CN114256507A - Lithium secondary battery and method for manufacturing the same - Google Patents
Lithium secondary battery and method for manufacturing the same Download PDFInfo
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- CN114256507A CN114256507A CN202011020638.3A CN202011020638A CN114256507A CN 114256507 A CN114256507 A CN 114256507A CN 202011020638 A CN202011020638 A CN 202011020638A CN 114256507 A CN114256507 A CN 114256507A
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- lithium
- negative electrode
- secondary battery
- positive electrode
- electrode material
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 9
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- QAXDWZROODOYRA-UHFFFAOYSA-N 2-[difluoro-[1,1,2,4,4,4-hexafluoro-2-(trifluoromethyl)butoxy]methyl]-1,1,1,2,4,4,4-heptafluorobutane Chemical compound FC(CC(C(F)(F)OC(C(C(F)(F)F)(CC(F)(F)F)F)(F)F)(C(F)(F)F)F)(F)F QAXDWZROODOYRA-UHFFFAOYSA-N 0.000 claims description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 3
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 claims description 2
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 claims description 2
- ALGVJKNIAOBBBJ-UHFFFAOYSA-N 3-[2,3-bis(2-cyanoethoxy)propoxy]propanenitrile Chemical compound N#CCCOCC(OCCC#N)COCCC#N ALGVJKNIAOBBBJ-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- VMUOSHREZKXCIV-UHFFFAOYSA-N cyclohexane-1,3,5-tricarbonitrile Chemical compound N#CC1CC(C#N)CC(C#N)C1 VMUOSHREZKXCIV-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 238000003860 storage Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011888 foil Substances 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2300/0088—Composites
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium secondary battery and a preparation method thereof, the battery comprises a non-aqueous electrolyte, a positive electrode and a negative electrode, the positive electrode comprises a first current collector and a positive electrode material arranged on the first current collector, and the density of the positive electrode material is not lower than 3.5g/cm3The negative electrode comprises a second current collector and a negative electrode material arranged on the second current collector, and the density of the negative electrode material is not lower than 1.5g/cm3. The non-aqueous electrolyte comprises fluoroethylene carbonate, fluoroether and a trinitrile compound; wherein the mass percentages of the three components in the non-aqueous electrolyte are 3-15%, 0.5-8% and 0.2-4% in sequence. The battery has high electrode density, and the lithium di-and tri-nitrile compounds are used as characteristic components of the electrolyte in specific proportions, so that under the condition of higher electrode density, the lithium di-and tri-nitrile compounds are matched with the three characteristic componentsThe secondary battery has excellent high-temperature characteristics and low-temperature input characteristics after high-temperature storage.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium secondary battery and a preparation method thereof.
Background
In recent years, the popularization of portable electronic devices such as mobile phones, tablet computers, and notebook computers has promoted the development of high energy density secondary batteries. Among many secondary batteries, a lithium ion secondary battery that realizes energy conversion by insertion and extraction of lithium ions has a higher energy density than a lead-acid battery and a nickel-metal hydride battery, and has been developed rapidly since the world, and its application fields include digital products, electric tools, electric vehicles, communication base stations, power grid energy storage, and the like.
The technology of lithium secondary batteries is continuously being innovated, which gradually pursues a balance of high energy density and high performance. If the unmanned aerial vehicle battery is required to have excellent cycle performance, power characteristic, high-temperature storage characteristic, low-temperature quick charging capability and the like, the development difficulty is large. In many application fields, it is desirable that the battery occupies a smaller volume to achieve portability or functional diversification of the terminal device. By increasing the density of the electrode (also referred to as the compaction density), the volumetric energy density of the battery can be increased, but it is easy to cause deterioration in the output and input characteristics of the battery. This problem is particularly pronounced at low temperature conditions. One simple method for judging the input characteristics is to observe the condition of the negative electrode interface, and if the negative electrode interface has white or gray attachments (the interface is uniform golden yellow under normal conditions) after the battery is disassembled in a full-electric state, the method is called to 'lithium precipitation'. The negative electrode lithium deposition will lead to accelerated deterioration of the battery performance.
In addition, when LiCoO is used2Or LiNixCoyMn1-x-yO2In the case of a positive electrode active material, in order to obtain a higher battery capacity, the charge cut-off voltage is sometimes set to 4.4V or more, and under such a high voltage environment, the oxidation of the positive electrode material increases, and the electrolytic solution is easily oxidized and decomposed on the positive electrode side; at the same time, the transition metal ions are eluted, reduced and deposited on the negative electrode side, and the migration of lithium ions is inhibited. Therefore, protection of the positive electrode surface of the battery at high voltage is particularly important. In practical applications, in order to provide the battery with better high-temperature characteristics, a higher amount of sultone (e.g., 1, 3-propane sultone, 1,3- (1-propene) sultone, etc.) is generally added to the electrolyte. However, the european union REACH regulation listed 1, 3-propane sultone as a high concern (SVHC) in 2015, which has led to the start of limited use of such materials.
Therefore, it is difficult to achieve both high-temperature characteristics and low-temperature charge/discharge capability for a lithium ion battery having a high electrode density.
In view of this, the invention is particularly proposed.
Disclosure of Invention
An object of the present invention is to provide a lithium secondary battery and a method for manufacturing the same, which improve the above problems.
The invention is realized by the following steps:
in a first aspect, the present invention provides a lithium secondary battery comprising a nonaqueous electrolytic solution, a positive electrode and a negative electrode, the positive electrode comprising a first current collector and a positive electrode material disposed on the first current collector, the positive electrode material having a density of not less than 3.5g/cm3The negative electrode comprises a second current collector and a negative electrode material arranged on the second current collector, and the density of the negative electrode material is not lower than 1.5g/cm3. The non-aqueous electrolyte comprises fluoroethylene carbonate, fluoroether and a trinitrile compound; wherein, the mass percent of the fluoroethylene carbonate in the non-aqueous electrolyte is 3-15%, the mass percent of the fluoroether in the non-aqueous electrolyte is 0.5-8%, and the mass percent of the trinitrile compound in the non-aqueous electrolyte is 0.2-4%.
In a second aspect, the present invention also provides a method for producing the above-described lithium secondary battery, in which a positive electrode, a negative electrode, a nonaqueous electrolytic solution, and a separator are manufactured into a battery.
The invention has the following beneficial effects: aiming at a lithium secondary battery with high electrode density, the lithium secondary battery has excellent high-temperature characteristics and low-temperature input characteristics after high-temperature storage under the condition of higher electrode density by adopting fluoroethylene carbonate, fluoroether and a trinitrile compound in a specific ratio as characteristic components of an electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The lithium secondary battery and the method for manufacturing the same according to the present invention will be described in detail below.
In the prior art, the volume energy density of the battery can be increased by increasing the density of the electrode (also referred to as compaction density), but the output and input characteristics of the battery are easily deteriorated. This problem is more pronounced, especially at low temperatures. And in the case of more demanding use conditions of batteries, the demand for high temperature characteristics thereof is also increasing. Therefore, it is a difficult point faced by those skilled in the art to combine excellent high-temperature characteristics and low-temperature input characteristics after high-temperature storage for a specific lithium secondary battery with high electrode density, and based on this, the inventors have creatively proposed, through a lot of practice and research, to solve the above technical problems by adjusting the density of the electrode material and the suitability of the electrolyte, and further proposed the following technical solutions.
Specifically, some embodiments of the present invention provide a lithium secondary battery including a nonaqueous electrolytic solution, a positive electrode including a first current collector and a positive electrode material disposed on the first current collector, the positive electrode material having a density of not less than 3.5g/cm3The negative electrode comprises a second current collector and a negative electrode material arranged on the second current collector, and the density of the negative electrode material is not lower than 1.5g/cm3. The non-aqueous electrolyte comprises fluoroethylene carbonate, fluoroether and a trinitrile compound; wherein, the mass percent of the fluoroethylene carbonate in the non-aqueous electrolyte is 3-15%, the mass percent of the fluoroether in the non-aqueous electrolyte is 0.5-8%, and the mass percent of the trinitrile compound in the non-aqueous electrolyte is 0.2-4%.
The inventor finds through extensive research and practice that the electrode density needs to be matched with the characteristic components of a specific electrolyte to achieve the high-temperature characteristic under the high electrode density and the low-temperature input-output characteristic after high-temperature storage, so that the density of the positive electrode material is not lower than 3.5g/cm3The density of the negative electrode material is not less than 1.5g/cm3Under the condition that fluoroethylene carbonate, fluoroether and trinitrile compound are selected as the non-aqueous electrolyteThe three characteristic components, and further selecting a specific adding ratio to enable the nonaqueous electrolytic solution to be sufficiently adapted to the high density of the cathode material, so that the formed lithium secondary battery can simultaneously obtain high-temperature characteristics and low-temperature input characteristics after high-temperature storage.
Among them, fluoroethylene carbonate has a positive and negative film-forming effect, and when the content is less than 3%, it is difficult to form a firm interfacial film, and when the content is more than 15%, the output characteristics and cycle characteristics are deteriorated due to a high viscosity and a high interfacial resistance of the electrolyte. The fluoroether has the function of improving the oxidation resistance of the electrolyte, and when the content is less than 0.5%, the function is not obvious, and when the content is more than 8%, the output and low-temperature characteristics are reduced due to higher viscosity and lower conductivity of the electrolyte. The trinitrile compound has the functions of improving the oxidation resistance of the electrolyte and strengthening the interface of the positive electrode, when the content is less than 0.2%, the effect is not obvious, and when the content is more than 4%, the output and low-temperature characteristics are reduced due to higher viscosity and lower conductivity of the electrolyte. It should be noted that the three characteristic components do not play a single role, but cooperate with each other to make the lithium secondary battery compatible with the high-electrode material, so as to obtain both the high-temperature characteristic and the low-temperature input characteristic after high-temperature storage.
Further, in order to optimize the effect of the characteristic components, certain requirements need to be made on the selection of the three characteristic components to meet the performance requirements. Wherein, the fluoroether can be one or more selected from 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 2,2, 2-trifluoroethyl-1, 1,2,3,3, 3-hexafluoropropyl ether, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, perfluorobutyl ethyl ether, perfluorobutyl methyl ether and perfluoro-n-propyl vinyl ether, and the preferred fluoroether is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether. The trinitrile compound may be selected from one or more of 1,2, 3-propanetricitrile, 1,3, 5-pentanenitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-cyclohexanetricarbonitrile, 1,2, 3-tris (2-cyanoethoxy) propane, preferably, the trinitrile compound is selected from one or two of 1,2, 3-propanetricitrile and 1,3, 6-hexanetricarbonitrile.
Generally, the nonaqueous electrolyte solution further comprises a lithium salt and an organic solvent, wherein the mass percent of the lithium salt in the nonaqueous electrolyte solution is 5-30%, and the mass percent of the organic solvent in the nonaqueous electrolyte solution is 60-90%.
Wherein the lithium salt includes, but is not limited to, at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium dioxalate borate, lithium monooxalatedifluoroborate, and lithium difluorosulfonimide. That is, the lithium salt may be one selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium monooxalatedifluoroborate and lithium difluorosulfonimide, or may be a mixture of two or more of the above. In some embodiments, the lithium salt is preferably lithium hexafluorophosphate.
The organic solvent includes, but is not limited to, at least one of ethylene carbonate, propylene carbonate, γ -butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, sulfolane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. Likewise, the organic solvent may also be any one of the above substances or a mixture of any two or more thereof. In some embodiments, preferably, the organic solvent comprises ethylene carbonate, propylene carbonate, diethyl carbonate and propyl propionate, and more preferably, the volume ratio of ethylene carbonate, propylene carbonate, diethyl carbonate and propyl propionate is: 10-20: 10-20: 10-20: 50-60.
In some embodiments, the nonaqueous electrolyte solution may further include tris (trimethylsilane) phosphate (TMSP) and/or tris (trimethylsilane) borate (TMSB).
Further, in some embodiments, the positive electrode material comprises a positive electrode active material comprising LiCoO2、LiNixCoyMn1-x-yO2And LiNixCoyAl1-x-yO2Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1. In some preferred embodiments, the positive active material comprises LiCoO2。
In some embodiments, the positive electrode material may further include conductive carbon black, polyvinylidene fluoride, and N-methylpyrrolidone.
In some embodiments, the negative electrode material comprises at least one of a carbon material, a silicon-based material, and lithium titanate, and in some preferred embodiments, the negative electrode material comprises a silicon-based material. Preferably, the negative electrode material includes graphite, styrene-butadiene rubber, and carboxymethyl cellulose.
Some embodiments of the present invention also provide a method of manufacturing the above lithium secondary battery, comprising: the positive electrode, the negative electrode, the nonaqueous electrolytic solution, and the separator were manufactured into a battery.
Specifically, the soft package battery is manufactured by adopting a winding process.
The preparation method of the anode mainly comprises the following steps: the raw material of the anode material (such as LiCoO) is mixed according to the proportion2、LiNi0.6Co0.2Mn0.2O2Conductive carbon black, PVDF, NMP, etc.) to obtain a positive electrode slurry. And coating the anode slurry on an aluminum foil, drying, rolling and cutting to obtain the anode.
The preparation steps of the negative electrode mainly comprise: mixing and stirring raw materials (such as graphite, styrene butadiene rubber, carboxymethyl cellulose and the like) of the anode material and deionized water according to a ratio to obtain anode slurry. And coating the negative electrode slurry on a copper foil, drying, rolling and cutting to obtain the negative electrode.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Firstly, manufacturing a positive electrode.
Weighing LiCoO according to the mass ratio of 47:47:3:32、LiNi0.6Co0.2Mn0.2O2And adding the conductive carbon black and the PVDF into NMP, fully stirring, and uniformly mixing to obtain the anode slurry. And coating the anode slurry on an aluminum foil, drying, rolling and cutting to obtain the anode. Positive electrode removing collectorThe density of the portion other than the fluid (positive electrode material) (positive electrode compacted density for short) was 3.85g/cm3。
And secondly, manufacturing a negative electrode.
Weighing graphite, styrene butadiene rubber and carboxymethyl cellulose according to the mass ratio of 95:3:2, adding the graphite, styrene butadiene rubber and carboxymethyl cellulose into deionized water, fully stirring, and uniformly mixing to obtain the cathode slurry. And coating the negative electrode slurry on a copper foil, drying, rolling and cutting to obtain the negative electrode. The density (abbreviated as negative electrode compacted density) of the negative electrode portion (negative electrode material) excluding the current collector was 1.65g/cm3。
And thirdly, preparing an electrolyte.
The nonaqueous electrolyte solution was prepared as follows: based on the total mass of the nonaqueous electrolyte, 1 mol/kg of lithium hexafluorophosphate, 7 wt% of fluoroethylene carbonate (FEC), 2 wt% of 1,3, 6-Hexanetricarbonitrile (HTN), 2 wt% of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (FE1) were added to an organic solvent, and mixed uniformly, wherein the organic solvent was prepared by mixing Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC) and Propyl Propionate (PP) in a volume ratio of 15:15:15: 55.
The FEC, HTN and FE1 are collectively called as characteristic components of the electrolyte.
And fourthly, manufacturing the battery.
The positive electrode, the negative electrode and the electrolyte are used, a PE diaphragm with the thickness of 12 micrometers is selected, and a winding process is adopted to manufacture the soft package battery with the model number of 053048.
Examples 2 to 16 and comparative examples 1 to 12
In examples 2 to 16 and comparative examples 1 to 12, the difference from example 1 is only that at least one of the positive and negative electrode compacted density, the characteristic components and the content of the electrolyte is changed.
Wherein fluoroethylene carbonate is abbreviated as FEC,1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether is abbreviated as FE1, 2,2, 2-trifluoroethyl-1, 1,2,3,3, 3-hexafluoropropyl ether is abbreviated as FE2, 1,2, 3-propanetricitrile is abbreviated as PTN,1,3, 6-hexanetricarbonitrile is abbreviated as HTN, and 1,3- (1-propene) sultone is abbreviated as PRS.
The positive and negative electrode compacted densities, the characteristic components and contents of the electrolytes of examples 1 to 16 and comparative examples 1 to 12 are shown in Table 1.
TABLE 1
Test example 1
High temperature property test
The high-temperature storage performance test is to charge the battery to 4.4V at a constant current of 0.5C under the condition of 25 ℃, charge the battery at a constant voltage until the current is reduced to 0.05C, and then store the battery in an oven at 60 ℃ for 14 days. Internal resistance before and after storage of the battery (full state) is tested. The internal resistance change rate is [ (internal resistance after storage-internal resistance before storage)/internal resistance before storage ]. 100%.
The high temperature cycle performance test is to calculate the capacity retention rate by cycling the battery at 50 ℃ for 400 weeks at 0.7C. Capacity retention rate (500-cycle discharge capacity/first-cycle discharge capacity) × 100%.
The batteries of examples 1 to 16 and comparative examples 1 to 12 were subjected to the high temperature characteristic test by the above test method, and the test results are shown in table 2.
TABLE 2
From comparative examples 1 to 6 in combination with tables 1 and 2, it is found that when the compacted densities of the positive and negative electrodes are increased, if the nonaqueous electrolytic solution does not fully adopt the combination of the characteristic components of the present invention, the internal resistance change rate of the battery is greatly increased, the capacity retention rate is greatly decreased, that is, the high-temperature characteristics of the battery are greatly deteriorated. From comparative examples 7 and 8, it is found that in the case of higher compacted densities of the positive and negative electrodes, the nonaqueous electrolytic solution has a large internal resistance change rate and a low capacity retention rate, i.e., the high-temperature characteristics of the battery, although it has the characteristic components, and the reason for this is that the content of the characteristic components of the nonaqueous electrolytic solution is insufficient, and the advantageous effects thereof are limited. From comparative examples 9 to 12, it was found that, in the case of higher compacted densities of the positive and negative electrodes, when the combination of the characteristic components in the nonaqueous electrolytic solution was adjusted or the content thereof exceeded the upper limit value, the relative performances with respect to the rate of change in internal resistance and the capacity retention rate of the batteries of examples were markedly lowered.
On the other hand, as shown by comparing examples 1 to 16 with comparative examples 3 to 12, under the condition of higher compacted densities of the positive electrode and the negative electrode, the internal resistance change rate and the capacity retention rate of the battery are obviously improved after the optimized combination of FEC, fluoroether and trinitrile compounds is adopted in the nonaqueous electrolytic solution, namely the high-temperature characteristic of the battery is optimized.
Test example 2
Low temperature input characteristic test after high temperature storage
The cells were first charged to 4.4V at 25 ℃ at a constant current of 0.5C, charged at constant voltage until the current dropped to 0.05C, and then stored in an oven at 60 ℃ for 7 days. The cell was then allowed to stand at ambient conditions for 3h and discharged to 3V at 0.5C.
The cell was allowed to stand at-5 ℃ for 3h, then charged at 0.3C constant current to 4.4V and then charged at constant voltage until the current dropped to 0.05C.
And (3) standing the battery for half an hour at normal temperature, disassembling the battery in a drying room, and observing the condition of a negative electrode interface.
The interface condition is divided into four conditions of no lithium precipitation, medium-light lithium precipitation, medium lithium precipitation and serious lithium precipitation, wherein the non-lithium precipitation indicates that the interface of the negative electrode is uniform golden yellow, the light lithium precipitation indicates that specky white or gray attachments exist on the interface (the distribution area does not exceed 10% of the coating area), the medium lithium precipitation indicates that white or gray attachments exist in 10-30% of the interface, and the serious lithium precipitation indicates that white or gray attachments exist in more than 30% of the interface.
The absence of lithium deposition indicates that the low-temperature input characteristics of the battery are excellent, and the more severe the lithium deposition degree, the worse the low-temperature input characteristics.
The low-temperature input characteristics after the high-temperature storage of the batteries of examples 1 to 16 and comparative examples 1 to 12 were tested by the above test methods, and the test results are shown in table 3.
TABLE 3
Combining tables 1 and 3, it can be seen from comparative examples 1 to 8 that the interface of the negative electrode does not significantly deteriorate with the increase in the compacted density of the positive and negative electrodes, i.e., the low-temperature input characteristics of the battery are better, because the nonaqueous electrolyte has fewer types of characteristic components and is moderate in content. As is clear from comparative examples 9 to 12, incomplete adoption of the combination of the characteristic components of the present invention with the nonaqueous electrolytic solution or too high content resulted in deterioration of the interface of the negative electrode, i.e., deterioration of the low-temperature input characteristics of the battery. On the other hand, it can be seen from examples 1 to 16 that the negative electrode interface condition, i.e., the low-temperature input characteristics of the battery, is better at higher positive and negative electrode compacted densities.
In summary, the lithium secondary battery according to the embodiment of the present invention can still achieve both good high-temperature characteristics and low-temperature input characteristics after high-temperature storage when the lithium secondary battery has a high compacted density of the negative electrode.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A lithium secondary battery is characterized by comprising a non-aqueous electrolyte, a positive electrode and a negative electrode, wherein the positive electrode comprises a first current collector and a positive electrode material arranged on the first current collector, and the density of the positive electrode material is not lower than 3.5g/cm3The negative electrode comprises a second current collector and a negative electrode material arranged on the second current collector, and the density of the negative electrode material is not lower than 1.5g/cm3；
The non-aqueous electrolyte comprises fluoroethylene carbonate, fluoroether and a trinitrile compound; wherein the mass percent of the fluoroethylene carbonate in the non-aqueous electrolyte is 3-15%, the mass percent of the fluoroether in the non-aqueous electrolyte is 0.5-8%, and the mass percent of the trinitrile compound in the non-aqueous electrolyte is 0.2-4%.
2. The lithium secondary battery as claimed in claim 1, wherein the fluoroethylene carbonate is 7 to 15% by mass of the nonaqueous electrolytic solution, the fluoroether is 0.5 to 2% by mass of the nonaqueous electrolytic solution, and the trinitrile compound is 2 to 4% by mass of the nonaqueous electrolytic solution.
3. The lithium secondary battery according to claim 1, wherein the density of the positive electrode material is not less than 3.7g/cm3The density of the negative electrode material is not lower than 1.6g/cm3。
4. The lithium secondary battery according to claim 1, wherein the fluoroether is selected from one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether and 2,2, 2-trifluoroethyl-1, 1,2,3,3, 3-hexafluoropropyl ether, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, perfluorobutyl ethyl ether, perfluorobutyl methyl ether, and perfluoro-n-propyl vinyl ether.
5. The lithium secondary battery according to claim 1, wherein the trinitrile compound is one or more selected from the group consisting of 1,2, 3-propanetricitrile, 1,3, 5-pentanetrimethylnitrile, 1,3, 6-hexanetricarbonitrile, 1,3, 5-cyclohexanetricarbonitrile, and 1,2, 3-tris (2-cyanoethoxy) propane.
6. The lithium secondary battery according to any one of claims 1 to 5, wherein the nonaqueous electrolytic solution further comprises a lithium salt and an organic solvent;
the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium dioxalate borate, lithium monooxalatedifluoroborate and lithium difluorosulfonylimide;
the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, gamma-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, sulfolane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether.
7. The lithium secondary battery according to any one of claims 1 to 5, wherein the positive electrode material comprises a positive electrode active material comprising LiCoO2、LiNixCoyMn1-x-yO2And LiNixCoyAl1-x-yO2Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1.
8. The lithium secondary battery according to any one of claims 1 to 5, wherein the negative electrode material comprises at least one of a carbon material, a silicon-based material, and lithium titanate.
9. The method for producing a lithium secondary battery according to any one of claims 1 to 8, characterized by comprising: the positive electrode, the negative electrode, the nonaqueous electrolytic solution, and a separator are manufactured into a battery.
10. The manufacturing method according to claim 9, wherein the laminate battery is manufactured by a winding process.
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