CN117393722A - Nickel-based positive electrode material, preparation method and application - Google Patents
Nickel-based positive electrode material, preparation method and application Download PDFInfo
- Publication number
- CN117393722A CN117393722A CN202311375837.XA CN202311375837A CN117393722A CN 117393722 A CN117393722 A CN 117393722A CN 202311375837 A CN202311375837 A CN 202311375837A CN 117393722 A CN117393722 A CN 117393722A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- nickel
- electrode material
- bismuth
- based positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 339
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 197
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 91
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 91
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 58
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010416 ion conductor Substances 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017698 Ni 1-x-y Co Inorganic materials 0.000 claims abstract description 7
- 230000000630 rising effect Effects 0.000 claims description 48
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- -1 bismuth halide Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 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 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940036348 bismuth carbonate Drugs 0.000 claims description 2
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 38
- 150000002500 ions Chemical class 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 34
- 239000003792 electrolyte Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 239000002033 PVDF binder Substances 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000011267 electrode slurry Substances 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000004321 preservation Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000007784 solid electrolyte Substances 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005253 cladding Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 229920001940 conductive polymer Polymers 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000010835 comparative analysis Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910017018 Ni0.8Co0.15Al0.05 Inorganic materials 0.000 description 1
- 229910017238 Ni0.8Co0.15Al0.05(OH)2 Inorganic materials 0.000 description 1
- 229910017229 Ni0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910005578 NiBi Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 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 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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Abstract
The invention relates to a nickel-based positive electrode material, a preparation method and application thereof. The nickel-based positive electrode material comprises a nickel-containing positive electrode material matrix and an oxygen ion conductor coated on the surface of the nickel-containing positive electrode material matrix, wherein bismuth is doped in a positive electrode material phase; the nickel-containing positive electrodeThe polar material matrix is Li z Ni 1‑x‑y Co x A y O 2 The method comprises the steps of carrying out a first treatment on the surface of the The oxygen ion conductor is delta-Bi 2‑p M p O q . The invention also provides a preparation method of the nickel-based positive electrode material, which comprises the following steps: adding a bismuth source, an M source and a nickel-based positive electrode material precursor into water, uniformly mixing and heating to obtain a first mixture; and then mixing and sintering with a lithium source to obtain the nickel-based anode material. The invention also provides application of the nickel-based positive electrode material, and the nickel-based positive electrode material is used as a positive electrode active material of a lithium ion battery. The invention solves the problems of poor thermal stability and low ion and electron transmission efficiency of the existing nickel-based material.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a nickel-based positive electrode material, a preparation method and application.
Background
Since the 21 st century, the shortage of energy and renewable problems have become the focus of growing attention, and the development of renewable energy and energy storage has become a critical issue. Lithium Ion Batteries (LIBs) are used as energy storage equipment, and are widely applied to the fields of mobile terminals, electric vehicles, energy storage power stations and the like due to the advantages of high working voltage, high energy density, small self-discharge rate, long cycle life, no memory effect, environmental friendliness and the like. Along with the development of technology, people put forward higher requirements on the aspects of safety, energy density, multiplying power performance and the like of lithium ion batteries.
The positive electrode material is one of key materials for determining the comprehensive performance of the lithium ion battery. Among the many successfully commercialized lithium ion battery cathode materials, nickel-based cathode materials, in particular nickel cobalt lithium manganate materials (NCM), show excellent comprehensive performance and higher cost performance by virtue of the synergistic effect of three elements, such as high specific capacity, high voltage, higher compaction density and excellent low-temperature performance, become a commercial hot spot of cathode materials and are a technical choice of power battery cells for electric vehicles.
With the increase of the high energy density demands of batteries in the market, nickel-based cathode materials are becoming increasingly new directions of industrialization interest. The nickel-based positive electrode material has the advantages that due to the high content of nickel components, the layered phase, the spinel phase and the rock salt phase are subjected to severe phase transition in the repeated charge and discharge process, the phase transition process brings a series of problems of cracks generated by material particles, release of oxygen and partial inactivation of the material, and a new interface generated by the cracks and electrolyte undergo side reaction to generate gas, increase interface impedance and the like, so that the capacity is finally attenuated rapidly in the circulation process and serious potential safety hazards are finally caused. In particular, in the thermal runaway process of the battery, decomposition of the positive electrode material and release of oxygen are considered to be main causes of ignition and explosion of the power battery. The stability of the positive electrode material is improved, the direct contact between the electrode material and the electrolyte is reduced, and the side reaction of the electrolyte is inhibited, so that the interface structure stability and the cycle stability of the positive electrode material are improved, and the safety of the power battery can be obviously improved.
CN 115132984A discloses a composite positive electrode material, a preparation method and application thereof. The composite positive electrode material consists of a positive electrode material, a conductive polymer coated on the surface of the positive electrode material in a composite manner and a solid electrolyte. The composite positive electrode material takes the positive electrode material as a core, the conductive polymer and the solid electrolyte of the conductive ions are coated on the surface of the positive electrode material particles, the solid electrolyte on the surface can enhance the ionic conductivity of the material, the problem of low ionic transmission efficiency between the positive electrode material particles is solved, the interface impedance between the solid electrolyte and the electrodes is reduced, in addition, the conductive polymer is used as a continuous coating layer to form a complete conductive network, the insulating solid electrolyte does not form a complete coating layer on the surface of the positive electrode material particles, and only the surface is coated in a particle form, and meanwhile, the problem of poor conductivity of the traditional electrolyte coated positive electrode composite material is solved. The preparation method of the composite positive electrode material comprises the following steps: dissolving a solid electrolyte, a positive electrode material and a conductive polymer in an organic solvent to obtain a mixed solution; and (3) injecting the mixed solution into spray drying equipment, and drying and granulating the mixed solution through high-temperature airflow spraying to obtain the composite anode material. The continuous and complete conductive network formed on the surface of the material particles by the conductive polymer in the composite material can lead to the reduction of the ion and electron transmission efficiency of the composite material, thereby affecting the rate capability of the battery cell. However, the composite positive electrode material does not improve the thermal stability of the nickel-based material for relieving the high delithiation state of oxygen release and improving the material.
CN 116014142A discloses a solid electrolyte coated modified cathode material, a preparation method and application thereof. The solid electrolyte coated and modified positive electrode material comprises a positive electrode material matrix and solid electrolyte coated on the surface of the positive electrode material matrix, wherein the solid electrolyte is lithium ion conductive glass Li 2 O-B 2 O 3 -M, M is at least one of lithium sulphate, silica, alumina, lithium iodide. By coating the solid electrolyte Li on the surface of the positive electrode 2 O-B 2 O 3 And M, the lithium ion conductivity of lithium ions at the electrode interface can be obviously improved while the surface of the positive electrode material is coated. The preparation method of the positive electrode material realizes in-situ synthesis of lithium ion conductive glass and surface coating of solid electrolyte Li in the process of synthesizing the positive electrode material 2 O-B 2 O 3 M (M is at least one of lithium sulfate, silicon dioxide, aluminum oxide and lithium iodide) to achieve a uniform coating effect, and the surface of the positive electrode material is coated, and meanwhile, the lithium ion conductivity of lithium ions at an electrode interface is remarkably improved. However, the solid electrolyte coated and modified cathode material has no improvement on the thermal stability of the nickel-based material for relieving the high delithiation state of oxygen release and improving the material.
Disclosure of Invention
The invention aims to provide a nickel-based positive electrode material, a preparation method and application thereof, which are used for solving the problems of poor thermal stability and low ion and electron transmission efficiency of the existing nickel-based material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the nickel-based positive electrode material comprises a nickel-containing positive electrode material matrix and an oxygen ion conductor coated on the surface of the nickel-containing positive electrode material matrix, wherein bismuth is doped in the positive electrode material bulk phase;
the oxygen ion conductor is delta-Bi 2-p M p O q Wherein p is more than or equal to 0 and less than or equal to 1.5, q is more than or equal to 1.5 and less than or equal to 3.0, and M is at least one of lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum and tungsten.
According to the technical means, the surface of the nickel-containing positive electrode material matrix is coated with delta-Bi 2-p M p O q Bismuth element doping in the bulk phase of the material, delta-Bi 2-p M p O q The bismuth element is doped with the bulk phase for synergistic modification, so that the interface and bulk phase dynamics performance are effectively improved, and the thermal stability of the material is improved; wherein the oxygen ion conductor delta-Bi 2-p M p O q Active ions of lattice oxygen on the surfaces of activated material particles can be captured, oxygen release on the surfaces of the positive electrodes is inhibited, further, the reaction heat release of oxygen and electrolyte is avoided, and the safety of the battery is improved; meanwhile, bismuth is introduced into the nickel-based positive electrode material, so that the growth of crystal grains can be promoted, defects in the crystal grains and grain boundaries among the grains are reduced, and the morphology and the grain size of a product are effectively controlled; bismuth doped in the bulk phase improves the diffusion coefficient of lithium ions by activating crystal lattices; therefore, the nickel-based positive electrode material disclosed by the invention has the advantages of heat stability and electrochemical performance, and the problems of poor heat stability and low ion and electron transmission efficiency of the existing nickel-based material are effectively solved.
Preferably, the molar ratio of the oxygen ion conductor to the nickel-containing positive electrode material matrix is 0.1-10:100.
Experiments prove that the molar ratio is too low, and the oxygen ion conductor delta-Bi 2-p M p O q The total amount of lattice oxygen active ions on the surfaces of the captured and activated material particles is very low, and oxygen release from the surfaces of the positive electrodes is difficult to effectively inhibit, so that the reaction heat release of oxygen and electrolyte is difficult to effectively avoid, the rapid thermal runaway is further caused, the safety performance of a battery cannot be obviously improved, the overall electrochemical performance is influenced if the molar ratio is too high, and the thermal stability and the electrochemical performance cannot be considered, therefore, the molar ratio of an oxygen ion conductor to a nickel-containing positive electrode material matrix is limited to be between 0.1 and 10:100, and the delta-Bi of the oxygen ion conductor is ensured 2- p M p O q Can capture enough active ions of lattice oxygen on the surface of activated material particles, and hasThe method can effectively inhibit the release of oxygen on the surface of the positive electrode, thereby avoiding the reaction heat release of oxygen and electrolyte, improving the safety of the battery, and simultaneously taking the overall electrochemical performance of the nickel-based positive electrode material into consideration, and has the advantage of synergy.
Preferably, the nickel-containing positive electrode material matrix is Li z Ni 1-x-y Co x A y O 2 Wherein A is selected from manganese or aluminum, z is more than or equal to 0.95 and less than or equal to 1.15,0, x is more than or equal to 0.5, and y is more than or equal to 0 and less than 0.5.
Preferably, the nickel-containing positive electrode material matrix is selected from at least one of lithium nickelate, lithium nickelate manganate and lithium nickelate cobalt aluminate.
Preferably, the bismuth is present as trivalent bismuth ions (Bi 3+ ) Is doped in a nickel-containing positive electrode material matrix.
Preferably, the doping proportion of bismuth is 0.1% -2%.
If the doping amount of bismuth is too small, the growth of the base grains of the nickel-based positive electrode material cannot be effectively promoted, so that the morphology and the grain size of a product are difficult to effectively control, defects in the grains and grain boundaries among the grains cannot be obviously reduced, meanwhile, the effect of activating crystal lattices is limited, the diffusion coefficient of lithium ions cannot be obviously improved, and finally, the aim of improving the electrochemical performance of the nickel-based positive electrode material cannot be achieved; if the doping amount of bismuth element is too large, it is difficult to synthesize a nickel-based positive electrode base material having a single phase structure, which may cause deterioration of electrochemical properties of the nickel-based positive electrode material, and the effect of the present invention cannot be achieved.
Preferably, the oxygen ion conductor is delta-Bi 2-p M p O q Wherein, p is more than or equal to 0 and less than or equal to 1.5, and q is more than or equal to 1.5 and less than or equal to 3; m is at least one selected from lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum and tungsten.
δ-Bi 2-p M p O q The material belongs to polymorphic substances, has four phase structures of alpha, beta, gamma and delta, and delta-Bi 2-p M p O q The disorder of anions in the structure leads to the existence of high intrinsic oxygen vacancy concentration, and trivalent bismuth can play a role in dynamic compensation on the charge which is asymmetric around the trivalent bismuth, so that the trivalent bismuth has high oxygen ion storage and transmission capacity.
The invention also provides a preparation method of the nickel-based positive electrode material, which comprises the following steps:
s1, adding a bismuth source, an M source and a nickel-based positive electrode material precursor into water according to a stoichiometric ratio of chemical elements, uniformly mixing and heating to obtain a first mixture;
s2, mixing and sintering the first mixture and a lithium source to obtain an oxygen ion conductor coated and bismuth phase doped modified nickel-based anode material;
wherein the M source is selected from nitrate, sulfate, chloride, oxalate, oxide or organometallic compounds; the nickel-based positive electrode material precursor is selected from Ni 1-x-y Co x A y (OH) 2 Or Ni 1-x-y Co x A y CO 3 Wherein A is selected from manganese or aluminum, 0.ltoreq.x < 0.5, 0.ltoreq.y < 0.5.
According to the technical means, the lithium source, the bismuth source and the M source are mixed into the nickel-based positive electrode material precursor for co-sintering, so that the in-situ synthesis and the surface coating of the oxygen ion conductor are simultaneously realized in the synthesis process of the nickel-based positive electrode material, the effect of uniform coating is achieved, the bulk doping of bismuth element is realized, and the oxygen ion conductor delta-Bi is realized 2-p M p O q Has low synthesis temperature similar to that of nickel-based positive electrode material, and can ensure the matrix of nickel-containing positive electrode material and oxygen ion conductor delta-Bi effectively 2-p M p O q The reaction is carried out simultaneously, thereby ensuring the structural uniformity and stability of the nickel-based anode material.
Preferably, in the step S1, the temperature of heating after mixing is 60-100 ℃ and the time is 30-200 min.
Preferably, in S2, sintering includes two-stage sintering in an oxygen atmosphere;
the first stage sintering conditions are as follows: preserving heat for 2-10 h at 350-650 ℃, wherein the temperature rising mode is programmed temperature rising, and the temperature rising rate is 2-10 ℃/min;
the second stage sintering condition is as follows: preserving heat for 10-24 h at 700-950 ℃, wherein the temperature rising mode is programmed temperature rising, and the temperature rising rate is 2-20 ℃/min.
Preferably, the oxygen volume concentration in the oxygen atmosphere is 50-99.999%.
Preferably, in S1, the bismuth source is at least one selected from bismuth nitrate, bismuth sulfate, bismuth carbonate, bismuth phosphate, bismuth acetate, bismuth oxide, bismuth halide, bismuth nitride, bismuth hydroxide and an organobismuth compound.
Preferably, the metal in the salt of the M source is selected from at least one of lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum and tungsten.
By selecting lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum and tungsten as metals in an M source, the capability of the formed oxygen ion conductor for successfully capturing active ions of lattice oxygen on the surface of activated material particles is improved, and the release of oxygen on the surface of an anode is effectively inhibited, so that the reaction heat release of oxygen and electrolyte is avoided, and the safety of a battery is improved.
Preferably, in S2, the lithium source is at least one selected from the group consisting of lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate and lithium nitrate.
The invention also provides application of the nickel-based positive electrode material, and the nickel-based positive electrode material is used as a positive electrode active material of a lithium ion battery.
The invention has the beneficial effects that:
1) The nickel-based positive electrode material is prepared by coating delta-Bi on the surface of a nickel-containing positive electrode material matrix 2-p M p O q Oxygen ion conductor and bismuth doping in nickel-based positive electrode material bulk phase, delta-Bi 2-p M p O q And bismuth are mutually synergistically modified, so that the interface and bulk phase dynamics performance are effectively improved, and the thermal stability of the material is improved, wherein, due to oxygen ion conductor delta-Bi 2-p M p O q The structure has high intrinsic oxygen vacancy concentration, so that active ions of lattice oxygen on the surface of activated material particles can be captured, oxygen release on the surface of an anode is inhibited, the reaction heat release of oxygen and electrolyte is avoided, and the safety of a battery is improved; meanwhile, the bismuth is introduced into the nickel-based positive electrode material to promote the growth of crystal grains, reduce the defects in the crystal grains and the grain boundaries among the particles, and effectively controlThe morphology and the particle size of a nickel-based positive electrode material product are prepared; bismuth doped in the bulk phase effectively improves the diffusion coefficient of lithium ions by activating crystal lattices; therefore, the nickel-based positive electrode material provided by the invention has the advantages of heat stability and electrochemical performance;
2) According to the preparation method of the nickel-based positive electrode material, the lithium source, the bismuth source and the M source are mixed into the nickel-based positive electrode material precursor to be sintered together, so that the in-situ synthesis and the surface coating of the oxygen ion conductor are simultaneously realized in the synthesis process of the nickel-based positive electrode material, the effect of uniform coating is achieved, the bulk doping of bismuth element is realized, and the oxygen ion conductor delta-Bi is realized 2-p M p O q The synthesis temperature is similar to that of the nickel-based positive electrode material, and the matrix of the nickel-based positive electrode material and the delta-Bi of the oxygen ion conductor are effectively ensured 2-p M p O q The synthesis reaction of the nickel-based anode material is carried out simultaneously, thereby ensuring the structural uniformity and stability of the nickel-based anode material, and having the advantages of simple and easy operation of the preparation method and mild and controllable process conditions;
3) According to the invention, the nickel-based positive electrode material is used as the positive electrode active material of the lithium ion battery, and experiments prove that the thermal stability of the nickel-based positive electrode material is obviously improved, so that the improvement of the safety of the battery is facilitated, the electrochemical performance of the battery is improved, and the nickel-based positive electrode material has popularization and application values in the technical field of battery materials.
Drawings
FIG. 1 is an SEM image of a nickel-based positive electrode material prepared in example 1;
FIG. 2 is an SEM image of the nickel-based positive electrode material prepared in comparative example 1;
FIG. 3 is an SEM image of the nickel-based positive electrode material prepared in example 3;
FIG. 4 is an SEM image of the nickel-based positive electrode material prepared in comparative example 3;
FIG. 5 is a differential scanning calorimetric comparison of full charge nickel-based positive electrode materials in the power down of example 6 and comparative example 4;
FIG. 6 is a differential scanning calorimetric comparison of full charge nickel-based positive electrode materials in the snap-down of example 7 and comparative example 5;
FIG. 7 is a differential scanning calorimetric comparison of full charge nickel-based positive electrode materials in the buckling of example 8 and comparative example 6.
Detailed Description
Further advantages and effects of the present invention will become readily apparent to those skilled in the art from the disclosure herein, by referring to the accompanying drawings and the preferred embodiments. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be understood that the preferred embodiments are presented by way of illustration only and not by way of limitation.
It should be noted that the illustrations provided in the following embodiments merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
In the following description, numerous details are discussed to provide a more thorough explanation of embodiments of the present application, however, it will be apparent to one skilled in the art that embodiments of the present application may be practiced without these specific details.
Example 1
The preparation method of the nickel-based positive electrode material comprises the following steps:
s1, 18mmol of Bi (NO 3 ) 3 ·5H 2 O,3mmol of La (NO) 3 ) 3 ·6H 2 O and 1mol Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 Adding a nickel-based positive electrode material precursor into 200mL of deionized water, magnetically stirring for 60min, uniformly mixing, and then distilling to remove a solvent under the condition of 90 ℃ oil bath to obtain a first mixture;
s2, mixing the first mixture with lithium hydroxide (LiOH) in a molar ratio of 1:1.05, then placing the mixture in a tube furnace,two-stage sintering in oxygen atmosphere, cooling and taking out to obtain delta-Bi 1.7 La 0.3 O 2.8 Oxygen ion conductor cladding and bismuth phase doping modified nickel-based anode material;
wherein the volume concentration of oxygen is 99%; the first stage sintering condition is that heat preservation is carried out for 10 hours at 350 ℃, the heating mode is temperature programming, and the heating rate is 5 ℃/min; the second stage sintering condition is that heat preservation is carried out for 12 hours at 750 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 10 ℃/min;
according to the measurement, in the embodiment, the molecular formula of the nickel-containing positive electrode material matrix in the prepared nickel-based positive electrode material is Li 1.01 Ni 0.9 Co 0.05 Mn 0.05 Bi 0.001 O 2 The proportion of bismuth doping is 0.1%; bismuth is distributed in both the oxygen ion conductor coating and the nickel-containing cathode material matrix.
Example 2
The preparation method of the nickel-based positive electrode material comprises the following steps:
s1, 45mmol Bi 2 O 3 25mmol C 10 H 5 NbO 20 And 1mol Ni 0.8 Co 0.15 Al 0.05 (OH) 2 Adding a nickel-based positive electrode material precursor into 1000mL of deionized water, magnetically stirring for 60min, uniformly mixing, and then distilling to remove a solvent under the condition of 90 ℃ oil bath to obtain a first mixture;
s2, mixing the first mixture with lithium carbonate (Li 2 CO 3 ) Mixing at a molar ratio of 1:0.52, placing in a tube furnace, sintering in oxygen atmosphere for two stages, cooling, and taking out to obtain delta-Bi 1.5 Nb 0.5 O 2.9 Oxygen ion conductor cladding and bismuth phase doping modified nickel-based anode material;
wherein the volume concentration of oxygen is 90%. The first stage sintering condition is that heat preservation is carried out for 7 hours at 500 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 3 ℃/min; the second stage sintering condition is that the temperature is kept for 10 hours at 800 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 5 ℃/min;
according to the measurement, in this example, nickel was producedThe molecular formula of the nickel-containing positive electrode material matrix in the base positive electrode material is Li 1.02 Ni 0.8 Co 0.15 Al 0.05 Bi 0.015 O 2 The proportion of bismuth doping is 1.5%; bismuth is distributed in both the oxygen ion conductor coating and the nickel-containing cathode material matrix.
Example 3
The preparation method of the nickel-based positive electrode material comprises the following steps:
s1, 80mmol of Bi (NO 3 ) 3 ·6H 2 O,60mmol Gd (NO) 3 ) 3 ·6H 2 O and 1mol Ni 0.8 Mn 0.2 CO 3 Adding a nickel-based positive electrode material precursor into 2000mL of deionized water, magnetically stirring for 60min, uniformly mixing, and then distilling to remove a solvent under the condition of 90 ℃ oil bath to obtain a first mixture;
s2, mixing the first mixture with lithium oxide (Li 2 O) are mixed according to the mol ratio of 1:0.55, then are placed in a tube furnace, are sintered for two sections in oxygen atmosphere, are cooled and are taken out to obtain delta-BiGdO 2.5 Oxygen ion conductor cladding and bismuth phase doping modified nickel-based anode material;
wherein the oxygen volume concentration is 75%. The first stage sintering condition is that heat preservation is carried out for 5 hours at 650 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 8 ℃/min; the second stage sintering condition is that heat preservation is carried out for 20 hours at 700 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 15 ℃/min;
according to the measurement, in the embodiment, the molecular formula of the nickel-containing positive electrode material matrix in the prepared nickel-based positive electrode material is Li 1.03 Ni 0.8 Mn 0.2 Bi 0.002 O 2 The proportion of bismuth doping is 0.2%; bismuth is distributed in both the oxygen ion conductor coating and the nickel-containing cathode material matrix.
Example 4
The preparation method of the nickel-based positive electrode material comprises the following steps:
s1, 60mmol of Bi (C 2 H 3 O 2 ) 3 WO 150mmol 3 And 1mol Ni (OH) 2 Precursor of nickel-based positive electrode materialAdding into 2500mL deionized water, magnetically stirring for 60min, mixing, and distilling at 90deg.C under oil bath to remove solvent to obtain a first mixture;
s2, mixing the first mixture with lithium nitrate (LiNO 3 ) Mixing at a molar ratio of 1:1.08, placing in a tube furnace, sintering in oxygen atmosphere for two stages, cooling, and taking out to obtain delta-Bi 0.5 W 1.5 O 2.75 Oxygen ion conductor cladding and bismuth phase doping modified nickel-based anode material;
wherein the oxygen volume concentration is 99.999%. The first stage sintering condition is that heat preservation is carried out for 5 hours at 550 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 6.5 ℃/min; the second stage sintering condition is that heat preservation is carried out for 15 hours at 720 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 10 ℃/min;
according to the measurement, in the embodiment, the molecular formula of the nickel-containing positive electrode material matrix in the prepared nickel-based positive electrode material is Li 1.04 NiBi 0.01 O 2 The proportion of bismuth doping is 1%; bismuth is distributed in both the oxygen ion conductor coating and the nickel-containing cathode material matrix.
Example 5
The preparation method of the nickel-based positive electrode material comprises the following steps:
s1, 10.75mmol of Bi (OH) 3 Pr (NO) 1.25mmol 3 ) 3 ·6H 2 O and 1mol Ni 0.5 Co 0.5 CO 3 Adding a nickel-based positive electrode material precursor into 2000mL of deionized water, magnetically stirring for 60min, uniformly mixing, and then distilling to remove a solvent under the condition of 90 ℃ oil bath to obtain a first mixture;
s2, mixing the first mixture with lithium oxalate (Li 2 C 2 O 4 ) Mixing at a molar ratio of 1:0.53, placing in a tube furnace, sintering in oxygen atmosphere for two stages, cooling, and taking out to obtain delta-Bi 1.75 Pr 0.25 O 2.33 Oxygen ion conductor cladding and bismuth phase doping modified nickel-based anode material;
wherein the oxygen volume concentration is 50%. The first stage sintering condition is that heat preservation is carried out for 5 hours at 500 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 5 ℃/min; the second stage sintering condition is that heat preservation is carried out for 20 hours at 950 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 12 ℃/min;
according to the measurement, in the embodiment, the molecular formula of the nickel-containing positive electrode material matrix in the prepared nickel-based positive electrode material is Li 1.01 Ni 0.5 Co 0.5 Bi 0.002 O 2 The proportion of bismuth doping is 0.2%; bismuth is distributed in both the oxygen ion conductor coating and the nickel-containing cathode material matrix.
Example 6
A preparation method of a lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in the embodiment 1 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 95:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Example 7
A preparation method of a lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in the embodiment 2 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 95:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 /EC+DMC+emc: DMC, EMC, EC is 1:1:1 by volume.
Example 8
A preparation method of a lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in the embodiment 3 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 95:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Example 9
A preparation method of a lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in the embodiment 4 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 95:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Example 10
A preparation method of a lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in the embodiment 5 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 95:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Comparative example 1
The preparation method of the conventional nickel-based positive electrode material comprises the following steps:
s1, ni is mixed with 0.9 Co 0.05 Mn 0.05 (OH) 2 Mixing a nickel-based positive electrode material precursor and lithium hydroxide (LiOH) in a molar ratio of 1:1.05, then placing the mixture in a tube furnace, performing two-stage sintering in an oxygen atmosphere, cooling, and taking out the mixture to obtain a conventional nickel-based positive electrode material;
wherein the oxygen volume concentration is 99%. The first stage sintering condition is that heat preservation is carried out for 10 hours at 350 ℃, the heating mode is temperature programming, and the heating rate is 5 ℃/min; the second stage sintering condition is that heat preservation is carried out for 12 hours at 750 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 10 ℃/min;
according to the measurement, in the comparative example, the molecular formula of the conventional nickel-based positive electrode material is Li 1.01 Ni 0.9 Co 0.05 Mn 0.05 O 2 。
Comparative example 2
The preparation method of the conventional nickel-based positive electrode material comprises the following steps:
s1, ni is mixed with 0.8 Co 0.15 Al 0.05 (OH) 2 Nickel-based positive electrode material precursor and lithium carbonate (Li 2 CO 3 ) Mixing in the molar ratio of 1:0.52, then placing in a tube furnace, performing two-stage sintering in oxygen atmosphere, cooling, and taking out to obtain a conventional nickel-based anode material;
wherein the oxygen volume concentration is 90%. The first stage sintering condition is that heat preservation is carried out for 7 hours at 500 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 3 ℃/min; the second stage sintering condition is that the temperature is kept for 10 hours at 800 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 5 ℃/min;
according to the measurement, in the comparative example, the molecular formula of the conventional nickel-based positive electrode material is Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 。
Comparative example 3
The preparation method of the conventional nickel-based positive electrode material comprises the following steps:
s1, ni is mixed with 0.8 Mn 0.2 CO 3 Nickel-based positive electrode material precursor and lithium oxide (Li 2 O) mixing in a molar ratio of 1:0.55, then placing in a tube furnace, performing two-stage sintering in an oxygen atmosphere, cooling, and taking out to obtain a conventional nickel-based anode material;
wherein the oxygen volume concentration is 75%. The first stage sintering condition is that heat preservation is carried out for 5 hours at 650 ℃, the temperature rising mode is temperature programming, and the temperature rising rate is 8 ℃/min; the second stage sintering condition is that heat preservation is carried out for 20 hours at 700 ℃, the temperature rising mode is programmed temperature rising, and the temperature rising rate is 15 ℃/min;
according to the measurement, in the comparative example, the molecular formula of the conventional nickel-based positive electrode material is Li 1.03 Ni 0.8 Mn 0.2 O 2 。
Comparative example 4
A preparation method of a conventional lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in comparative example 1 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 90:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Comparative example 5
A preparation method of a conventional lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in comparative example 2 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 90:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Comparative example 6
A preparation method of a conventional lithium ion battery comprises the following steps:
s1, taking the nickel-based positive electrode material prepared in comparative example 3 as a positive electrode active material of a lithium ion battery, and mixing the positive electrode active material with conductive carbon black and an adhesive PVDF to prepare positive electrode slurry; wherein, the positive electrode active material: conductive carbon black: the mass ratio of the adhesive PVDF is 90:5:5, coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode plate, wherein a metal lithium plate is used as a negative electrode plate;
s2, assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte which are manufactured in the S1 together to form a button cell; wherein the diaphragm is Celgard2400 porous polyethylene diaphragm, and the electrolyte is 1mol/L LiPF 6 Ec+dmc+emc: DMC, EMC, EC is 1:1:1 by volume.
Detection analysis
1) SEM analysis
The nickel-based positive electrode materials prepared in example 1 and example 3, and the conventional nickel-based positive electrode materials prepared in comparative example 1 and comparative example 3 were subjected to scanning electron microscope analysis, and the results are shown in fig. 1 to 4.
Among them, fig. 1 is an SEM image of the nickel-based positive electrode material manufactured in example 1, fig. 2 is an SEM image of the conventional nickel-based positive electrode material manufactured in comparative example 1, fig. 3 is an SEM image of the nickel-based positive electrode material manufactured in example 3, and fig. 4 is an SEM image of the conventional nickel-based positive electrode material manufactured in comparative example 3.
From the comparative analysis of fig. 1 and 2 and fig. 3 and 4, the in-situ synthesis of the oxygen ion conductor and the uniform punctiform coating on the surface of the substrate particles are realized by the co-sintering of the nickel-based positive electrode material substrate and the oxygen ion conductor; compared with the traditional coating method of simply mixing the substrate material and the coating material, the co-sintering realizes the in-situ synthesis of the oxygen ion conductor on the surface of the active substrate material, can obviously improve the binding force between the substrate material and the active substrate material, reduces the side reaction between the active substrate material and the electrolyte, and improves the structural stability and the thermal stability of the surface layer of the active substrate material.
2) Charge-discharge cycle test
The button cells assembled in examples 6 to 10 and comparative examples 4 to 6 were subjected to 0.2C charging at room temperature of 25 ℃ and a voltage interval of 3.0 to 4.35V, and then to 0.1C and 1C rate discharge, respectively, 1C charging and 1C discharging at room temperature of 25 ℃ and 50-week cycle retention test, 45 ℃ high temperature 0.5C charging and 0.5C discharging and 50-week cycle retention test, and the button test results are shown in table 1.
TABLE 1 cycle test results
From the analysis in Table 1, it can be seen from the comparison of example 6 and comparative example 4, example 7 and comparative example 5, example 8 and comparative example 6 that the 0.1C discharge capacity and the 1C discharge capacity of the nickel-based positive electrode material of the present invention are both higher, and the cycle effect at 25℃and 45℃are both better, which fully indicates the oxygen ion conductor delta-Bi of the present invention 2- p M p O q The coated bismuth phase doped modified nickel-based positive electrode material has excellent electrochemical performance.
3) DSC test
The button cells assembled in examples 6, 7 and 8, comparative example 4, comparative example 5 and comparative example 6 were charged to a cut-off voltage of 4.35V using a 0.1C charging current, then the button cells were disassembled in an argon atmosphere, the nickel-based positive electrode material and the conventional nickel-based positive electrode material were taken out, and DSC test was performed at a temperature rise rate of 5 ℃/min, and the test results are shown in fig. 5, 6 and 7.
Fig. 5 is a DSC test result of the fully charged nickel-based positive electrode material after disassembly of the button cell in example 6 and the fully charged conventional nickel-based positive electrode material after disassembly of the conventional button cell in comparative example 4, and as can be seen from comparative analysis in fig. 5, the thermal decomposition peak temperatures of the fully charged nickel-based positive electrode material after disassembly of the button cell in example 6 and the fully charged conventional nickel-based positive electrode material after disassembly of the conventional button cell in comparative example 4 are 228 ℃ and 207 ℃, respectively. Fig. 6 is a DSC test result of the fully charged nickel-based positive electrode material after disassembly of the button cell in example 7 and the conventional nickel-based positive electrode material after disassembly of the fully charged conventional button cell in comparative example 5, and as can be seen from comparative analysis in fig. 6, the thermal decomposition peak temperatures of the fully charged nickel-based positive electrode material after disassembly of the button cell in example 7 and the conventional nickel-based positive electrode material after disassembly of the fully charged conventional button cell in comparative example 5 are 238 ℃ and 213 ℃, respectively. Fig. 7 is a DSC test result of the fully charged nickel-based positive electrode material after disassembly of the coin in example 8 and the fully charged conventional nickel-based positive electrode material after disassembly of the conventional coin in comparative example 6, and as can be seen from comparative analysis in fig. 7, the thermal decomposition peak temperatures of the fully charged nickel-based positive electrode material after disassembly of the coin in example 8 and the fully charged conventional nickel-based positive electrode material after disassembly of the conventional coin in comparative example 6 are 253 ℃ and 218 ℃, respectively. Thus, it has been demonstrated that the invention employs oxygen ion conductor delta-Bi 2-p M p O q The thermal decomposition reaction temperature of the nickel-based positive electrode material doped and modified by the coated bismuth element phase is increased, so that the safety and stability of the lithium ion battery manufactured by the material are effectively improved.
In conclusion, experiments prove that the nickel-based positive electrode material is prepared byNickel-containing positive electrode material substrate surface cladding delta-Bi 2-p M p O q Oxygen ion conductor and bismuth doping in the bulk phase of the material, delta-Bi 2-p M p O q And bismuth phase doping and synergistic modification, effectively improving interface and bulk phase dynamics and improving thermal stability, wherein oxygen ion conductor delta-Bi 2-p M p O q The high intrinsic oxygen vacancy concentration exists in the structure to capture active ions of lattice oxygen on the surface of activated material particles, inhibit oxygen release on the surface of the positive electrode, further avoid the reaction heat release of oxygen and electrolyte, and improve the safety of the battery; the bismuth element is introduced in the material synthesis process, so that the growth of crystal grains can be promoted, defects in the crystal grains and grain boundaries among the grains are reduced, and the morphology and the grain size of a product are effectively controlled; bismuth doped in the bulk phase improves the diffusion coefficient of lithium ions by activating crystal lattices; therefore, the nickel-based positive electrode material provided by the invention has both thermal stability and electrochemical performance.
According to the preparation method of the nickel-based positive electrode material, the lithium source, the bismuth source and the M source are mixed into the nickel-based positive electrode material precursor to be sintered together, so that the in-situ synthesis and the surface coating of the oxygen ion conductor are simultaneously realized in the synthesis process of the nickel-based positive electrode material, the effect of uniform coating is achieved, the bulk doping of bismuth element is realized, and the oxygen ion conductor delta-Bi is realized 2- p M p O q The synthesis temperature is similar to that of the nickel-based positive electrode material, and the matrix of the nickel-based positive electrode material and the delta-Bi of the oxygen ion conductor are effectively ensured 2- p M p O q The synthesis reaction of the nickel-based anode material is carried out simultaneously, thereby ensuring the structural uniformity and stability of the nickel-based anode material, having the advantages of simple and easy operation of the preparation method, mild and controllable process conditions, being suitable for large-scale application in industrial production, and having popularization and application values in the technical field of battery materials.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those of ordinary skill in the art without departing from the spirit and scope of the present application. It is therefore contemplated that the appended claims will cover all such equivalent modifications and changes as fall within the true spirit and scope of the disclosure.
Claims (13)
1. The nickel-based positive electrode material is characterized by comprising a nickel-containing positive electrode material matrix and an oxygen ion conductor coated on the surface of the nickel-containing positive electrode material matrix, wherein bismuth is doped in the positive electrode material bulk phase;
the oxygen ion conductor is delta-Bi 2-p M p O q Wherein, p is more than or equal to 0 and less than or equal to 1.5, q is more than or equal to 1.5 and less than or equal to 3, and M is at least one of lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum and tungsten.
2. The nickel-based positive electrode material according to claim 1, wherein the molar ratio of the oxygen ion conductor to the nickel-containing positive electrode material matrix is 0.1-10:100.
3. The nickel-based positive electrode material according to claim 1, wherein the nickel-containing positive electrode material matrix is Li z Ni 1-x-y Co x A y O 2 Wherein, A is selected from manganese or aluminum, z is more than or equal to 0.95 and less than or equal to 1.15,0, x is more than or equal to 0.5, and y is more than or equal to 0 and less than 0.5.
4. The nickel-based positive electrode material according to claim 1, wherein the bismuth is doped in the form of trivalent bismuth ions in a matrix of the nickel-containing positive electrode material; the doping proportion of bismuth is 0.1% -2%.
5. The nickel-based positive electrode material according to claim 1, wherein the nickel-containing positive electrode material matrix is selected from at least one of lithium nickelate, lithium nickelate and lithium nickelate aluminate.
6. The nickel-based positive electrode material according to claim 1, wherein the oxygen ion conductor is δ -Bi 2-p M p O q Wherein, p is more than or equal to 0 and less than or equal to 1.5, q is more than or equal to 1.5 and less than or equal to 3, M is selected from lanthanum, tantalum, praseodymium and neodymium,At least one of gadolinium, niobium, molybdenum and tungsten.
7. A method for producing the nickel-based positive electrode material according to any one of claims 1 to 6, comprising the steps of:
s1, adding a bismuth source, an M source and a nickel-based positive electrode material precursor into water, mixing and heating to obtain a first mixture;
s2, mixing and sintering the first mixture and a lithium source to obtain an oxygen ion conductor coated and bismuth phase doped modified nickel-based anode material;
wherein the M source is selected from nitrate, sulfate, chloride, oxalate, oxide or organometallic compounds; the nickel-based positive electrode material precursor is selected from Ni 1-x-y Co x A y (OH) 2 Or Ni 1-x-y Co x A y CO 3 Wherein A is selected from manganese or aluminum, 0.ltoreq.x < 0.5, 0.ltoreq.y < 0.5.
8. The preparation method according to claim 7, wherein in the step S1, the temperature of heating after mixing is 60-100 ℃ for 30-200 min.
9. The method of claim 7, wherein in S2, sintering comprises two-stage sintering in an oxygen atmosphere;
the first stage sintering conditions are as follows: preserving heat for 2-10 hours at the temperature of 350-650 ℃, wherein the temperature rising mode is programmed temperature rising, and the temperature rising rate is 2-10 ℃/min;
the second stage sintering condition is as follows: and preserving heat for 10-24 hours at the temperature of 700-950 ℃, wherein the temperature rising mode is programmed temperature rising, and the temperature rising rate is 2-20 ℃/min.
10. The method according to claim 7, wherein in S1, the bismuth source is at least one selected from the group consisting of bismuth nitrate, bismuth sulfate, bismuth carbonate, bismuth phosphate, bismuth acetate, bismuth oxide, bismuth halide, bismuth nitride, bismuth hydroxide, and an organobismuth compound.
11. The method of claim 7, wherein the metal in the salt of the M source is selected from at least one of lanthanum, tantalum, praseodymium, neodymium, gadolinium, niobium, molybdenum, and tungsten.
12. The method according to claim 7, wherein in S2, the lithium source is at least one selected from the group consisting of lithium hydroxide, lithium carbonate, lithium oxide, lithium oxalate and lithium nitrate.
13. Use of a nickel-based positive electrode material according to any one of claims 1 to 6 as positive electrode active material for a lithium ion battery.
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