CN113845152A - Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN113845152A CN113845152A CN202111007832.2A CN202111007832A CN113845152A CN 113845152 A CN113845152 A CN 113845152A CN 202111007832 A CN202111007832 A CN 202111007832A CN 113845152 A CN113845152 A CN 113845152A
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- lithium
- nickel
- manganese oxide
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000010406 cathode material Substances 0.000 claims abstract description 55
- 238000001354 calcination Methods 0.000 claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000011572 manganese Substances 0.000 claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 32
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 32
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 32
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 32
- 229960004853 betadex Drugs 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000008139 complexing agent Substances 0.000 claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000003792 electrolyte 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
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 3
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims description 3
- AIFGVOMWPFMOCN-UHFFFAOYSA-L manganese(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O AIFGVOMWPFMOCN-UHFFFAOYSA-L 0.000 claims description 3
- OQTQHQORDRKHFW-UHFFFAOYSA-L manganese(2+);sulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O OQTQHQORDRKHFW-UHFFFAOYSA-L 0.000 claims description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 18
- 239000011029 spinel Substances 0.000 abstract description 18
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000004873 anchoring Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 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 abstract description 2
- 239000000047 product Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012535 impurity Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910005689 Li1.05Ni0.5Mn1.5O4 Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery. The preparation method of the lithium nickel manganese oxide positive electrode material comprises the following steps: carrying out gel reaction on a lithium source, a nickel source, a manganese source, water, beta-cyclodextrin, a complexing agent and an alkaline regulator to obtain precursor gel, wherein the molar ratio of lithium element in the lithium source, nickel element in the nickel source and manganese element in the manganese source is (1.00-1.06): (0.45-0.55): 1.45-1.85); and dehydrating and calcining the precursor gel to obtain the lithium nickel manganese oxide cathode material. The preparation method can realize the anchoring of nickel and manganese, thereby reducing the probability of mixed discharging of lithium ions and nickel ions in the lithium nickel manganese oxide cathode material, being beneficial to improving the structural stability of the lithium nickel manganese oxide cathode material and forming a spinel structure, and leading the prepared lithium nickel manganese oxide cathode material to have good first discharge efficiency, rate capability, capacity recovery and cycling stability.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathode materials, in particular to a lithium nickel manganese oxide cathode material, a preparation method thereof and a lithium ion battery.
Background
The power battery of the electric vehicle is required to have characteristics of high power and high energy performance. The power battery commonly used at present is mainly lithium cobaltate (LiCoO)2) Battery, lithium iron phosphate (LiFePO)4) Battery and spinel lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) A battery. Among them, lithium cobaltate (LiCoO)2) The working discharge voltage platform of the battery is low and is only 3.7V, and the manufacturing cost of the battery is increased due to the shortage of cobalt resources, and the battery is harmful to the environment. Lithium iron phosphate (LiFePO)4) The discharge voltage plateau of the battery is lower, and is only 3.2V. And spinel lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) The material is a material with high specific energy, has the characteristics of higher theoretical capacity (146.7mAh/g), high voltage platform (4.7V), excellent cycle performance, small capacity loss rate, low preparation cost, environmental friendliness and the like, and has energy density as high as 650Wh/kg, so that the material has great potential to be applied to high-energy-density lithium ion batteries.
The most common method for synthesizing lithium nickel manganese oxide at present is a solid-phase synthesis method. The preparation process of the solid phase synthesis method comprises the following three steps: accurately weighing the raw materials in proportion, mechanically mixing the raw materials to obtain an initial product, grinding and dispersing the initial product to obtain an intermediate product, and calcining the intermediate product at high temperature to obtain a final product. The method has simple preparation process, but has the problems of uneven phase distribution, easy impurity mixing in the preparation process, high temperature required by preparation and high energy consumption, and the problems can further influence the electrochemical performance of the lithium ion battery.
In order to solve the above problems, a sol-gel method has been reported to be used for synthesizing a lithium nickel manganese oxide positive electrode material. The sol-gel method has the advantages of low synthesis temperature and small particle size of the product, but the existing reported sol-gel method mostly adopts a single complexing agent in the preparation process, so that the complexing effect is poor, and the prepared lithium nickel manganese oxide cathode material has poor crystallinity and low purity, thereby influencing the exertion of the electrochemical performance. In the first charging process, lithium ions in the lithium layer and the transition metal layer can be removed, but when the lithium battery is discharged, if mixed discharging of the lithium ions and nickel ions exists in the positive electrode material, part of lithium cannot return to the positive electrode lattice of the lithium nickel manganese oxide, and the first discharging efficiency of the material is reduced.
On the basis, a preparation method capable of improving the structural stability of the lithium nickel manganese oxide positive electrode material is researched and developed, and the preparation method has important significance for slowing down the phenomenon of cation mixing and discharging and improving the electrochemical properties of the lithium nickel manganese oxide positive electrode material, such as first discharge efficiency, rate capability, capacity recovery and cycling stability.
Disclosure of Invention
The invention mainly aims to provide a lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery, and aims to solve the problem that the lithium nickel manganese oxide positive electrode material prepared by the existing sol-gel method is poor in structural stability and poor in electrochemical performance.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing a lithium nickel manganese oxide positive electrode material, where the method for preparing a lithium nickel manganese oxide positive electrode material includes: carrying out gel reaction on a lithium source, a manganese source, a nickel source, water, beta-cyclodextrin, a complexing agent and an alkaline regulator to obtain precursor gel, wherein the molar ratio of lithium element in the lithium source to nickel element in the nickel source to manganese element in the manganese source is (1.00-1.06) to (0.45-0.55) to (1.45-1.85); and dehydrating and calcining the precursor gel to obtain the lithium nickel manganese oxide cathode material.
Furthermore, the molar ratio of the nickel element, the beta-cyclodextrin and the complexing agent is (0.45-0.55): (0.0022-0.022): 0.0045-0.12).
Further, the molar ratio of the beta-cyclodextrin to the complexing agent is (0.17-0.22): 1.
Further, the alkaline modifier is one or more selected from the group consisting of ammonia water, sodium hydroxide, sodium bicarbonate and sodium carbonate, and the pH of the gel reaction is 5.0 to 7.0.
Further, the complexing agent is selected from one or more of the group consisting of citric acid, tartaric acid and amino acids.
Further, the lithium source is one or more selected from the group consisting of lithium acetate, lithium ethoxide, lithium hydroxide and lithium carbonate; the manganese source is one or more selected from the group consisting of manganese acetate tetrahydrate, manganese sulfate heptahydrate, manganese chloride tetrahydrate, manganese nitrate hexahydrate and manganese perchlorate hexahydrate; the nickel source is one or more selected from the group consisting of nickel acetate tetrahydrate, nickel sulfate heptahydrate, nickel chloride hexahydrate, nickel chloride and nickel nitrate.
Further, the calcining process comprises a first calcining treatment and a second calcining treatment, wherein the temperature of the first calcining treatment is 780-850 ℃, and the treatment time is 8-10 hours; the temperature of the second calcination treatment is 600-700 ℃, and the treatment time is 8-14 h.
Further, before the calcination process, the preparation method of the lithium nickel manganese oxide positive electrode material further comprises the following steps: pre-sintering the product obtained by the dehydration step; preferably, the temperature of the pre-sintering treatment is 300-370 ℃, and the treatment time is 4-5 h.
The invention also provides a lithium nickel manganese oxide positive electrode material, which is prepared by the preparation method of the lithium nickel manganese oxide positive electrode material, and the chemical formula of the lithium nickel manganese oxide positive electrode material is LiaNixMn2-xO4Wherein a is more than or equal to 1.00 and less than or equal to 1.06, and x is more than or equal to 0.45 and less than or equal to 0.55.
The invention further provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and electrolyte, wherein the positive electrode comprises the lithium nickel manganese oxide positive electrode material.
By applying the technical scheme of the invention, the complexing agent can perform a complexing reaction with metal ions generated by the hydrolysis of the nickel source and the manganese source to form a complex product. The addition of the alkaline regulator can provide a proper chemical reaction environment for the gel reaction, and is beneficial to obtaining precursor gel after the gel reaction is finished. And dehydrating and calcining the precursor gel to carbonize and remove organic matter molecules in the gel so as to form the lithium nickel manganese oxide cathode material. By limiting the molar ratio of the lithium element, the manganese element and the nickel element in the above range, the spinel type lithium nickel manganese oxide cathode material with good crystal form purity can be formed.
The beta-cyclodextrin is composed of a hydrophilic outer edge and a hydrophobic inner cavity, and can form an inclusion compound with a complex product with a proper size in a gel reaction process, so that the anchoring of nickel and manganese is realized, the probability of mixing and discharging lithium ions and nickel ions in the subsequently prepared lithium nickel manganese oxide cathode material is reduced, and the structural stability of the lithium nickel manganese oxide cathode material is improved. On the basis, the spinel type lithium nickel manganese oxide cathode material prepared by the method has the advantages of high theoretical capacity, high voltage plateau, excellent cycle performance and small capacity loss rate, and when the spinel type lithium nickel manganese oxide cathode material is applied to a lithium ion battery, the electrochemical performances of the lithium ion battery, such as first discharge efficiency, rate capability, capacity recovery, cycle stability and the like, can be improved. In addition, the preparation method has simple process, does not use toxic and harmful substances in the preparation process, and has no pollution to the environment.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a powder X-ray diffraction pattern (XRD pattern) of a lithium nickel manganese oxide positive electrode material obtained in example 1 of the present invention;
FIG. 2 shows a scanning electron micrograph (SEM image, 2000 times magnification) of a lithium nickel manganese oxide cathode material prepared in example 1 of the present invention;
FIG. 3 is a powder X-ray diffraction pattern (XRD pattern) of the lithium nickel manganese oxide positive electrode material obtained in comparative example 1 of the present invention;
FIG. 4 is a powder X-ray diffraction pattern (XRD pattern) of the lithium nickel manganese oxide positive electrode material obtained in comparative example 2 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the lithium nickel manganese oxide cathode material prepared by the existing sol-gel method has the problem of poor structural stability and poor electrochemical performance. In order to solve the technical problem, the application provides a preparation method of a spinel lithium nickel manganese oxide positive electrode material, and the preparation method of the lithium nickel manganese oxide positive electrode material comprises the following steps: carrying out gel reaction on a lithium source, a manganese source, a nickel source, water, beta-cyclodextrin, a complexing agent and an alkaline regulator to obtain precursor gel, wherein the molar ratio of lithium element in the lithium source, nickel element in the nickel source and manganese element in the manganese source is (1.00-1.06): (0.45-0.55): 1.45-1.85); and dehydrating and calcining the precursor gel to obtain the lithium nickel manganese oxide cathode material.
The complexing agent can perform a complexing reaction with metal ions generated by the hydrolysis of the nickel source and the manganese source to form a complexing product. The addition of the alkaline regulator can provide a proper chemical reaction environment for the gel reaction, and is beneficial to obtaining precursor gel after the gel reaction is finished. And dehydrating and calcining the precursor gel to carbonize and remove organic matter molecules in the gel so as to form the lithium nickel manganese oxide cathode material. By limiting the molar ratio of the lithium element, the nickel element and the manganese element in the above range, the spinel type lithium nickel manganese oxide cathode material with good crystal form purity can be formed.
The beta-cyclodextrin is composed of a hydrophilic outer edge and a hydrophobic inner cavity, and can form an inclusion compound with a complex product with a proper size in a gel reaction process, so that the anchoring of nickel and manganese is realized, the probability of mixing and discharging lithium ions and nickel ions in the subsequently prepared lithium nickel manganese oxide cathode material is reduced, and the structural stability of the lithium nickel manganese oxide cathode material is improved. On the basis, the spinel type lithium nickel manganese oxide cathode material prepared by the method has the advantages of high theoretical capacity, high voltage plateau, excellent cycle performance and small capacity loss rate, and when the spinel type lithium nickel manganese oxide cathode material is applied to a lithium ion battery, the electrochemical performances of the lithium ion battery, such as first discharge efficiency, rate capability, capacity recovery, cycle stability and the like, can be improved. In addition, the preparation method has simple process, does not use toxic and harmful substances in the preparation process, and has no pollution to the environment.
In an aqueous solution, the inner cavity of the beta-cyclodextrin is occupied by water molecules and is in an unstable energy state, and in the gel reaction process, the inner cavity of the beta-cyclodextrin is replaced by a complex product with lower polarity than the water molecules, so that a non-covalent bond is formed between a host and an object, and the beta-cyclodextrin can be in a more stable energy state. That is, the complex product and the β -cyclodextrin can form an inclusion compound containing manganese and nickel. In order to improve the capture efficiency of a complexing agent on manganese ions and nickel ions, a complex product formed by a complexing reaction can form an inclusion compound with a more stable structure with beta-cyclodextrin, and the anchoring effect on nickel and manganese is enhanced, in a preferred embodiment, the molar ratio of nickel element, beta-cyclodextrin and the complexing agent is (0.45-0.55): (0.0022-0.022): (0.0045-0.12).
In a preferred embodiment, the molar ratio of the beta-cyclodextrin to the complexing agent is (0.17-0.22): 1. Compared with other ranges, the mol ratio of the beta-cyclodextrin to the complexing agent is limited in the range, so that a more stable inclusion compound is further formed, the anchoring effect on nickel and manganese is further enhanced, the probability of mixed arrangement of lithium ions and nickel ions in the subsequently prepared lithium nickel manganese oxide positive electrode material is reduced, and the structural stability of the lithium nickel manganese oxide positive electrode material is improved.
The gel reaction process is performed under the conventional conditions, for example, as long as manganese ions, nickel ions and lithium ions can be precipitated, and the specific conditions are not limited. In a preferred embodiment, the alkaline modifier includes, but is not limited to, one or more of the group consisting of ammonia, sodium hydroxide, sodium bicarbonate and sodium carbonate, and the pH of the gel reaction is 5.0 to 7.0. The alkaline regulator can be converted into gas or directly decomposed in the calcining process, so that the adoption of the alkaline regulator is beneficial to reducing impurity elements in the lithium nickel manganese oxide positive electrode material, and is further beneficial to improving the subsequent application performance of the positive electrode material.
The complexing agent can be complexed with metal ions generated by the hydrolysis of the nickel source and the manganese source to form a complex product. In a preferred embodiment, the complexing agent includes, but is not limited to, one or more of the group consisting of citric acid, tartaric acid and amino acids.
The lithium source in the present application may be selected from lithium salts commonly used in the art. In a preferred embodiment, the lithium source includes, but is not limited to, lithium acetate (CH)3COOLi), lithium ethoxide (C)2H5OLi), lithium hydroxide (LiOH) and lithium carbonate (LiCO)3) One or more of the group consisting of.
The manganese source in the present application may be selected from manganese salts commonly used in the art. In a preferred embodiment, the manganese source includes, but is not limited to, manganese acetate tetrahydrate (Mn (CH)3COO)2·4H2O), manganese sulfate heptahydrate (MnSO)4·7H2O), manganese chloride tetrahydrate (MnCl)2·7H2O), manganese nitrate hexahydrate (Mn (NO)3)2·6H2O) and manganese perchlorate hexahydrate (Mn (ClO)4)2·6H2O) is used as a solvent.
The nickel source in the present application may be selected from nickel salts commonly used in the art. In a preferred embodiment, the nickel source includes, but is not limited to, one or more of the group consisting of nickel acetate tetrahydrate, nickel sulfate heptahydrate, nickel chloride hexahydrate, nickel chloride, and nickel nitrate.
In a preferred embodiment, the calcination process comprises a first calcination treatment and a second calcination treatment, wherein the temperature of the first calcination treatment is 780-850 ℃, and the treatment time is 8-10 h; the temperature of the second calcination treatment is 600-700 ℃, and the treatment time is 8-14 h.
Compared with direct one-time calcination, the twice calcination treatment is favorable for enabling the dehydrated product to be oxidized at high temperature to form the lithium nickel manganese oxide cathode material with a more stable structure, and the crystallinity is favorably improved. Compare in other scopes, inject the temperature and the time of first calcination processing and second calcination processing respectively in above-mentioned scope, be favorable to making the nickel lithium manganate cathode material that makes form spinel type structure, simultaneously, further got rid of its inside impurity, improved the purity of spinel type structure, be convenient for improve its structural stability to be favorable to improving electrochemical properties such as nickel lithium manganate cathode material's first discharge efficiency, rate capability, capacity recovery and cycle stability.
In order to remove organic compounds such as inclusion compounds contained in the dehydrated precursor gel product and reduce impurities in the material to be calcined, in a preferred embodiment, before the calcining process, the preparation method of the lithium nickel manganese oxide cathode material further comprises the following steps: and (4) performing presintering treatment on the product obtained by the dehydration step. In order to improve the removal rate of organic compounds such as inclusion compounds and reduce impurities in the material to be calcined, the temperature of the pre-sintering treatment is preferably 300-370, and the treatment time is preferably 4-5 h.
In order to facilitate the subsequent calcination treatment and make the heating of the product to be pre-sintered during the calcination treatment more uniform, in a preferred embodiment, the preparation method of the lithium nickel manganese oxide cathode material before the pre-sintering treatment further comprises: and grinding the product obtained in the dehydration step to ensure that the average particle size of the ground product is 8.5 +/-1 mu m.
The second aspect of the application provides a lithium nickel manganese oxide positive electrode material, wherein the lithium nickel manganese oxide positive electrode material is prepared by the preparation method of the lithium nickel manganese oxide positive electrode material, and the chemical formula of the lithium nickel manganese oxide positive electrode material is LiaNixMn2-xO4Wherein a is more than or equal to 1.00 and less than or equal to 1.06, and x is more than or equal to 0.45 and less than or equal to 0.55. By the above-mentioned systemThe lithium nickel manganese oxide cathode material prepared by the preparation method has a spinel structure, and is good in structural stability, and further has good first discharge efficiency, rate capability and cycle stability.
The third aspect of the present application further provides a lithium ion battery, where the lithium ion battery includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, and the positive electrode includes the lithium nickel manganese oxide positive electrode material. The lithium nickel manganese oxide cathode material has a spinel structure with high purity and good stability, and is applied to a lithium ion battery, so that the electrochemical properties of the lithium nickel manganese oxide cathode material, such as first discharge efficiency, rate capability, cycling stability and the like, of the lithium ion battery can be improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The lithium nickel manganese oxide positive electrode materials prepared in the examples and the comparative examples are respectively adopted for electricity deduction, the positive electrode material, the carbon black conductive agent and the binder PVDF (solid content is 6.25%) are weighed according to the weight ratio of 92:4:4, NMP is added to adjust the solid content of the slurry to 49%, and the slurry is uniformly mixed to prepare the positive electrode slurry. And coating the prepared positive electrode slurry on an aluminum foil with the thickness of 20 mu m, and carrying out vacuum drying and rolling to prepare a positive electrode plate. The positive pole piece is used as a positive pole, the lithium metal piece is used as a negative pole, and the lithium metal piece contains 1mol/L LiPF6DMC (volume ratio of 2:3) is used as electrolyte, and the button cell is assembled and manufactured.
The electrical property test of the material is carried out by adopting a blue battery test system at 25 ℃, and the test voltage range is 3.5-5V; the first discharge capacity, the first discharge efficiency and the capacity retention rate after 50 weeks of cycling were tested.
Example 1
(1) Weighing CH according to the mol numbers of Li, Ni and Mn of 1.05mol, 0.5mol and 1.5mol respectively3COOLi、Ni(CH3COO)2·4H2O and Mn (CH)3COO)2·4H2Dissolving O in 500mL of deionized water, and stirring at room temperature for 40min at the rotating speed of 300 r/min by using a mechanical stirrer to obtain a transparent solution. Then to283.74g and 0.25mol of beta-cyclodextrin are added into the transparent solution and stirred uniformly to obtain a mixed solution, so that the concentration of the beta-cyclodextrin in the mixed solution is 0.5 mol/L.
(2) 283.74g and 1.48mol of citric acid are weighed, the weight ratio of beta-cyclodextrin to citric acid is 1:1, the beta-cyclodextrin and the citric acid are dissolved in a proper amount of deionized water and are uniformly mixed, so that the citric acid is dissolved, and the mixture is added into the mixed solution prepared in the step (1); wherein the molar ratio of Ni to beta-cyclodextrin to citric acid is 0.5:0.0125: 0.074.
(3) And (3) mixing the mixed solution prepared in the step (2) with alkaline regulator ammonia water, regulating the pH of the solution to 6.5, transferring the solution to a constant-temperature water bath at 50 ℃, stirring for 3 hours, heating to 95 ℃, keeping the temperature to continuously evaporate water to obtain precursor sol, and then obtaining precursor gel. And drying the precursor gel in a vacuum drying oven at 150 ℃ for 6h to obtain dry gel, and grinding to obtain powder to be pre-sintered with the average particle size of 9.5 +/-1 mu m.
(4) And (3) placing the powder to be presintered in an experimental furnace for presintering at 370 ℃ for 5 hours in an air atmosphere, and grinding and sieving to obtain the powder to be presintered with the average particle size of 8.5 +/-1 mu m. Carrying out primary calcination treatment on the powder to be sintered at 800 ℃, wherein the calcination time is 10 h; and then, cooling to 650 ℃ for secondary calcination treatment, wherein the calcination time is 10h, naturally cooling to room temperature after the calcination process is finished, and grinding and sieving to obtain the spinel lithium nickel manganese oxide cathode material with the average particle size of 8.5 +/-1 mu m.
The XRD pattern of the lithium nickel manganese oxide cathode material prepared in the way is shown in figure 1, and the sample has the diffraction peak intensity ratio, the peak shape and the peak position and LiNi0.5Mn1.5O4Compared with the standard PDF card (80-2183), the position matching degree of the main peak pattern is very high, all diffraction peaks can be proved to be in a spinel cubic structure by comparing with the standard peak, and the chemical formula of the prepared lithium nickel manganese oxide cathode material is Li1.05Ni0.5Mn1.5O4。
An SEM image of the prepared lithium nickel manganese oxide cathode material is shown in figure 2, the lithium nickel manganese oxide cathode material has good dispersibility, and single particles are in irregular shapes and are large single crystals.
The electrochemical performance parameters of the lithium ion battery assembled by the prepared lithium nickel manganese oxide cathode material are tested, and the test results are shown in table 1.
Example 2
The difference from example 1 is that: the lithium source is lithium ethoxide, and the molar ratio of the lithium element in the lithium source, the nickel element in the nickel source and the manganese element in the manganese source is 1.00:0.45: 1.55.
According to the XRD test result, the chemical formula of the lithium nickel manganese oxide cathode material prepared in the embodiment is Li1.00Ni0.45Mn1.55O4. The results of the electrochemical performance parameter tests are shown in table 1.
Example 3
The difference from example 1 is that: the lithium source was lithium carbonate, and the molar ratio of the lithium element in the lithium source, the nickel element in the nickel source, and the manganese element in the manganese source was 1.06:0.55: 1.45.
According to the XRD test result, the chemical formula of the lithium nickel manganese oxide cathode material prepared in the embodiment is Li1.06Ni0.55Mn1.45O4. The results of the electrochemical performance parameter tests are shown in table 1.
Example 4
The difference from example 1 is that: the molar ratio of the nickel element, the beta-cyclodextrin and the citric acid is 0.55:0.022: 0.10.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 5
The difference from example 1 is that: the molar ratio of the nickel element, the beta-cyclodextrin and the citric acid is 0.45:0.022: 0.10.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 6
The difference from example 1 is that: the molar ratio of the nickel element, the beta-cyclodextrin and the citric acid is 0.30:0.022: 0.10.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 7
The difference from example 1 is that: the alkaline modifier was sodium carbonate and the pH of the gelling reaction was 5.0.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 8
The difference from example 1 is that: the alkaline modifier was sodium carbonate and the pH of the gelling reaction was 7.0.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 9
The difference from example 1 is that: the pH of the gel reaction was 8.0.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 10
The difference from example 1 is that: the complexing agent is tartaric acid.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 11
The difference from example 1 is that: the complexing agent is glutamic acid.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 12
The difference from example 1 is that: the temperature of the first calcination treatment is 780 ℃, and the treatment time is 10 h; the temperature of the second calcination treatment was 600 ℃ and the treatment time was 14 hours.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 13
The difference from example 1 is that: the temperature of the first calcination treatment is 850 ℃, and the treatment time is 8 h; the temperature of the second calcination treatment was 700 ℃ and the treatment time was 8 hours.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 14
The difference from example 1 is that: only one time of calcination treatment is carried out, the temperature of the calcination treatment is 800 ℃, and the calcination time is 12 h.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 15
The difference from example 1 is that: the temperature of the first calcination treatment is 700 ℃, and the treatment time is 4 h; the temperature of the second calcination treatment was 400 ℃ and the treatment time was 4 hours.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 16
The difference from example 1 is that: the temperature of the pre-sintering treatment is 300 ℃, and the treatment time is 5 h.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 17
The difference from example 1 is that: the temperature of the pre-sintering treatment is 370 ℃, and the treatment time is 4 h.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 18
The difference from example 1 is that: the temperature of the pre-sintering treatment is 280 ℃, and the treatment time is 3 h.
The results of the electrochemical performance parameter tests are shown in table 1.
Example 19
The difference from example 1 is that: will CH3COOLi、Mn(CH3COO)2·4H2O and Ni (CH)3COO)2·4H2Mixing the O and water, and stirring for 30min at a rotating speed of 250 revolutions per minute by adopting a mechanical stirrer to obtain a transparent solution; and drying the precursor gel in a vacuum drying oven at 120 ℃ to obtain dry gel.
The results of the electrochemical performance parameter tests are shown in table 1.
Comparative example 1
The difference from example 1 is that: no beta-cyclodextrin was added.
The XRD pattern of the lithium nickel manganese oxide cathode material prepared in the way is shown in figure 3. Compared with the lithium nickel manganese oxide cathode material prepared in example 1 (fig. 1), the lithium nickel manganese oxide cathode material prepared without adding beta-cyclodextrin has wider peak width and more miscellaneous peaks, which indicates that the crystal form purity is lower. According to the comparison of the standard cards, the chemical formula of the lithium nickel manganese oxide cathode material prepared by the comparative example is Li1.05Ni0.5Mn1.5O4. Electrochemistry methodThe results of the performance parameter tests are shown in table 1.
Comparative example 2
The difference from example 1 is that: no citric acid was added.
The XRD pattern of the lithium nickel manganese oxide cathode material prepared as described above is shown in fig. 4, and compared with the lithium nickel manganese oxide cathode material prepared in example 1 (fig. 1), the lithium nickel manganese oxide cathode material prepared without adding citric acid has a wider peak width and more peaks, which indicates that the crystal purity is lower. According to the comparison of the standard cards, the chemical formula of the lithium nickel manganese oxide cathode material prepared by the comparative example is Li1.05Ni0.5Mn1.5O4. The results of the electrochemical performance parameter tests are shown in table 1.
Comparative example 3
The difference from example 1 is that: beta-cyclodextrin is not added, and a complex complexing agent is adopted, including citric acid, triethanolamine and polyethylene glycol (PEG).
The results of the electrochemical performance parameter tests are shown in table 1.
Comparative example 4
The procedure was the same as in example 1. The difference from example 1 is that: weighing CH according to the molar ratio of Li to Ni to Mn of 1 to 0.53COOLi、Ni(CH3COO)2·4H2O and Mn (CH)3COO)2·4H2O。
The results of the electrochemical performance parameter tests are shown in table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
as can be seen from comparison of examples 1 to 3 and 19 and comparative example 4, the molar ratio of the lithium element, the nickel element and the manganese element is limited in the preferred range of the present application, so that the subsequent treatment is facilitated to form the spinel-type lithium nickel manganese oxide cathode material with good crystal purity, and when the spinel-type lithium nickel manganese oxide cathode material is applied to a lithium ion battery, the electrochemical properties such as the first discharge efficiency, rate capability, capacity recovery and cycle stability of the lithium ion battery can be improved.
Comparing examples 1, 4 to 6, it is known that limiting the molar ratio of the nickel element, the beta-cyclodextrin and the complexing agent within the preferred range of the present application is beneficial to improving the capturing efficiency of the complexing agent on manganese ions and nickel ions, so that the complex product formed by the complexing reaction and the beta-cyclodextrin can form an inclusion compound with a more stable structure, and the anchoring effect on nickel and manganese is enhanced.
As can be seen from comparison of examples 1 and 7 to 9, the above-mentioned alkaline regulator is converted into gas or directly decomposed during the calcination process, so that the use of the alkaline regulator of the preferred kind in the present application is beneficial to reducing the impurity elements in the lithium nickel manganese oxide positive electrode material, thereby being beneficial to improving the subsequent application performance of the positive electrode material.
Comparing examples 1, 10 and 11 with comparative examples 1 and 3, it can be seen that the beta-cyclodextrin preferred in the present application can form an inclusion compound with a complex product with a suitable size, thereby realizing anchoring of nickel and manganese, facilitating reduction of probability of mixing of lithium ions and nickel ions in the lithium nickel manganese oxide positive electrode material, improving structural stability of the lithium nickel manganese oxide positive electrode material, and facilitating improvement of electrochemical properties such as first discharge efficiency, rate capability, capacity recovery and cycle stability of the lithium nickel manganese oxide positive electrode material.
Comparing example 1 with comparative example 2, it can be seen that the complexing agent is capable of forming a complex product by a complex reaction with the manganese source and the nickel source.
Comparing examples 1 and 12 to 15, it can be seen that compared with direct one-time calcination, the twice calcination treatment provided by the present application is beneficial to make the structure of the lithium nickel manganese oxide positive electrode material formed by oxidizing the dehydrated product at high temperature more stable, and improve the crystallinity. Compare in other scopes, inject the temperature and the time of first calcination processing and second calcination processing respectively in this application preferred range, be favorable to making the nickel lithium manganate cathode material that makes form spinel type structure, simultaneously, further got rid of its inside impurity, improved the purity of spinel type structure, be convenient for improve its structural stability to be favorable to improving electrochemical properties such as nickel lithium manganate cathode material's first discharge efficiency, rate capability, capacity recovery and cycle stability.
It is understood from comparative examples 1 and 16 to 18 that limiting the temperature and time of the preliminary sintering treatment to the preferable ranges in the present application is advantageous in increasing the removal rate of the organic compounds such as the inclusion compound and reducing the impurities in the material to be calcined, as compared with other ranges.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a lithium nickel manganese oxide positive electrode material is characterized by comprising the following steps:
carrying out gel reaction on a lithium source, a nickel source, a manganese source, water, beta-cyclodextrin, a complexing agent and an alkaline regulator to obtain precursor gel, wherein the molar ratio of lithium element in the lithium source, nickel element in the nickel source and manganese element in the manganese source is (1.00-1.06): (0.45-0.55): 1.45-1.85);
and dehydrating and calcining the precursor gel to obtain the lithium nickel manganese oxide cathode material.
2. The method for preparing the lithium nickel manganese oxide cathode material of claim 1, wherein the molar ratio of the nickel element, the beta-cyclodextrin and the complexing agent is (0.45-0.55): (0.0022-0.022): (0.0045-0.12).
3. The preparation method of the lithium nickel manganese oxide cathode material according to claim 1 or 2, wherein the molar ratio of the beta-cyclodextrin to the complexing agent is (0.17-0.22): 1.
4. The method for preparing the lithium nickel manganese oxide cathode material according to claim 1, wherein the alkaline modifier is one or more selected from the group consisting of ammonia water, sodium hydroxide, sodium bicarbonate and sodium carbonate, and the pH of the gel reaction is 5.0-7.0.
5. The method according to any one of claims 1 to 3, wherein the complexing agent is one or more selected from the group consisting of citric acid, tartaric acid, and an amino acid.
6. The method for preparing a lithium nickel manganese oxide positive electrode material according to claim 1, characterized in that the lithium source is one or more selected from the group consisting of lithium acetate, lithium ethoxide, lithium hydroxide and lithium carbonate;
the manganese source is selected from one or more of the group consisting of manganese acetate tetrahydrate, manganese sulfate heptahydrate, manganese chloride tetrahydrate, manganese nitrate hexahydrate and manganese perchlorate hexahydrate;
the nickel source is selected from one or more of the group consisting of nickel acetate tetrahydrate, nickel sulfate heptahydrate, nickel chloride hexahydrate, nickel chloride and nickel nitrate.
7. The method for preparing the lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 6, wherein the calcination process comprises a first calcination treatment and a second calcination treatment, wherein the temperature of the first calcination treatment is 780-850 ℃, and the treatment time is 8-10 h; the temperature of the second calcination treatment is 600-700 ℃, and the treatment time is 8-14 h.
8. The method of preparing a lithium nickel manganese oxide positive electrode material according to claim 7, wherein, before the calcining process, the method further comprises: pre-sintering the product obtained in the dehydration step;
preferably, the temperature of the pre-sintering treatment is 300-370 ℃, and the treatment time is 4-5 h.
9. The lithium nickel manganese oxide positive electrode material is characterized by being prepared by the preparation method of the lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 8, and the chemical formula of the lithium nickel manganese oxide positive electrode material is LiaNixMn2-xO4Wherein a is more than or equal to 1.00 and less than or equal to 1.06, and x is more than or equal to 0.45 and less than or equal to 0.55.
10. A lithium ion battery, comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the positive electrode comprises the lithium nickel manganese oxide positive electrode material of claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695877A (en) * | 2022-05-06 | 2022-07-01 | 广东工业大学 | High-nickel cobalt-free lithium ion battery material and preparation method thereof |
| CN114715955A (en) * | 2022-04-19 | 2022-07-08 | 湖南桑瑞新材料有限公司 | Cobalt-free cathode material, preparation method thereof and lithium ion battery |
| CN115215390A (en) * | 2022-09-15 | 2022-10-21 | 深圳中芯能科技有限公司 | Preparation method of multiphase nickel-manganese binary lithium battery cathode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150219A1 (en) * | 2009-06-25 | 2010-12-29 | Wockhardt Research Centre | Pharmaceutical composition of duloxetine or pharmaceutically acceptable salts thereof |
| CN102509804A (en) * | 2011-11-11 | 2012-06-20 | 东莞市迈科科技有限公司 | Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material |
| CN105655582A (en) * | 2016-02-05 | 2016-06-08 | 北京理工大学 | Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source |
| CN108400320A (en) * | 2018-03-05 | 2018-08-14 | 福建师范大学 | A method of in spinel nickel manganate cathode material for lithium surface sulfide |
| CN109037654A (en) * | 2018-08-16 | 2018-12-18 | 芜湖乾凯材料科技有限公司 | Nickel manganese anode material for lithium-ion batteries and preparation method thereof |
-
2021
- 2021-08-30 CN CN202111007832.2A patent/CN113845152A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010150219A1 (en) * | 2009-06-25 | 2010-12-29 | Wockhardt Research Centre | Pharmaceutical composition of duloxetine or pharmaceutically acceptable salts thereof |
| CN102509804A (en) * | 2011-11-11 | 2012-06-20 | 东莞市迈科科技有限公司 | Preparation method for lithium ion battery Li3V2 (Po4)3/C composite material |
| CN105655582A (en) * | 2016-02-05 | 2016-06-08 | 北京理工大学 | Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source |
| CN108400320A (en) * | 2018-03-05 | 2018-08-14 | 福建师范大学 | A method of in spinel nickel manganate cathode material for lithium surface sulfide |
| CN109037654A (en) * | 2018-08-16 | 2018-12-18 | 芜湖乾凯材料科技有限公司 | Nickel manganese anode material for lithium-ion batteries and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114715955A (en) * | 2022-04-19 | 2022-07-08 | 湖南桑瑞新材料有限公司 | Cobalt-free cathode material, preparation method thereof and lithium ion battery |
| CN114715955B (en) * | 2022-04-19 | 2023-11-03 | 湖南桑瑞新材料有限公司 | Cobalt-free positive electrode material, preparation method thereof and lithium ion battery |
| CN114695877A (en) * | 2022-05-06 | 2022-07-01 | 广东工业大学 | High-nickel cobalt-free lithium ion battery material and preparation method thereof |
| CN114695877B (en) * | 2022-05-06 | 2023-10-27 | 广东工业大学 | High-nickel cobalt-free lithium ion battery material and preparation method thereof |
| CN115215390A (en) * | 2022-09-15 | 2022-10-21 | 深圳中芯能科技有限公司 | Preparation method of multiphase nickel-manganese binary lithium battery cathode material |
| CN115215390B (en) * | 2022-09-15 | 2022-11-18 | 深圳中芯能科技有限公司 | Preparation method of multiphase nickel-manganese binary lithium battery cathode material |
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