CN116169267A - V (V) 2 O 5 Coated modified lithium-rich positive electrode material, and preparation method and application thereof - Google Patents
V (V) 2 O 5 Coated modified lithium-rich positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN116169267A CN116169267A CN202310144003.1A CN202310144003A CN116169267A CN 116169267 A CN116169267 A CN 116169267A CN 202310144003 A CN202310144003 A CN 202310144003A CN 116169267 A CN116169267 A CN 116169267A
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- lithium
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- cathode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 62
- 150000002641 lithium Chemical class 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 112
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 79
- 239000010406 cathode material Substances 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 59
- 239000011572 manganese Substances 0.000 claims description 51
- 238000005245 sintering Methods 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- 239000008139 complexing agent Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- 229910052720 vanadium Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000010405 anode material Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000975 co-precipitation Methods 0.000 claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011363 dried mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 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
- 239000012798 spherical particle Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071257 lithium acetate Drugs 0.000 claims description 3
- 229940008015 lithium carbonate Drugs 0.000 claims description 3
- 229940006114 lithium hydroxide anhydrous Drugs 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 28
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 241000080590 Niso Species 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 229910015118 LiMO Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- NPDXHCPLBBTVKX-UHFFFAOYSA-K [Zr+4].P(=O)([O-])([O-])[O-].[Li+] Chemical compound [Zr+4].P(=O)([O-])([O-])[O-].[Li+] NPDXHCPLBBTVKX-UHFFFAOYSA-K 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 241000669618 Nothes Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present disclosure relates to a V 2 O 5 The coated modified lithium-rich positive electrode material comprises a lithium-rich positive electrode material and a metal oxide layer coated on the surface of the lithium-rich positive electrode material; the chemical formula of the lithium-rich positive electrode material is shown as the formula (I): li (Li) a Ni x Co y M z O 2 Wherein a is more than or equal to 1.13 and less than or equal to 1.27,0.10 and x is more than or equal toY is more than or equal to 0.30,0.04 and less than or equal to 0.12,0.45 and less than or equal to 0.59,0.73 and less than or equal to x+y+z is more than or equal to 0.87, M comprises Mn and Cu, and the molar ratio of Mn to Cu is 3-117: 1, a step of; the metal oxide layer includes V 2 O 5 . By elemental doping and V of the present disclosure 2 O 5 Coating the prepared V 2 O 5 The coated high-lithium-rich positive electrode material has higher first coulombic efficiency and rate capability and better stability.
Description
Technical Field
The present disclosure relates to the field of lithium ion battery positive electrode material preparation, and in particular, to a V 2 O 5 Coated modified lithium-rich positive electrode material, and a preparation method and application thereof.
Background
With the development of science and technology, energy shortage and environmental crisis are gradually developed, and people start to study the development of green energy. For the current commercialized positive and negative electrode materials, it is difficult to achieve high specific energy by optimizing the positive and negative electrode ratio, and the positive electrode material is a bottleneck limiting the improvement of the energy density of the battery, so it is necessary to use a positive electrode material having a higher capacity to improve the energy density of the battery. The lithium-rich manganese-based positive electrode material has the advantages of high theoretical specific capacity, low production cost, environmental protection and the like, and becomes a hot spot for people to study.
The first charge curve of the lithium-rich positive electrode material is different from that of a common ternary material, two different charge platforms are arranged, an S-shaped charge platform before the lithium-rich positive electrode material is charged to 4.5V is correspondingly LiMO 2 Li in (III) + Is accompanied by the release of (1)With transition metal Ni 2 + /Ni 4+ 、Co 3+ /Co 4+ Is consistent with the lithium intercalation and deintercalation mechanism of the ternary cathode material; when the charging voltage is higher than 4.5V, a very gentle L-shaped charging platform appears, li 2 MnO 3 The phase is activated to release Li + Forming active layered oxide MnO 2 High oxidizing property, causing oxygen to be separated out from the surface of the material, and Li 2 MnO 3 Activation of the phase provides additional high specific discharge capacity. Subsequently during discharge, due to Li 2 MnO 3 Oxygen vacancy moieties formed after phase oxygen removal are partially bound by LiMO 2 The transition metal ions of the phase occupy, so that Li is taken out + Not all intercalating back into the material, which results in a first coulombic inefficiency of the lithium-rich material. In addition, li in the lithium-rich material 2 MnO 3 The phase has poor electron conductivity and Li + Diffusion coefficient, a CEI film is formed during cycling and a very large charge transfer resistance is created at the material/electrolyte interface.
Therefore, the lithium-rich material has low coulombic efficiency for the first time and poor rate capability, and the like, which restrict the practical application. To solve these problems, coating methods are often used to improve the properties of the material. For example, the invention patent with the patent number of CN111952562A discloses a lithium-rich material coated by lithium zirconium phosphate, which is prepared by a sol-gel method and then coated by lithium zirconium phosphate, so that the 1C rate charge and discharge performance of the material is improved. However, the prior art still has the defect of low specific discharge capacity.
Disclosure of Invention
The purpose of the present disclosure is to provide a V 2 O 5 Coated modified lithium-rich positive electrode material, preparation method and application thereof, V prepared by method 2 O 5 The coated modified lithium-rich positive electrode material has good stability and high first coulombic efficiency and rate capability.
To achieve the above object, a first aspect of the present disclosure provides a V 2 O 5 The modified lithium-rich positive electrode material comprises a lithium-rich positive electrode material and a lithium-rich positive electrode coated on the lithium-rich positive electrode materialA metal oxide layer on the surface of the electrode material; the chemical formula of the lithium-rich positive electrode material is shown as the formula (I): li (Li) a Ni x Co y M z O 2 Wherein a is more than or equal to 1.13 and less than or equal to 1.27,0.10, x is more than or equal to 0.30,0.04 and y is more than or equal to 0.12,0.45 and z is more than or equal to 0.59,0.73, x+y+z is more than or equal to 0.87, and M comprises Mn and Cu; the metal oxide layer includes V 2 O 5 。
Optionally, the chemical formula of the lithium-rich positive electrode material is shown as formula (I): li (Li) a Ni x Co y M z O 2 (Ⅰ)，1.183≤a≤1.212，0.175≤x≤0.225，0.070≤y≤0.090，0.502≤z≤0.538，0.788≤x+y+z≤0.817；
Optionally, in the lithium-rich cathode material, the molar ratio of Mn to Cu is 3 to 117:1, preferably 8 to 21:1.
optionally, the metal oxide layer is present in an amount of 0.10 to 9.10 wt%, preferably 3.38 to 5.21 wt%, based on the total weight of the modified lithium-rich cathode material; optionally, the weight ratio of the lithium-rich cathode material to the metal oxide layer is 1:0.001 to 0.100, preferably 1:0.035 to 0.055;
optionally, the thickness of the metal oxide layer is 1-15 nm, preferably 5-12 nm;
the modified lithium-rich positive electrode material is a granular material, preferably spherical particles, and the average particle size of the granular material is 10-20 mu m, preferably 13-16 mu m.
A second aspect of the present disclosure provides a method of preparing V 2 O 5 A method of coating a modified lithium-rich cathode material, the method comprising the steps of:
s1, mixing a nickel source, a cobalt source, a manganese source, a copper source and deionized water to obtain a metal mixed solution;
s2, contacting the metal mixed solution, the precipitant and the complexing agent for coprecipitation reaction to obtain a precipitation precursor;
s3, contacting the precipitation precursor with a lithium source, and performing first sintering to obtain a lithium-rich anode material;
and S4, contacting the lithium-rich anode material with a vanadium source, and performing second sintering.
Optionally, in step S1, the molar ratio of the nickel source, the cobalt source, the manganese source and the copper source is (0.100 to 0.300) in terms of metal element: (0.040-0.120): (0.350-0.590): (0.005-0.100); preferably (0.175 to 0.225): (0.070-0.090): (0.447 to 0.513): (0.025-0.055);
the total concentration of metal ions in the metal mixed solution is 0.5-3 mol/L, preferably 1.5-2.2 mol/L;
optionally, the nickel source is a soluble salt of nickel, preferably, the nickel source is selected from one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate;
optionally, the cobalt source is a soluble salt of cobalt, preferably, the cobalt source is one or more selected from cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate;
optionally, the manganese source is a soluble salt of manganese, preferably, the manganese source is selected from one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate;
optionally, the copper source is selected from one or more of copper sulfate pentahydrate, copper chloride and copper nitrate.
Optionally, in step S2, the precipitant and the complexing agent are used in the form of aqueous solutions with a concentration of 1-5 mol/L and 2-15 mol/L, respectively, the precipitant is selected from one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the complexing agent includes ammonia water;
preferably, step S2 includes: adding a metal mixed solution, a precipitator and a complexing agent into a reaction kettle in a three-solution parallel flow mode by taking the complexing agent as a substrate to contact for coprecipitation reaction;
optionally, the flow rate of the metal mixed solution is 5-15 mL/min, the flow rate of the precipitant is 0.5-45 mL/min, and the flow rate of the complexing agent is 0.35-15 mL/min;
optionally, the reaction conditions of the coprecipitation reaction include: the temperature is 45-70 ℃, preferably 50-65 ℃; the pH is 7.5-9.5, preferably 7.8-8.5; the time is 10 to 50 hours, preferably 24 to 40 hours;
optionally, the method further comprises: aging the product obtained by the coprecipitation reaction for 6-12 hours at 15-30 ℃; and then carrying out centrifugal treatment, washing treatment and drying treatment to obtain the precipitate precursor.
Optionally, in step S3, the molar ratio of the precursor to lithium is 1, calculated as metal element: (1.30 to 1.74), preferably 1: (1.40-1.60);
optionally, the lithium source is selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate;
optionally, in step S3, the first sintering includes two-stage sintering; wherein the conditions of the first stage sintering include: heating to 450-680 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 4-15 h; the conditions for the second stage sintering include: heating to 800-980 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 10-20 h;
preferably, the conditions of the first stage sintering include: heating to 500-600 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 5-10 h; the conditions for the second stage sintering include: heating to 830-950 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 12-15 h;
wherein the first sintering is performed under an air atmosphere.
Optionally, in step S4, the vanadium source is selected from one or more of ammonium metavanadate and vanadium pentoxide; optionally, the vanadium source is used in the form of an aqueous and/or alcoholic solution;
preferably, the weight ratio of the vanadium source to the lithium-rich cathode material is 0.005-0.129: 1, preferably 0.045 to 0.071:1, a step of;
preferably, in step S4, the second sintering condition includes: the temperature is 300-600 ℃, preferably 400-500 ℃; the time is 3 to 12 hours, preferably 4 to 8 hours;
wherein the second sintering is performed under an air atmosphere;
optionally, the method comprises: carrying out ultrasonic mixing on the lithium-rich anode material and a vanadium source; stirring the mixed solution after the ultrasonic treatment at a constant temperature of 50-90 ℃ to remove the solvent; drying at 60-80 deg.c for 4-10 hr; and carrying out the second sintering on the dried mixture.
A third aspect of the present disclosure provides a V prepared according to the method of the second aspect 2 O 5 Coated modified lithium-rich cathode material.
A fourth aspect of the present disclosure provides a lithium ion battery comprising V according to the first and third aspects 2 O 5 Coated modified lithium-rich cathode material.
Through the technical scheme, the present disclosure relates to a V 2 O 5 Coated modified lithium-rich positive electrode material, preparation method and application thereof, and Cu is used for preparing lithium-rich positive electrode material 2+ The doping of the lithium-rich anode material effectively enhances the structural stability of the lithium-rich anode material and improves the conductivity of the lithium-rich anode material; v (V) 2 O 5 The surface of the lithium-rich positive electrode material is coated to form a protective layer, so that direct contact between the electrode material and electrolyte is reduced, the corrosion of electrolyte decomposition products on electrode active substances is inhibited, the surface structure of the material is stabilized, and the performance of the lithium-rich positive electrode material is effectively improved; v (V) 2 O 5 Coating while effectively reducing Li 2 MnO 3 Li in (B) 2 O is taken out, so that oxygen loss during first-week charging is reduced, and the first coulomb efficiency of the material is effectively improved. By elemental doping and V 2 O 5 And the coating improves the first coulombic efficiency and the rate capability of the lithium-rich anode material. The preparation method disclosed by the invention has the advantages of good uniformity of the components of the synthesized product, easy control of the conditions and capability of being used for commercially preparing batteries.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
fig. 1 is a first charge-discharge curve of the lithium-rich cathode materials prepared in example 1 and comparative example 1 of the present disclosure.
Fig. 2 is a graph showing the rate performance of the lithium-rich cathode materials prepared in example 1 and comparative example 1 of the present disclosure.
Fig. 3 is a mapping picture of the lithium-rich cathode material prepared in example 1 of the present disclosure.
Fig. 4 is a TEM image of a lithium-rich cathode material prepared in example 1 of the present disclosure.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The first aspect of the present disclosure provides a V 2 O 5 The modified lithium-rich cathode material comprises a lithium-rich cathode material and a metal oxide layer coated on the surface of the lithium-rich cathode material; in one embodiment of the present disclosure, the chemical formula of the lithium-rich positive electrode material is shown in formula (i): li (Li) a Ni x Co y M z O 2 (I), wherein a is more than or equal to 1.13 and less than or equal to 1.27,0.10, x is more than or equal to 0.30,0.04, y is more than or equal to 0.12,0.45 and z is more than or equal to 0.59,0.73, x+y+z is more than or equal to 0.87, M comprises Mn and Cu, the metal oxide layer includes V 2 O 5 。
As shown in fig. 3 and 4, V provided by the present disclosure 2 O 5 Coated modified lithium-rich positive electrode material is prepared by Cu 2+ The doping of the lithium-rich anode material effectively enhances the structural stability of the lithium-rich anode material and improves the conductivity of the lithium-rich anode material; v (V) 2 O 5 The surface of the lithium-rich positive electrode material is coated to form a protective layer, so that direct contact between the electrode material and electrolyte can be reduced, the corrosion of electrolyte decomposition products on electrode active substances can be inhibited, the surface structure of the material is stabilized, and the performance of the lithium-rich positive electrode material is effectively improved; v (V) 2 O 5 Coating while effectively reducing Li 2 MnO 3 Li in (B) 2 O release amount so as to reduce oxygen loss during first-week charging and effectively improve materialHead partSecondary coulombic efficiency. By elemental doping and V 2 O 5 And the coating improves the first coulombic efficiency and the rate capability of the lithium-rich anode material.
In a preferred embodiment of the present disclosure, the chemical formula of the lithium-rich positive electrode material is represented by formula (i): the chemical formula of the lithium-rich positive electrode material is shown as the formula (I): li (Li) a Ni x Co y M z O 2 A is more than or equal to 1.183 and less than or equal to 1.212,0.175, x is more than or equal to 0.225,0.070 and y is more than or equal to 0.090,0.502 and z is more than or equal to 0.538,0.788, and x+y+z is more than or equal to 0.817; optionally, in the lithium-rich cathode material, the molar ratio of Mn to Cu is 3 to 117:1, preferably 8 to 21:1.
in the present disclosure, "a" represents the number of moles of Li element, "x" represents the number of moles of Ni element, "y" represents the number of moles of Co element, "z" Mn and the number of moles of Cu element. In the above embodiment, a+x+y+z=2 is preferable, and by preferably selecting the molar ratio of Mn to Cu, a cu—o bond having a strong bond energy can be formed better, and the stability of the structure of the lithium-rich cathode material can be improved.
In one embodiment of the present disclosure, the metal oxide layer is present in an amount of 0.10 to 9.10 wt%, preferably 3.38 to 5.21 wt%, based on the total weight of the modified lithium-rich cathode material; optionally, the weight ratio of the lithium-rich cathode material to the metal oxide layer is 1:0.001 to 0.100, preferably 1:0.035 to 0.055;
in a preferred embodiment of the present disclosure, the metal oxide layer has a thickness of 1 to 15nm, preferably 5 to 12nm.
V provided by the present disclosure 2 O 5 The coated modified lithium-rich positive electrode material has good cycle stability, good first coulombic efficiency and rate capability, and can obviously improve the cycle stability and rate capability of the battery under high temperature and high pressure when being applied to the battery. In the above embodiments, the thickness of the preferable oxide layer can better reduce direct contact between the electrode material and the electrolyte, protecting the electrode from the electrolyte.
In one embodiment of the present disclosure, the modified lithium-rich cathode material is a particulate material, preferably spherical particles, in which the average particle size of the spherical particles may vary within a wide range, and the average particle size of the particulate material is 10 to 20 μm, preferably 13 to 16 μm.
A second aspect of the present disclosure provides a method of preparing V 2 O 5 A method of coating a modified lithium-rich cathode material, the method comprising the steps of:
s1, mixing a nickel source, a cobalt source, a manganese source, a copper source and deionized water to obtain a metal mixed solution;
s2, contacting the metal mixed solution, the precipitant and the complexing agent for coprecipitation reaction to obtain a precipitation precursor;
s3, contacting the precipitation precursor with a lithium source, and performing first sintering to obtain a lithium-rich anode material;
and S4, contacting the lithium-rich anode material with a vanadium source, and performing second sintering.
The method provided by the present disclosure is by doping Cu 2+ Form Cu-O bond and due to Cu 2+ The characteristic of peripheral electron arrangement can effectively enhance the structural stability of the lithium-rich positive electrode material and improve the conductivity of the lithium-rich positive electrode material; in addition, a layer of V is formed on the surface of the lithium-rich positive electrode material by sintering after the lithium-rich positive electrode material is contacted with a vanadium source 2 O 5 The protective layer can reduce direct contact between the electrode material and the electrolyte, inhibit the electrolyte decomposition products from eroding electrode active substances to stabilize the surface structure of the material, improve the stability of the material and effectively improve the performance of the lithium-rich positive electrode material.
In a preferred embodiment of the present disclosure, in step S1, the molar ratio of the nickel source, the cobalt source, the manganese source and the copper source is (0.100 to 0.300) in terms of metal element: (0.040-0.120): (0.350-0.590): (0.005-0.100); preferably (0.175 to 0.225): (0.070-0.090): (0.447 to 0.513): (0.025-0.055). In the above embodiment, the reaction is carried out by selecting the raw materials in the preferable ratio, which is advantageous for improving V 2 O 5 The first coulombic efficiency and the multiplying power performance of the coated modified lithium-rich cathode material.
In one embodiment of the present disclosure, the total concentration of metal ions in the metal mixture is 0.5 to 3mol/L, preferably 1.5 to 2.2mol/L.
In one embodiment of the present disclosure, the nickel source may be a soluble salt of nickel, preferably, the nickel source may be selected from one or more of nickel sulfate, nickel chloride, nickel nitrate, and nickel acetate; the cobalt source may be a soluble salt of cobalt, preferably, the cobalt source may be one or more selected from cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese source may be a soluble salt of manganese, preferably, the manganese source may be one or more selected from manganese sulfate, manganese chloride, manganese nitrate and manganese acetate; alternatively, the copper source may be selected from one or more of copper sulfate pentahydrate, copper chloride and copper nitrate. In the above embodiment, the V is prepared by selecting the preferred nickel source, cobalt source, manganese source and copper source 2 O 5 The coated modified high-lithium-rich positive electrode material has stronger stability and better conductivity.
In a specific embodiment of the present disclosure, in step S2, the precipitant and the complexing agent are used in the form of aqueous solutions having a concentration of 1 to 5mol/L and 2 to 15mol/L, respectively, the precipitant is selected from one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the complexing agent includes aqueous ammonia.
In a preferred embodiment of the present disclosure, a complexing agent is used as a substrate, and a metal mixed solution, a precipitant and the complexing agent are added into a reaction kettle in a mode of parallel flow of three solutions to contact for coprecipitation reaction; optionally, the flow rate of the metal mixed solution is 5-15 mL/min, the flow rate of the precipitant is 0.5-45 mL/min, and the flow rate of the complexing agent is 0.35-15 mL/min. In the above embodiment, the concentration of the complexing agent may be 2 to 15mol/L, and the concentration of the complexing agent as a substrate may be 0.05 to 1mol/L; the three-liquid parallel flow mode is adopted, so that the relative content of the obtained precursor is close to that of a target product, the uniformity is good, and the layered structure of the sintered material is complete.
In one embodiment of the present disclosure, the reaction conditions of the coprecipitation reaction include: the temperature is 45-70 ℃, preferably 50-65 ℃; the pH is 7.5-9.5, preferably 7.8-8.5; the time is 10 to 50 hours, preferably 24 to 40 hours; optionally, the method further comprises: aging the product obtained by the coprecipitation reaction for 6-12 hours at 15-30 ℃; and then carrying out centrifugal treatment, washing treatment and drying treatment to obtain the precipitate precursor.
In this disclosure, "centrifugation," "washing," and "drying" all employ apparatus and methods conventional in the art.
In a specific embodiment of the present disclosure, in step S3, the molar ratio of the precursor to lithium is 1 in terms of metal element: (1.30 to 1.74), preferably 1: (1.40-1.60). In the above embodiment, the precursor and the lithium source are selected to react in a preferable ratio to prepare V 2 O 5 The first coulombic efficiency and the rate capability of the coated modified high-lithium-rich cathode material are higher.
In a preferred embodiment of the present disclosure, the lithium source may be selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide, and lithium nitrate. In a preferred embodiment of the present disclosure, the lithium source may be lithium carbonate; in the above embodiment, cu is doped by carbonate coprecipitation 2+ Then apply V to it 2 O 5 The method is used for treatment and modification, the uniformity of the components of the synthesized product is good, the condition is easy to control, and the method can be used for commercialization.
In one embodiment of the present disclosure, in step S3, the first sintering comprises two-stage sintering; wherein the conditions of the first stage sintering include: heating to 450-680 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 4-15 h; the conditions for the second stage sintering include: heating to 800-980 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 10-20 h; preferably, the conditions of the first stage sintering include: heating to 500-600 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 5-10 h; the conditions for the second stage sintering include: heating to 830-950 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 12-15 h; wherein the first sintering is performed under an air atmosphere.
In a specific embodiment of the present disclosure, in step S4, the vanadium source may be selected from one or more of ammonium metavanadate and vanadium pentoxide;optionally, the vanadium source is used in the form of an aqueous and/or alcoholic solution; in one specific embodiment of the disclosure, the weight ratio of the vanadium source to the lithium-rich cathode material is 0.005-0.129: 1, preferably 0.045 to 0.071:1. in the above embodiments, V is prepared by preferably vanadium source, preferably the weight ratio of vanadium source to lithium-rich cathode material 2 O 5 The first coulombic efficiency and the rate capability of the coated modified lithium-rich cathode material are higher.
In a specific embodiment of the present disclosure, in step S4, the second sintering condition includes: the temperature is 300-600 ℃, preferably 400-500 ℃; the time is 3 to 12 hours, preferably 4 to 8 hours; wherein the second sintering is performed under an air atmosphere; optionally, the method comprises: carrying out ultrasonic mixing on the lithium-rich anode material and a vanadium source; stirring the mixed solution after the ultrasonic treatment at a constant temperature of 50-90 ℃ to remove the solvent; drying at 60-80 deg.c for 4-10 hr; and carrying out the second sintering on the dried mixture.
A third aspect of the present disclosure provides a V prepared according to the method of the second aspect 2 O 5 Coated modified lithium-rich cathode material.
A fourth aspect of the present disclosure provides a lithium ion battery comprising the modified lithium-rich cathode material of the first and third aspects. The lithium ion battery in the present disclosure may be of a structure and composition conventionally employed in the art.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
In the following examples, all materials used, unless otherwise specified, were commercially available products.
The centrifugation process in this disclosure employs a conventional centrifuge.
The drying process in this disclosure employs a conventional drying oven.
In the following examples, specific test methods are as follows:
the thickness of the oxide layer was measured by TEM with an instrument model JEOL JEM-2100F.
The average particle size was measured by SEM, instrument model Nova Nano SEM 450FEI.
The test method of a, x, y, z is ICP, and the instrument model is Agilent 5100/5110.
Example 1
(1) According to the element mole ratio Ni: co: mn: cu=0.20: 0.08:0.49:0.03 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O and CuSO 4 ·5H 2 O preparing a metal mixed solution with the concentration of 2.0 mol/L; configuration of Na of 2.0mol/L 2 CO 3 3.0mol/L NH as precipitant 3 ·H 2 The O solution is used as a complexing agent; adding complexing agent solution into a reaction kettle as base solution, wherein the concentration of the base solution is 0.2mol/L; adding the mixture into a reaction kettle in a mode of parallel flow of three liquids, wherein the reaction temperature is 60 ℃, the pH value is 8.0, performing coprecipitation reaction, and aging at normal temperature after the reaction is finished. Centrifuging the reaction product, washing the reaction product with deionized water to neutrality to obtain a precipitate, and drying the washed precursor precipitate to obtain dried Cu 2+ Precursor Ni of doped lithium-rich material 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 ；
(2) Calculated as metal element, according to metal element M: the metal element Li is 1:1.54 molar ratio of precursor Ni 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 And Li (lithium) 2 CO 3 Ball milling and mixing, grinding the ball milled mixture, performing first sintering under air atmosphere, heating to 510 ℃ at a heating rate of 5 ℃/min for presintering for 5 hours, heating to 850 ℃ at a heating rate of 5 ℃/min for 13 hours, and cooling to room temperature along with a furnace to obtain the lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 。
(3) The mass ratio is 1:0.051 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And ammonium metavanadate, firstly dissolving ammonium metavanadate in 25mL of mixed solution of water and ethanol (water: ethanol=22.5:2.5), and then adding the weighed lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And (3) performing ultrasonic dispersion, placing the mixed solution subjected to ultrasonic treatment in a water bath kettle at 70 ℃, stirring at constant temperature until the solvent is evaporated, and drying in a drying oven at 70 ℃ for 4 hours. Placing the dried mixture in a muffle furnace for secondary sintering, calcining at 400 ℃ for 6 hours in air atmosphere, and cooling to room temperature along with the furnace to obtain V 2 O 5 Coated modified lithium-rich cathode material C1.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
The mapping graph of the modified lithium-rich cathode material C1 is shown in FIG. 3, and represents distribution characterization of nickel element, cobalt element, manganese element, copper element and vanadium element in the modified lithium-rich cathode material.
TEM image of the modified lithium-rich cathode material C1 is shown in FIG. 4, which shows the nano microstructure of the modified lithium-rich cathode material C1, and it can be seen that the coated metal oxide layer is V 2 O 5 。
Example 2
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich cathode material is different in that the second sintering temperature is 300 ℃; thus obtaining V 2 O 5 Coated modified lithium-rich cathode material C2.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 3
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich cathode material is different in that the second sintering temperature is 550 ℃; thus obtaining V 2 O 5 And C3, coating the modified lithium-rich cathode material.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 4
Preparation of V by the same method as in example 1 2 O 5 Coated modified lithium-rich cathode material, noThe method is characterized by comprising the following steps of: 0.007 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And ammonium metavanadate; thus obtaining V 2 O 5 And C4, a coated modified lithium-rich positive electrode material.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 5
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich anode material is characterized by comprising the following components in percentage by mass: 0.026 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And ammonium metavanadate; thus obtaining V 2 O 5 And C5, coating the modified lithium-rich cathode material.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 6
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich anode material is characterized by comprising the following components in percentage by mass: 0.103 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And ammonium metavanadate; thus obtaining V 2 O 5 Coated modified lithium-rich cathode material C6.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 7
(1) According to the element mole ratio Ni: co: mn: cu=0.20: 0.08:0.42:0.1 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O and CuSO 4 ·5H 2 O preparing a metal mixed solution with the concentration of 1.0 mol/L; configuration of K of 2.0mol/L 2 CO 3 The solution is used as a precipitator, and 3.0mol/L ammonia water solution is used as a complexing agent; adding complexing agent solution into a reaction kettle as base solution, wherein the concentration of the base solution is 0.8mol/L; by usingAdding the three solutions into a reaction kettle in a parallel flow mode, wherein the reaction temperature is 60 ℃, the pH value is 8.0, performing coprecipitation reaction, and aging at normal temperature after the reaction is finished. Centrifuging the reaction product, washing the reaction product with deionized water to neutrality to obtain a precipitate, and drying the washed precursor precipitate to obtain dried Cu 2+ Precursor Ni of doped lithium-rich material 0.25 Co 0.1 Mn 0.525 Cu 0.125 CO 3 ；
(2) Calculated as metal element, according to metal element M: the metal element Li is 1:1.54 molar ratio of precursor Ni 0.25 Co 0.1 Mn 0.525 Cu 0.125 CO 3 And Li (lithium) 2 CO 3 Ball milling and mixing, grinding the ball milled mixture, performing first sintering under air atmosphere, heating to 570 ℃ at a heating rate of 10 ℃/min for presintering for 7h, heating to 900 ℃ at a heating rate of 10 ℃/min for calcining for 20h, and cooling to room temperature along with a furnace to obtain the lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.42 Cu 0.1 O 2 。
(3) The mass ratio is 1:0.051 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.42 Cu 0.1 O 2 And ammonium metavanadate, firstly dissolving ammonium metavanadate in 25mL of mixed solution of water and ethanol (water: ethanol=22.5:2.5), and then adding the weighed lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.42 Cu 0.1 O 2 And (3) performing ultrasonic dispersion, placing the mixed solution subjected to ultrasonic treatment in a water bath kettle at 70 ℃, stirring at constant temperature until the solvent is evaporated, and drying in a drying oven at 70 ℃ for 4 hours. Placing the dried mixture in a muffle furnace for secondary sintering, calcining at 400 ℃ for 6 hours in air atmosphere, and cooling to room temperature along with the furnace to obtain V 2 O 5 Coated modified lithium-rich cathode material C7.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 8
(1) According to the element mole ratio Ni: co: mn: cu=0.2: 0.08:0.49:0.03 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O and CuSO 4 ·5H 2 O preparing a metal mixed solution with the concentration of 2.0 mol/L; configuration of Na of 2.0mol/L 2 CO 3 3.0mol/L NH as precipitant 3 ·H 2 The O solution is used as a complexing agent; adding complexing agent solution into a reaction kettle as base solution, wherein the concentration of the base solution is 0.2mol/L; adding the mixture into a reaction kettle in a mode of parallel flow of three liquids, wherein the reaction temperature is 60 ℃, the pH value is 8.0, performing coprecipitation reaction, and aging at normal temperature after the reaction is finished. Centrifuging the reaction product, washing the reaction product with deionized water to neutrality to obtain a precipitate, and drying the washed precursor precipitate to obtain dried Cu 2+ Precursor Ni of doped lithium-rich material 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 ；
(2) Calculated as metal element, according to metal element M: the metal element Li is 1:1.54 molar ratio of precursor Ni 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 And Li (lithium) 2 CO 3 Ball milling and mixing, grinding the ball milled mixture, performing first sintering under air atmosphere, heating to 510 ℃ at the heating rate of 10 ℃/min for presintering for 5 hours, heating to 850 ℃ at the heating rate of 10 ℃/min for calcining for 13 hours, and cooling to room temperature along with a furnace to obtain lithium-rich Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 。
(3) The mass ratio is 1:0.04 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And vanadium pentoxide, firstly dissolving the vanadium pentoxide into 25mL of water solution, and then adding the weighed lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And (3) performing ultrasonic dispersion, placing the mixed solution subjected to ultrasonic treatment in a water bath kettle at 80 ℃, stirring at constant temperature until the solvent is evaporated, and drying in a drying oven at 80 ℃ for 4 hours. Placing the dried mixture in a muffle furnace for secondary sintering, calcining at 400 ℃ for 6 hours in air atmosphere, and cooling to room temperature along with the furnace to obtain V 2 O 5 Coated modificationAnd C8, a lithium-rich positive electrode material.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Example 9
According to the element mole ratio Ni: co: mn: cu=0.30: 0.12:0.42:0.03 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O and CuSO 4 ·5H 2 O preparing a metal mixed solution with the concentration of 2.0 mol/L; configuration of Na of 2.0mol/L 2 CO 3 3.0mol/L NH as precipitant 3 ·H 2 The O solution is used as a complexing agent; adding complexing agent solution into a reaction kettle as base solution, wherein the concentration of the base solution is 0.2mol/L; adding the mixture into a reaction kettle in a mode of parallel flow of three liquids, wherein the reaction temperature is 60 ℃, the pH value is 8.0, performing coprecipitation reaction, and aging at normal temperature after the reaction is finished. Centrifuging the reaction product, washing the reaction product with deionized water to neutrality to obtain a precipitate, and drying the washed precursor precipitate to obtain dried Cu 2+ Precursor Ni of doped lithium-rich material 0.375 Co 0.15 Mn 0.525 Cu 0.0375 CO 3 ；
(2) Calculated as metal element, according to metal element M: the metal element Li is 1:1.32 molar ratio of precursor Ni 0.375 Co 0.15 Mn 0.525 Cu 0.0375 CO 3 And Li (lithium) 2 CO 3 Ball milling and mixing, grinding the ball milled mixture, performing first sintering under air atmosphere, heating to 510 ℃ at a heating rate of 5 ℃/min for presintering for 5 hours, heating to 850 ℃ at a heating rate of 5 ℃/min for 13 hours, and cooling to room temperature along with a furnace to obtain the lithium-rich material Li 1.13 Ni 0.3 Co 0.12 Mn 0.42 Cu 0.03 O 2 。
(3) The mass ratio is 1:0.051 weighing Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And ammonium metavanadate, firstly dissolving ammonium metavanadate in 25mL of mixed solution of water and ethanol (water: ethanol=22.5:2.5), and then adding the weighed lithium-rich material Li 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 And (3) performing ultrasonic dispersion, placing the mixed solution subjected to ultrasonic treatment in a water bath kettle at 70 ℃, stirring at constant temperature until the solvent is evaporated, and drying in a drying oven at 70 ℃ for 4 hours. Placing the dried mixture in a muffle furnace for secondary sintering, calcining at 400 ℃ for 6 hours in air atmosphere, and cooling to room temperature along with the furnace to obtain V 2 O 5 Coated modified lithium-rich cathode material C9.
Metal oxide layer V 2 O 5 The results of the thickness of the positive electrode material and the average particle diameter are shown in Table 1.
Comparative example 1
(1) According to the element mole ratio Ni: co: mn: cu=0.20: 0.08:0.49:0.03 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O and CuSO 4 ·5H 2 O preparing a metal mixed solution with the concentration of 2.0 mol/L; configuration of Na of 2.0mol/L 2 CO 3 3.0mol/L NH as precipitant 3 ·H 2 The O solution is used as a complexing agent; adding complexing agent solution into a reaction kettle as base solution, wherein the concentration of the base solution is 0.2mol/L; adding the mixture into a reaction kettle in a mode of parallel flow of three liquids, wherein the reaction temperature is 60 ℃, the pH value is 8.0, performing coprecipitation reaction, standing for 2 hours at constant temperature after the reaction is finished, and aging at normal temperature. Centrifuging the reaction product, washing the reaction product with deionized water to neutrality to obtain a precipitate, and drying the washed precursor precipitate to obtain dried Cu 2+ Precursor Ni of doped lithium-rich material 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 ；
(2) Calculated as metal element, according to metal element M: the metal element Li is 1:1.54 molar ratio of precursor Ni 0.25 Co 0.1 Mn 0.6125 Cu 0.0375 CO 3 And lithium salt Li 2 CO 3 Ball milling and mixing, grinding the ball milled mixture, performing first sintering under air atmosphere, heating to 510 ℃ at a heating rate of 10 ℃/min for presintering 5h, heating to 850 ℃ at a heating rate of 10 ℃/min for calcining 13h, and cooling to the temperature along with a furnaceObtaining lithium-rich material Li at room temperature 1.2 Ni 0.2 Co 0.08 Mn 0.49 Cu 0.03 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Denoted as D1.
The average particle diameter results of the positive electrode materials are shown in table 1.
Comparative example 2
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich cathode material is characterized in that a copper source is not added, and the molar ratio of Ni: co: mn=0.20: 0.08:0.52 respectively weighing NiSO with certain mass 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 O preparing a metal mixed solution with the concentration of 2.0 mol/L; thus obtaining V 2 O 5 And (3) a coated modified lithium-rich cathode material D2.
Metal oxide layer V 2 O 5 The thickness of (c) and the average particle diameter of the positive electrode material are shown in table 1.
Comparative example 3
Preparation of V by the same method as in example 1 2 O 5 The coated modified lithium-rich cathode material is different in that no complexing agent is added; thus obtaining V 2 O 5 And D3, coating the modified lithium-rich cathode material.
Metal oxide layer V 2 O 5 The thickness of (c) and the average particle diameter of the positive electrode material are shown in table 1.
TABLE 1
Test example 1
Electrochemical properties of the lithium-rich cathode materials prepared in example 1 and comparative example 1 were evaluated using a coin cell. The method specifically comprises the following steps: 96% by weight of active material (i.e., the product obtained in example 1 and comparative example 1) and 2% by weight of acetylene black were used as the conductive materialThe agent and 2 wt% PVDF as binder were dissolved in an appropriate amount of NMP to prepare a slurry. The resulting slurry was uniformly coated on an aluminum foil which was wiped with alcohol, dried at 70℃in a forced air drying oven for 1 hour and dried at 110℃in vacuo for 2 hours. After the drying is completed, rolling the electrode plate by a tabletting machine, keeping the pressure moderate in the tabletting process to ensure certain compaction density, and punching the tabletting electrode plate into a round electrode plate with the diameter of 10 mm. The positive electrode sheet and the negative electrode sheet (metallic lithium sheet) were separated by a separator (Celgard 2400 porous polypropylene film), and an appropriate amount of electrolyte (1 mol/LLiPF) was added 6 Ec+emc+dmc volume ratio 1:1:1), button cells are assembled in a dry inert gas glove box.
And carrying out the charge and discharge test on the assembled battery in a blue electric test system, wherein the temperature is 25+/-1 ℃. Performing discharge tests under different multiplying powers (0.1C, 0.2C, 0.5C, 1C and 2C), wherein the charge and discharge currents are set to be 1 C=250mAh/g, and the test voltage ranges from 2.0V to 4.8V; the test results are shown in fig. 1 and 2, and specific values are shown in table 2 below.
TABLE 2
As can be seen from Table 2, V obtained in examples 1 to 8 of the present disclosure was used as compared with the products obtained in comparative examples 1 to 3 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2C discharge specific capacity of the battery taking the coated modified lithium-rich positive electrode material as the positive electrode material are all higher than those of comparative examples 1-3. Battery performance test data in which the products obtained in example 1 and comparative example 1 were used were referred to fig. 1 and 2, as can be seen from the data set forth in fig. 1, 2 and table 2: the specific capacity at 0.1C, the specific capacity at 0.2C, the specific capacity at 0.5C, the specific capacity at 1.0C and the specific capacity at 2C of example 1 are all higher than those of comparative example 1, indicating that V is represented by 2 O 5 Coating, and preparing V 2 O 5 The coated high-lithium-rich positive electrode material has higher first coulombic efficiency and rate capability. And as can be seen from the data in table 2, the 0.1C first discharge specific capacity and the 2C discharge specific capacity of example 1 are both higher than those of comparative example 2, indicating that the copper source can effectively enhance the structural stability of the lithium-rich cathode material and can improve the conductivity of the lithium-rich cathode material.
Further, as can be seen from the data of tables 1 and 2, in examples 1 to 9:
(1) V obtained in example 1 2 O 5 The composition of the coated lithium-rich positive electrode material meets the requirement that "a is more than or equal to 1.183 and less than or equal to 1.212,0.175, x is more than or equal to 0.225,0.070, y is more than or equal to 0.090,0.502, z is more than or equal to 0.538,0.788, x+y+z is more than or equal to 0.817", and compared with other example 9 which is not in the preferred range, V prepared by adopting the example 1 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2.0C discharge specific capacity of the battery of the coated lithium-rich positive electrode material are higher, which indicates that the coulombic efficiency and the rate capability are better.
(2) V obtained in example 1 2 O 5 The composition of the coated lithium-rich positive electrode material satisfies the mole ratio of Mn to Cu of 8-21: 1, compared to other examples 7 which are not within the preferred range, V prepared in example 1 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2.0C discharge specific capacity of the battery of the coated lithium-rich positive electrode material are higher, which indicates that the coulombic efficiency and the rate capability are better.
(3) V obtained by the preparation method of the preferred second sintering temperature in example 1 of the present disclosure compared to the products obtained in examples 2 and 3 2 O 5 The metal oxide layer thickness of the coated modified lithium-rich cathode material was better than that of examples 2 and 3, and V obtained in example 1 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2.0C discharge specific capacity of the battery using the coated modified lithium-rich cathode material as the cathode material are all higher than those of examples 2 and 3, which illustrate the beneficial effects of the preferred second sintering temperature on the thickness of the metal oxide layer, the first coulombic efficiency and the rate capability.
(4) Compared with the products prepared in examples 4 and 5, the method adoptsV obtained by the preparation method of the weight ratio of the vanadium source to the lithium-rich cathode material in the embodiment 1 of the disclosure 2 O 5 The metal oxide layer thickness of the coated modified lithium-rich cathode material was better than examples 4 and 5, and V obtained in example 1 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2.0C discharge specific capacity of the battery using the coated modified lithium-rich cathode material as the cathode material are all higher than those of examples 4 and 5, and the beneficial effects of the preferred weight ratio of the vanadium source to the lithium-rich cathode material on the first coulombic efficiency and the rate capability are illustrated.
(5) Compared with the product obtained in example 6, V obtained in example 1 2 O 5 The first discharge specific capacity of 0.1C, the first coulombic efficiency and the second discharge specific capacity of 2.0C of the battery using the coated modified lithium-rich cathode material as the cathode material are all higher than those of example 6, so that the beneficial effects of the weight ratio of the preferred vanadium source to the lithium-rich cathode material on the first coulombic efficiency and the rate capability are further illustrated.
(6) V prepared by the preferred molar ratios of the Nickel source, cobalt source, manganese source and copper source of example 1 of the present disclosure, as compared to the product prepared in example 7 2 O 5 The 0.1C first discharge specific capacity, the first coulombic efficiency and the 2.0C discharge specific capacity of the battery using the coated modified lithium-rich cathode material as the cathode material are all higher than those of example 7, which illustrates the beneficial effects of the preferred molar ratios of the nickel source, the cobalt source, the manganese source and the copper source on the first coulombic efficiency and the rate capability.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (10)
1. V (V) 2 O 5 The coated modified lithium-rich cathode material is characterized by comprising a lithium-rich cathode material and a metal oxide layer coated on the surface of the lithium-rich cathode material; the chemical formula of the lithium-rich positive electrode material is shown as the formula (I): li (Li) a Ni x Co y M z O 2 Wherein a is more than or equal to 1.13 and less than or equal to 1.27,0.10, x is more than or equal to 0.30,0.04 and y is more than or equal to 0.12,0.45 and z is more than or equal to 0.59,0.73, x+y+z is more than or equal to 0.87, and M comprises Mn and Cu; the metal oxide layer includes V 2 O 5 。
2. The modified lithium-rich cathode material of claim 1, wherein the lithium-rich cathode material has a chemical formula as shown in formula (i): li (Li) a Ni x Co y M z O 2 (Ⅰ)，1.183≤a≤1.212，0.175≤x≤0.225，0.070≤y≤0.090，0.502≤z≤0.538，0.788≤x+y+z≤0.817；
Optionally, in the lithium-rich cathode material, the molar ratio of Mn to Cu is 3 to 117:1, preferably 8 to 21:1.
3. the modified lithium-rich cathode material according to claim 1, wherein the metal oxide layer is present in an amount of 0.10 to 9.10 wt%, preferably 3.38 to 5.21 wt%, based on the total weight of the modified lithium-rich cathode material; optionally, the weight ratio of the lithium-rich cathode material to the metal oxide layer is 1:0.001 to 0.100, preferably 1:0.035 to 0.055;
optionally, the thickness of the metal oxide layer is 1-15 nm, preferably 5-12 nm;
the modified lithium-rich positive electrode material is a granular material, preferably spherical particles, and the average particle size of the granular material is 10-20 mu m, preferably 13-16 mu m.
4. Preparation V 2 O 5 A method of coating a modified lithium-rich cathode material, the method comprising the steps of:
s1, mixing a nickel source, a cobalt source, a manganese source, a copper source and deionized water to obtain a metal mixed solution;
s2, contacting the metal mixed solution, the precipitant and the complexing agent for coprecipitation reaction to obtain a precipitation precursor;
s3, contacting the precipitation precursor with a lithium source, and performing first sintering to obtain a lithium-rich anode material;
and S4, contacting the lithium-rich anode material with a vanadium source, and performing second sintering.
5. The method according to claim 4, wherein in the step S1, the molar ratio of the nickel source, cobalt source, manganese source and copper source is (0.100 to 0.300) in terms of metal element: (0.040-0.120): (0.350-0.590): (0.005-0.100); preferably (0.175 to 0.225): (0.070-0.090): (0.447 to 0.513): (0.025-0.055);
the total concentration of metal ions in the metal mixed solution is 0.5-3 mol/L, preferably 1.5-2.2 mol/L;
optionally, the nickel source is a soluble salt of nickel, preferably, the nickel source is selected from one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate;
optionally, the cobalt source is a soluble salt of cobalt, preferably, the cobalt source is one or more selected from cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate;
optionally, the manganese source is a soluble salt of manganese, preferably, the manganese source is selected from one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate;
optionally, the copper source is selected from one or more of copper sulfate pentahydrate, copper chloride and copper nitrate.
6. The method according to claim 4, wherein in step S2, the precipitant and the complexing agent are used in the form of aqueous solutions having a concentration of 1 to 5mol/L and 2 to 15mol/L, respectively, the precipitant is selected from one of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the complexing agent includes aqueous ammonia;
preferably, step S2 includes: adding a metal mixed solution, a precipitator and a complexing agent into a reaction kettle in a three-solution parallel flow mode by taking the complexing agent as a substrate to contact for coprecipitation reaction;
optionally, the flow rate of the metal mixed solution is 5-15 mL/min, the flow rate of the precipitant is 0.5-45 mL/min, and the flow rate of the complexing agent is 0.35-15 mL/min;
optionally, the reaction conditions of the coprecipitation reaction include: the temperature is 45-70 ℃, preferably 50-65 ℃; the pH is 7.5-9.5, preferably 7.8-8.5; the time is 10 to 50 hours, preferably 24 to 40 hours;
optionally, the method further comprises: aging the product obtained by the coprecipitation reaction for 6-12 hours at 15-30 ℃; and then carrying out centrifugal treatment, washing treatment and drying treatment to obtain the precipitate precursor.
7. The method according to claim 4, wherein in step S3, the molar ratio of the precursor to lithium is 1, calculated as metal element: (1.30 to 1.74), preferably 1: (1.40-1.60);
optionally, the lithium source is selected from one or more of lithium hydroxide monohydrate, lithium hydroxide anhydrous, lithium carbonate, lithium acetate, lithium oxalate, lithium oxide and lithium nitrate;
optionally, in step S3, the first sintering includes two-stage sintering; wherein the conditions of the first stage sintering include: heating to 450-680 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 4-15 h; the conditions for the second stage sintering include: heating to 800-980 ℃ at a heating rate of 1-10 ℃/min, and then keeping the temperature for 10-20 h;
preferably, the conditions of the first stage sintering include: heating to 500-600 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 5-10 h; the conditions for the second stage sintering include: heating to 830-950 ℃ at a heating rate of 3-7 ℃/min, and then keeping the temperature for 12-15 h;
wherein the first sintering is performed under an air atmosphere.
8. The method according to claim 4, wherein in step S4, the vanadium source is selected from one or more of ammonium metavanadate and vanadium pentoxide; optionally, the vanadium source is used in the form of an aqueous and/or alcoholic solution;
preferably, the weight ratio of the vanadium source to the lithium-rich cathode material is 0.005-0.129: 1, preferably 0.045 to 0.071:1, a step of;
preferably, in step S4, the second sintering condition includes: the temperature is 300-600 ℃, preferably 400-500 ℃; the time is 3 to 12 hours, preferably 4 to 8 hours;
wherein the second sintering is performed under an air atmosphere;
optionally, the method comprises: carrying out ultrasonic mixing on the lithium-rich anode material and a vanadium source; stirring the mixed solution after the ultrasonic treatment at a constant temperature of 50-90 ℃ to remove the solvent; drying at 60-80 deg.c for 4-10 hr; and carrying out the second sintering on the dried mixture.
9. V prepared by the method according to any one of claims 4 to 8 2 O 5 Coated modified lithium-rich cathode material.
10. A lithium ion battery comprising V according to any one of claims 1 to 3 and 9 2 O 5 Coated modified lithium-rich cathode material.
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