CN113892207B - Electrolyte solution, electrochemical device, and electronic device - Google Patents
Electrolyte solution, electrochemical device, and electronic device Download PDFInfo
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- CN113892207B CN113892207B CN202080038334.1A CN202080038334A CN113892207B CN 113892207 B CN113892207 B CN 113892207B CN 202080038334 A CN202080038334 A CN 202080038334A CN 113892207 B CN113892207 B CN 113892207B
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- ion battery
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- 239000008151 electrolyte solution Substances 0.000 title claims description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 131
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 150000002148 esters Chemical class 0.000 claims description 43
- -1 fluoropropyl propionate Chemical compound 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 41
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 34
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 34
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 25
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- 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
- PVDYNYCZGYOXAF-UHFFFAOYSA-N 2-fluoroethyl acetate Chemical compound CC(=O)OCCF PVDYNYCZGYOXAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 3
- 125000004450 alkenylene group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 80
- 229910001416 lithium ion Inorganic materials 0.000 description 80
- 230000014759 maintenance of location Effects 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 230000001351 cycling effect Effects 0.000 description 14
- 230000006872 improvement Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000011056 performance test Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229940021013 electrolyte solution Drugs 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 5
- 238000001035 drying Methods 0.000 description 5
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- LNLFLMCWDHZINJ-UHFFFAOYSA-N hexane-1,3,6-tricarbonitrile Chemical compound N#CCCCC(C#N)CCC#N LNLFLMCWDHZINJ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006255 coating slurry Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical group [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 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
- 230000008901 benefit Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical group [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01M10/056—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
- H01M10/052—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
- H01M10/42—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Provided are an electrolyte including at least one of compounds represented by formula (I-A); in the formula (I-A), A 1 、A 2 、A 3 、A 4 Each independently selected from any one of the structures represented by formula (I-B), formula (I-C), formula (I-D) or formula (I-E). By adding the compound with special function in the formula (I-A) into the electrolyte, the generation of more stable anode and cathode protective films can be promoted, side reactions and impedance increase can be effectively inhibited, direct current impedance of the electrochemical device after high-voltage circulation can be effectively reduced, and the circulation performance of the electrochemical device can be improved.
Description
[ technical field ] A method for producing a semiconductor device
The present disclosure relates to the field of electrolyte solutions, and particularly, to an electrolyte solution, an electrochemical device, and an electronic device.
[ background of the invention ]
With the recent reduction in weight and size of electrical products, lithium ion batteries have become indispensable products for modern electronic products. The development of lithium ion secondary batteries with high energy density is gradually promoted, and the designed upper limit voltage for use is also improved, for example, the current rated voltage of a lithium cobalt oxide system on the market can reach 4.45-4.5V. The damage to the positive and negative electrode structures is increasingly serious in the high-voltage storage and charge and discharge of the lithium ion battery, and higher requirements are put forward on the oxidation resistance and the film forming stability of the electrolyte, so that the electrolyte capable of forming a stable positive and negative electrode protective film is required to be developed so as to improve the electrochemical performance of an electrochemical device under high voltage.
[ summary of the invention ]
In view of this, the present application provides an electrolyte, an electrochemical device, and an electronic device, where the electrolyte can form a stable positive and negative protective film, and can effectively reduce dc impedance of the electrochemical device after high voltage cycling, and improve cycling stability of the electrochemical device.
In a first aspect, the present application provides an electrolyte comprising at least one of the compounds represented by formula (I-a):
in the formula (I-A), A 1 、A 2 、A 3 、A 4 Each independently selected from any one of the structures represented by formula (I-B), formula (I-C), formula (I-D) or formula (I-E):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from C 1-6 Alkyl radical, C 2-6 Alkenyl or C 2-6 An alkynyl group;
In one possible embodiment in combination with the first aspect, formula (I-A) includes at least one of the compounds of formulae I-1 to I-4:
with reference to the first aspect, in a possible embodiment, the content of the compound represented by formula I in the electrolyte is 0.05% to 8% by mass.
With reference to the first aspect, in a possible embodiment, the content of the compound represented by formula I in the electrolyte is 0.5% to 4% by mass.
In one possible embodiment in combination with the first aspect, the electrolyte further includes a fluorocarboxylic acid ester and/or a non-fluorocarboxylic acid ester.
With reference to the first aspect, in one possible embodiment, the electrolyte satisfies at least one of the following characteristics a to c:
a. the mass percentage content of the fluorocarboxylate in the electrolyte is 5-50%;
b. the mass percentage content of the non-fluorinated carboxylic ester in the electrolyte is 5-50%;
c. the total mass percentage content of the fluorinated carboxylic ester and the non-fluorinated carboxylic ester in the electrolyte is 5-50%, and the mass ratio n of the non-fluorinated carboxylic ester to the fluorinated carboxylic ester is 0.5-10, preferably 0.5-4.
In one possible embodiment in combination with the first aspect, the non-fluorocarboxylic acid ester includes at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, or butyl propionate.
In one possible embodiment in combination with the first aspect, the fluorocarboxylic acid ester includes at least one of fluoroethyl acetate, fluoropropyl propionate, and fluoropropyl propionate, wherein at least one hydrogen atom in the fluorocarboxylic acid ester molecule is substituted by a fluorine atom.
With reference to the first aspect, in one possible embodiment, the electrolyte further includes at least one of fluoroethylene carbonate, 1, 3-propane sultone, vinylene carbonate, or nitrile compound.
With reference to the first aspect, in one possible embodiment, the electrolyte satisfies at least one of the following features d to g:
d. the mass percentage content of the fluoroethylene carbonate in the electrolyte is 0.1-10%;
e. the content of the vinylene carbonate in the electrolyte is 0.001-2% by mass;
f. the mass percentage content of the 1, 3-propane sultone in the electrolyte is 0.1-5%;
g. the nitrile compound accounts for 0.1-12% of the electrolyte by mass percent.
In one possible embodiment in combination with the first aspect, the nitrile compound includes at least one of the following compounds:
wherein R is 11 Is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group; r 21 、R 22 Each independently selected from the group consisting of a single bond, C 1-12 Alkylene or substituted C 1-12 An alkylene group;
R 31 、R 32 、R 33 each independently selected from the group consisting of a single bond, C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group;
R 41 is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 2-12 Alkenylene, substituted C 2-12 Alkenylene radical, C 6-26 Arylene, substituted C 6-26 Arylene radical, C 2-12 Heterocyclylene or substituted C 2-12 A heterocyclylene group;
wherein, when substituted, the substituent is a halogen atom.
In one possible embodiment in combination with the first aspect, the nitrile compound includes
With reference to the first aspect, in one possible embodiment, the electrolyte further includes fluoroethyl acetate, ethyl propionate, fluoroethylene carbonate, 1, 3-propane sultone, vinylene carbonate, 1,3, 6-hexanetricarbonitrile, and glutaronitrile.
In a second aspect, the present application provides an electrochemical device comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is the above-mentioned electrolyte.
In a third aspect, the present application provides an electronic device comprising the electrochemical device described above.
Compared with the prior art, the method has the following beneficial effects:
the electrolyte provided by the application comprises the compound shown in the formula I, and the compound shown in the formula I is beneficial to forming positive and negative protective films on positive and negative electrodes at the initial charging and discharging stages of an electrochemical device, so that the electrochemical device can be stably circulated under high voltage (for example, the voltage is 4.5V), and the circulation performance of the electrochemical device under the high voltage is improved. The compound shown in the formula I can promote the generation of a more stable anode and cathode protective film, effectively inhibit side reactions and impedance growth, and effectively reduce the direct current impedance (DCR) after circulation.
The fluorocarboxylate can improve the cycle capacity retention rate at high voltage of an electrochemical device using the electrolyte, and the non-fluorocarboxylate can further reduce the Direct Current Resistance (DCR) after cycling. When the mass content of the carboxylic acid ester in the electrolyte is too high, the cycle performance may be deteriorated, and thus it is necessary to control the mass content of the fluorocarboxylic acid ester and the non-fluorocarboxylic acid ester in the electrolyte. When the proportion of the fluorocarboxylic acid ester to the non-fluorocarboxylic acid ester is too low, the battery impedance is too high; if the ratio of the two is too high, the electrolyte is easily decomposed at a high voltage, and the cycle performance is not facilitated.
The fluoroethylene carbonate or 1, 3-propane sultone can improve the film forming stability of the electrochemical device on the negative electrode, and can effectively inhibit impedance increase and improve circulation by the synergistic effect of the compound shown in the formula I. The nitrile compound can form an organic protective layer on the surface of the anode, and organic molecules on the surface of the anode can well separate easily-oxidizable components in the electrolyte from the surface of the anode, so that the oxidation of the surface of the anode on the electrolyte under high voltage is greatly reduced, and the cycle performance of the electrochemical device is improved.
Therefore, according to the electrolyte, the electrochemical device and the electronic device, the electrolyte can form a stable anode and cathode protective film, the direct current impedance of the electrochemical device after high-voltage circulation can be effectively reduced, and the circulation stability of the electrochemical device is improved.
[ detailed description ] embodiments
While the following is a preferred embodiment of the embodiments of the present application, it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the embodiments of the present application, and such improvements and modifications are also considered to be within the scope of the embodiments of the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" means "a plurality of" is two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
The present application relates to an electrolyte comprising at least one of the compounds represented by formula (I-a):
in the formula (I-A), A 1 、A 2 、A 3 、A 4 Each independently selected from any one of the structures represented by formula (I-B), formula (I-C), formula (I-D) or formula (I-E):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from C 1-6 Alkyl radical, C 2-6 Alkenyl or C 2-6 An alkynyl group; wherein,representing the binding site to the adjacent atom.
By adding the compound shown in the formula I into the electrolyte, the oxygen resistance of the electrolyte can be improved, an effective and stable solid electrolyte phase interface film can be generated on the positive electrode and the negative electrode of an electrochemical device, side reactions and impedance increase are effectively inhibited, and the circulation stability and direct current impedance (DCR) performance of the electrochemical device under high pressure can be obviously improved.
As an alternative embodiment of the present application, the compound represented by formula (I-A) includes at least one of the compounds represented by formula I-1 to formula I-4:
as an optional technical scheme of the application, the mass percentage content of the compound shown in the formula I in the electrolyte is 0.05-8%; when the content of the compound shown in the formula I is lower than 0.05%, the high-temperature cycle performance of the lithium battery under high voltage is not obviously improved; when the content of the compound represented by the formula I is higher than 8%, the interface film impedance is large due to excessive compounds in the electrolyte, so that irreversible lithium precipitation is caused, an ion transport channel of the electrolyte is blocked, and capacity fading of the battery is accelerated.
Alternatively, the content of the compound represented by formula I in the electrolyte solution may be specifically 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8% by mass, or the like, and may be other values within the above range, which is not limited herein. The compound shown in the formula I is added into the electrolyte, and participates in film formation of the anode and the cathode, so that the stability of the SEI film is improved, and the impedance increase and the cycle performance of the lithium ion battery under high voltage can be effectively improved. Preferably, the mass percentage content of the compound shown in the formula I in the electrolyte is 0.5-4%.
As an alternative embodiment of the present invention, the electrolyte includes a fluorocarboxylic acid ester and/or a non-fluorocarboxylic acid ester. It is understood that the fluorocarboxylate and the non-fluorocarboxylate are oxygen-inert solvents, which can improve the oxidation resistance of the electrolyte and effectively improve the cycle stability of the electrochemical device.
As an alternative embodiment of the present invention, the content of the fluorocarboxylate in the electrolyte solution is 5% to 50% by mass, specifically 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, and the like, and may be other values within the above range, which is not limited herein. Through a plurality of tests, the fact that the fluorocarboxylate is added into the electrolyte can effectively improve the high-temperature cycle stability of the lithium ion battery under high voltage, but the fluorocarboxylate has small influence on the direct-current impedance of the lithium ion battery.
As an optional technical scheme of the application, the mass percentage of the non-fluorocarboxylic acid ester in the electrolyte is 5-50%. Specifically, the amount may be 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., or may be other values within the above range, which is not limited herein. Through a plurality of tests, the non-fluorinated carboxylic ester is added into the electrolyte, so that the direct current impedance of the lithium battery under high voltage is obviously reduced, but the capacity retention rate is also obviously reduced; that is, the addition of the non-fluorocarboxylic acid ester significantly improves the dc resistance of the battery, but deteriorates the high-temperature cycle performance of the lithium ion battery at high voltage.
As an optional technical scheme of the application, the electrolyte comprises fluorinated carboxylic ester and non-fluorinated carboxylic ester, and the mass ratio n of the non-fluorinated carboxylic ester to the fluorinated carboxylic ester is more than or equal to 0.5 and less than or equal to 10. Specifically, the mass ratio may be specifically 0.5, 1.0, 2, 2.5, 4, 7, 8, 9, or 10, etc., and may be other values within the above range, which is not limited herein. Multiple tests show that when the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is too low, the direct-current impedance of the battery is high, and the battery is not favorable for realizing quick charge and discharge; when the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is too high, the electrolyte is largely decomposed by the solvent at a high voltage, which is disadvantageous in cycle performance at a high voltage. Preferably, the mass ratio n of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is 0.5. ltoreq. n.ltoreq.4.
As an alternative embodiment of the present application, the non-fluorocarboxylic acid ester includes at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, and butyl propionate.
As an alternative embodiment of the present invention, the fluorocarboxylic acid ester includes at least one of fluoroethyl acetate, fluoropropyl propionate and fluoropropyl propionate, wherein at least one hydrogen atom in the fluorocarboxylic acid ester molecule is substituted by a fluorine atom.
As an optional technical solution of the present application, the electrolyte further includes at least one of fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), Vinylene Carbonate (VC), or nitrile compounds.
As an optional technical scheme of the application, the mass percentage content of fluoroethylene carbonate (FEC) in the electrolyte is 0.1-10%. The content of fluoroethylene carbonate (FEC) in the electrolyte solution may be specifically 0.1%, 0.5%, 1%, 2%, 3%, 5%, 8%, or 10% by mass, or may be other values within the above range, and is not limited herein. Through multiple tests, the electrolyte is added with a proper amount of fluoroethylene carbonate (FEC), so that the film forming stability of an electrochemical device at a high voltage on a negative electrode can be improved, the impedance increase can be inhibited under the synergistic action of the fluoroethylene carbonate (FEC) and a compound shown in a formula I, and the cycle performance of a lithium ion battery at the high voltage can be improved.
Preferably, the content of fluoroethylene carbonate (FEC) in the electrolyte is 0.1-5% by mass.
As an optional technical scheme of the application, the mass percentage content of the 1, 3-Propane Sultone (PS) in the electrolyte is 0.1-5%. The content of 1, 3-Propane Sultone (PS) in the electrolyte solution may be specifically 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% by mass, or the like, or may be other values within the above range, and is not limited herein. Through multiple tests, the fact that when a proper amount of 1, 3-Propane Sultone (PS) is added into the electrolyte, the film forming stability of an electrochemical device at a high voltage under a negative electrode can be improved, and the impedance increase can be inhibited and the cycle performance of a lithium ion battery at the high voltage can be improved under the synergistic effect of the electrolyte and a compound shown in a formula I.
Preferably, the content of the 1, 3-Propane Sultone (PS) in the electrolyte is 0.1-5% by mass.
As an optional technical scheme of the application, the content of Vinylene Carbonate (VC) in the electrolyte is 0.001-2% by mass. The content of Vinylene Carbonate (VC) in the electrolyte may be, specifically, 0.001%, 0.1%, 0.5%, 1%, 1.5%, or 2% by mass, or the like, and may be other values within the above range, which is not limited herein. Through multiple tests, the fact that when a proper amount of Vinylene Carbonate (VC) is added into the electrolyte, the film forming stability of an electrochemical device at a high voltage under a negative electrode can be improved, and the resistance increase can be inhibited and the cycle performance of a lithium ion battery at the high voltage can be improved under the synergistic effect of the Vinylene Carbonate (VC) and the compound shown in the formula I.
Preferably, the content of the Vinylene Carbonate (VC) in the electrolyte is 0.001-1% by mass.
As an optional technical scheme of the application, the nitrile compound accounts for 0.1-12% of the electrolyte in percentage by mass. The content of the nitrile compound in the electrolyte solution may be specifically 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, or 12% by mass, or may be other values within the above range, and is not limited herein. Through multiple tests, the nitrile compound can form an organic protective layer on the surface of the anode when a proper amount of the nitrile compound is added into the electrolyte, and organic molecules on the surface of the anode can well separate easily-oxidized components in the electrolyte from the surface of the anode, so that the oxidation of the surface of the anode on the electrolyte under high voltage is greatly reduced, and the cycle performance of the lithium ion battery under high voltage is improved.
Preferably, the nitrile compound accounts for 0.1-5% of the electrolyte by mass percent.
As an alternative embodiment of the present application, the nitrile compound includes at least one of the following compounds:
wherein R is 11 Is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group; r 21 、R 22 Each independently selected from the group consisting of a single bond, C 1-12 Alkylene or substituted C 1-12 An alkylene group;
R 31 、R 32 、R 33 each independently selected from the group consisting of a single bond, C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group;
R 41 is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 2-12 Alkenylene, substituted C 2-12 Alkenylene radical, C 6-26 Arylene, substituted C 6-26 Arylene radical, C 2-12 Heterocyclylene or substituted C 2-12 A heterocyclylene group;
wherein, when substituted, the substituent is halogen atom, and the halogen can be selected from fluorine, chlorine and bromine.
As an alternative solution, the nitrile compound may be at least one selected from the group consisting of nitrile compounds represented by the following structures;
as an optional technical solution of the present application, the electrolyte of the present application is a nonaqueous electrolyte, and the organic solvent is at least one selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, fluoroethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone (GBL), methyl propionate, methyl valerate, methyl isobutyrate, methyl butyrate, propyl propionate, ethyl acetate, ethyl propionate, and ethyl butyrate.
As an alternative solution, the lithium salt is selected from at least one of organic lithium salt or inorganic lithium salt.
As an optional technical scheme, the lithium salt is selected from lithium hexafluorophosphate LiPF 6 Lithium bis (trifluoromethanesulfonylimide) LiN (CF) 3 SO 2 ) 2 (abbreviated as LiTFSI), lithium bis (fluorosulfonyl) imide Li (N (SO2F) 2 ) (abbreviated as LiFSI) and lithium LiB (C) bis (oxalato-borate 2 O 4 ) 2 (abbreviation)LiBOB), lithium difluoro (oxalato) borate LiBF 2 (C 2 O 4 ) (abbreviated as LiDFOB).
The application also provides an electrochemical device, which comprises a positive electrode, a negative electrode, an isolating membrane and electrolyte, wherein the electrolyte is the electrolyte. The electrochemical device may be a lithium ion battery.
As an alternative solution, the positive electrode of the present application includes a positive electrode active material, a binder, and a conductive agent.
As an improvement in the electrochemical device of the present application, the positive electrode active material of the present application is optionally selected from lithium cobaltate LiCoO 2 At least one of lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganese iron phosphate and lithium manganate.
As an improvement of the electrochemical device of the present application, the negative electrode of the present application includes a negative active material, a binder, and a conductive agent.
As an improvement of the electrochemical device of the present application, the negative active material of the present application is graphite and/or silicon.
The technical solution of the present application is exemplarily described below by specific embodiments:
(1) preparation of positive electrode
The positive electrode active material lithium cobaltate (LiCoO) 2 ) The conductive agent SuperP and the adhesive polyvinylidene fluoride are mixed according to the weight ratio of 97.9: 0.4: 1.7, adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain anode slurry; uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil; and drying the aluminum foil, then carrying out cold pressing, cutting and slitting, and drying under a vacuum condition to obtain the anode.
(2) Preparation of negative electrode
Preparing a negative electrode active material artificial graphite, a conductive agent SuperP, a thickening agent carboxymethylcellulose sodium (CMC), and a binder Styrene Butadiene Rubber (SBR) according to a weight ratio of 97: 1.5: 0.5: 1, mixing, adding deionized water, and obtaining cathode slurry under the action of a vacuum stirrer; uniformly coating the negative electrode slurry on a copper foil of a negative electrode current collector; and drying the copper foil, then carrying out cold pressing, cutting and slitting, and drying under a vacuum condition to obtain the negative plate.
(3) Preparation of electrolyte
In a dry argon atmosphere glove box, the solvent is mixed, then the first compound and the second compound are added, the lithium salt LiPF is added after the first compound and the second compound are dissolved and fully stirred 6 And mixing uniformly to obtain an electrolyte, wherein the types or the contents of the first compound, the second compound or the solvent added in each example and each comparative example are different.
(4) Preparation of the separator
Boehmite is mixed with polyacrylate and dispersed into deionized water to form a coating slurry. The coating slurry was then uniformly coated on both surfaces of the porous substrate by a gravure coating method, and subjected to a drying treatment to obtain a desired separator.
(5) Preparation of lithium ion battery
Stacking the anode, the isolating film and the cathode in sequence to enable the isolating film to be positioned between the anode sheet and the cathode sheet to play an isolating role, and then winding to obtain a bare cell; and (3) after welding the lug, placing the bare cell in an outer packaging foil aluminum-plastic film, injecting the prepared electrolyte into the dried bare cell, and performing vacuum packaging, standing, formation, shaping, capacity test and other procedures to obtain the lithium ion battery.
Examples and comparative examples were prepared according to the above method, and the specific parameters are shown in tables 1, 2 and 3 below.
And (3) performance testing:
(1) lithium ion battery cycle performance test
And (3) placing the lithium ion battery in a constant temperature box with the temperature of 45 ℃ (25 ℃), and standing for 30 minutes to keep the temperature of the lithium ion battery constant. The lithium ion battery reaching a constant temperature is charged with a constant current of 1C to a voltage of 4.5V, then charged with a constant voltage of 4.5V to a current of 0.025C, and then discharged with a constant current of 1C to a voltage of 3.0V, which is a charge-discharge cycle. The capacity of the first discharge is taken as 100%, the charge-discharge cycle is repeated for 300 circles, the test is stopped, and the cycle capacity retention rate is recorded and used as an index for evaluating the cycle performance of the lithium ion battery.
The cycle capacity retention ratio is the capacity at the time of cycling to a certain cycle divided by the capacity at the time of first discharge.
(2) Lithium ion battery direct current impedance (DCR) testing
And (3) placing the lithium ion battery in an environment of 25 ℃, and standing for 30 minutes to keep the temperature of the lithium ion battery constant. Constant current charging to 4.5V at 0.5C, constant voltage charging to 0.025C, standing for 30 minutes, and extracting the direct current impedance (DCR) at 70% SOC with 0.1CDC10s (100ms dotted), 1CDC360s (100ms dotted).
Examples 1-1 to 1-21 and comparative example 1-1 were prepared according to the above-described preparation method, wherein the first compounds added in examples 1-1 to 1-21 and comparative example 1-1 were as shown in table 1 below, and the solvents used were a mixture of Ethylene Carbonate (EC), Propylene Carbonate (PC) and diethyl carbonate (DEC), wherein the mass ratio of EC: PC: DEC was 1:1:1, and the corresponding performance test results were as shown in table 1.
TABLE 1
In the tables of the present application, "/" indicates that the substance was not added, and the wt% s are mass percentage contents calculated based on the total mass of the electrolyte.
As can be seen from the performance test results of comparative examples 1-1, when the compound represented by formula I is not added to the electrolyte, the capacity retention rate of the lithium ion battery after cycling for 300 cycles at 4.5V and 45 ℃ is poor, the Direct Current Resistance (DCR) is large, and the high-temperature cycling performance of the lithium ion battery under high voltage is poor.
From the performances of examples 1-1 to 1-17, it can be seen from the results, that after the compound represented by formula I is added to the electrolyte, the capacity retention rate of the lithium ion battery is increased after cycling for 300 cycles at 45 ℃ at 4.5V, and the DCR is reduced remarkably. The high-temperature cycle performance of the lithium ion battery under high voltage can be improved by adding the compound shown in the formula I into the electrolyte, and probably because the silicon oxygen group, the phosphorus oxygen group, the titanium oxygen group or the aluminum oxygen group shown in the formula I participates in film formation of the lithium ion battery, the failure of an interface film of a positive electrode solid electrolyte and a negative electrode solid electrolyte can be effectively delayed in high-temperature storage, the generation of electrolyte decomposition byproducts is inhibited, and the high-temperature cycle performance of the lithium ion battery is improved.
From the performance test results of examples 1-1 to 1-17, it can be seen that the mass percentage content of the compound represented by formula I in the electrolyte of example 1-1 is only 0.02%, the mass content of the compound represented by formula I is too small, the stability of the positive and negative electrode protective films is reduced, and the capacity retention rate of the lithium ion battery after being cycled for 300 cycles at 45 ℃ at 4.5V is not significantly improved compared with that of comparative example 1-1, and is also poor compared with that of examples 1-2 to 1-6. The mass percentage of the compound represented by formula I in the electrolytes of examples 1 to 7 was 9%, and the mass content of the compound represented by formula I was too large, which resulted in a large film resistance, irreversible lithium deposition, and, on the contrary, it was possible to obstruct the ion transport channel of the electrolyte and accelerate capacity fade.
According to the performance test results of the examples 1-1 to 1-17, when the mass content of the compound shown in the formula I in the electrolyte is 0.05-8%, the impedance increase of the lithium ion battery under high voltage can be improved. When the mass content of the compound shown in the formula I in the electrolyte is 0.5-4%, the capacity retention rate of the lithium ion battery after being cycled for 300 circles at 4.5V and 45 ℃ is obviously improved compared with that of a comparative example 1-1, namely the cycle performance and impedance increase of the lithium ion battery under high voltage are obviously improved. The reason is that the compound represented by the formula I participates in film formation of the positive electrode and the negative electrode, so that stability of the SEI film is improved, and improvement of cycle performance of the lithium ion battery under high voltage is facilitated, and therefore, in some embodiments of the present application, the content of the compound represented by the formula I in the electrolyte is 0.05% to 8%, and further preferably, the content of the compound represented by the formula I in the electrolyte is 0.5% to 4% by mass.
As can be seen from the results of the performance tests of examples 1-1 to 1-17, the performance improvement effect on the lithium ion battery is the best when the compound of formula I is specifically the compound of formula I-1.
Further, the first compound and the second compound used in examples 2-1 to 2-33 and comparative example 2-1, 2-1 to 2-33 were prepared according to the above-mentioned preparation method and are shown in table 2, the solvent used in examples 2-1 to 2-33 is the same as that used in examples 1-4, and data of examples 1-4 is added to table 2 for comparison.
TABLE 2
Referring to table 2, as can be seen from comparative analysis of the data of examples 1 to 4 and 2 to 1 to 2 to 3, when only 0.1% to 5% of fluoroethylene carbonate (FEC) is added to the electrolyte and 1, 3-Propane Sultone (PS), Vinylene Carbonate (VC), 1,3, 6-hexanetrinitrile or glutaronitrile is absent, the retention rate of the cycle capacity of the lithium ion battery increases after 300 cycles of cycling at 4.5V and 45 ℃, and the lithium ion battery can effectively inhibit the impedance increase and improve the cycle performance of the lithium ion battery at high voltage under the synergistic effect with the compound shown in formula I.
By analyzing the data of examples 2-1, 2-4 and 2-5, it can be seen that the dc impedance of the lithium ion battery increases significantly when the fluoroethylene carbonate (FEC) is added to the electrolyte in an amount of 10% by mass or even 12% by mass.
From the performance test results of examples 2-1 to 2-5, it can be seen that the performance improvement effect on the lithium ion battery is best when the mass percentage content of the fluoroethylene carbonate (FEC) in the electrolyte is controlled to be 0.1% -5%.
By analyzing the data of examples 1-4 and 2-6 to 2-8, it can be seen that when only 0.1-5% of 1, 3-Propane Sultone (PS) is added to the electrolyte and the fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), 1,3, 6-hexanetricarbonitrile or glutaronitrile is absent, the retention ratio of the cycle capacity of the lithium ion battery after cycling at 45 ℃ and 4.5V for 300 cycles is increased, and the impedance increase can be suppressed and the cycle performance of the lithium ion battery under high voltage can be improved under the synergistic effect with the compound of formula I.
By analyzing the data of the embodiments 2 to 6, 2 to 9 and 2 to 10, it can be known that when the mass percentage content of the 1, 3-Propane Sultone (PS) added to the electrolyte reaches 10%, even 12%, the retention rate of the cycle capacity of the lithium ion battery after the lithium ion battery is cycled for 300 cycles at 45 ℃ and 4.5V is reduced, and the direct current impedance of the lithium ion battery is remarkably increased.
From the performance test results of examples 2-6 to examples 2-10, it can be seen that the performance improvement effect on the lithium ion battery is best when the mass percentage content of the 1, 3-Propane Sultone (PS) in the electrolyte is controlled to be 0.1% -5%.
By analyzing the data of examples 1 to 4 and 2 to 11 to 2 to 13, it can be seen that when only 0.001 to 1% of Vinylene Carbonate (VC) is added to the electrolyte and 1, 3-Propane Sultone (PS), fluoroethylene carbonate (FEC), 1,3, 6-hexanetricarbonitrile or glutaronitrile is absent, the retention ratio of the cycle capacity of the lithium ion battery after cycling at 45 ℃ and 4.5V for 300 cycles is increased, and the impedance increase can be suppressed and the cycle performance of the lithium ion battery under high voltage can be improved by the synergistic effect with the compound of formula I.
It can be seen from the analysis of the data of examples 2 to 11, examples 2 to 14, and examples 2 to 15 that when the content of Vinylene Carbonate (VC) added to the electrolyte reaches 2% by mass, the cycle capacity retention of the lithium ion battery after cycling at 45 ℃ for 300 cycles at 4.5V is increased, but the dc impedance of the lithium ion battery is increased. When the content of Vinylene Carbonate (VC) added into the electrolyte reaches 3% by mass, the retention rate of the cycle capacity of the lithium ion battery after the lithium ion battery is cycled for 300 circles at 4.5V and 45 ℃ is reduced, and the direct current impedance of the lithium ion battery is remarkably increased.
From the performance test results of examples 2-11 to examples 2-15, it can be seen that the performance improvement effect on the lithium ion battery is best when the content of Vinylene Carbonate (VC) in the electrolyte is controlled to be 0.001% -1% by mass.
By analyzing the data of examples 1 to 4 and examples 2 to 16 to examples 2 to 26, it can be seen that when only 0.1% to 5% of nitrile compound is added to the electrolyte and 1, 3-Propane Sultone (PS), fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) are absent, the retention rate of the cycle capacity of the lithium ion battery after 300 cycles of cycling at 45 ℃ and 4.5V is increased, and the impedance increase can be suppressed and the cycle performance of the lithium ion battery at high voltage can be improved by the synergistic effect of the compound shown in formula I.
When the mass percentage content of the nitrile compound added into the electrolyte reaches 7%, the cycle capacity retention rate of the lithium ion battery is increased after the lithium ion battery is cycled for 300 circles at the temperature of 45 ℃ at 4.5V, but the direct current impedance of the lithium ion battery is increased. When the mass percentage content of the nitrile compound added into the electrolyte reaches 12%, the cycle capacity retention rate of the lithium ion battery is reduced after the lithium ion battery is cycled for 300 circles at 4.5V and 45 ℃, and the direct current impedance of the lithium ion battery is remarkably increased.
From the performance test results of examples 2-11 to examples 2-15, it can be seen that the performance improvement effect on the lithium ion battery is best when the mass percentage content of the nitrile compound in the electrolyte is controlled to be 0.1% -5%.
By analyzing the data of comparative examples 2-1, examples 2-27 to examples 2-33, it can be seen that when a nitrile compound, 1, 3-Propane Sultone (PS), fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) are added to the electrolyte, the retention rate of the cycle capacity of the lithium ion battery after 300 cycles at 45 ℃ at 4.5V is increased under the synergistic effect with the compound of formula I, and the increase of the impedance can be suppressed, thereby improving the cycle performance of the lithium ion battery at high voltage.
The compound polyalkoxy group shown in the formula I improves the interface infiltration capacity of electrolyte, a diaphragm and a negative electrode, so that other compounds can form a film more uniformly and compactly, and the cycle performance of the lithium ion battery under high voltage is improved. When at least one of FEC, PS, VC, 1,3, 6-hexanetricarbonitrile or glutaronitrile is added in the electrolyte in a compounding way, the performance of the battery can be greatly improved.
Further, examples 3-1 to 3-13 and comparative examples 3-1 to 3-6 were prepared according to the above-described preparation method, and the first compound and the second compound used in the comparative examples and examples were the same as those used in examples 1-10 except that the solvents used were different. Comparative examples 3-1 to 3-6, and examples 3-1 to 3-13 used solvents in which the mass ratio of fluorinated carboxylic acid ester to non-fluorinated carboxylic acid ester was as shown in Table 3, and the remaining solvent components were still supplemented at a mass ratio of EC: PC: DEC of 1:1: 1.
TABLE 3
Referring to Table 3, by analyzing the data of examples 1-4, comparative examples 3-1 to 3-3, it can be seen that: after the non-fluorinated carboxylic ester is added into the electrolyte, the direct current impedance of the lithium ion battery is reduced after the lithium ion battery is cycled for 300 circles at the temperature of 4.5V and 45 ℃, but the capacity retention rate is also obviously reduced, namely, the impedance of the battery is obviously improved by adding the non-fluorinated carboxylic ester into the electrolyte, but the high-temperature cycle performance of the lithium ion battery under the high voltage is deteriorated.
By analyzing the data of examples 1 to 4, comparative examples 3 to 4 to comparative examples 3 to 6, it can be seen that: after the fluorocarboxylate is added into the electrolyte, the direct current impedance of the lithium ion battery is slightly increased or decreased after the lithium ion battery is cycled for 300 circles at 4.5V and 45 ℃, but the capacity retention rate is greatly increased, namely, the fluorocarboxylate is added into the electrolyte, so that the impedance is slightly influenced, and the high-temperature cycle performance of the lithium ion battery under high voltage can be remarkably improved.
By analyzing the data of examples 1 to 4, comparative example 3 to 1, and examples 3 to 1 to 3 to 6, it was found that: the direct current impedance of the lithium ion batteries of the embodiments 3-1 to 3-6 after being cycled for 300 cycles at 4.5V and 45 ℃ is higher than that of the lithium ion batteries of the embodiments 1-4, and the capacity retention rate of the lithium ion batteries of the embodiments 3-1 to 3-6 after being cycled for 300 cycles at 4.5V and 45 ℃ is obviously lower than that of the lithium ion batteries of the comparative example 3-1, namely, the DCR of the electrolyte can still be improved along with the increase of the mass content of the non-substituted carboxylic ester and the increase of the mass ratio of the non-fluorinated carboxylic ester to the fluorinated carboxylic ester, and the degradation of the non-fluorinated carboxylic ester to high-voltage high-temperature cycling can be inhibited by adding the fluorinated carboxylic ester.
By analyzing the data of comparative example 3-1, example 3-4, example 3-7 to example 3-9, it can be seen that: when the mass content of the non-fluorocarboxylic acid ester is not changed, the capacity retention ratio of the lithium ion battery after being cycled for 300 circles at 4.5V and 45 ℃ is increased along with the increase of the mass content of the fluorocarboxylic acid ester and the decrease of the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester, so that the high-temperature cycling performance of the lithium ion battery under high voltage can be improved.
By analyzing the data of comparative example 3-1 to comparative example 3-3, example 3-7, example 3-10 to example 3-11: the ethyl acetate has the most obvious effect of improving the direct-current impedance of the lithium ion battery, but has no advantage of improving the capacity retention rate after high-voltage high-temperature circulation; propyl propionate is less effective in improving the dc resistance of a lithium ion battery, but is most effective in improving the high temperature cycle performance. By analyzing comparative examples 3-4 to 3-6, examples 3-7, and examples 3-12 to 3-13, it can be seen that: the ethyl difluoroacetate deteriorates the direct-current impedance of the lithium ion battery to a lesser extent, and the improvement effect on the high-temperature cycle performance is relatively poor.
In order to balance the impedance and the high-temperature cycle performance at high voltage, the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is set to n, and n is 0.5. ltoreq. n.ltoreq.10. When the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is too low, the direct current impedance of the battery is high, and the battery is not favorable for realizing quick charge and discharge; when the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is too high, the electrolyte is largely decomposed by the solvent at a high voltage, which is disadvantageous in cycle performance at a high voltage. Therefore, 0.5. ltoreq. n.ltoreq.4 is preferable.
By analyzing examples 3 to 14 to comparative examples 3 to 17, examples 3 to 10, it can be seen that: the first compound and the second compound are added into the electrolyte, and the mass ratio of the non-fluorocarboxylic acid ester to the fluorocarboxylic acid ester is adjusted, so that the high-temperature cycle performance of the electrochemical device can be effectively improved on the premise of greatly reducing the direct-current impedance.
In conclusion, in the embodiments of the present application, the electrolyte includes the compound represented by formula I, so that a highly stable anode and cathode protective film is formed at the initial stage of charge and discharge of the electrochemical device, stable circulation can be achieved at a high voltage of not less than 4.4V, and the cycle performance of the electrochemical device at the high voltage is improved; the failure of the SEI films of the positive electrode and the negative electrode is effectively delayed in the circulation, the impedance is inhibited from increasing, and the charge and discharge performance of the electrochemical device is improved.
In some embodiments, the electrolyte further comprises a fluorocarboxylate ester and a non-fluorocarboxylate ester, and the mass ratio of the two is defined to reduce the DCR of the electrolyte and improve the rapid charge and discharge capability of the electrochemical device at high voltage. The compound shown in the formula I and the fluorocarboxylic acid ester participate in negative electrode film formation, the compound shown in the formula I and the non-fluorocarboxylic acid ester participate in positive electrode film formation, and the stability of an SEI film of an electrochemical device under high voltage can be improved by reasonably combining and adjusting the using amount.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (12)
1. An electrolytic solution characterized by comprising at least one of the compounds represented by the formula (I-a):
in the formula (I-A), A 1 、A 2 、A 3 、A 4 Each independently selected from any one of the structures represented by formula (I-B), formula (I-C), formula (I-D) or formula (I-E):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from C 1-6 Alkyl radical, C 2-6 Alkenyl or C 2-6 An alkynyl group;
3. the electrolyte of claim 1, wherein the compound of formula I is present in the electrolyte in an amount of 0.05% to 8% by weight.
4. The electrolyte of claim 1, further comprising a fluorocarboxylic acid ester and/or a non-fluorocarboxylic acid ester.
5. The electrolyte of claim 4, wherein at least one of the following characteristics a to c is satisfied:
a. the mass percentage content of the fluorocarboxylate in the electrolyte is 5-50%;
b. the mass percentage content of the non-fluorinated carboxylic ester in the electrolyte is 5-50%;
c. the total mass percentage content of the fluorinated carboxylic ester and the non-fluorinated carboxylic ester in the electrolyte is 5-50%, and the mass ratio n of the non-fluorinated carboxylic ester to the fluorinated carboxylic ester is 0.5-10.
6. The electrolyte of claim 4 or 5,
the non-fluorocarboxylic acid ester comprises at least one of ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate or butyl propionate;
the fluorocarboxylic acid ester comprises at least one of fluoroethyl acetate, fluoropropyl propionate and fluoropropyl propionate, wherein at least one hydrogen atom in the fluorocarboxylic acid ester molecule is replaced by a fluorine atom.
7. The electrolyte of claim 1, further comprising at least one of fluoroethylene carbonate, 1, 3-propane sultone, vinylene carbonate, or nitrile compounds.
8. The electrolyte of claim 7, wherein at least one of the following features d-g is satisfied:
d. the mass percentage content of the fluoroethylene carbonate in the electrolyte is 0.1-10%;
e. the content of the vinylene carbonate in the electrolyte is 0.001-2% by mass;
f. the mass percentage content of the 1, 3-propane sultone in the electrolyte is 0.1-5%;
g. the nitrile compound accounts for 0.1-12% of the electrolyte by mass percent.
9. The electrolyte of claim 7, wherein the nitrile compound comprises at least one of the following compounds:
wherein R is 11 Is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group; r 21 、R 22 Each independently selected from the group consisting of a single bond, C 1-12 Alkylene or substituted C 1-12 An alkylene group;
R 31 、R 32 、R 33 each independently selected from the group consisting of a single bond, C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 1-12 Alkyleneoxy or substituted C 1-12 An alkyleneoxy group;
R 41 is selected from C 1-12 Alkylene, substituted C 1-12 Alkylene radical, C 2-12 Alkenylene, substituted C 2-12 Alkenylene radical, C 6-26 Arylene, substituted C 6-26 Arylene radical, C 2-12 Heterocyclylene or substituted C 2-12 A heterocyclylene group;
wherein, when substituted, the substituent is a halogen atom.
11. An electrochemical device comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte is the electrolyte according to any one of claims 1 to 10.
12. An electronic device comprising the electrochemical device according to claim 11.
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CN110073528A (en) * | 2016-12-15 | 2019-07-30 | 昭和电工株式会社 | Granular composite material, lithium ion secondary battery cathode and its manufacturing method |
CN109524713A (en) * | 2017-09-20 | 2019-03-26 | 株式会社东芝 | Secondary cell, battery pack and vehicle |
CN111342135A (en) * | 2020-03-13 | 2020-06-26 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
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