种高电压电池,特别是一种具有较好高温性能的高电压电池。
背景技术
锂离子电池自从商业化以来,因它的轻便、比能量高、无记忆效应、循环性能好,被广泛用于数码、储能、动力、军用航天和通讯设备等领域。随着锂离子电池的广泛应用,消费者对锂离子电池的能量密度、循环寿命、高温性能、安全性等性能提出了更高的要求。提高能量密度,一方面可以通过提高正极的充电电压,或者采用容量更高的硅负极,另一方面希望提高电池的设计,更高的压实更高的面密度,让单位体积集流体上获得更多的活性物质,再就是通过降低铜箔、铝箔、隔膜等的厚度,提高能量密度。
然而,随着正极电压的提高,正极表面的过渡金属氧化性变高,电解液容易在正极表面发生氧化分解反应,同时电解液会产生氢氟酸(HF),HF会腐蚀正极,导致正极过渡金属离子溶出,溶出的过渡金属离子迁移到负极,会破坏负极的SEI膜,导致电池循环和45℃间隔循环性能变差甚至跳水等问题的出现。
发明内容
为了改善现有技术的不足,本发明提供一种高电压电池。本发明通过采用特殊处理的正极集流体,解决了电解液体系中由于氢氟酸(HF)的存在导致的高电压(4.45V以上)电池的常温循环性能、高温循环性能、高温存储性能和45℃间隔循环性能差的问题。
本发明通过如下技术方案实现的:
一种高电压电池,所述高电压电池包括正极片、负极片、隔膜和电解液;所述正极片包括正极集流体、保护层和正极活性物质层;所述保护层设置在正极集流体至少一侧表面,所述正极活性物质层设置在保护层表面;所述电解液包括有机溶剂和锂盐,所述电池满足如下关系式:
1≤a≤5;
0.05≤b≤4;
其中,a为保护层的厚度,单位μm;b为电解液中锂盐的浓度,单位mol/L(简写M)。
根据本发明的实施方式,a为1、2、3、4或5。当a<1时,保护层太薄,无法彻底防止电解液对铝箔的腐蚀,还会存在铝箔腐蚀的问题,而且对电池的高温循环性能和45℃间隔循环性能改善效果不明显,反而还会劣化电池的性能;当a>5时,保护层较厚,会影响电池的能量密度。
根据本发明的实施方式,0.5≤b≤3;优选地,1≤b≤2;例如b为0.5、0.8、1、1.1、1.2、1.3、1.4、1.5、1.8、2、2.5、2.8或3。
根据本发明的实施方式,所述保护层包括保护材料,所述保护材料选自以下物质中的一种或几种:碳、Al2O3、TiO2、MgO、FeO、Fe2O3、Fe3O4、Cr2O3、CoO、Ce2O3、In2O3、Ti2O3、V2O5、WO3、TiO2、ZnO、Nb2O5、NiO、SnO2、AlF3,其中部分物质可包含多种同分异构体,如Al2O3的同分异构体有:α-Al2O3,β-Al2O3,γ-Al2O3,其中碳可以是无定型碳、炭黑、硬碳、软碳、碳纳米管、导电石墨等等。
根据本发明的实施方式,所述保护层还可以包括导电剂和粘结剂中的至少一种。所述导电剂和所述粘结剂的定义如下所述。
根据本发明的实施方式,所述保护层中各组分的质量百分含量为:90~100wt%的保护材料、0~5wt%的导电剂、0~5wt%的粘结剂。
根据本发明的实施方式,所述有机溶剂选自碳酸酯和/或羧酸酯中的一种或几种。
示例性地,所述碳酸酯选自氟代或未取代的下述溶剂中的一种或几种:碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯。
示例性地,所述羧酸酯选自氟代或未取代的下述溶剂中的一种或几种:乙酸丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、丙酸乙酯、丙酸正丙酯、丁酸甲酯、正丁酸乙酯。
根据本发明的实施方式,所述电解液还包括以下添加剂中的一种或几种:碳酸亚乙烯酯、乙烯基碳酸乙烯酯、氟代碳酸乙烯酯、亚硫酸乙烯酯、二氟磷酸锂、甲烷二磺酸亚甲酯、硫酸乙烯酯、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、葵二腈、1,3,6-己烷三腈、3-甲氧基丙腈、甘油三腈、1,2-二(2-氰乙氧基)乙烷、1,3-丙烷磺酸内酯、丙烯基-1,3-磺酸内酯。
根据本发明的实施方式,所述锂盐包括双氟磺酰亚胺锂和/或双三氟甲基磺酰亚胺锂。
根据本发明的实施方式,所述锂盐还包括六氟磷酸锂、二氟磷酸锂、四氟硼酸锂中的一种或多种。
根据本发明的实施方式,所述正极活性物质层包括正极活性物质、导电剂和粘结剂。
根据本发明的实施方式,所述负极片包括负极集流体和涂覆在负极集流体一侧或两侧表面的负极活性物质层,所述负极活性物质层包括负极活性物质、导电剂和粘结剂。
根据本发明的实施方式,所述正极活性物质层中各组分的质量百分含量为:80~99.8wt%的正极活性物质、0.1~10wt%的导电剂、0.1~10wt%的粘结剂。
优选地,所述正极活性物质层中各组分的质量百分含量为:90~99.6wt%的正极活性物质、0.2~5wt%的导电剂、0.2~5wt%的粘结剂。
根据本发明的实施方式,所述负极活性物质层中各组分的质量百分含量为:80~99.8wt%的负极活性物质、0.1~10wt%的导电剂、0.1~10wt%的粘结剂。
优选地,所述负极活性物质层中各组分的质量百分含量为:90~99.6wt%的负极活性物质、0.2~5wt%的导电剂、0.2~5wt%的粘结剂。
根据本发明的实施方式,所述导电剂选自导电炭黑、乙炔黑、科琴黑、导电石墨、导电碳纤维、碳纳米管、金属粉中的至少一种。
根据本发明的实施方式,所述粘结剂选自羧甲基纤维素钠、羧甲基纤维素锂、丁苯胶乳、聚四氟乙烯、聚偏氟乙烯、聚氧化乙烯中的至少一种。
根据本发明的实施方式,所述正极活性物质层中的正极活性物质选自层状锂复合氧化物、锰酸锂、三元材料中的一种或几种。所述层状锂复合氧化物的化学式为Li(1+x)NiyCozM(1-y-z)O2,其中,-0.1≤x≤1;0≤y≤1,0≤z≤1,且0≤y+z≤1;其中,M为Mg、Zn、Ga、Ba、Al、Fe、Cr、Sn、V、Mn、Sc、Ti、Nb、Mo、Zr中的一种或几种。
根据本发明的实施方式,所述负极活性物质层中的负极活性物质选自碳基负极材料、硅基负极材料、锡基负极材料或它们对应的合金材料中的一种或几种。
根据本发明的实施方式,所述碳基负极材料包括人造石墨、天然石墨、中间相碳微球、硬碳、软碳中的至少一种。
根据本发明的实施方式,所述硅基负极材料选自纳米硅(Si)、硅氧负极材料(SiOx(0<x<2))和硅碳负极材料中的至少一种。
根据本发明的实施方式,所述锡基负极材料选自金属锡、锡的氧化物、锡合金材料、和锡基复合氧化物中的一种或几种。
根据本发明的实施方式,所述电池的工作截止电压为4.45V及以上。
本发明的有益效果:
本发明提供了一种高电压电池。本发明的电池是在正极集流体上涂覆一定厚度的保护层,可以解决六氟磷酸锂对正极集流体的腐蚀,同时相比于六氟磷酸锂,电解液中包括双氟磺酰亚胺锂和/或双三氟甲基磺酰亚胺锂时,不产生氢氟酸,从而不会对正极表面腐蚀,不会导致过渡金属离子溶出,此外还可以减少正极表面的副反应及发生副反应带来的产气和界面保护层被破坏、相变等问题,故通过两者的上述的协同效应,解决了高电压电池常温循环性能、高温循环性能、高温存储性能和45℃间隔循环差性能差的问题。
具体实施方式
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
对比例1
(1)正极片制备
将正极活性材料4.5V钴酸锂(LCO)、粘结剂聚偏氟乙烯(PVDF)、导电剂乙炔黑按照重量比98:1.5:0.5进行混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌,直至混合体系成均一流动性的正极浆料;将正极浆料均匀涂覆于厚度为9μm的铝箔上;将上述涂覆好的铝箔在5段不同温度梯度的烘箱烘烤后,再将其在120℃的烘箱干燥8h,然后经过辊压、分切得到正极片。
(2)负极片制备
将负极活性材料石墨、增稠剂羧甲基纤维素钠(CMC-Na)、粘结剂丁苯橡胶、导电剂乙炔黑按照重量比97:1:1:1进行混合,加入去离子水,在真空搅拌机作用下获得负极浆料;将负极浆料均匀涂覆在厚度为8μm的铜箔上;将铜箔在室温晾干后转移至80℃烘箱干燥10h,然后经过冷压、分切得到负极片,负极的压实为1.80g/cm3,面密度为9.5mg/cm2。
(3)电解液制备
在充满氩气水氧含量合格的手套箱中,将碳酸乙烯酯、碳酸丙烯酯、丙酸正丙酯,按照质量比15:15:70的比例混合均匀(溶剂和添加剂需一起进行归一化),将溶剂在-10℃左右的低温下冷冻2-5h,然后往其中快速加入充分干燥的锂盐(具体如表1所示),搅拌均匀,再加入8wt%的氟代碳酸乙烯酯,4wt%的1,3-丙烷磺酸内酯,1wt%的丁二腈,1wt%的己二腈,3wt%的1,3,6-己烷三腈,0.3wt%的二氟磷酸锂,再次搅拌至均匀,经过水分和游离酸检测合格后,得到对比例1的电解液。
(4)隔膜的制备
选用8μm厚的聚乙烯隔膜(旭化成公司提供)。
(5)锂离子电池的制备
将上述准备的正极片、隔膜、负极片按顺序叠放好,保证隔膜处于正、负极片之间起到隔离的作用,然后通过卷绕得到未注液的裸电芯;将裸电芯置于外包装箔中,将上述制备好的电解液注入到干燥后的裸电芯中,经过真空封装、静置、化成、整形、分选等工序,获得所需的锂离子电池。
(6)25℃常温循环实验及循环后解剖
测试前测试满电电芯的厚度D0,将电池置于(25±3)℃环境中,静置3小时,待电芯本体达到(25±3)℃时,电池按照1C充到4.2V,再0.7C充到4.5V,再4.5V恒压充到截止电流0.05C,再以0.5C放电到3V,记录初始容量Q0,当循环达到所需的次数时,以此次的放电容量作为电池的容量Q2,计算容量保持率(%),再把电池满电,电芯取出后,常温静置3小时,测试满电厚度D2,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D2-D0)/D0×100%;容量保持率(%)=Q2/Q0×100%。
循环后的电池,进行满电拆解,判别其铝箔是否有腐蚀。
(7)45℃高温循环实验
测试前测试满电电芯的厚度D0,将电池置于(45±3)℃环境中,静置3小时,待电芯本体达到(45±3)℃时,电池按照0.7C恒流充到4.5V,在4.5V恒压充到截止电流0.05C,再以0.5C放电,记录初始容量Q0,如此循环,当循环达到所需的次数时,以此次的放电容量作为电池的容量Q3,计算容量保持率(%),再把电池满电,芯取出后,常温静置3小时,测试此时满电厚度D3,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D3-D0)/D0×100%;容量保持率(%)=Q3/Q0×100%。
(8)45℃间隔循环实验
测试前测试满电电芯的厚度D0,将电池置于(45±3)℃环境中,静置3小时,待电芯本体达到(45±3)℃时,电池按照0.7C恒流充到4.5V,在4.5V恒压充到截止电流0.05C,在45℃下静置一定时间,保证恒流恒压充电时间加上静置时间为24H,再以0.5C放电,记录初始能量E0,如此循环,当循环达到所需的次数时,以此次的放电能量作为电池的能量E1,计算能量保持率(%),再把电池满电,芯取出后,常温静置3小时,测试此时满电厚度D4,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D4-D0)/D0×100%;能量保持率(%)=E1/E0×100%。
(9)60℃高温存储实验
在25℃下,测试满电电芯的厚度D0,将分选后的电池按照0.7C充到4.5V,再4.5V恒压充到截止电流0.05C,然后用0.5C恒流放电至3.0V,然后0.7C充到4.5V,再4.5V恒压充到截止电流0.05C,置于60℃的环境中搁置35天后,测试满电厚度D5,计算厚度变化率(%),记录结果如表2。其中用到的计算公式如下:
厚度变化率(%)=(D5-D0)/D0×100%。
实施例1-11和对比例2-4
实施例1-11和对比例2-4的制备过程同对比例1,区别在于铝箔上是否含有保护层和电解液的锂盐的含量和种类不同,具体为:
在铝箔表面涂覆保护层,形成保护层的材料如表1所示,保护层的厚度为2μm。电解液制备同对比例1,区别仅在于锂盐的加入量和种类不同,具体如表1所示。
表1实施例和对比例的电解液中保护层的组成和电解液的组成
从表2可以看出,本申请实施例制备得到的电池均取得了更好的电学性能,通过电池的循环过程中容量保持率和厚度膨胀率的改善幅度能够证明本申请的正极集流体采用特殊的保护涂层,组合和特殊锂盐或锂盐组合的电解液所达到的效果,具体分析如下所述:
通过对比例2-4和对比例1对比可发现,当正极集流体铝箔上无涂层时,用六氟磷酸锂、双氟磺酰亚胺锂或双三氟甲基磺酰亚胺锂作为锂盐时,均存在铝箔被腐蚀,循环性能和存储性能变差的问题。
通过实施例1-2、9和对比例2-3,或者实施例3-4、10和对比例2-3,或者实施例5-6、11和对比例2-3,或者实施例7和对比例4,对比后可发现,在正极集流体铝箔上涂覆了一层碳、Al2O3或TiO2等保护层时,相比于六氟磷酸锂,用双氟磺酰亚胺锂或双三氟甲基磺酰亚胺锂作为锂盐时,电池的常温循环性能、45℃循环性能及45℃间隔循环性能和60℃存储性能均得到了改善。
通过实施例8和实施例3对比可发现,适当提高双氟磺酰亚胺锂的含量对电池性能影响不大。
表2实施例和对比例的电池的实验结果对比
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种高电压电池,其特征在于,所述高电压电池包括正极片、负极片、隔膜和电解液;所述正极片包括正极集流体、保护层和正极活性物质层;所述保护层设置在正极集流体至少一侧表面,所述正极活性物质层设置在保护层表面;所述电解液包括有机溶剂和锂盐;
所述电池满足如下关系式:
a≥1;
0.05≤b≤4;
其中,a为保护层的厚度,单位μm;b为电解液中锂盐的浓度,单位mol/L。
2.根据权利要求1所述的电池,其特征在于,0.5≤b≤3。
3.根据权利要求2所述的电池,其特征在于,所述锂盐包括双氟磺酰亚胺锂和/或双三氟甲基磺酰亚胺锂。
4.根据权利要求1所述的电池,其特征在于,所述保护层包括保护材料,所述保护材料选自以下物质中的一种或几种:碳、Al2O3、TiO2、MgO、FeO、Fe2O3、Fe3O4、Cr2O3、CoO、Ce2O3、In2O3、Ti2O3、V2O5、WO3、TiO2、ZnO、Nb2O5、NiO、SnO2、AlF3。
5.根据权利要求4所述的电池,其特征在于,所述保护层还包括导电剂和粘结剂中的至少一种。
6.根据权利要求1或3所述的电池,其特征在于,所述锂盐还包括六氟磷酸锂、二氟磷酸锂、四氟硼酸锂中的一种或多种。
7.根据权利要求1所述的电池,其特征在于,所述电解液还包括以下添加剂中的一种或几种:碳酸亚乙烯酯、乙烯基碳酸乙烯酯、氟代碳酸乙烯酯、亚硫酸乙烯酯、二氟磷酸锂、甲烷二磺酸亚甲酯、硫酸乙烯酯、丁二腈、戊二腈、己二腈、庚二腈、辛二腈、葵二腈、1,3,6-己烷三腈、3-甲氧基丙腈、甘油三腈、1,2-二(2-氰乙氧基)乙烷、1,3-丙磺酸内酯、丙烯基-1,3-磺酸内酯。
8.根据权利要求1所述的电池,其特征在于,所述正极活性物质层中的正极活性物质选自层状锂复合氧化物、锰酸锂、三元材料中的一种或几种;所述层状锂复合氧化物的化学式为Li(1+x)NiyCozM(1-y-z)O2,其中,-0.1≤x≤1;0≤y≤1,0≤z≤1,且0≤y+z≤1;其中,M为Mg、Zn、Ga、Ba、Al、Fe、Cr、Sn、V、Mn、Sc、Ti、Nb、Mo、Zr中的一种或几种。
9.根据权利要求1所述的电池,其特征在于,所述负极活性物质层中的负极活性物质选自碳基负极材料、硅基负极材料、锡基负极材料或它们对应的合金材料中的一种或几种。
10.根据权利要求1所述的电池,其特征在于,所述电池的工作截止电压为4.45V及以上。
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