CN113745472A - Preparation method of single crystal ternary cathode material and ternary lithium ion battery - Google Patents
Preparation method of single crystal ternary cathode material and ternary lithium ion battery Download PDFInfo
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- CN113745472A CN113745472A CN202010475382.9A CN202010475382A CN113745472A CN 113745472 A CN113745472 A CN 113745472A CN 202010475382 A CN202010475382 A CN 202010475382A CN 113745472 A CN113745472 A CN 113745472A
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- salt
- cathode material
- manganese
- lithium
- ternary cathode
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- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 239000010406 cathode material Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 18
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 238000009766 low-temperature sintering Methods 0.000 claims description 16
- 229940071125 manganese acetate Drugs 0.000 claims description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000606 toothpaste Substances 0.000 claims description 2
- 229940034610 toothpaste Drugs 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 46
- 238000009826 distribution Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- 230000001351 cycling effect Effects 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 10
- 241001391944 Commicarpus scandens Species 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 42
- 229910052744 lithium Inorganic materials 0.000 description 42
- 239000000047 product Substances 0.000 description 39
- 239000011572 manganese Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 33
- 229910013716 LiNi Inorganic materials 0.000 description 30
- 239000000463 material Substances 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 150000002500 ions Chemical group 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 9
- 238000005056 compaction Methods 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 229940078494 nickel acetate Drugs 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 8
- 229940011182 cobalt acetate Drugs 0.000 description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Chemical class 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 3
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940071257 lithium acetate Drugs 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 239000003021 water soluble solvent Substances 0.000 description 3
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 2
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013410 LiNixCoyAlzO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Chemical group 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [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
- 230000003446 memory effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/362—Composites
-
- 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
- H01M4/36—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
- H01M2004/026—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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a ternary cathode material, which comprises the following steps of mixing lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water to obtain a mixed solution; ultrasonically mixing the mixed solution obtained in the step and an organic solvent which is mutually soluble with water, and heating to obtain dry gel; grinding the dried gel obtained in the step to obtain gel dried powder; and sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material. According to the invention, the uniform mixing of the raw material metal salt can be ensured, the distribution uniformity of each metal element in the ternary precursor is ensured, and the prepared ternary cathode material has the advantages of single crystal structure, low specific surface area, concentrated particle size distribution, high stability and the like, and is beneficial to improving the high-temperature performance and the cycling stability of the battery, prolonging the service life and being more beneficial to improving the safety performance of the battery; and the compacting process is not easy to break, the preparation process is simple, the cost is low, the environment is friendly, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of ternary lithium ion batteries, relates to a preparation method of a ternary cathode material and a ternary lithium ion battery, and particularly relates to a preparation method of a single-crystal ternary cathode material and a ternary lithium ion battery.
Background
The lithium ion battery generally comprises a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, has the advantages of high working voltage, high specific energy, long cycle life, light weight, less self-discharge, no memory effect, high cost performance and the like, and becomes a main selection object of a rechargeable power supply in the fields of high-power electric vehicles, artificial satellites, aerospace and the like. In all components of the lithium ion battery, particularly after the invention of the super-concentrated electrolyte, the electrode material is always the main bottleneck for improving the energy density of the lithium ion battery, and the anode is one of the key materials of the lithium ion battery, determines the performance of the lithium ion battery, and therefore is also always a research hotspot of researchers. The positive electrode, i.e., the positive electrode sheet, of the lithium ion battery generally includes a positive active material, a conductive agent, a binder, a solvent, and a current collector, among which the most critical is the positive active material. Particularly, beginning in 2015, the new energy automobile industry is in full outbreak period, and compared with the traditional automobile, the endurance and the safety of the new energy automobile determined by the power battery are always the core of attention of new energy automobile manufacturers and consumers; the key point of improving the endurance mileage of the vehicle is to improve the energy density of the power battery, and more battery manufacturers begin to vigorously develop research and development work of the high-energy-density power battery.
In the current power lithium ion battery anode materials, a nickel cobalt lithium manganate ternary anode material (NCM) and a nickel cobalt lithium aluminate ternary anode material (NCA) have the advantages of high energy density, low cost, environmental friendliness and the like due to the synergistic effect of the three elements, and become anode active materials with great increment in the power lithium ion battery application field in the global market in recent years. With the continuous development of downstream application industries, large-scale terminals such as electric vehicles and the like put higher requirements on the energy density of lithium ion batteries, and ternary materials (nickel cobalt lithium manganate) are the first choice of lithium ion battery anode materials due to higher energy density and better cycle performance. However, the conventional IIIThe component material is composed of spherical or sphere-like secondary particles formed by the aggregation of nanoscale primary particles, i.e. nano-microstructure, which has a low compacted density (generally 3.5 g/cm)3Left and right), the defect of secondary particle breakage easily occurs during rolling, and the application of ternary materials in high-energy density batteries is limited. And researches show that compared with the traditional ternary material with a spherical structure, the single crystal ternary material has higher specific discharge capacity and cycling stability at high temperature and high pressure. Meanwhile, the single crystal ternary material has the following advantages: (1) the mechanical strength is high, the single crystal is not easy to break during compaction (2) the single crystal is in a shape with a lower specific surface area, the contact interface between an electrode and electrolyte is reduced, the side reaction is reduced, and (3) the special crystal structure of the single crystal particles is reduced, so that the single crystal particles are in more sufficient contact with a conductive agent, and the transmission of lithium ions is facilitated. Therefore, the single crystal ternary material is produced. For example, chinese patent application CN 108172819 a discloses a method for preparing a single crystal ternary material, which comprises preparing a mixture solution of three metal salts of nickel, cobalt and manganese, preparing a ternary precursor from the mixture solution, and finally mixing the precursor with a lithium source and sintering the mixture to obtain the single crystal ternary positive electrode material.
However, in the prior art, the preparation of such single crystal ternary materials mostly adopts a precipitation method or a sol-gel method, and usually requires a precipitator or a complexing agent, and then adjusts the pH value, such as oxalic acid, citric acid, ammonia water, diethylamine, triethylamine, urea, and the like. Not only is the production cost increased, but also the pH value of the prepared mixed solution is difficult to stably control, and in an alkaline environment, bivalent manganese is easy to oxidize, the morphology of the precursor is influenced, and the tap density of the material is reduced; meanwhile, the precipitation sequence problem caused by different solubilities of three metal salts of nickel, cobalt and manganese cannot be avoided in the recrystallization process of the mixture solution, and the problem of uniform mixing of the metal salts cannot be completely solved.
Therefore, how to find a suitable preparation method of the single crystal ternary cathode material to solve the above technical problems of the existing preparation process has become one of the focuses of great attention of many manufacturers and first-line researchers in the industry.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for preparing a ternary cathode material and a ternary lithium ion battery, in particular, a method for preparing a single crystal ternary cathode material. The single crystal ternary cathode material prepared by the invention has the advantages of low specific surface area, concentrated particle size distribution, stable crystal form and the like, so that the compaction density and the cycle life of the cathode material are greatly improved; and the preparation process is simple, the conditions are mild, the cost is low, and the method is suitable for large-scale production and application.
The invention provides a preparation method of a ternary cathode material, which comprises the following steps:
1) mixing lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water to obtain a mixed solution;
2) ultrasonically mixing the mixed solution obtained in the step and an organic solvent which is mutually soluble with water, and heating to obtain dry gel;
3) grinding the dried gel obtained in the step to obtain gel dried powder;
4) and sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material.
Preferably, the lithium salt includes one or more of lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide and lithium oxalate;
the manganese salt comprises one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese hydroxide, manganese sulfate and manganese oxalate;
the aluminum salt comprises one or more of aluminum nitrate, aluminum hydroxide and aluminum sulfate;
the nickel salt comprises one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese hydroxide, manganese sulfate and manganese oxalate.
Preferably, the mixed solution comprises a saturated mixed solution;
the lithium salt is an excess lithium salt;
the excess proportion is 1 to 10 percent;
in the mixed solution, the concentration of the metal salt is 0.5-2 mol/L.
Preferably, in the mixed solution, the concentration of the lithium salt is 0.5-2 mol/L;
in the mixed solution, the concentration of the manganese salt is 0.1-0.4 mol/L;
in the mixed solution, the concentration of the cobalt salt is 0.17-0.67 mol/L;
in the mixed solution, the concentration of the nickel salt is 0.25-1 mol/L;
in the mixed solution, the concentration of the aluminum salt is 0.1-0.4 mol/L;
the xerogel is a precursor of the ternary cathode material.
Preferably, the water-miscible organic solvent includes one or more of alcohols, aldehydes, ketones and esters;
the volume ratio of the organic solvent mutually soluble with water to the water is (1-9): 1;
the ultrasonic mixing is ultrasonic stirring and mixing;
the frequency of ultrasonic mixing is 30-50 KHz;
the rotating speed of the ultrasonic mixing is 200-500 r/min;
the ultrasonic mixing time is 10-180 min.
Preferably, the water-miscible organic solvent comprises one or more of ethanol, methanol, ethylene glycol, glycerol, formaldehyde and acetone;
the heating temperature is 30-100 ℃;
after heating, continuously carrying out ultrasonic mixing, wherein the mixed system does not precipitate and gradually becomes viscous until the solution is in a toothpaste state to obtain gel, and drying to obtain dry gel;
the grinding mode comprises ball milling;
the fineness of the gel dry powder is 1-10 mu m.
Preferably, the grinding time is 10-180 min;
the step of tabletting is also included after grinding;
the pressure of the tablet is 3.0-6.0 Mpa;
the tabletting time is 1-5 min;
the sintering includes low-temperature sintering and high-temperature sintering.
Preferably, the heating rate of the low-temperature sintering is 3-8 ℃/min;
the temperature of the low-temperature sintering is 300-600 ℃;
the low-temperature sintering time is 3-8 h;
the heating rate of the high-temperature sintering is 1-10 ℃/min;
the temperature of the high-temperature sintering is 800-1000 ℃;
the high-temperature sintering time is 5-20 h.
Preferably, the cooling rate of the annealing is 1-5 ℃/min;
the annealing temperature is 500-750 ℃;
the annealing time is 5-15 h;
the ternary cathode material is a single crystal ternary cathode material;
the ternary positive electrode material includes NCM or NCA.
The invention also provides a ternary lithium ion battery which comprises the ternary cathode material prepared by the preparation method in any one of the technical schemes.
The invention provides a preparation method of a ternary cathode material, which comprises the following steps of firstly mixing lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water to obtain a mixed solution; then ultrasonically mixing the mixed solution obtained in the step with an organic solvent which is mutually soluble with water, and heating to obtain dry gel; grinding the dried gel obtained in the step to obtain gel dried powder; and finally, sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material. Compared with the prior art, the method provided by the invention is mainly used for preparing the single crystal ternary material by adopting a precipitation method or a sol-gel method, the precipitation rate of the metal salt is controlled by adjusting the pH value of a reaction system, and the metal salt is mixed with a lithium source after pre-calcination. The method has the advantages of more reaction parameters required to be controlled, complex preparation process, long reaction period and increased production cost; moreover, the traditional preparation method can not ensure that the metal salt is completely precipitated in equal proportion in the process of metal salt coprecipitation, the uniformity of the prepared single crystal ternary particle size is poor, the surface residual alkali is high, the material is easy to absorb water in the processes of homogenizing and coating, the processing performance of slurry is poor, and the stability of the battery is poor. And the pH value of the prepared mixed solution is difficult to stably control, and bivalent manganese is easy to oxidize in an alkaline environment, so that the morphology of the precursor is influenced, the tap density of the material is reduced, and the like.
The method adopts water which is easy to dissolve metal salt to completely dissolve the metal mixed salt, the metal mixed salt exists in an ion form, and the step can ensure that the metal mixed salt is uniformly mixed on the ion level, reduce the use amount of other solvents and achieve the purpose of saving the cost; the invention further creatively selects the water-soluble solvents such as alcohols and the like, and adds the water-soluble solvents into the mixed salts, the insolubility of the metal mixed salts in the organic solvents, namely the weak solvation hydration of the metal salts in the solvents such as alcohols and the like, and the metal salts derived from ions such as nickel, cobalt, manganese and lithium are difficult to ionize in the organic solvents, so that the metal salts in the solvents exist in the form of colloid (the observation of enhanced Tyndall effect) or the metal mixed salts exist in the form of ion pairs, namely sol. And removing solvent molecules in the sol by heating and evaporation, gelatinizing the sol to form gel, and drying the gel to form dry gel. The step ensures the uniform mixing state of the metal mixed salt in the drying process, and avoids the problem of precipitation sequence caused by different solubilities of the nickel-cobalt-manganese metal salt; furthermore, the invention also ball-mills the dry gel to obtain gel dry powder, then uses a tablet press to press the gel dry powder and calcines the gel dry powder, and the process not only ensures that the metal mixed salt can be well mixed, but also ensures the close contact of the metal mixed salt, and is beneficial to the crystal forming and growing.
The method can ensure the uniform mixing of metal salts such as lithium, nickel, cobalt, manganese or aluminum and the like, ensures the distribution uniformity of all metal elements in the single crystal ternary precursor, and the prepared single crystal ternary cathode material has the advantages of single crystal structure, low specific surface area, concentrated particle size distribution, high stability and the like. The lower specific surface area can reduce the liquid contact interface between the electrode and the electrolysis, is beneficial to improving the high-temperature performance and the cycling stability of the battery and prolonging the service life; the positive electrode particles with the concentrated distribution of the particle sizes have higher mechanical strength and are not easy to break in the compaction process; higher cycling stability is more beneficial to the improvement of the safety performance of the battery. And the preparation process is simple, the cost is low, the environment is friendly, the precursor preparation does not need the assistance of other complex equipment, and the industrial production is easy to realize.
Experimental results show that the single crystal ternary cathode material prepared by the invention has higher mechanical strength, is not easy to break in the compaction process, and has the compaction density as high as 3.97g/cm3The specific surface area is 1.8-6.8 m2*g-1。
Drawings
FIG. 1 is an SEM scanning electron microscope image of a single-crystal Ni-Co-Mn ternary material prepared in example 1 of the present invention;
FIG. 2 is a view showing LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O2A charge-discharge curve graph of the half cell;
FIG. 3 is a view showing LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O22Cycle performance curve at high temperature of 60 ℃;
FIG. 4 is an SEM scanning electron microscope image of the single crystal Ni-Co-Mn ternary material prepared in example 2 of the present invention;
FIG. 5 is an SEM scanning electron microscope image of the single crystal Ni-Co-Mn ternary material prepared in comparative example 1 of the present invention.
Detailed Description
In order to further understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a ternary cathode material, which comprises the following steps:
1) mixing lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water to obtain a mixed solution;
2) ultrasonically mixing the mixed solution obtained in the step and an organic solvent which is mutually soluble with water, and heating to obtain dry gel;
3) grinding the dried gel obtained in the step to obtain gel dried powder;
4) and sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material.
Lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water are mixed to obtain mixed liquid.
The invention has no particular limitation on the specific type of the ternary cathode material in principle, and a person skilled in the art can select and adjust the ternary cathode material according to the application condition, the product performance and the quality requirement.
The proportion of the lithium salt, the manganese salt or the aluminum salt, the nickel salt and the cobalt salt is not particularly limited in principle, and the conventional proportion in the ternary cathode material well known to the skilled in the art can be adopted, and the skilled in the art can select and adjust the proportion according to the application condition, the product performance and the quality requirementxCoyMnzO2Where X + Y + Z is 1, the X, Y, Z ratio may be any one of 811, 622, 523, 111, 424, and 442. The chemical formula of the nickel-cobalt-aluminum ternary positive electrode material is preferably LiNixCoyAlzO2Where X + Y + Z is 1, the X, Y, Z ratio may be 8:1.5: 0.5.
The actual content of the lithium salt in the mixed solution is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the application condition, product performance and quality requirements, and the lithium salt is preferably an excess lithium salt, more specifically, the excess proportion is 1% to 10%, more preferably 3% to 8%, and more preferably 5% to 6%, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the uniformity and stability of the particle size, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The specific selection of the lithium salt is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the application, product performance and quality requirements, and the lithium salt preferably includes a soluble lithium salt, more preferably includes one or more of lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide and lithium oxalate, and more preferably includes lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide or lithium oxalate, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the uniformity and stability of the particle size, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The specific selection of the manganese salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, and the invention is to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The specific selection of the aluminum salt is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the application, product performance and quality requirements, and the invention is to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery, and the aluminum salt preferably comprises a soluble aluminum salt, more preferably comprises one or more of aluminum nitrate, aluminum hydroxide and aluminum sulfate, and more preferably comprises aluminum nitrate, aluminum hydroxide or aluminum sulfate.
The specific selection of the nickel salt is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to application conditions, product performance and quality requirements, and the invention is to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The specific selection of the mixed solution is not particularly limited in principle, and a person skilled in the art can select and adjust the mixed solution according to the application condition, the product performance and the quality requirement, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery, the mixed solution preferably comprises a saturated mixed solution, more preferably a 50-100% saturated mixed solution, also can be a 60-90% saturated mixed solution, and also can be a 70-80% saturated mixed solution. The invention adopts saturated mixed solution or high-concentration mixed solution, can more effectively make the system enter a colloid state, and reduces the time and energy consumption of subsequent evaporation.
The concentration of the metal salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better ensured, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the concentration of the metal salt in the mixed solution is preferably 0.5-2 mol/L, more preferably 0.8-1.7 mol/L, and more preferably 1.1-1.4 mol/L.
The concentration of the lithium salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and in the mixed solution, the concentration of the lithium salt is preferably 0.5-2 mol/L, more preferably 0.8-1.7 mol/L, and more preferably 1.1-1.4 mol/L.
The concentration of the manganese salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the concentration of the manganese salt in the mixed solution is preferably 0.1-0.4 mol/L, more preferably 0.15-0.35 mol/L, and more preferably 0.2-0.3 mol/L.
The concentration of the cobalt salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better ensured, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the concentration of the cobalt salt in the mixed solution is preferably 0.17-0.67 mol/L, more preferably 0.27-0.57 mol/L, and more preferably 0.37-0.47 mol/L.
The concentration of the nickel salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better ensured, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the concentration of the nickel salt in the mixed solution is preferably 0.25-1 mol/L, more preferably 0.4-0.85 mol/L, and more preferably 0.55-0.6 mol/L.
The concentration of the aluminum salt is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the concentration of the aluminum salt in the mixed solution is preferably 0.1-0.4 mol/L, more preferably 0.15-0.35 mol/L, and more preferably 0.2-0.3 mol/L.
The mixed solution obtained in the step and the organic solvent which is mutually soluble with water are ultrasonically mixed and heated to obtain the xerogel.
The definition of the xerogel is not particularly limited in principle, and can be selected and adjusted by the skilled person according to the application condition, product performance and quality requirements.
The specific selection of the water-miscible organic solvent is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to application conditions, product performance and quality requirements, and the invention is to better ensure the structure of the single-crystal ternary cathode material, reduce the specific surface area, and improve the uniformity and stability of particle size, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The invention has no special limitation on the adding amount of the organic solvent mutually soluble with water in principle, and a person skilled in the art can select and adjust the organic solvent according to the application condition, the product performance and the quality requirement, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area and improve the uniformity and the stability of the particle size, thereby improving the mechanical strength and the cycling stability of the lithium battery, the volume ratio of the organic solvent mutually soluble with water to the water is preferably (1-9): 1, more preferably (2.5 to 7.5): 1, more preferably (4-6): 1.
the specific mode of ultrasonic mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the application condition, the product performance and the quality requirement.
The frequency of the ultrasonic mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the frequency of the ultrasonic mixing is preferably 30-50 KHz, more preferably 33-47 KHz, more preferably 36-44 KHz, and more preferably 39-41 KHz.
The rotating speed of the ultrasonic mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the rotating speed of the ultrasonic mixing is preferably 200-500 r/min, more preferably 250-450 r/min, and more preferably 300-400 r/min.
The time for ultrasonic mixing is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the time for ultrasonic mixing is preferably 10-180 min, more preferably 40-150 min, and more preferably 70-120 min, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the uniformity and stability of particle size, thereby improving the mechanical strength and the cycle stability of the lithium battery.
The heating temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the heating temperature is preferably 30-100 ℃, more preferably 40-90 ℃, more preferably 50-80 ℃, and more preferably 60-70 ℃.
The invention is a complete and refined preparation process, better ensures the structure of the single crystal ternary cathode material, reduces the specific surface area, and improves the uniformity and the stability of the granularity, thereby improving the mechanical strength and the cycling stability of the lithium battery. The drying temperature is preferably 60-120 ℃, more preferably 70-110 ℃, and more preferably 80-100 ℃.
The invention adopts water and a specific organic system to form a gel system, has obvious difference and advantages compared with the conventional sol-gel method, forms gel without complexing different metal ions by virtue of a complexing agent, does not need a precipitator, a pH regulator or a complexing agent, effectively solves the uneven condition existing in the complexing and precipitating processes, simplifies the preparation steps and the control steps, and solves the instability and the side effect existing in the pH value control process of the existing precipitation method and the gel method. The invention adopts water as a system solvent, acetate is weak in solvation hydration in ethanol due to insolubility in an organic solvent (such as ethanol and the like), the acetate is difficult to ionize in the ethanol and is self-derived ions, and the acetate of nickel, cobalt, manganese or aluminum and lithium exists in the ethanol in a colloid form (observed through the Tyndall effect), namely the sol, solvent molecules in the sol are removed through heating and evaporation, the sol is gelatinized, and the gel is dried to form xerogel.
The invention effectively solves the problems that in the prior art, oxalic acid is used as a precipitator or a complexing agent, the pH value is adjusted by ammonia water (the pH value can also be considered as the complexing agent), and the sol-gel method is biased to a coprecipitation method, wherein nickel oxalate, cobalt oxalate and manganese oxalate are all metal salts which are difficult to dissolve in water, and after the oxalic acid is added, the generated precipitation ions of the nickel oxalate, the cobalt oxalate and the manganese are easy to perform secondary agglomeration to form larger secondary particles, which is not beneficial to subsequent treatment; but also has the problems of large smell, environment harmlessness, high subsequent treatment cost and the like of the used ammonia water.
Meanwhile, the invention also solves the problems that in the prior art, citric acid is used as a complexing agent, ammonia water is used as a pH regulator, and a solvent system is deionized water, and the problems that in the existing system, citric acid is used as a ligand, the complexing capability in an acidic solution is poor, the complexing capability is enhanced along with the increase of the pH of the solution system, but a metal hydroxide precipitate is generated in an alkaline solution, and the citric acid is used as the complexing agent, so that the operation is complex, and the complexing stability is difficult to control.
The invention further grinds the xerogel obtained in the step to obtain the gel dry powder.
The grinding mode is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements.
The fineness of the gel dry powder is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of a lithium battery are improved, and the fineness of the gel dry powder is preferably 1-10 micrometers, more preferably 3-8 micrometers, and more preferably 5-6 micrometers.
The grinding time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the grinding time is preferably 10-180 min, more preferably 40-150 min, and more preferably 70-120 min.
The invention is a complete and refined preparation process, better ensures the structure of the single crystal ternary anode material, reduces the specific surface area, and improves the uniformity and the stability of the granularity, thereby improving the mechanical strength and the cycling stability of the lithium battery, and the preferable step after grinding also comprises a tabletting step.
The invention has no special limitation on the pressure of the tabletting in principle, and a person skilled in the art can select and adjust the pressure according to the application condition, the product performance and the quality requirement, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery, the pressure of the tabletting is preferably 3.0-6.0 MPa, more preferably 3.5-5.5 MPa, and more preferably 4-5 MPa.
The tabletting time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the tabletting time is preferably 1-5 min, more preferably 1.5-4.5 min, more preferably 2-4 min, and more preferably 2.5-3.5 min, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery.
Finally, sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material.
The invention is not particularly limited in principle to the specific manner of sintering, and can be selected and adjusted by those skilled in the art according to the application condition, product performance and quality requirements, and the invention is to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area, and improve the uniformity and stability of the particle size, thereby improving the mechanical strength and the cycle stability of the lithium battery, wherein the sintering preferably comprises low-temperature sintering and high-temperature sintering, and more preferably comprises low-temperature sintering and high-temperature sintering.
The heating rate of the low-temperature sintering is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single-crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the heating rate of the low-temperature sintering is preferably 3-8 ℃/min, more preferably 4-7 ℃/min, and more preferably 5-6 ℃/min.
The low-temperature sintering temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single-crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the low-temperature sintering temperature is preferably 300-600 ℃, more preferably 350-550 ℃, and more preferably 400-500 ℃.
The time of the low-temperature sintering is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single-crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the time of the low-temperature sintering is preferably 3-8 hours, more preferably 4-7 hours, and more preferably 5-6 hours.
The temperature rise rate of the high-temperature sintering is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single-crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the temperature rise rate of the high-temperature sintering is preferably 1-10 ℃/min, more preferably 3-8 ℃/min, and more preferably 5-6 ℃/min.
The high-temperature sintering temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the high-temperature sintering temperature is preferably 800-1000 ℃, more preferably 830-970 ℃, more preferably 860-940 ℃, and more preferably 890-910 ℃.
The time of the high-temperature sintering is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single-crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the time of the high-temperature sintering is preferably 5-20 hours, more preferably 8-17 hours, and more preferably 11-14 hours.
The invention has no special limitation on the annealing cooling rate in principle, and a person skilled in the art can select and adjust the cooling rate according to the application condition, the product performance and the quality requirement, in order to better ensure the structure of the single crystal ternary cathode material, reduce the specific surface area and improve the particle size uniformity and stability, thereby improving the mechanical strength and the cycle stability of the lithium battery, the annealing cooling rate is preferably 1-5 ℃/min, more preferably 1.5-4.5 ℃/min, more preferably 2-4 ℃/min, and more preferably 2.5-3.5 ℃/min.
The annealing temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the annealing temperature is preferably 500-750 ℃, more preferably 550-700 ℃, and more preferably 600-650 ℃.
The annealing time is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to application conditions, product performance and quality requirements, the structure of the single crystal ternary cathode material is better guaranteed, the specific surface area is reduced, and the particle size uniformity and stability are improved, so that the mechanical strength and the cycle stability of the lithium battery are improved, and the annealing time is preferably 5-15 hours, more preferably 7-13 hours, and more preferably 9-11 hours.
The specific selection of the ternary cathode material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the application condition, the product performance and the quality requirement.
The invention provides a ternary lithium ion battery which comprises a ternary cathode material prepared by the preparation method in any one of the technical schemes.
The invention provides a preparation method of a single crystal ternary cathode material and a ternary lithium ion battery. The method adopts water which is easy to dissolve metal salt to completely dissolve the metal mixed salt, the metal mixed salt exists in an ion form, and the step can ensure that the metal mixed salt is uniformly mixed on the ion level, reduce the use amount of other solvents and achieve the purpose of saving the cost; the invention further creatively selects the water-soluble solvents such as alcohols and the like, and adds the mixed salts, the insolubility of the metal mixed salts in the organic solvents, namely the weak solvation hydration of the metal salts in the solvents such as alcohols and the like, and the metal salts derived from ions such as nickel, cobalt, manganese and lithium are difficult to ionize in the organic solvents, so that the metal salts in the solvents exist in the form of colloid (observed by the Tyndall effect) or the metal mixed salts are considered to exist in the form of ion pairs, namely sol. And removing solvent molecules in the sol by heating and evaporation, gelatinizing the sol to form gel, and drying the gel to form dry gel. The step ensures the uniform mixing state of the metal mixed salt in the drying process, and avoids the problem of precipitation sequence caused by different solubilities of the nickel-cobalt-manganese metal salt; furthermore, the invention also ball-mills the dry gel to obtain gel dry powder, then uses a tablet press to press the gel dry powder and calcines the gel dry powder, and the process not only ensures that the metal mixed salt can be well mixed, but also ensures the close contact of the metal mixed salt, and is beneficial to the crystal forming and growing.
The method can ensure the uniform mixing of metal salts such as lithium, nickel, cobalt, manganese or aluminum and the like, ensures the distribution uniformity of all metal elements in the single crystal ternary precursor, and the prepared single crystal ternary cathode material has the advantages of single crystal structure, low specific surface area, concentrated particle size distribution, high stability and the like. The lower specific surface area can reduce the liquid contact interface between the electrode and the electrolysis, is beneficial to improving the high-temperature performance and the cycling stability of the battery and prolonging the service life; the positive electrode particles with the concentrated distribution of the particle sizes have higher mechanical strength and are not easy to break in the compaction process; higher cycling stability is more beneficial to the improvement of the safety performance of the battery. And the preparation process is simple, the cost is low, the environment is friendly, the precursor preparation does not need the assistance of other complex equipment, and the industrial production is easy to realize.
Experimental results show that the single crystal ternary cathode material prepared by the invention has higher mechanical strength, is not easy to break in the compaction process, and has the compaction density as high as 3.97g/cm3The specific surface area is 1.8-6.8 m2*g-1。
For further illustration of the present invention, the following will describe the preparation method of a ternary cathode material and the ternary lithium ion battery in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
The starting materials in the following examples are all commercially available products.
Example 1
(1) Dissolving lithium acetate, nickel acetate, manganese acetate and cobalt acetate in 50ml of deionized water according to a fixed ratio of 1.02:0.5:0.2:0.3, wherein the preparation concentration of metal salt is 2.0mol/L, and ultrasonically stirring until the mixture solution is in a clear and transparent state; subsequently, 150ml of ethanol was added, and the mixture was stirred with constant ultrasound without precipitation and slowly thickened until the solution became toothpaste-like.
(2) Heating the paste prepared in the step (1) in a vacuum oven at 80 ℃ to obtain dry gel, and placing the dry gel in a ball mill to perform ball milling for 10min at the rotating speed of 500 r/min;
(3) and (3) putting the gel dry powder obtained in the step (2) into a tablet press for pressing, wherein the pressure of the tablet press is 4.5Mpa, and the pressure maintaining time is 150 s.
(4) Heating the precursor pressed into tablets to 500 ℃ at the heating rate of 3 ℃/min, and preserving the heat for 6 hours; then heating to 950 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 12 hours; then cooling to 700 ℃ at a cooling rate of 3 ℃/min, preserving heat for 6h, finally naturally cooling, and cooling to room temperature to prepare the LiNi with the single crystal morphology0.5Co0.2Mn0.3O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 1 of the present invention0.5Co0.2Mn0.3O2And (5) characterizing the ternary cathode material.
Referring to fig. 1, fig. 1 is an SEM scanning electron microscope image of the single crystal nickel-cobalt-manganese ternary material prepared in example 1 of the present invention.
As can be seen from FIG. 1, the single crystal nickel-cobalt-manganese ternary material prepared by the method has uniform particle size distribution and regular morphology, is beneficial to forming a compact and stable SEI film, reduces the occurrence of side reactions, and improves the cycling stability of the battery.
LiNi with single crystal morphology prepared in example 1 of the present invention0.5Co0.2Mn0.3O2Ternary cathode material progressivityCan be detected.
Referring to FIG. 2, FIG. 2 shows LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O2Charge and discharge curves of the half-cell.
Referring to FIG. 3, FIG. 3 is a view showing LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O22Cycle performance curve at high temperature of 60 ℃.
Relevant electrochemical performance test of ternary cathode material
(1) The single crystal ternary materials prepared in examples 1 to 4 and comparative examples 1 to 3 were used as positive electrode active materials, respectively, and were mixed with acetylene black and PVDF in a mass ratio of 90:5:5, and N-methyl pyrrolidone (NMP) was added to prepare black slurry.
(2) The prepared slurry is uniformly coated on the surface of an aluminum foil, and the aluminum foil is placed in a vacuum drying oven to be dried for 12 hours at 120 ℃ to prepare a wafer with the diameter of 14mm as a positive electrode. The positive plate, the negative plate (metal lithium plate with the diameter of 14.5 mm), the diaphragm and the electrolyte (1mo1/LLIPF6/EC + DMC (volume ratio of 1: 1)) are assembled into a CR2025 button cell in a glove box filled with argon. And (3) carrying out an electrochemical performance test after the battery is kept stand for 12h, wherein the charging and discharging voltage range is 2.8-4.2V, the temperature is kept at 25 ℃, and the test results are shown in Table 1.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
TABLE 1
As can be seen from the test results in table 1, compared with the conventional comparative example, the single crystal ternary cathode material prepared by the present embodiment has good processability, is not easily broken during rolling, and has high compaction density; it has a higher discharge capacity at discharge; meanwhile, the single crystal ternary particles have good structural stability, can avoid excessive corrosion of electrolyte and prolong the cycle life of the battery.
Example 2
The preparation method of the single crystal ternary cathode material provided in this embodiment 2 is the same as the preparation method of the single crystal ternary cathode material provided in the above embodiment 1, except that the lithium acetate, the nickel acetate, the manganese acetate, and the cobalt acetate are mixed according to a molar ratio of 1.05:0.5:0.2:0.3, so as to prepare the LiNi material having a single crystal morphology0.5Co0.2Mn0.3O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 1 of the present invention0.5Co0.2Mn0.3O2And (5) characterizing the ternary cathode material.
Referring to fig. 4, fig. 4 is an SEM scanning electron microscope image of the single crystal nickel-cobalt-manganese ternary material prepared in example 2 of the present invention.
As can be seen from FIG. 4, the single crystal nickel-cobalt-manganese ternary material prepared by the method has uniform particle size distribution and regular morphology, is more favorable for forming a compact and stable SEI film, reduces the occurrence of side reactions, and improves the cycling stability of the battery.
LiNi with single crystal morphology prepared in example 2 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to FIG. 2, FIG. 2 shows LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O2Charge and discharge curves of the half-cell.
Referring to FIG. 3, FIG. 3 is a view showing LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O22Cycle performance curve at high temperature of 60 ℃.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Example 3
The single crystal ternary cathode material provided in this example 3 is prepared by the following methodThe difference from the preparation method of the single crystal ternary cathode material provided in the above embodiment 1 is that lithium acetate, nickel acetate, manganese acetate and cobalt acetate are mixed according to a molar ratio of 1.05:0.6:0.2:0.2, and thereby the single crystal-shaped LiNi material can be prepared0.6Co0.2Mn0.2O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 3 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Example 4
The preparation method of the single crystal ternary cathode material provided in this embodiment 4 is the same as the preparation method of the single crystal ternary cathode material provided in embodiment 1, except that the lithium acetate, the nickel acetate, the manganese acetate, and the cobalt acetate are mixed according to a molar ratio of 1.05:0.8:0.1:0.1, so as to prepare the LiNi material having a single crystal morphology0.8Co0.1Mn01O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 4 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Example 5
The preparation method of the single crystal ternary cathode material provided in this embodiment 5 is the same as the preparation method of the single crystal ternary cathode material provided in embodiment 1, except that the organic solvent ethanol used in this embodiment is replaced by methanol, and other conditions are not changed, so that LiNi in a single crystal morphology can be prepared0.5Co0.2Mn0.3O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 5 of the present invention0.5Co0.2Mn0.3O2Performance of ternary cathode materialAnd (6) detecting.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Example 6
The preparation method of the single crystal ternary cathode material provided in this embodiment 6 is the same as the preparation method of the single crystal ternary cathode material provided in embodiment 1, except that the metal salts lithium acetate, nickel acetate, manganese acetate, and cobalt acetate in this embodiment are replaced with lithium nitrate, nickel nitrate, manganese nitrate, and cobalt nitrate, so as to prepare the LiNi with a single crystal morphology0.5Co0.2Mn0.3O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 6 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Example 7
The preparation method of the single crystal ternary cathode material provided in this embodiment 7 is the same as the preparation method of the single crystal ternary cathode material provided in embodiment 1, except that the lithium acetate, the nickel acetate, the manganese acetate, and the aluminum nitrate are mixed according to a molar ratio of 1.05:0.8:0.15:0.05, so as to prepare the LiNi material having a single crystal morphology0.8Co0.15Al0.05O2A ternary positive electrode material.
LiNi with single crystal morphology prepared in example 7 of the present invention0.8Co0.15Al0.05O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Comparative example 1
(1) Uniformly mixing three metal salts of nickel acetate, cobalt acetate and manganese acetate according to a molar ratio of 5:2:3 to obtain a mixed solution A of 2.0 mol/L; weighing 200g and 340g of sodium hydroxide solution with the concentration of 40% and deionized water respectively, and uniformly stirring to obtain a mixed solution B; weighing 100g of 25% concentrated ammonia water and 200g of deionized water, and uniformly stirring to obtain a mixed solution C.
(2) 250g, 350g and 100g of the mixed solution A, B, C are respectively weighed, 2000g of deionized water is added into a reactor, A, B, C is added into a reaction kettle at the same time, and the stirring speed of the reaction kettle is controlled to be 900 rpm/min. And introducing nitrogen for protection in the reaction process, wherein the flow is 25L/min, the reaction temperature is 80 ℃, the pH is controlled to be 12, and the reaction time is 45 h. And then, carrying out suction filtration, washing and drying on the slurry to obtain a precursor.
(3) 300g of lithium acetate and the precursor were weighed and mixed according to a molar ratio of 1.05:1, and 0.9g of boron oxide was added simultaneously.
(4) Putting the uniformly mixed material into an atmosphere furnace for calcination at 950 ℃ for 12h, and preparing the LiNi with the single crystal morphology after calcination0.5Co0.2Mn0.3O2A ternary positive electrode material.
LiNi having single crystal morphology prepared for comparative example 1 of the present invention0.5Co0.2Mn0.3O2And (5) characterizing the ternary cathode material.
Referring to fig. 5, fig. 5 is an SEM scanning electron microscope image of the single crystal nickel-cobalt-manganese ternary material prepared in comparative example 1 of the present invention.
As can be seen from FIG. 5, the grain size distribution of the single crystal nickel-cobalt-manganese ternary material prepared by the method is uneven, the aggregation phenomenon is obvious, a typical nano-microstructure is formed, the grain size of the structure is small, the surface of an electrode is easy to be corroded by electrolyte, and the cycle performance and the safety performance of a battery are influenced.
LiNi having single crystal morphology prepared for comparative example 1 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to FIG. 2, FIG. 2 shows LiNi prepared in examples 1 and 2 of the present invention and comparative example 10.5Co0.2Mn0.3O2Charge and discharge curves of the half-cell.
Referring to FIG. 3, FIG. 3 shows examples 1, 2 and 3 of the present inventionLiNi prepared in comparative example 10.5Co0.2Mn0.3O22Cycle performance curve at high temperature of 60 ℃.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Comparative example 2
The preparation method of the single crystal ternary cathode material provided by the comparative example 2 is the same as the preparation method of the single crystal ternary cathode material provided by the comparative example 1, except that nickel acetate, manganese acetate and cobalt acetate are mixed according to the molar ratio of 0.6:0.2:0.2 to prepare the LiNi with the single crystal morphology0.6Co0.2Mn0.2O2A ternary positive electrode material.
LiNi having single crystal morphology prepared for comparative example 2 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
Comparative example 3
The preparation method of the single crystal ternary cathode material provided by the comparative example 3 is the same as the preparation method of the single crystal ternary cathode material provided by the comparative example 1, except that nickel acetate, manganese acetate and cobalt acetate are mixed according to the molar ratio of 0.8:0.1:0.1 to prepare the LiNi with the single crystal morphology0.8Co0.1Mn0.1O2A ternary positive electrode material.
LiNi having single crystal morphology prepared for comparative example 3 of the present invention0.5Co0.2Mn0.3O2And (5) carrying out performance detection on the ternary cathode material.
Referring to table 1, table 1 shows electrochemical performance test results of the ternary cathode materials prepared in the examples of the present invention and the comparative examples.
The foregoing detailed description of the method for preparing a single crystal ternary cathode material and a ternary lithium ion battery provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate the understanding of the method and its core ideas, including the best mode, of the present invention and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The preparation method of the ternary cathode material is characterized by comprising the following steps of:
1) mixing lithium salt, manganese salt or aluminum salt, nickel salt, cobalt salt and water to obtain a mixed solution;
2) ultrasonically mixing the mixed solution obtained in the step and an organic solvent which is mutually soluble with water, and heating to obtain dry gel;
3) grinding the dried gel obtained in the step to obtain gel dried powder;
4) and sintering and annealing the gel dry powder obtained in the step to obtain the ternary cathode material.
2. The method of claim 1, wherein the lithium salt comprises one or more of lithium acetate, lithium carbonate, lithium nitrate, lithium hydroxide, and lithium oxalate;
the manganese salt comprises one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese hydroxide, manganese sulfate and manganese oxalate;
the aluminum salt comprises one or more of aluminum nitrate, aluminum hydroxide and aluminum sulfate;
the nickel salt comprises one or more of manganese acetate, manganese nitrate, manganese carbonate, manganese hydroxide, manganese sulfate and manganese oxalate.
3. The method according to claim 1, wherein the mixed solution comprises a saturated mixed solution;
the lithium salt is an excess lithium salt;
the excess proportion is 1 to 10 percent;
in the mixed solution, the concentration of the metal salt is 0.5-2 mol/L.
4. The method according to claim 1, wherein the concentration of the lithium salt in the mixed solution is 0.5 to 2 mol/L;
in the mixed solution, the concentration of the manganese salt is 0.1-0.4 mol/L;
in the mixed solution, the concentration of the cobalt salt is 0.17-0.67 mol/L;
in the mixed solution, the concentration of the nickel salt is 0.25-1 mol/L;
in the mixed solution, the concentration of the aluminum salt is 0.1-0.4 mol/L;
the xerogel is a precursor of the ternary cathode material.
5. The method of claim 1, wherein the water-miscible organic solvent comprises one or more of an alcohol, an aldehyde, a ketone, and an ester solvent;
the volume ratio of the organic solvent mutually soluble with water to the water is (1-9): 1;
the ultrasonic mixing is ultrasonic stirring and mixing;
the frequency of ultrasonic mixing is 30-50 KHz;
the rotating speed of the ultrasonic mixing is 200-500 r/min;
the ultrasonic mixing time is 10-180 min.
6. The method of claim 1, wherein the water-miscible organic solvent comprises one or more of ethanol, methanol, ethylene glycol, glycerol, formaldehyde, and acetone;
the heating temperature is 30-100 ℃;
after heating, continuously carrying out ultrasonic mixing, wherein the mixed system does not precipitate and gradually becomes viscous until the solution is in a toothpaste state to obtain gel, and drying to obtain dry gel;
the grinding mode comprises ball milling;
the fineness of the gel dry powder is 1-10 mu m.
7. The method according to claim 1, wherein the grinding time is 10 to 180 min;
the step of tabletting is also included after grinding;
the pressure of the tablet is 3.0-6.0 Mpa;
the tabletting time is 1-5 min;
the sintering includes low-temperature sintering and high-temperature sintering.
8. The preparation method according to claim 7, wherein the heating rate of the low-temperature sintering is 3-8 ℃/min;
the temperature of the low-temperature sintering is 300-600 ℃;
the low-temperature sintering time is 3-8 h;
the heating rate of the high-temperature sintering is 1-10 ℃/min;
the temperature of the high-temperature sintering is 800-1000 ℃;
the high-temperature sintering time is 5-20 h.
9. The method according to any one of claims 1 to 8, wherein the temperature reduction rate of the annealing is 1 to 5 ℃/min;
the annealing temperature is 500-750 ℃;
the annealing time is 5-15 h;
the ternary cathode material is a single crystal ternary cathode material;
the ternary positive electrode material includes NCM or NCA.
10. A ternary lithium ion battery, which is characterized by comprising the ternary cathode material prepared by the preparation method of any one of claims 1 to 9.
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