CN116454400A - Electrochemical device and electronic device including the same - Google Patents
Electrochemical device and electronic device including the same Download PDFInfo
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- CN116454400A CN116454400A CN202310330424.3A CN202310330424A CN116454400A CN 116454400 A CN116454400 A CN 116454400A CN 202310330424 A CN202310330424 A CN 202310330424A CN 116454400 A CN116454400 A CN 116454400A
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- positive electrode
- less
- compound
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- electrochemical device
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- 239000007774 positive electrode material Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000011163 secondary particle Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 17
- 239000011164 primary particle Substances 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
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- 230000002776 aggregation Effects 0.000 claims abstract description 6
- 238000004220 aggregation Methods 0.000 claims abstract description 5
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000011329 calcined coke Substances 0.000 description 1
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
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- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SNQXJPARXFUULZ-UHFFFAOYSA-N dioxolane Chemical compound C1COOC1 SNQXJPARXFUULZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- CSXCEQPWXHUSIX-UHFFFAOYSA-N pentan-2-yl hydrogen carbonate Chemical compound CCCC(C)OC(O)=O CSXCEQPWXHUSIX-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- PNYNRMYUWZPARE-UHFFFAOYSA-N propan-2-yl carbonofluoridate Chemical compound CC(C)OC(F)=O PNYNRMYUWZPARE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrochemical device and an electrochemical deviceThe electronic device comprises the positive electrode and an electrolyte, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer comprises secondary particles, the secondary particles are formed by aggregation of primary particles, and D2 of the secondary particles V50 D1 with primary particles V50 The method meets the following conditions: D2D 2 V50 ≥20×D1 V50 The method comprises the steps of carrying out a first treatment on the surface of the The electrolyte comprises a compound of the formula I,x is selected from Si, ti, Y 1 、Y 2 、Y 3 、Y 4 At least one of (a) comprises at least one C 2‑8 Alkenyl or C 2‑8 Alkynyl, Y 1 、Y 2 、Y 3 、Y 4 Independently selected from H, halogen, and substituted or unsubstituted groups of: c (C) 1‑8 Alkyl, C 2‑8 Alkenyl, C 2‑8 Alkynyl, C 6‑12 Aryl, C 1‑8 Alcohol group and C 2‑8 An ester group.
Description
Technical Field
The present disclosure relates to the field of energy storage technologies, and in particular, to an electrochemical device and an electronic device including the same.
Background
Electrochemical devices (e.g., lithium ion batteries) are widely used as portable chemical energy sources in consumer electronics such as mobile phones, notebooks, cameras, etc., or energy storage products such as home energy storage, energy storage power stations, UPS power sources, etc., and in new energy automobiles, etc., due to their high energy density, high working voltage level, small self-discharge, long service life, and environmental friendliness. As the market for products continues to expand, higher demands are placed on the performance and production costs of the batteries.
The positive electrode active material having the secondary particle structure can achieve better rate performance due to lower ion transport resistance. However, the secondary particle structure has poor stability, so that the secondary particles cannot be widely commercialized.
Accordingly, there is a need in the art for an electrochemical device that can prevent breakage of secondary particles while using a positive electrode active material having a secondary particle structure, thereby maintaining desired stability while improving the rate performance of the electrochemical device.
Disclosure of Invention
In the first place of the present applicationIn one aspect, the present application provides an electrochemical device comprising a positive electrode and an electrolyte, wherein the positive electrode comprises a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer comprises secondary particles formed by aggregation of primary particles, and D2 of the secondary particles V50 D1 with primary particles V50 The method meets the following conditions: D2D 2 V50 ≥20×D1 V50 ；
The electrolyte comprises a compound of formula I,
wherein X is selected from Si and Ti,
Y 1 、Y 2 、Y 3 、Y 4 at least one of (a) comprises at least one C 2-8 Alkenyl or C 2-8 Alkynyl, Y 1 、Y 2 、Y 3 、Y 4 Independently selected from H, halogen, and substituted or unsubstituted groups of: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 1-8 Alcohol group and C 2-8 An ester group.
In some embodiments, the compound of formula I comprises at least one of the following compounds:
in some embodiments, the compound of formula I is present in an amount W based on the total weight of the electrolyte I Meeting the requirement of 0.01 weight percent to less than or equal to W I Less than or equal to 5 weight percent.
In some embodiments, the compound of formula I is present in an amount W based on the total weight of the electrolyte I Meeting the requirement of 0.01 weight percent to less than or equal to W I Less than or equal to 3 weight percent.
In some embodiments, the electrolyte further comprises a compound of formula II,
wherein R is 21 、R 22 Independently selected from the group consisting of halogen and substituted or unsubstituted: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 2-8 And wherein M + Selected from Li + 、Na + 、K + 、Cs + 。
In some embodiments, the compound of formula II comprises at least one of the following
In some embodiments, the compound of formula II is present in an amount W II Meet the weight percentage of W of 0.5 to less than or equal to II Less than or equal to 10 weight percent.
In some embodiments, the electrolyte further comprises a compound of formula III MDFOB,
wherein the compound of formula III comprises at least one of lithium difluorooxalato borate, sodium difluorooxalato borate, potassium difluorooxalato borate, cesium difluorooxalato borate, and wherein the content of the compound of formula III is 0.01 wt% or less W based on the total weight of the electrolyte III Less than or equal to 5 weight percent.
In some embodiments, D2 of the secondary particle V50 Satisfies that D2 is less than or equal to 5 mu m V50 ≤20μm。
In some embodiments, the positive electrode active material layer comprises positive electrode active material Li 1+x M 1-y Mg y O 2 Wherein M is selected from one or more of Ni, co, mn, al, fe, cu, ru, nb, W, cr, zr, mo, V, ti, la, Y, and 0 < x.ltoreq.2, and 0 < y.ltoreq.0.02.
In a second aspect of the present application, the present application provides an electronic device comprising an electrochemical device according to the first aspect of the present application.
Drawings
Fig. 1 schematically shows a secondary particle structure of a positive electrode active material.
Detailed Description
Embodiments of the present application will be described in detail below. The examples of the present application should not be construed as limiting the scope of the claims of the present application. The following terms used herein have the meanings indicated below, unless explicitly indicated otherwise.
As used herein, the term "about" is used to describe and illustrate small variations. When used in connection with an event or circumstance, the terms can refer to instances where the event or circumstance occurs precisely and instances where it occurs to the close approximation. For example, when used in connection with a numerical value, the term can refer to a range of variation of less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
In the detailed description and claims, a list of items connected by the term "one of" may mean any of the listed items. For example, if items a and B are listed, the phrase "one of a and B" means either only a or only B. In another example, if items A, B and C are listed, one of the phrases "A, B and C" means only a; only B; or only C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
In the detailed description and claims, a list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" or "at least one of a or B" means only a; only B; or A and B. In another example, if items A, B and C are listed, the phrase "at least one of A, B and C" or "at least one of A, B or C" means only a; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
In the description and in the claims, the number following the expression concerning the number of carbons, i.e. the capital letter "C", for example "C 1 -C 10 ”、“C 3 -C 10 In "etc., the number following" C "such as" 1"," 3 "or" 10 "represents the number of carbons in a particular functional group. That is, the functional groups may include 1 to 10 carbon atoms and 3 to 10 carbon atoms, respectively. For example, "C 1 -C 4 Alkyl "or" C 1-4 Alkyl "means an alkyl group having 1 to 4 carbon atoms, e.g. CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 CH 2 CH 2 CH 2 -、CH 3 CH 2 CH(CH 3 ) -or (CH) 3 ) 3 C-。
As used herein, the term "alkyl" refers to a straight chain saturated hydrocarbon structure having 1 to 10 carbon atoms. "alkyl" is also intended to be a branched or cyclic hydrocarbon structure having 3 to 10 carbon atoms. For example, the alkyl group may be an alkyl group of 1 to 10 carbon atoms, an alkyl group of 1 to 8 carbon atoms, an alkyl group of 1 to 6 carbon atoms, or an alkyl group of 1 to 4 carbon atoms. When alkyl groups having a specific carbon number are specified, all geometric isomers having that carbon number are contemplated; thus, for example, reference to "butyl" is intended to include n-butyl, sec-butyl, isobutyl, tert-butyl and cyclobutyl; "propyl" includes n-propyl, isopropyl and cyclopropyl. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, and the like. In addition, the alkyl group may be optionally substituted.
The term "alkenyl" refers to a monovalent unsaturated hydrocarbon group that may be straight or branched and has at least one and typically 1,2, or 3 carbon-carbon double bonds. Unless otherwise defined, the alkenyl group typically contains 2 to 10 carbon atoms, for example, can be 2 to 8 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Representative alkenyl groups include, for example, vinyl, n-propenyl, isopropenyl, n-but-2-enyl, but-3-enyl, n-hex-3-enyl, and the like. In addition, alkenyl groups may be optionally substituted.
The term "alkynyl" refers to a monovalent unsaturated hydrocarbon group that may be straight or branched and has at least one and typically 1,2, or 3 carbon-carbon triple bonds. Unless otherwise defined, the alkynyl group typically contains an alkynyl group of 2 to 10, 2 to 8, 2 to 6, or 2 to 4 carbon atoms. Representative alkynyl groups include, for example, ethynyl, prop-2-ynyl (n-propynyl), n-but-2-ynyl, n-hex-3-ynyl, and the like. In addition, alkynyl groups may be optionally substituted.
The term "aryl" encompasses both monocyclic and polycyclic systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is aromatic, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. For example, an aryl group may contain an aryl group of 6 to 12 carbon atoms or 6 to 10 carbon atoms. Representative aryl groups include, for example, phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl, and naphthalen-1-yl, naphthalen-2-yl, and the like. In addition, aryl groups may be optionally substituted.
When the above substituents are substituted, they are substituted with one or more halogens unless otherwise indicated.
As used herein, the term "halogen" encompasses F, cl, br and I, preferably F or Cl.
The term "positive electrode active material" refers to a material capable of reversibly intercalating and deintercalating lithium ions. In some embodiments of the present application, the positive electrode active material includes, but is not limited to, lithium-containing transition metal oxides.
1. Electrochemical device
The electrochemical device of the present application includes any device in which an electrochemical reaction occurs, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, or capacitors. In particular, the electrochemical device is a lithium secondary battery or a sodium secondary battery, including a lithium metal secondary battery, a lithium ion secondary battery, a sodium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery. In some embodiments, an electrochemical device of the present application comprises a positive electrode, a negative electrode, a separator, and an electrolyte.
In some embodiments, an electrochemical device of the present application includes a positive electrode including a positive electrode current collector and a positive electrode active material layer including secondary particles formed by aggregation of primary particles, and D2 of the secondary particles V50 D1 with primary particles V50 The method meets the following conditions: D2D 2 V50 ≥20×D1 V50 。
In some embodiments, the content of the secondary particles is 90 wt% or more based on the total weight of the positive electrode active material layer.
In some embodiments, the electrolyte comprises a compound of formula I,
wherein X is selected from Si and Ti,
Y 1 、Y 2 、Y 3 、Y 4 at least one of (a) comprises at least one C 2-8 Alkenyl or C 2-8 Alkynyl, Y 1 、Y 2 、Y 3 、Y 4 Independently selected from H, halogen and warpSubstituted or unsubstituted: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 1-8 Alcohol group and C 2-8 An ester group.
In some embodiments, the electrochemical device of the present application further comprises a negative electrode and a separator.
Positive electrode
In some embodiments, a positive electrode includes a current collector and a positive electrode active material layer on the current collector, the positive electrode active material layer including a positive electrode active material.
The positive electrode active material includes at least one lithiated intercalation compound that reversibly intercalates and deintercalates lithium ions. In some embodiments of the present application, the positive electrode active material layer comprises a lithium-containing transition metal oxide. In some embodiments, the positive electrode active material layer comprises a composite oxide. In some embodiments, the composite oxide contains lithium and at least one element selected from cobalt, manganese, magnesium, and nickel, and in particular, the composite oxide contains magnesium.
In some embodiments, the positive electrode active material layer comprises positive electrode active material Li 1+x M 1-y Mg y O 2 Wherein M is selected from one or more of Ni, co, mn, al, fe, cu, ru, nb, W, cr, zr, mo, V, ti, la, Y, and 0 < x.ltoreq.2, and 0 < y.ltoreq.0.02. By introducing Mg element into the positive electrode active material, stability of the material structure is increased, however, when y exceeds 0.02, the introduction of excessive Mg element will cause a decrease in capacity exertion of the positive electrode material.
In some embodiments, the positive electrode active material layer further comprises LiCoO 2 、LiNiCoMnO 2 、LiFePO 4 、LiMn 2 O 4 。
In some embodiments, the positive electrode active material layer includes secondary particles formed of a positive electrode active material, and in particular, the secondary particles are formed of primary particles.
In some embodiments, wherein the positive electrode active material has a secondary particle structure, the secondary particles are formed by stacking primary particles,Agglomeration or aggregation, as shown in fig. 1, the secondary particles are aggregated from primary particles, the primary particles have a particle size distribution, the secondary particles have a particle size distribution, and D2 of the secondary particles V50 D1 with primary particles V50 The method meets the following conditions: D2D 2 V50 ≥20×D1 V50 . In some embodiments, the positive active material LiCoO 2 、LiNiCoMnO 2 、LiFePO 4 、LiMn 2 O 4 Or Li (lithium) 1+x M 1- y Mg y O 2 With the secondary particle structure, by using the secondary particles in the positive electrode active material layer, the structural stability of the positive electrode active material, particularly the lithium-rich material, can be enhanced, and when the particle diameters of the secondary particles and the primary particles satisfy D2 V50 ≥20×D1 V50 And meanwhile, by using the compound of the formula I in the electrolyte, an elastic protection layer with binding force can be formed on the surface of the positive electrode active material, so that the outward expansion of the secondary particles is reduced, the secondary particles are prevented from being broken due to uneven stress caused by lithium removal in the circulation process, the cycle life of the battery is remarkably prolonged, and the volume expansion caused by long-term use is reduced.
In some embodiments, D2 of the secondary particle sphere V50 Satisfies that D2 is less than or equal to 5 mu m V50 ≤20μm。
In some embodiments, the positive electrode active material layer further includes a binder, and optionally includes a conductive material. The binder enhances the bonding of the positive electrode active material particles to each other, and also enhances the bonding of the positive electrode active material to the current collector.
In some embodiments, the adhesive includes, but is not limited to: polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
In some embodiments, the conductive material includes, but is not limited to: carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from the group consisting of metal powder, metal fiber, copper, nickel, aluminum, silver. In some embodiments, the conductive polymer is a polyphenylene derivative. In some preferred embodiments, the conductive material comprises carbon nanotubes and the carbon nanotubes have a diameter of 5nm to 50nm.
In some embodiments, the current collector may be aluminum, but is not limited thereto.
The positive electrode may be prepared by a preparation method well known in the art. For example, the positive electrode can be obtained by: the active material, the conductive material, and the binder are mixed in a solvent to prepare an active material composition, and the active material composition is coated on a current collector. In some embodiments, the solvent may include N-methylpyrrolidone, etc., but is not limited thereto.
In some embodiments, the positive electrode is manufactured by forming a positive electrode material using a positive electrode active material layer including a lithium transition metal-based compound powder and a binder on a current collector.
In some embodiments, the positive electrode active material layer may be generally fabricated by: the positive electrode material and the binder (conductive material and thickener, etc. as needed) are dry-mixed to form a sheet, the obtained sheet is pressed against the positive electrode current collector, or these materials are dissolved or dispersed in a liquid medium to form a slurry, and the slurry is applied to the positive electrode current collector and dried.
Negative electrode
The materials, compositions, and methods of making the negative electrode used in the electrochemical devices of the present application may include any of the techniques disclosed in the prior art. In some embodiments, the negative electrode is the negative electrode described in U.S. patent application US9812739B, which is incorporated by reference herein in its entirety.
In some embodiments, the anode includes a current collector and an anode active material layer on the current collector. The anode active material includes a material that reversibly intercalates/deintercalates lithium ions. In some embodiments, the material that reversibly intercalates/deintercalates lithium ions includes a carbon material. In some embodiments, the carbon material may be any carbon-based negative electrode active material commonly used in lithium ion rechargeable batteries. In some embodiments, the carbon material includes, but is not limited to: crystalline carbon, amorphous carbon, or mixtures thereof. The crystalline carbon may be amorphous, platelet-shaped, spherical or fibrous natural graphite or artificial graphite. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbide, calcined coke, and the like.
In some embodiments, the anode active material layer includes an anode active material. The specific kind of the anode active material is not particularly limited, and may be selected according to the need. In some embodiments, the negative electrode active material includes, but is not limited to: lithium metal, structured lithium metal, natural graphite, artificial graphite, intermediate phase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composites, li-Sn alloys, li-Sn-O alloys, sn, snO, snO 2 Lithiated TiO of spinel structure 2 -Li 4 Ti 5 O 12 A Li-Al alloy, or any combination thereof. Wherein the silicon-carbon composite means that it comprises at least about 5 wt% silicon based on the weight of the silicon-carbon anode active material.
When the anode includes a silicon carbon compound, silicon: carbon=about 1:10 to 10:1, median particle diameter Dv of the silicon carbon compound 50 About 0.1 microns to 20 microns. When the anode includes an alloy material, the anode active material layer may be formed using a method such as vapor deposition, sputtering, plating, or the like. When the anode includes lithium metal, for example, an anode active material layer is formed with a conductive skeleton having a spherical twisted shape and metal particles dispersed in the conductive skeleton. In some embodiments, the spherical twisted conductive backbone may have a porosity of about 5% to about 85%. In some embodiments, a protective layer may also be provided on the lithium metal anode active material layer.
In some embodiments, the anode active material layer may include a binder, and optionally, a conductive material. The binder enhances the bonding of the anode active material particles to each other and the bonding of the anode active material to the current collector. In some embodiments, the adhesive includes, but is not limited to: polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, an ethyleneoxy-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene 1, 1-difluoroethylene, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, and the like.
In some embodiments, the conductive material includes, but is not limited to: a carbon-based material, a metal-based material, a conductive polymer, or a mixture thereof. In some embodiments, the carbon-based material is selected from natural graphite, synthetic graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof. In some embodiments, the metal-based material is selected from the group consisting of metal powder, metal fiber, copper, nickel, aluminum, silver. In some embodiments, the conductive polymer is a polyphenylene derivative.
In some embodiments, the current collector includes, but is not limited to: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, conductive metal coated polymeric substrates, and any combination thereof.
The negative electrode may be prepared by a preparation method well known in the art. For example, the anode may be obtained by: the active material, the conductive material, and the binder are mixed in a solvent to prepare an active material composition, and the active material composition is coated on a current collector. In some embodiments, the solvent may include water or the like, but is not limited thereto.
Isolation film
In some embodiments, the electrochemical device of the present application is provided with a separator between the positive electrode and the negative electrode to prevent short circuit. The material and shape of the separator used in the electrochemical device of the present application are not particularly limited, and may be any of the techniques disclosed in the prior art. In some embodiments, the separator comprises a polymer or inorganic, etc., formed from a material that is stable to the electrolyte of the present application.
For example, the release film may include a substrate layer and a surface treatment layer. The substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous membrane, a polyethylene porous membrane, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric or a polypropylene-polyethylene-polypropylene porous composite membrane can be selected. The substrate layer may be one or more layers, and when the substrate layer is a plurality of layers, the compositions of the polymers of different substrate layers may be the same or different, and the weight average molecular weights of the polymers of different substrate layers are not completely the same; when the substrate layer is a multilayer, the polymers of different substrate layers differ in closed cell temperature.
In some embodiments, the surface treatment layer is disposed on at least one surface of the substrate layer, and the surface treatment layer may be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic material.
In some embodiments, the separator includes a porous substrate and a coating layer including inorganic particles and a binder.
In some embodiments, the coating layer thickness is from about 0.5 microns to about 10 microns, from about 1 micron to about 8 microns, or from about 3 microns to about 5 microns.
In some embodiments, the inorganic particles are selected from the group consisting of SiO 2 、Al 2 O 3 、CaO、TiO 2 、ZnO 2 、MgO、ZrO 2 、SnO 2 、Al(OH) 3 Or AlOOH. In some embodiments, the particle size of the inorganic particles is from about 0.001 microns to about 3 microns.
In some embodiments, the binder is selected from at least one of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoroethylene copolymer (PVDF-HFP), polyvinylpyrrolidone (PVP), polyacrylate, pure acrylic emulsion (anionic acrylic emulsion copolymerized from acrylate and special function monomers), styrene-acrylic emulsion (styrene-acrylate emulsion) obtained by emulsion copolymerization of styrene and acrylate monomers, and styrene-butadiene emulsion (SBR obtained by emulsion copolymerization of butadiene and styrene).
Electrolyte solution
In some embodiments, the electrolyte includes a lithium salt, an organic solvent, and a compound of formula I,
wherein X is selected from Si, ti, Y 1 、Y 2 、Y 3 、Y 4 At least one of (a) comprises at least one C 2-8 Alkenyl or C 2-8 Alkynyl, Y 1 、Y 2 、Y 3 、Y 4 Independently selected from H, halogen, and substituted or unsubstituted groups of: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 1-8 Alcohol group, C 2-8 Ester groups of (a) are present.
In some embodiments, the compound of formula I comprises at least one of the following compounds:
in some embodiments, the compound of formula I is present in an amount W based on the total weight of the electrolyte I Meeting the requirement of 0.01 weight percent to less than or equal to W I Less than or equal to 5 weight percent, preferably 0.01 weight percent less than or equal to W I Less than or equal to 3 weight percent.
In some embodiments, the compound of formula I is present in an amount W based on the total weight of the electrolyte I Meet the weight percentage of W of 0.1 percent or less I Less than or equal to 3.0 wt.%, for example, 0.1 wt.% less than or equal to W I Less than or equal to 1.0 wt.%, the compounds of the formula I may be present, for example, in an amount of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%. When W is I At less than 0.01% by weight, too little content results in a compound of formula IThe object cannot produce an effect sufficiently, and when W I Greater than 5 wt.%, excessive amounts of the compound of formula I may increase the impedance of the positive electrode interface.
In some embodiments, the electrolyte further comprises a compound of formula II,
wherein R is 21 、R 22 Independently selected from the group consisting of halogen and substituted or unsubstituted: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 2-8 And wherein M + Selected from Li + 、Na + 、K + 、Cs + 。
In some embodiments, the compound of formula II includes at least one of the following
In some embodiments, the compound of formula II is present in an amount W II Meet the weight percentage of W of 0.5 to less than or equal to II 10 wt.% or less, for example 0.5 wt.% or less of W II Less than or equal to 9 weight percent, 0.5 weight percent or less than or equal to W II Less than or equal to 8 weight percent, 0.5 weight percent and less than or equal to W II Less than or equal to 7 weight percent, 0.5 weight percent or less than or equal to W II Less than or equal to 6 weight percent, 0.5 weight percent or less than or equal to W II Less than or equal to 5 weight percent, 0.5 weight percent or less than or equal to W II 4 weight percent or less, 0.5 weight percent or less W II Less than or equal to 3 weight percent, 0.5 weight percent or less than or equal to W II Less than or equal to 2 weight percent, 0.5 weight percent and less than or equal to W II Less than or equal to 1 weight percent. By setting the content of the compound of the formula II in a proper amount, the storage thickness expansion rate can be reduced while the cycle capacity retention rate of the battery is improved, and in addition, the direct current internal resistance of the battery can be reduced. This is because the compound of formula II can form Li on the electrode surface 2 SO 3 And a protective layer, thereby reducing Li + Transmitting impedance and reducing internal DC resistance.
In some embodiments, the electrolyte further comprises a compound of formula III MDFOB, wherein M may be Li, na, K, cs.
In some embodiments, the compound of formula III includes at least one of lithium difluorooxalato borate (lidaob), sodium difluorooxalato borate (nadob), potassium difluorooxalato borate (KDFOB), cesium difluorooxalato borate (CsDFOB).
In some embodiments, the compound of formula III is present in an amount of 0.01 weight percent +.ltoreq.W based on the total weight of the electrolyte III Less than or equal to 5 wt%, for example, 0.01 wt% less than or equal to W III 4 wt% or less, 0.01 wt% or less of W III Less than or equal to 3 weight percent, 0.01 weight percent and less than or equal to W III Less than or equal to 2 weight percent, 0.01 weight percent and less than or equal to W III Less than or equal to 1 weight percent, 0.01 weight percent and less than or equal to W III Less than or equal to 0.9 weight percent, and less than or equal to 0.01 weight percent of W III Less than or equal to 0.8 weight percent, and 0.01 weight percent of W III Less than or equal to 0.7 weight percent, and 0.01 weight percent of W III Less than or equal to 0.6 weight percent, and 0.01 weight percent of W III Less than or equal to 0.5 weight percent, and less than or equal to 0.01 weight percent of W III Less than or equal to 0.4 weight percent, and 0.01 weight percent of W III Less than or equal to 0.3 weight percent, and less than or equal to 0.01 weight percent of W III Less than or equal to 0.2 weight percent, and 0.01 weight percent of W III Less than or equal to 0.1 weight percent.
By setting the appropriate content of the compound of formula III, the cycle performance can be further improved, since the compound of formula III can reduce the risk of corrosion of the aluminum foil, which may be caused by the compound of formula II, in addition to forming a protective layer on the electrode surface, thereby improving the overall performance of the battery.
In some embodiments, D2 of the secondary particles V50 Satisfies that D2 is less than or equal to 5 mu m V50 ≤20μm。
In some embodiments, the lithium salt is selected from one or more of an inorganic lithium salt and an organic lithium salt. In some embodiments, the lithium salt contains at least one of a fluorine element, a boron element, or a phosphorus element. In some embodiments, the lithium salt is selected from one or more of the following lithium salts: lithium hexafluorophosphate LiPF 6 Lithium hexafluoroarsenate LiAsF 6 Lithium perchlorate LiClO 4 Or lithium triflate LiCF 3 SO 3 。
In some embodiments, the concentration of the lithium salt is 0.3mol/L to 1.5mol/L. In some embodiments, the concentration of the lithium salt is 0.5mol/L to 1.3mol/L or about 0.8mol/L to 1.2mol/L. In some embodiments, the concentration of the lithium salt is about 1.10mol/L.
The organic solvent includes at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), ethylmethyl carbonate (DEC), dimethyl carbonate (DMC), sulfolane (SF), γ -butyrolactone (γ -BL), propylethyl carbonate, methyl Formate (MF), ethyl formate (MA), ethyl Acetate (EA), ethyl Propionate (EP), propylpropionate (PP), methyl propionate, methyl butyrate, ethyl butyrate, methylethyl fluorocarbonate, dimethylfluorocarbonate, or diethyl fluorocarbonate, etc.
In some embodiments, wherein the solvent comprises 70 wt% to 95 wt% of the electrolyte.
In some embodiments, the organic solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof. The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof. Examples of chain carbonate compounds are dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and combinations thereof. Examples of cyclic carbonate compounds are Ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), vinyl Ethylene Carbonate (VEC) and combinations thereof. Examples of fluorocarbonate compounds are fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethyl ethylene carbonate, and combinations thereof. Examples of carboxylate compounds are methyl formate, methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, gamma-butyrolactone, decalactone, valerolactone, mevalonic acid lactone, caprolactone, and combinations thereof. Examples of ether compounds are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof.
In some embodiments, examples of other organic solvents are dimethyl sulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphoric acid esters, and combinations thereof.
The electrolyte used in the electrochemical device of the present application is any of the electrolytes described above in the present application. The electrolyte used in the electrochemical device of the present application may also include other electrolytes within a range not departing from the gist of the present application.
2. Electronic device
The electronic device of the present application may be any device using the electrochemical device of the present application.
In some embodiments, the electronic device includes, but is not limited to: notebook computers, pen-input computers, mobile computers, electronic book players, portable telephones, portable facsimile machines, portable copiers, portable printers, headsets, video recorders, liquid crystal televisions, hand-held cleaners, portable CD-players, mini-compact discs, transceivers, electronic notebooks, calculators, memory cards, portable audio recorders, radios, stand-by power supplies, motors, automobiles, motorcycles, mopeds, bicycles, lighting fixtures, toys, game machines, watches, electric tools, flash lamps, cameras, household large-sized batteries or lithium-ion capacitors, and the like.
To achieve the above objects and to enable those skilled in the art to understand the present invention, the following examples are given by way of illustration of specific embodiments in which the invention may be practiced, and it is intended that the described examples be merely illustrative of some, not all, of the examples.
3. Test method
1. Lithium ion battery cycle retention test
And placing the lithium ion battery in a 45 ℃ incubator, and standing for 30 minutes to keep the lithium ion battery at a constant temperature. The lithium ion battery which reached the constant temperature was charged to a voltage of 4.35V at a constant current of 1C, then charged to a current of 0.05C at a constant voltage of 4.35V, and then discharged to a voltage of 3.0V at a constant current of 1C, which is described as one charge-discharge cycle. The charge and discharge cycle was repeated for 500 cycles with the capacity of the first discharge being 100%. As an index for evaluating the cycle performance of the lithium ion battery, the cycle capacity retention rate was calculated by:
cycle retention = capacity at 500 cycles/capacity at first discharge.
2. High temperature storage test of lithium ion battery
Discharging the lithium ion battery to 3.0V at room temperature at 0.2C, standing for 15min, charging to 4.35V at 1C constant current, charging to 0.05C at constant voltage, recording the thickness d0 of the battery, placing the lithium ion battery in a high-temperature furnace at 80 ℃, standing for 12 hours, and recording the thickness d1 of the battery.
Storage thickness expansion ratio= (d 0-d 1)/d 0.
3. Direct current internal resistance test of lithium ion battery
And (3) placing the lithium ion battery at room temperature, discharging to 3.0V at 0.2C, standing for 15min, charging to 4.35V at 1C constant current, charging to 0.05C at constant voltage, standing for 15min, discharging the lithium ion battery at 0.1C for 300min, recording the voltage V1 of the battery at the moment, and continuously recording the voltage V2 at the moment at 1C for 1s, wherein the direct current internal resistance of the battery is (V2-V1)/(1C-0.1C).
Examples 1-1 to 1-12
Preparation of the negative electrode: mixing negative active material artificial graphite, thickener sodium carboxymethylcellulose (CMC) and binder styrene-butadiene rubber (SBR) according to a weight ratio of 97:1:2, adding deionized water, and obtaining negative slurry under the action of a vacuum stirrer, wherein the solid content of the negative slurry is 54 weight percent; uniformly coating the negative electrode slurry on a negative electrode current collector copper foil; and drying the coated copper foil at 85 ℃, cold pressing, cutting, slitting and drying for 12 hours under the vacuum condition of 120 ℃ to obtain the negative electrode.
Preparation of positive electrode: commercially available positive electrode active material (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) The conductive agent Super P, the binder polyvinylidene fluoride were mixed in a weight ratio of 97:1.4:1.6, and the commercially available positive electrode active material had D2 of secondary particles as shown in table 1 V50 D1 with primary particles V50 Adding N-methyl pyrrolidone (NMP), and uniformly stirring under the action of a vacuum stirrer to obtain positive electrode slurry, wherein the solid content of the positive electrode slurry is 72 wt%; uniformly coating the anode slurry on an anode current collector aluminum foil; and drying the coated aluminum foil at 85 ℃, cold pressing, cutting and slitting, and drying for 4 hours under the vacuum condition at 85 ℃ to obtain the anode.
Preparation of electrolyte: in a dry argon atmosphere glove box, ethylene Carbonate (EC), propylene Carbonate (PC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) were mixed in mass ratio EC: PC: EMC: dec=20:10:30:40, followed by addition of the compound according to formula I shown in table 1, dissolution and thorough stirring, followed by addition of lithium salt LiPF 6 And (5) uniformly mixing to obtain the electrolyte. Wherein, liPF 6 The concentration of (C) was 1.10mol/L. The additives used in the electrolyte and the contents thereof are shown in table 1.
Preparation of a separation film: selecting Polyethylene (PE) isolating film with thickness of 9 mu m, passing through polyvinylidene fluoride (PVDF) slurry and Al 2 O 3 And (5) coating and drying the slurry to obtain the final isolating film.
Assembling a lithium ion battery: and sequentially stacking the positive electrode, the isolating film and the negative electrode, enabling the isolating film to be positioned between the positive electrode sheet and the negative electrode sheet, then placing the isolating film in an outer packaging foil aluminum plastic film after winding and welding the electrode lugs, injecting the electrolyte, and obtaining the soft package lithium ion battery after vacuum packaging, standing, formation, shaping and capacity testing.
Comparative examples 1-1 to 1-2
A soft-pack lithium ion battery was prepared in substantially the same manner as in example I, except that the parameters shown in table 1 were used.
The soft pack lithium ion batteries obtained from examples 1-1 to 1-12 and comparative examples 1-1 to comparative examples 1-2 were subjected to a cycle retention test and a stored gas production test according to the methods described herein. The results of the test are shown in table 1.
TABLE 1
By comparing comparative examples 1-1, comparative examples 1-2 with examples 1-1 to examples 1-12, it is explained that D2 is present in the secondary particles V50 D1 with primary particles V50 In the scope according to the present application, it is possible to improve the cycle capacity retention rate of the battery and reduce the generation of gas caused by side reactions.
Examples 2-1 to 2-11
Examples 2-1 to 2-11 were carried out with reference to examples 1-2, with the difference that compounds of the formula I, compounds of the formula II and compounds of the formula III were used in the electrolyte according to Table 2.
The soft pack lithium ion batteries obtained from examples 2-1 to 2-11 were subjected to a cycle retention test, a storage thickness expansion test, and a direct current internal resistance test according to the methods described herein. The results of the test are shown in table 2.
TABLE 2
Comparison of examples 2-1 to 2-6 with examples 1-2 shows that the addition of the compound of formula II can further improve the battery cycle capacity retention and reduce the storage thickness expansion rate, and can also reduce the DC internal resistance of the battery.
Comparative examples 2-3, examples 2-7 to examples 2-11 show that the addition of the compound of formula III can further improve the cycle performance because oxalic acid groups and fluorine in the compound of formula III can form an effective protective layer on the electrode surface, and hydrolysis of the oxalic acid groups consumes part of the impurity water inside the cell to reduce the occurrence of side reactions, thereby improving the overall performance of the battery.
Examples 3-1 to 3-5
Examples 3-1 to 3-5 were carried out with reference to examples 1-2, except that a commercially available positive electrode active material Li was used in the positive electrode 1.12 (Ni 0.44 Co 0.001 Mn 0.559 ) 1-y Mg y O 2 Wherein y is shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, when the magnesium-doped lithium-rich positive electrode active material having the secondary particle structure is used, the stability of the positive electrode can be further improved, and thus improvement in the storage thickness expansion rate and the cycle capacity retention rate is achieved, because magnesium doping increases the structural stability of the lithium-rich positive electrode, and thus the performance can be further improved.
Although illustrative embodiments have been shown and described, it will be understood by those skilled in the art that the foregoing embodiments are not to be construed as limiting the present application and that changes, substitutions and alterations of the embodiments may be made without departing from the spirit, principles and scope of the present application, which also fall within the scope of the present application.
Claims (11)
1. An electrochemical device comprising a positive electrode and an electrolyte, wherein,
the positive electrode comprises a positive electrode current collector and a positive electrode active material layer, wherein the positive electrode active material layer comprises secondary particles, the secondary particles are formed by aggregation of primary particles, and D2 of the secondary particles V50 D1 with primary particles V50 The method meets the following conditions:
D2 V50 ≥20×D1 V50 ；
the electrolyte comprises a compound of formula I,
wherein X is selected from Si and Ti,
Y 1 、Y 2 、Y 3 、Y 4 at least one of (a) comprises at least one C 2-8 Alkenyl or C 2-8 Alkynyl, Y 1 、Y 2 、Y 3 、Y 4 Independently selected from H, halogen, and substituted or unsubstituted groups of: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 1-8 Alcohol group and C 2-8 An ester group.
2. The electrochemical device of claim 1, wherein the compound of formula I comprises at least one of the following compounds:
3. the electrochemical device according to claim 1 or 2, characterized in that the content W of the compound of formula I is based on the total weight of the electrolyte I Meeting the requirement of 0.01 weight percent to less than or equal to W I Less than or equal to 5 weight percent.
4. The electrochemical device according to claim 1 or 2, characterized in that the content W of the compound of formula I is based on the total weight of the electrolyte I Meeting the requirement of 0.01 weight percent to less than or equal to W I Less than or equal to 3 weight percent.
5. The electrochemical device of claim 1, wherein the electrolyte further comprises a compound of formula II,
wherein R is 21 、R 22 Independently selected from the group consisting of halogen and substituted or unsubstituted: c (C) 1-8 Alkyl, C 2-8 Alkenyl, C 2-8 Alkynyl, C 6-12 Aryl, C 2-8 And wherein M + Selected from Li + 、Na + 、K + 、Cs + 。
6. The electrochemical device of claim 5, wherein the compound of formula II comprises at least one of:
7. the electrochemical device according to claim 5, wherein the compound of formula II has a content W II Meet the weight percentage of W of 0.5 to less than or equal to II Less than or equal to 10 weight percent.
8. The electrochemical device according to claim 1 or 5, wherein the electrolyte solution further comprises a compound MDFOB of formula III,
wherein the compound of formula III comprises at least one of lithium difluorooxalato borate, sodium difluorooxalato borate, potassium difluorooxalato borate, cesium difluorooxalato borate, and wherein,
the compound of formula III is present in an amount of 0.01 wt% W or less based on the total weight of the electrolyte III Less than or equal to 5 weight percent.
9. The electrochemical device of claim 1, wherein D2 of the secondary particles V50 Satisfies that D2 is less than or equal to 5 mu m V50 ≤20μm。
10. The electrochemical device according to claim 1, wherein the positive electrode active material layer contains positive electrode active material Li 1+x M 1-y Mg y O 2 Wherein M is selected from one or more of Ni, co, mn, al, fe, cu, ru, nb, W, cr, zr, mo, V, ti, la, Y, and 0 < x.ltoreq.2, and 0 < y.ltoreq.0.02.
11. An electronic device characterized in that it comprises the electrochemical device according to any one of claims 1 to 10.
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