CN115312768A - Positive electrode lithium supplement composite additive and preparation method and application thereof - Google Patents
Positive electrode lithium supplement composite additive and preparation method and application thereof Download PDFInfo
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- CN115312768A CN115312768A CN202111676839.3A CN202111676839A CN115312768A CN 115312768 A CN115312768 A CN 115312768A CN 202111676839 A CN202111676839 A CN 202111676839A CN 115312768 A CN115312768 A CN 115312768A
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- lithium supplement
- positive electrode
- additive
- transition metal
- lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 329
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 327
- 239000013589 supplement Substances 0.000 title claims abstract description 289
- 239000000654 additive Substances 0.000 title claims abstract description 197
- 230000000996 additive effect Effects 0.000 title claims abstract description 194
- 239000002131 composite material Substances 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 97
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 93
- 239000011247 coating layer Substances 0.000 claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 claims abstract description 33
- 239000010410 layer Substances 0.000 claims description 89
- 238000004806 packaging method and process Methods 0.000 claims description 44
- 150000003624 transition metals Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 238000005538 encapsulation Methods 0.000 claims description 23
- 238000002955 isolation Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 239000003575 carbonaceous material Substances 0.000 claims description 15
- 239000010416 ion conductor Substances 0.000 claims description 15
- 239000011532 electronic conductor Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- -1 transition metal ammonium salt Chemical class 0.000 claims description 7
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910000299 transition metal carbonate Inorganic materials 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 2
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 20
- 230000007613 environmental effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 description 20
- 230000008569 process Effects 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 9
- 230000001502 supplementing effect Effects 0.000 description 9
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910018091 Li 2 S Inorganic materials 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 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 3
- 239000011149 active material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 239000002041 carbon nanotube Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000016507 interphase Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
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- 239000004020 conductor Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020719 Li0.33 La0.56 Inorganic materials 0.000 description 1
- 229910003055 Li0.33 La0.57 TiO3 Inorganic materials 0.000 description 1
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 1
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006406 SnO 2 At Inorganic materials 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of battery materials, and particularly relates to a positive electrode lithium supplement composite additive and a preparation method thereof, as well as a positive electrode material, a positive plate and a secondary battery. The anode lithium supplement composite additive comprises a lithium supplement material core and a carbon coating layer growing on the outer surface of the lithium supplement material core; wherein the lithium supplement material core comprises a lithium supplement additive and a transition metal element doped in the structure and/or between the structures of the lithium supplement additive. The positive electrode lithium supplement composite additive improves the coating degree and quality of a carbon coating layer to a lithium supplement material core, and improves the combination stability of the carbon coating layer and the lithium supplement material core, so that the environmental stability of the positive electrode lithium supplement composite additive is improved. In addition, the transition metal element doped in the structure and/or between the structures of the lithium supplement additive can further improve the structural stability of the lithium supplement additive through the influence of electrostatic acting force and the like between elements.
Description
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a positive electrode lithium supplement composite additive and a preparation method and application thereof.
Background
With the rapid development of energy storage technology, the use of portable digital devices and vehicle-mounted power supplies is increasing, people have higher and higher requirements on the energy density of batteries, and the development of secondary batteries with large capacity, long service life and high safety is imperative. During the first charge and discharge of the lithium ion battery, an SEI film is formed on the interface of a negative electrode material, and researches show that the SEI mainly comprises LiF and Li 2 CO 3 、R-COOLi、R-CH 2 OLi and the like lithium salt materials. SEI formation is an irreversible process, li being used to form SEI + Can no longer be embedded in the positive electrode material during discharge, thus causing a loss in battery capacity.
It was found that the formation of the SEI film consumes a part of Li in the cathode material + Which in turn leads to irreversible capacity loss of the electrode material. Therefore, in order to further increase the energy density of the lithium ion battery, the capacity loss can be compensated by pre-replenishing lithium. The lithium pre-supplement technology is mainly divided into two types, one is a lithium supplement technology for a negative electrode material, the technology has higher requirement on the operation environment, and lithium supplement agents are generally metal lithium foil and inert lithium powder, so that the activity is too high, the long-time stable storage cannot be realized, and the operation difficulty and the production risk are increased; and the other is a lithium supplementing technology for the anode material, which requires relatively safer and more convenient operation.
At present, although the commonly used positive electrode lithium supplement composite additive has the advantages of higher theoretical specific capacity, moderate working voltage, less influence on the existing production process, better safety and the like, the existing lithium supplement additive has the problems of poor structural stability, higher residual alkali value and the like, and the gel phenomenon is easy to occur when the battery is homogenized. In addition, a large amount of gas is easily generated in the charging and discharging processes, and a series of side reactions are caused due to the unstable structure of the lithium supplement additive. Aiming at the problem of poor structural stability of the positive electrode lithium supplement composite additive, the stability of the lithium supplement additive is generally improved by means of element substitution doping, a carbon coating and the like at present, wherein although the element substitution doping can optimize the crystal frame structure of the lithium supplement additive, the effect of improving the environmental stability of the lithium supplement additive is poor; the existing carbon coating layer and lithium supplement additive have poor combination stability. Therefore, the effect of improving the stability of the lithium supplement additive needs to be further improved.
Disclosure of Invention
The application aims to provide a positive electrode lithium supplement composite additive and a preparation method thereof, a positive electrode material, a positive plate and a secondary battery, and aims to solve the problems that the existing positive electrode lithium supplement additive is poor in environmental stability and the carbon coating layer is poor in combined coating effect to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a positive electrode lithium supplement composite additive, which includes a lithium supplement material core and a carbon coating layer grown on an outer surface of the lithium supplement material core; wherein the lithium supplement material core comprises a lithium supplement additive and a transition metal element doped in the structure and/or between the structures of the lithium supplement additive.
In a second aspect, the present application provides a method for preparing a positive electrode lithium supplement composite additive, comprising the following steps:
obtaining a lithium supplement additive, and mixing the lithium supplement additive with a transition metal precursor to prepare a transition metal element-doped composite lithium supplement material;
and generating a carbon coating layer on the surface of the composite lithium supplement material to obtain the anode lithium supplement composite additive.
In a third aspect of the present application, a positive electrode material is provided, which comprises a positive electrode active material and the positive electrode lithium supplement additive or the positive electrode lithium supplement additive prepared by the method.
In a fourth aspect, the present application provides a positive plate, where the positive plate includes the positive electrode lithium supplement composite additive, or includes the positive electrode lithium supplement composite additive prepared by the above method.
In a fifth aspect, the present application provides a secondary battery comprising the positive electrode sheet described above.
The positive electrode lithium supplement composite additive provided by the first aspect of the application comprises a lithium supplement material core, transition metal elements are doped in a crystal structure frame and/or between crystal structures of the lithium supplement additive instead of replacing frame sites in the crystal structure of the lithium supplement additive, the doping form enables the transition metal elements doped in the lithium supplement material core to keep catalytic activity, and the doped transition metal elements and a carbon source have strong affinity, so that the carbon source takes the doped transition metal elements as a catalytic activity center, and the carbon source is continuously precipitated and grows into a carbon coating layer on the outer surface of the lithium supplement material core. Compared with the carbon coating layer formed by deposition, the carbon coating layer directly catalytically grows on the surface of the lithium supplement material core, so that the coating degree and quality of the carbon coating layer on the lithium supplement material core are effectively improved, the combination stability of the carbon coating layer and the lithium supplement material core is improved, and the environmental stability of the anode lithium supplement composite additive is improved. In addition, the transition metal element doped in the structure and/or between the structures of the lithium supplement additive can further improve the structural stability of the lithium supplement additive through the influence of electrostatic acting force and the like between elements.
In the preparation method of the positive electrode lithium supplement composite additive provided by the second aspect of the application, the lithium supplement additive and the transition metal precursor are mixed to fully disperse and dope the transition metal precursor in the lithium supplement additive, and then the composite lithium supplement material doped with the transition metal element is prepared; and then preparing a carbon coating layer on the surface of the composite lithium supplement material. Because the composite lithium supplement material is doped with the transition metal element, the composite lithium supplement material has higher catalytic activity and can adsorb and react with carbon atoms to generate carbide, so that a carbon source grows on the surface of the composite lithium supplement material to form a carbon coating layer, and the combination stability and the compactness of the carbon coating layer and the core lithium supplement material are improved. The preparation method of the positive electrode lithium supplement composite additive is simple in process, the prepared positive electrode lithium supplement composite additive takes the lithium supplement material doped with the transition metal element in the gap as the inner core, and takes carbon growing on the outer surface of the inner core of the lithium supplement material as the coating layer, so that the structural stability and the environmental stability of the positive electrode lithium supplement composite additive are improved, and the lithium supplement effect of the positive electrode lithium supplement composite additive is improved.
The positive electrode material provided by the third aspect of the application comprises a positive electrode active material and the positive electrode lithium supplement composite additive, the additive takes a lithium supplement material doped with transition metal elements in gaps as an inner core, and takes carbon growing on the outer surface of the inner core of the lithium supplement material as a coating layer, so that the positive electrode material has good lithium supplement capacity, good structural stability and good environmental stability, and can effectively resist the influence of environmental factors such as external moisture, carbon dioxide and the like, thereby ensuring the lithium supplement effect of the additive.
The positive plate provided by the fourth aspect of the application comprises the positive electrode material, and the positive electrode material comprises the positive active material and the positive lithium supplement composite additive, so that the positive electrode plate not only has better lithium supplement capacity, but also has good structural stability and environmental stability, and can effectively resist the influence of environmental factors such as external moisture, carbon dioxide and the like, thereby ensuring the lithium supplement effect of the additive. The lithium-supplementing effect on the positive plate is good, the safety is high, and the electrochemical properties of the positive plate, such as capacity retention rate, cycle life, safety and the like, can be effectively improved.
According to the secondary battery provided by the fifth aspect of the application, the positive plate is added with the positive lithium supplement composite additive, so that active lithium ions consumed due to the formation of an SEI (solid electrolyte interphase) film during the first charging of the battery can be effectively compensated, active lithium in a battery system is effectively maintained, and the capacity retention rate of the battery is improved. Therefore, the secondary battery provided by the application has high energy density and good capacity retention rate.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a positive electrode lithium supplement composite additive provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In a first aspect, an embodiment of the present invention provides a positive electrode lithium supplement composite additive, which includes a lithium supplement material core and a carbon coating layer grown on an outer surface of the lithium supplement material core; wherein, the lithium supplement material core comprises a lithium supplement additive and transition metal elements doped in the structure and/or between the structures of the lithium supplement additive.
The positive electrode lithium supplement composite additive provided by the first aspect of the embodiment of the application comprises a lithium supplement material core, wherein the lithium supplement material core comprises a lithium supplement additive and a transition metal element doped in the structure and/or between the structures of the lithium supplement additive, and specifically, the transition metal element is doped in the crystal structure framework and/or between the crystal structures of the lithium supplement additive instead of replacing the framework sites in the crystal structure of the lithium supplement additive. The doping form enables the transition metal element doped in the lithium supplement material inner core to keep catalytic activity, and the doped transition metal element has strong affinity with the carbon source, so that the carbon source takes the doped transition metal element as a catalytic activity center, and the carbon source is continuously precipitated on the outer surface of the lithium supplement material inner core to grow into a carbon coating layer. Compared with the carbon coating layer formed by deposition, the carbon coating layer directly catalytically grows on the surface of the lithium supplement material core, so that the coating degree and quality of the carbon coating layer on the lithium supplement material core are effectively improved, the combination stability of the carbon coating layer and the lithium supplement material core is improved, and the environmental stability of the anode lithium supplement composite additive is improved. In addition, the transition metal element doped in the structure and/or between the structures of the lithium supplement additive can further improve the structural stability of the lithium supplement additive through the influence of electrostatic acting force and the like between elements.
In some embodiments, the transition metal element is selected from: at least one of Ti, mn, mo, W and Ce; the transition metal elements not only have stronger affinity to carbon atoms, but also have higher catalytic activity, and can not maintain corresponding metal forms in the carbon coating process, but react with carbon to form a new carbide, so that the bonding stability and tightness of a growing carbon coating and a lithium supplement material core can be improved, the carbide can be further used as a catalyst in the carbon coating growing process, the growth and formation of the carbon coating can be better promoted, and the coating degree and quality of the carbon coating on the outer surface of the lithium supplement material core are improved.
In some embodiments, the transition metal element is doped within and/or between the crystal structures of the lithium supplement additive in the form of elemental transition metal and/or transition metal oxide. The transition metal element doped in the crystal structure and/or between the crystal structures of the lithium supplement additive can be doped in the form of a transition metal simple substance or in the form of a transition metal oxide, and can be reasonably selected according to the catalytic effect of the transition metal element in the practical application process. If the simple substance form of the transition metal element has better catalytic activity, doping is carried out in the form of the transition metal simple substance; doping is carried out in the form of transition metal oxides if the oxide form of the transition metal element has better catalytic activity.
In some embodiments, the molar ratio of the lithium supplement additive to the doped transition metal element in the core of the lithium supplement material is 1: (0.001-0.1), the doping molar ratio of the transition metal element not only ensures the improvement of the coating stability and the coating effect of the transition metal element on the carbon coating layer, but also improves the structural stability of the lithium supplement material. If the doping molar ratio of the transition metal element is too high, the grown carbon coating layer is too thick, the ion transmission in the core of the lithium supplement material is hindered, and the lithium supplement capacity of the positive electrode lithium supplement composite additive is reduced, so that the lithium supplement effect is reduced. In some embodiments, the molar ratio of the lithium supplement additive to the doped transition metal element in the core of the lithium supplement material includes, but is not limited to, 1: (0.001 to 0.09), 1: (0.01 to 0.08), 1: (0.03-0.07), 1: (0.04-0.06).
In some embodiments, in the positive electrode lithium supplement composite additive, the mass percentage of the carbon coating layer is 2.0-5.5%. According to the positive electrode lithium supplement composite additive, the transition metal element doped in the inner core of the lithium supplement material is adopted, so that the coating amount of the carbon coating layer is effectively increased, and the coating effect and the coating stability are improved. In some embodiments, the mass percentage of the carbon coating layer in the positive electrode lithium-supplementing composite additive includes, but is not limited to, 2.0% -5.5%, 2.8% -5.0%, 4.0% -5.0%, 3.3% -4.8%, 4.5% -4.8%, and the like.
In some embodiments, the lithium supplement additive has the formula Li x M y O z Wherein x is more than 0 and less than or equal to 5, y is more than 0 and less than or equal to 3, z is more than 0 and less than or equal to 4, and M is selected from at least one of Fe, co, ni, mn and Cu. The lithium supplement material can provide rich lithium, can effectively release lithium in the first circle of charging process and supplement irreversible lithium ions consumed by an SEI (solid electrolyte interphase) film formed by a negative electrode, thereby improving the content of lithium in a lithium anode material in the electrode and improving the capacity and cycle performance of the electrode.
In some embodiments, the positive lithium supplement composite additive further comprises an encapsulation layer coated on the outer surface of the carbon coating layer, wherein the encapsulation layer comprises at least one of an isolation encapsulation layer, an ion conductor encapsulation layer and an electron conductor encapsulation layer. The packaging layers can effectively improve the electronic and ionic conduction performance of the lithium supplement material in the core and improve the lithium removal in the charging process; the lithium ion composite additive can also play a certain role in isolating moisture, improve the stability of the lithium ion composite additive for the anode and realize a stable lithium ion supplementing effect. In addition, the stability, the dispersion uniformity and the good processability of the positive electrode lithium supplement composite additive in electrode active slurry and an active layer can be further improved. Specifically, the isolation packaging layer plays a further role in protecting the positive electrode lithium supplement composite additive, and prevents the inner core of the lithium supplement material from contacting water and carbon dioxide in the environment; the electronic conductor packaging layer can enhance the electronic conductivity of the coating layer, so that the electronic conductivity of the lithium supplement composite additive is enhanced, and the impedance in the electrode is reduced; the ion conductor packaging layer can enhance the ionic conductivity of the positive lithium supplement composite additive, thereby enhancing the ionic conductivity of the lithium supplement additive and being beneficial to the outward transportation of lithium ions in the lithium supplement material core.
In some embodiments, the encapsulation layer may be an isolation encapsulation layer, and fully encapsulates the lithium supplement material core and the carbon coating layer, so as to protect the lithium supplement material core and further improve the stability of the lithium supplement material core. Or a composite laminated structure of an isolation packaging layer and an electronic conductor packaging layer, wherein the isolation packaging layer is coated on the outer surface of the carbon coating layer, and the electronic conductor packaging layer is coated on the outer surface of the isolation packaging layer. The composite laminated structure of the isolation packaging layer and the ion conductor packaging layer can also be adopted, the preferred structure is that the isolation packaging layer is coated on the outer surface of the carbon coating layer, and the ion conductor packaging layer is coated on the outer surface of the isolation packaging layer. The composite laminated structure of the isolation packaging layer, the electronic conductor packaging layer and the ion conductor packaging layer can also be adopted, the preferred structure is that the isolation packaging layer is coated on the outer surface of the carbon coating layer, the ion conductor packaging layer is coated on the outer surface of the isolation packaging layer, and the electronic conductor packaging layer is coated on the outer surface of the ion conductor packaging layer; or the isolation packaging layer is coated on the outer surface of the carbon coating layer, the electronic conductor packaging layer is coated on the outer surface of the isolation packaging layer, and the ion conductor packaging layer is coated on the outer surface of the electronic conductor packaging layer.
In some embodiments, the material of the isolation encapsulation layer comprises at least one of a ceramic, a high molecular polymer, or a carbon material. In some embodiments, the ceramic comprises Al 2 O 3 、SiO 2 Boehmite, si 3 N 4 At least one of SiC and BN. In some embodiments, the polymer comprises [ C ] 6 H 7 O 6 Na] n An organic polymer having the structure [ C ] 6 H 7 O 2 (OH) 2 OCH 2 COONa] n An organic polymer of structure [ C ] 3 H 4 O 2 ] n An organic polymer having the structure [ C ] 3 H 3 O 2 M a ] n An organic polymer having the structure [ C ] 3 H 3 N] n An organic polymer of the structure containing- [ CH ] 2 -CF 2 ] n Organic Polymer having-Structure containing- [ NHCO ]]An organic polymer having a structure of-containing an imide ring- [ CO-N-CO ] in the main chain]One or more of an organic polymer of structure and polyvinylpyrrolidone, where M a Is an alkali metal element. Specifically, the polymer comprises one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose, polyacrylic acid, polyacrylate, polyacrylonitrile, polyamide, polyimide, polyvinylpyrrolidone, polyethylene oxide (PEO), polypyrrole (PPy), polytetrafluoroethylene (PTFE), and Polyurethane (PU). Further, the polymer includes one or more of sodium carboxymethylcellulose and polyacrylic acid. The sodium carboxymethylcellulose and the polyacrylic acid are two-dimensional surface type high molecular polymers, have good bonding effect, and can effectively coat the lithium-rich material core, so that the lithium-rich material core is prevented from contacting with air, and the stability of the lithium supplement additive is improved. In some embodiments, the molecular weight of the polymer is greater than or equal to 10 ten thousand. The molecular weight of the polymer may specifically be, but not limited to, 10 ten thousand, 15 ten thousand, 20 ten thousand, 30 ten thousand, 50 ten thousand or 100 ten thousand. The larger the molecular weight of the polymer is, the higher the compactness and structural strength of the polymer layer are, and the protection of the lithium-rich material inner core is more favorably realized. In some embodiments, the carbon material comprises at least one of graphene, carbon nanotubes, amorphous carbon, graphite, carbon black.
In some embodiments, the isolation encapsulation layer has a thickness of 5-200nm; further preferably 5 to 50nm. This application embodiment is through adjusting material and the thickness of keeping apart the encapsulation layer, can further improve the contact of lithium source karyon in high resistance water, carbon dioxide and the benefit lithium material kernel, improves the stability of lithium source karyon.
In some embodiments, the material of the electronic conductor encapsulation layer comprises at least one of a carbon material, a conductive polymer, or a conductive oxide. In some embodiments, the carbon material includes at least one of mesoporous carbon, carbon nanotubes, graphite, carbon black, graphene, and the like, the conductive polymer may be, but is not limited to, the conductive polymer contained In the isolation encapsulation layer above, and the conductive oxide includes In 2 O 3 、ZnO、SnO 2 At least one of (a).
In some embodiments, the electronic conductor encapsulation layer has a thickness of 5-200nm; further preferably 5 to 50nm. According to the embodiment of the application, the electronic conductivity of the positive electrode lithium supplement composite additive can be further improved by adjusting the thickness of the electronic conductor packaging layer.
In some embodiments, the material of the ion conductor encapsulation layer comprises at least one of a perovskite-type, NASICON-type, garnet-type, or polymer-type solid electrolyte. In some embodiments, the perovskite type comprises Li 3x La 2/3-x TiO 3 (LLTO), in particular Li 0.5 La 0.5 TiO 3 、Li 0.33 La 0.57 TiO 3 、Li 0.29 La 0.57 TiO 3 、Li 0.33 Ba 0.25 La 0.39 TiO 3 、(Li 0.33 La 0.56 ) 1.005 Ti 0.99 Al 0.01 O 3 、Li 0.5 La 0.5 Ti 0.95 Zr 0.05 O 3 And the like; NASICON types include, but are not limited to, li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP); garnet types include, but are not limited to, li 7 La 3 Zr 2 O 12 (LLZO)、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 ，Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 At least one of; the polymer type solid electrolyte includes at least one of PEO/PPO/PVDF, etc. dissolving a lithium salt.
In some embodiments, the ion conductor encapsulation layer has a thickness of 5-200nm; further preferably 5 to 50nm. According to the embodiment of the application, the ionic conductivity of the positive lithium supplement composite additive can be further improved by adjusting the thickness and the material of the ion conductor packaging layer.
Based on the structure and performance of the positive electrode lithium supplement composite additive in the embodiment of the application, the positive electrode lithium supplement composite additive has excellent storage property and processability and stable electrochemical performance. According to the detection, the positive plate directly prepared by the positive lithium supplement composite additive in the embodiment of the application, such as the positive plate prepared by the positive lithium supplement additive, the binder and the conductive agent, has a capacity decay rate of not more than 30%, further not more than 25% and further not more than 17.3% when stored for 24 hours under the ambient humidity of 25% relative to the capacity decay rate of 0 hour. Ideally, the lithium supplement additive of the above application is stored in a dry and oxygen-free favorable environment such as a vacuum environment, so that the electrochemical performance of the lithium supplement additive of the above application is exerted to the maximum extent.
The positive electrode lithium supplement composite additive of the embodiment of the application can be prepared by the method of the following embodiment.
As shown in fig. 1, a second aspect of the embodiments of the present application provides a method for preparing a positive electrode lithium supplement composite additive, including the following steps:
s10, obtaining a lithium supplement additive, and mixing the lithium supplement additive with a transition metal precursor to prepare a transition metal element doped composite lithium supplement material;
and S20, generating a carbon coating layer on the surface of the composite lithium supplement material to obtain the anode lithium supplement composite additive.
In the preparation method of the positive electrode lithium supplement composite additive provided by the second aspect of the embodiment of the application, the lithium supplement additive and the transition metal precursor are mixed to fully disperse and dope the transition metal precursor in the lithium supplement additive, and then the transition metal element doped composite lithium supplement material is prepared; and then preparing a carbon coating layer on the surface of the composite lithium supplement material. Because the composite lithium supplement material is doped with the transition metal element, the composite lithium supplement material has higher catalytic activity and can adsorb and react with carbon atoms to generate carbide, so that a carbon source grows on the surface of the composite lithium supplement material to form a carbon coating layer, and the combination stability and the compactness of the carbon coating layer and the core lithium supplement material are improved. The preparation method of the positive electrode lithium supplement composite additive is simple in process, the prepared positive electrode lithium supplement composite additive takes the lithium supplement material doped with the transition metal element in the gap as the inner core, and takes the carbon growing on the outer surface of the inner core of the lithium supplement material as the coating layer, so that the structural stability and the environmental stability of the positive electrode lithium supplement composite additive are improved, and the lithium supplement effect of the positive electrode lithium supplement composite additive is improved.
In the embodiment of the present application, the type of the lithium supplement additive in step S10 is not specifically limited, and any lithium supplement additive meeting the application requirement may be used. The preparation method of the lithium supplement additive includes, but is not limited to, mixing a lithium source, a metal source and the like, and calcining in an inert atmosphere to obtain the lithium supplement additive.
In some embodiments, the step of preparing the transition metal element doped composite lithium supplement material comprises: and mixing and grinding the lithium supplement additive and the transition metal precursor, and then performing reduction or oxidation treatment to obtain the transition metal element doped composite lithium supplement material. In the embodiment of the application, the lithium supplement additive and the transition metal precursor are mixed and ground, so that the transition metal precursor can fully mix and dope the lithium supplement additive and uniformly distribute the lithium supplement additive in the lithium supplement additive; and then reducing the transition metal precursor into a transition metal simple substance by reduction treatment, or converting the transition metal precursor into a transition metal oxide by oxidation treatment, thereby obtaining the transition metal element-doped composite lithium supplement material. In the actual preparation process, reduction treatment or oxidation treatment can be selected according to the catalytic activity of the transition metal element; namely, if the transition metal has higher catalytic activity in the form of simple substance, the reduction treatment is carried out; the oxidation treatment is carried out if the transition metal has a higher catalytic activity in the form of an oxide.
In other embodiments, the transition metal precursor may also be mixed with a precursor of the lithium supplement material, and the transition metal precursor is converted into a transition metal oxide and doped into or between structures of the lithium supplement additive material while the lithium supplement material precursor reacts to generate the lithium supplement additive material, so as to achieve more uniform doping of the transition metal element.
In some embodiments, the transition metal precursor comprises: at least one of transition metal nitrate, transition metal sulfate, transition metal carbonate, transition metal hydroxide, and transition metal ammonium salt. In some embodiments, the transition metal element in the transition metal precursor comprises at least one of titanium, manganese, molybdenum, tungsten, cerium, and the like. In some embodiments, the transition metal precursor includes, but is not limited to, ce (NO) 3 ) 3 、(NH 4 ) 10 W 12 O 41 、(NH 4 ) 2 MoO 4 And the transition metal precursors are easily reduced into transition metal simple substances or oxidized into transition metal oxides, and other elements are volatilized and removed in a gaseous form and are not easy to remain.
In some embodiments, in step S20, the step of generating the carbon coating layer on the surface of the composite lithium supplement material includes: the composite lithium supplement material and the carbon material are mixed and then calcined, the carbon material takes a transition metal element doped in the composite lithium supplement material as a catalytic center under the high-temperature calcination condition, the carbon material is adsorbed to react to generate a transition metal carbide, the carbide can be further used as a catalyst generated by a carbon coating layer, the growth of the carbon coating layer is better promoted, and the combination stability and the compactness of the carbon coating layer and the composite lithium supplement material can be improved. The prepared anode lithium supplement composite additive with the carbon coating layer growing on the surface has better structural stability and environmental stability, thereby improving the lithium supplement effect.
In some embodiments, the conditions of the calcination treatment include: keeping the temperature for 1 to 3 hours in an inert atmosphere and/or a reducing atmosphere at the temperature of between 400 and 600 ℃; the calcination condition is beneficial to the growth of the carbon coating layer, and if the temperature is too low or the heat preservation time is too short, the growth rate and the effect of the carbon coating layer can be reduced; if the temperature is too high or the heat preservation time is too long, the performance of the composite lithium supplement material is affected, and the lithium supplement effect is reduced.
In some embodiments, the carbon material is selected from: the organic carbon materials are easy to react with transition metal elements to generate carbides in the high-temperature calcination process, so that the carbon materials are converted and grown into the carbon coating layer on the surface of the composite lithium supplement material.
In some embodiments, after the carbon coating layer is generated on the surface of the composite lithium supplement material, the method further comprises the step of preparing at least one of an isolation packaging layer, an ion conductor packaging layer and an electron conductor packaging layer on the surface of the carbon coating layer. Methods for preparing the isolation packaging layer, the ion conductor packaging layer and the electronic conductor packaging layer include but are not limited to chemical deposition, magnetron sputtering or atomic layer deposition and the like.
In some embodiments, when the material of the encapsulation layer is a ceramic layer, the step of preparing the ceramic encapsulation layer may, but is not limited to, sputter a ceramic target on the surface of the carbon coating layer by magnetron sputtering to deposit a ceramic off-encapsulation layer, where the magnetron sputtering conditions are adjusted according to specific target properties.
In some embodiments, when the material of the encapsulation layer is a polymer layer, the step of forming the polymer isolation encapsulation layer may be: and dispersing the carbon-coated composite lithium supplement material in a solution containing a high molecular polymer, and then carrying out vacuum drying to form a compact polymer packaging layer on the surface of the carbon coating layer. Wherein the solvent of the solution is a solvent capable of uniformly dispersing or dissolving the high molecular polymer, such as one or more of N-methylpyrrolidone, methanol, ethanol, isopropanol, acetone, tetrahydrofuran and diethyl ether.
In some embodiments, when the material of the encapsulation layer is a carbon material layer, the method for forming the carbon material isolation encapsulation layer comprises the following steps: and dispersing the carbon-coated composite lithium supplement material in a solution containing a carbon source, drying, and then carbonizing to form a compact carbon packaging layer on the surface coated with carbon. The carbon source may be, but is not limited to, PEO, and may be other carbon sources. Any material that can form a carbon source layer on the surface of the lithium supplement material is suitable for the present invention. Specifically, the carbon-coated lithium supplement material and PEO are mixed uniformly, the PEO reaches a melting point at 300 ℃, the PEO is uniformly coated on the surface of the carbon-coated lithium supplement material, the coated material is sintered in an inert atmosphere, the temperature is 600 ℃, the temperature is kept for 6 hours, and a compact carbon layer is formed after the sintering is finished.
In a third aspect, the embodiment of the application also provides a positive electrode material. The positive electrode material of the embodiment of the application comprises a positive electrode active material and the positive electrode lithium supplement additive of the embodiment of the application. Therefore, the positive electrode material disclosed by the embodiment of the application has excellent lithium supplement performance and good processing performance, and the quality of the positive electrode active material layer can be improved, so that the quality of the positive electrode active material layer is improved, and the electrochemical performance of a corresponding positive electrode plate is endowed.
In the embodiment, the content of the lithium supplement additive for the positive electrode in the embodiment of the present application can control the mass content of the positive electrode material in the active layer of the positive electrode in the embodiment of the present application to be 0.1-10%.
In some embodiments, the mass percentage of the positive electrode lithium supplement composite additive in the positive electrode material is 0.1-10%. The proportion can just make up the loss of active lithium in the first charging process of the battery. Because most of lithium provided by the addition of the positive electrode lithium supplement cannot be circulated in the operation process of the battery, if the addition amount of the positive electrode lithium supplement composite additive in the positive electrode plate is too high, excessive lithium can cause lithium ions to be separated out on the surface of the negative electrode in the operation process of the battery to form lithium dendrites; if the addition amount of the positive electrode lithium supplement composite additive in the positive electrode plate is too low, active lithium lost in the positive electrode material cannot be completely supplemented, and the improvement of the energy density, the capacity retention rate and the like of the battery is not facilitated. In some embodiments, the mass percentage of the positive lithium supplement composite additive in the positive electrode material includes, but is not limited to, 0.1-1%, 1-2%, 2-5%, 5-8%, 8-10%, and the like.
In other embodiments, the positive electrode active material contained in the positive electrode material of the embodiments of the present disclosure may be a phosphate positive electrode active material, a ternary positive electrode active material, or a lithium transition metal oxide, and specific embodiments include one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl fluorophosphate, lithium titanate, lithium nickel cobalt manganese oxide, and lithium nickel cobalt aluminate.
In a fourth aspect of the embodiments of the present application, a positive electrode sheet is provided, where the positive electrode sheet includes the positive electrode lithium supplement composite additive described above, or includes the positive electrode lithium supplement composite additive prepared by the above method.
The positive plate provided by the fourth aspect of the embodiment of the application comprises the positive lithium supplement composite additive, the additive takes the lithium supplement material doped with the transition metal element in the gap as the core, and takes the carbon growing on the outer surface of the core of the lithium supplement material as the coating layer, so that the positive plate has good lithium supplement capacity, good structural stability and good environmental stability, and can effectively resist the influence of environmental factors such as external moisture, carbon dioxide and the like, thereby ensuring the lithium supplement effect of the additive. Therefore, the lithium supplement effect on the positive plate is good, the safety is high, and the electrochemical properties of the positive plate, such as capacity retention rate, cycle life, safety and the like, can be effectively improved.
In some embodiments, the positive plate comprises a current collector and an active material layer which are laminated and attached, and the mass percentage of the positive lithium supplement composite additive in the active material layer is 0.1-10%. The proportion can just make up the loss of active lithium in the first charging process of the battery. Because most of lithium provided by the addition of the positive electrode lithium supplement cannot be circulated in the operation process of the battery, if the addition amount of the positive electrode lithium supplement composite additive in the positive electrode plate is too high, excessive lithium can cause lithium ions to be separated out on the surface of the negative electrode in the operation process of the battery, so that lithium dendrites are formed; if the addition amount of the positive electrode lithium supplement composite additive in the positive electrode plate is too low, active lithium lost in the positive electrode material cannot be completely supplemented, and the improvement of the energy density, the capacity retention rate and the like of the battery is not facilitated. In some embodiments, the mass percentage of the positive electrode lithium supplement composite additive in the active material layer of the positive electrode sheet includes, but is not limited to, 0.1-1%, 1-2%, 2-5%, 5-8%, 8-10%, and the like.
In some embodiments, the positive active material in the positive plate includes, but is not limited to, at least one of lithium iron phosphate, lithium cobaltate, lithium iron manganese phosphate, lithium manganate, lithium nickel cobalt manganese, and lithium nickel manganese.
In some embodiments, the positive electrode current collector includes, but is not limited to, any one of a copper foil and an aluminum foil.
In some embodiments, the positive active layer further includes a conductive agent, a binder, and other components, and the materials are not particularly limited in this application, and may be selected according to the actual application requirement.
In some embodiments, the binder is present in the positive active layer in an amount of 2wt% to 4wt%. In particular embodiments, the binder may be present in an amount of 2wt%, 3wt%, 4wt%, etc., which is typical and not limiting. In a particular embodiment, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene butadiene rubber, hydroxypropyl methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives.
In some embodiments, the conductive agent is present in the positive electrode active layer in an amount of 3wt% to 5wt%. In specific embodiments, the content of the conductive agent may be 3wt%, 4wt%, 5wt%, and the like, which are typical but not limiting contents. In particular embodiments, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fibers, C60, and carbon nanotubes.
In some embodiments, the positive electrode sheet is prepared by the following steps: mixing the positive active material, the positive lithium-supplementing composite additive, the conductive agent and the binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die-cutting and the like to obtain the positive plate.
A fifth aspect of the embodiments of the present application provides a secondary battery including the positive electrode sheet described above.
The secondary battery provided by the fifth aspect of the embodiment of the application comprises the positive plate, and the positive electrode lithium supplement composite additive is added to the positive plate, so that active lithium ions consumed due to the formation of an SEI (solid electrolyte interphase) film during the first charging of the battery can be effectively compensated, active lithium in a battery system can be effectively maintained, and the capacity retention rate of the battery is improved. Therefore, the secondary battery provided by the embodiment of the application has high energy density and good capacity retention rate.
The secondary battery of the embodiment of the present application may be a lithium ion battery or a lithium metal battery.
The negative electrode sheet, the electrolyte, the separator and the like of the secondary battery in the embodiment of the present application are not particularly limited, and may be applied to any battery system.
In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to make the advanced performances of the positive electrode lithium-supplementing composite additive and the preparation method thereof, the positive electrode sheet, and the secondary battery of the embodiments of the present application obviously manifest, the above technical solutions are exemplified by a plurality of examples below.
Example 1
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. mixing Li 2 CO 3 And Fe (OH) 3 Mechanically crushing the mixture according to a molar ratio of 2.5 5 FeO 4 And (3) a lithium supplement additive.
2. Mixing the above Li 5 FeO 4 Lithium supplement additive and Ce (NO) 3 ) 3 Uniformly mixing the components according to a molar ratio of 1 5 FeO 4 ·0.01Ce 2 O 3 Compounding lithium supplementing additive.
3. Dissolving polyaniline in NMP, uniformly mixing with a composite lithium supplement additive, placing in a reaction kettle, reacting for 2 hours at 200 ℃, and then drying in vacuum to obtain C coated with a carbon layer&Li 5 FeO 4 ·0.01Ce 2 O 3 。
Example 2
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. reacting LiOH and CS 2 Mechanically crushing and uniformly stirring the materials according to a molar ratio of 4 2 And S is a lithium supplement additive.
2. Mixing the above Li 2 S lithium supplement additive and (NH) 4 ) 10 W 12 O 41 Uniformly mixing the components according to the molar ratio of 1Sintering at 550 ℃ for 3h under argon atmosphere, crushing and sieving to obtain Li 2 S·0.06WO 3 Compounding lithium supplementing additive.
3. Uniformly mixing polyethylene and the composite lithium supplement additive, placing the mixture in a muffle furnace in nitrogen atmosphere, and sintering the mixture for 2 hours at 500 ℃ to obtain C coated with a carbon layer&Li 2 S·0.06WO 3 。
Example 3
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. mixing Li 2 O and Ni (OH) 2 Mechanically crushing according to a molar ratio of 1 2 NiO 2 And (3) a lithium supplement additive.
2. Mixing the above Li 2 NiO 2 Lithium supplementing additives and (NH) 4 ) 2 MoO 4 Uniformly mixing the materials according to a molar ratio of 1 2 NiO 2 0.005Mo composite lithium supplement additive.
3. Firstly, uniformly mixing benzene and the composite lithium supplement additive, placing the mixture in a reaction kettle, reacting for 2 hours at 300 ℃, and then drying in vacuum to obtain C coated with a carbon layer&Li 2 NiO 2 ·0.005Mo。
Example 4
A positive electrode lithium-supplementing composite additive, the preparation of which differs from that of example 1 in that: li in step 2 5 FeO 4 Lithium supplement additive and Ce (NO) 3 ) 3 Mixing according to the proportion of 1.
Example 5
A positive electrode lithium supplement composite additive, the preparation of which differs from example 1 in that: li in step 2 5 FeO 4 Lithium supplement additive and Ce (NO) 3 ) 3 Mixing according to the proportion of 1.
Comparative example 1
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. mixing Li 2 CO 3 And Fe (OH) 3 In molar ratio of massage2.5 5 FeO 4 And (3) a lithium supplement additive.
2. Firstly, polyaniline is dissolved in NMP and is reacted with Li 5 FeO 4 After lithium supplement additive is mixed evenly, the mixture is placed in a reaction kettle to react for 2 hours at 200 ℃, and then vacuum drying is carried out to obtain C coated with a carbon layer&Li 5 FeO 4 。
Comparative example 2
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. reacting LiOH and CS 2 Mechanically crushing and uniformly stirring the materials according to a molar ratio of 4 2 And S is a lithium supplement additive.
2. Firstly, polyethylene and Li 2 S lithium supplement additive is evenly mixed and then placed in a muffle furnace in nitrogen atmosphere to be sintered for 2 hours at 500 ℃ to obtain C coated with a carbon layer&Li 2 S·0.06WO 3 。
Comparative example 3
A positive electrode lithium supplement composite additive is prepared by the following steps:
1. mixing Li 2 O and Ni (OH) 2 Mechanically crushing according to a molar ratio of 1 2 NiO 2 And (3) a lithium supplement additive.
2. Mixing the above Li 2 NiO 2 Lithium supplement additive and Al (NO) 3 ) 3 Uniformly mixing the materials according to the proportion of 1 2 NiO 2 ·Al 2 O 3 Compounding lithium supplementing additive.
3. Firstly, uniformly mixing benzene and the composite lithium supplement additive, placing the mixture in a reaction kettle, reacting for 2 hours at 300 ℃, and then drying in vacuum to obtain C coated with a carbon layer&Li 2 NiO 2 ·Al 2 O 3 。
To verify the improvement of the examples of the present application, the gram capacity and the carbon content of the positive electrode lithium supplement composite materials prepared in examples 1 to 5 and comparative examples 1 to 3 were respectively tested, and the test results are shown in table 1 below:
TABLE 1
The test results in table 1 show that the positive lithium supplement composite additives prepared in examples 1 to 5 of the present application maintain a high gram capacity and improve the coating amount of the carbon coating layer, the gram capacity of example 3 after being placed for 24 hours under a humidity of about 25% is attenuated to a certain extent, the gram capacity attenuation rate is not more than 17.3% relative to 0h, the attenuation rates of other examples of the present application are not more than 16%, and the gram capacity of the composite lithium supplement additive under a humidity of 25% is far higher than that of the conventional lithium supplement additive, which indicates that the carbon coating layer and the inner core of the lithium supplement material have good combination stability, and the doping can effectively improve the environmental stability of the additive. In contrast, in comparative examples 1 and 2, no transition metal element is doped, the carbon coating effect is low, and the gram capacity of the composite additive is reduced, especially the gram capacity of the composite additive is sharply reduced after the composite additive is placed under 25% humidity for 24 hours. The non-transition metal Al doped in the comparative example 2 does not improve the coating effect of the carbon material, and simultaneously reduces the gram volume of the composite additive. (note: decay rate = (1-gram volume left for 24 h/gram volume left for 0 h) × 100%.
Further, in order to verify the lithium supplementing effect of the positive electrode lithium supplementing composite additive in the battery, the following components were used: SP: PVDF =95, 2: mixing PVDF, wherein the mixing mode is ball milling, and the ball milling time is 60min; the rotation speed is set to 30HZ: and respectively preparing the anode plates by homogenizing, coating, drying and cutting. And then assembling the button type lithium ion battery in an inert atmosphere glove box according to the assembling sequence of the lithium metal sheet, the diaphragm, the electrolyte and the positive plate. For the lithium ion batteries prepared in examples 1 to 5 and comparative examples 1 to 2, charging was performed at 0.05C to 4.3v,4.3v was constant voltage to a current of less than 0.01C, respectively; the first charge gram capacity and the cycle capacity retention rate are tested, and the test results are shown in the following table 2:
TABLE 2
From the test results, compared with the lithium supplement composite additives prepared by the comparative examples 1 and 2 without doping the transition metal element and the non-transition metal aluminum doped in the comparative example 3, the positive electrode lithium supplement composite materials prepared in the examples 1 to 5 of the present application show higher first charge capacity, cycle capacity retention rate and cycle stability when added to lithium iron phosphate, which indicates that the positive electrode material added with the positive electrode lithium supplement composite additive prepared in the examples of the present application has higher charge capacity and stability. In addition, the carbon coating layer is too thick due to too high doping of the transition metal element in example 5, the lithium ion transfer and transmission efficiency is reduced to some extent, and the lithium supplementing effect is lower than that in examples 1 to 4 in which the doping molar ratio is 0.001 to 0.1.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (13)
1. The positive electrode lithium supplement composite additive is characterized by comprising a lithium supplement material inner core and a carbon coating layer growing on the outer surface of the lithium supplement material inner core; wherein the lithium supplement material core comprises a lithium supplement additive and a transition metal element doped in the structure and/or between the structures of the lithium supplement additive.
2. The positive lithium supplement composite additive of claim 1, wherein the transition metal element is selected from the group consisting of: at least one of Ti, mn, mo, W and Ce;
and/or the transition metal element is doped in the crystal structure and/or between the crystal structures of the lithium supplement additive in the form of transition metal simple substance and/or transition metal oxide.
3. The positive electrode lithium supplement composite additive according to claim 2, wherein the molar ratio of the lithium supplement additive to the doped transition metal element in the lithium supplement material core is 1: (0.001 to 0.1);
and/or in the positive electrode lithium supplement composite additive, the mass percentage of the carbon coating layer is 2.0-5.5%.
4. The positive electrode lithium supplement composite additive according to any one of claims 1 to 3, wherein the chemical formula of the lithium supplement additive is Li x M y O z Wherein x is more than 0 and less than or equal to 5, y is more than 0 and less than or equal to 3, z is more than 0 and less than or equal to 4, and M is selected from at least one of Fe, co, ni, mn and Cu.
5. The positive electrode lithium supplement composite additive according to claim 4, further comprising an encapsulation layer coated on the outer surface of the carbon coating layer;
and/or the packaging layer comprises at least one of an isolation packaging layer, an ion conductor packaging layer and an electronic conductor packaging layer.
6. The positive electrode lithium supplement composite additive according to any one of claims 1 to 3 or 5, wherein a positive electrode sheet prepared from the positive electrode lithium supplement composite additive, a conductive agent and a binder has a capacity decay rate of not more than 25% when stored at an ambient humidity of 25% for 24 hours relative to 0 hour.
7. The preparation method of the positive electrode lithium supplement composite additive is characterized by comprising the following steps of:
obtaining a lithium supplement additive, and mixing the lithium supplement additive with a transition metal precursor to prepare a transition metal element-doped composite lithium supplement material;
and generating a carbon coating layer on the surface of the composite lithium supplement material to obtain the anode lithium supplement composite additive.
8. The method of preparing the positive lithium supplement composite additive according to claim 7, wherein the step of preparing the transition metal element-doped composite lithium supplement material comprises: mixing and grinding the lithium supplement additive and the transition metal precursor, and then carrying out reduction or oxidation treatment to obtain the transition metal element doped composite lithium supplement material;
and/or the step of generating the carbon coating layer on the surface of the composite lithium supplement material comprises the following steps: mixing the composite lithium supplement material with a carbon material, and then calcining to obtain the anode lithium supplement composite additive with a carbon coating layer growing on the surface;
and/or after a carbon coating layer is generated on the surface of the composite lithium supplement material, preparing at least one of an isolation packaging layer, an ion conductor packaging layer and an electronic conductor packaging layer on the surface of the carbon coating layer.
9. The method of preparing a positive lithium supplement composite additive according to claim 8, wherein the transition metal precursor comprises: at least one of transition metal nitrate, transition metal sulfate, transition metal carbonate, transition metal hydroxide, and transition metal ammonium salt;
and/or the transition metal element in the transition metal precursor comprises at least one of titanium, manganese, molybdenum, tungsten and cerium;
and/or the conditions of the calcination treatment include: keeping the temperature for 1 to 3 hours in an inert atmosphere and/or a reducing atmosphere at the temperature of between 400 and 600 ℃;
and/or, the carbon material is selected from: at least one of polyaniline, polyethylene and benzene.
10. A positive electrode material comprising the positive electrode lithium supplement composite additive according to any one of claims 1 to 6, or the positive electrode lithium supplement composite additive prepared by the method according to any one of claims 7 to 9.
11. The positive electrode material according to claim 10, wherein the positive electrode lithium supplement composite additive is contained in the positive electrode material in an amount of 0.1 to 10% by mass.
12. A positive electrode sheet, characterized by comprising the positive electrode material according to claim 11.
13. A secondary battery comprising the positive electrode sheet according to claim 12.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024099106A1 (en) * | 2022-11-09 | 2024-05-16 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing material, and preparation method therefor and use thereof |
| WO2024145762A1 (en) * | 2023-01-03 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Lithium replenishment composite material and preparation method therefor, positive electrode sheet, separator, secondary battery, and electrical device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024099106A1 (en) * | 2022-11-09 | 2024-05-16 | 深圳市德方创域新能源科技有限公司 | Lithium supplementing material, and preparation method therefor and use thereof |
| WO2024145762A1 (en) * | 2023-01-03 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Lithium replenishment composite material and preparation method therefor, positive electrode sheet, separator, secondary battery, and electrical device |
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