CN108417826A - A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution - Google Patents
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution Download PDFInfo
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- CN108417826A CN108417826A CN201810104588.3A CN201810104588A CN108417826A CN 108417826 A CN108417826 A CN 108417826A CN 201810104588 A CN201810104588 A CN 201810104588A CN 108417826 A CN108417826 A CN 108417826A
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 96
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000004411 aluminium Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000009826 distribution Methods 0.000 title claims abstract description 41
- 239000010406 cathode material Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 88
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 45
- 239000010941 cobalt Substances 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims description 230
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 238000002156 mixing Methods 0.000 claims description 85
- 239000003795 chemical substances by application Substances 0.000 claims description 81
- 239000012266 salt solution Substances 0.000 claims description 77
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 55
- 239000011734 sodium Substances 0.000 claims description 55
- 229910052708 sodium Inorganic materials 0.000 claims description 55
- 150000001868 cobalt Chemical class 0.000 claims description 47
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 40
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 150000002815 nickel Chemical class 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011833 salt mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910014330 LiNi1-x-yCoxAlyO2 Inorganic materials 0.000 claims description 4
- 229910014360 LiNi1−x−yCoxAlyO2 Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 54
- 239000002245 particle Substances 0.000 abstract description 31
- 229910052759 nickel Inorganic materials 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 24
- 238000001556 precipitation Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 7
- 229940044175 cobalt sulfate Drugs 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000012687 aluminium precursor Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000009938 salting Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- -1 nickel cobalt aluminum Chemical compound 0.000 description 2
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical group [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910019421 CoxAly Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910011456 LiNi0.80Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, the concentration of aluminium and cobalt is continuously enlarged by radial direction from core to particle surface in prepared precursor material and the positive electrode particle prepared based on precursor material, the concentration of nickel is continuously reduced by radial direction from core to particle surface, obtained material tap density is high, it is insensitive to environment, processing performance is good, and specific capacity is high, and stability characteristic (quality) is good.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, specifically relate to a kind of three graded elemental of nickel cobalt aluminium
The preparation method of the nickel cobalt lithium aluminate cathode material of distribution.
Background technology
Currently, nickelic system's positive electrode becomes current lithium because of its height ratio capacity, lower cost, advantages of environment protection
The hot spot of ion battery investigation of materials.
Bulk phase-doped and surface cladding is to improve the nickelic most common method of based material stability.Nickel cobalt lithium aluminate
LiNi1-x-yCoxAlyO2（NCA）Material is as LiNiO2、LiCoO2And LiAlO2The isomorphism solid solution of three, is provided simultaneously with
The advantages that energy density is high, and thermal stability is good, inexpensive environmental protection, has become the high-end energy storage in the fields 3C and power battery field
Material.But due to Ni under charged state4+Thermodynamic phase, limit the extensive popularization and application of NCA materials.This
Outside, NCA due to the presence of the residual lithium in surface cause material easily in air moisture and carbon dioxide effect generate lithium hydroxide
And lithium carbonate, greatly reduce the processing performance and safety and stability performance of such material.So NCA materials are needed in 10% humidity
It produces and preserves below.
The architectural characteristic of NCA materials itself cause preparation structure stablize NCA materials and function admirable with NCA be anode
The lithium battery of material still suffers from huge challenge.Currently, the nickel cobalt aluminium lithium anode material of domestic production still has charge and discharge
The problems such as capacity attenuation is very fast in the process, high rate performance is bad and storge quality is poor.And the pass of nickelic positive electrode technology of preparing
Key is forerunner's body technique.For this purpose, for the problem above for overcoming NCA materials to face, it is necessary to develop the production of green high-efficient
Technique develops novel nickel cobalt aluminium presoma, with the superior nickel cobalt aluminum material of processability.
In the preparation process of nickel cobalt lithium aluminate cathode material, because being limited by calcinating system, Al3+Ion is ~ 750
It is difficult the method for forming solid solution with Ni-Co and being seldom sintered with independent nickel, cobalt, aluminum feedstock solid phase mixing at DEG C.Currently, coprecipitated
Shallow lake method is to prepare LiNi1-x-yCoxAlyO2And its one kind of surface modification is simply, practical method.The co-precipitation of Ni, Co and Al,
Key is to overcome Al3+Facile hydrolysis individually precipitates, the difficult persursor material that single structure is formed with nickel cobalt element.For Al3+The Yishui River
Solution problem, patent CN103094546A and CN103553152A are proposed using the complex solution for individually preparing aluminium as silicon source, are used
Cocurrent adding material mode and nickel cobalt salting liquid, sodium hydroxide solution and ammonia solution prepare the side of spherical nickel-cobalt aluminium by controlling crystallization
Method.But there are the following problems for disclosed method：Material prepared by the method is the spherical shape of Ni, Co and Al Uniform Doped
NCA presomas, the concentration using the NCA material surfaces Ni of this kind of precursor synthesis are more than 80%, can not extenuate under charging and discharging state
Ni4+The humidity sensitive problem of material in thermal runaway caused by decomposing and preparation process.Material can be improved by improving the doping of aluminium
Cyclical stability, security performance, processing performance and storge quality, however the introducing of a large amount of light metal alloy Al can reduce material
The real density of material itself, leads to the reduction of material volume energy density, and does not have the introducing of electroactive Al elements necessarily to lead
Cause the reduction of material energy density itself.So preparing high-energy density, high stable in the case of lower Al dopings
The nickelic positive electrode of property, excellent storge quality and processing performance at current research a big hot issue.
Nickel-cobalt-manganese ternary gradient lithium ion battery is just had developed early in South Korea Han Yang University Yang-Kook Sun in 2008
The kernel of material, the material is the higher nickel-cobalt-manganese ternary material of nickel content, and outer roll cover is nickel content continuously decreases and manganese
The nickel cobalt manganese material gradually risen with cobalt content.This special positive electrode shows high-energy density, long-life and very
Good security performance.Also there are many documents and patent report doped chemical in the country（Ni, Co, Mn, Mg, Al, Ti, Zr etc.）Gradient
The preparation method of the anode material for lithium-ion batteries of variation.Wherein CN102214819 A, 103078109 CN A, CN
Coprecipitation is contained in the patents of invention such as 103715424 A and CN 201510233112.6 prepares the distribution of Al graded elementals
Hydroxide precursor.But in the precursor material for preparing of involved method the concentration of aluminium by radial from core to particle surface
Gradually increase, it is maximum in most surface concentration, and the concentration of nickel cobalt is gradually decreased by radial direction from core to particle surface.This model exists
The chemical property of material is improved to a certain extent, however, since the incorporation of Al in material is very small, ＜ 5%, and be sintered
It certainly will be spread in the process along with Al migration of elements, it is difficult to ensure that the lower Ni concentration of granular boundary.
Invention content
The present invention relates to a kind of preparation methods of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, prepare
Nickel cobalt lithium aluminate NCA persursor materials in the concentration of aluminium and cobalt gradually increase from core to particle surface by radial direction, in most surface
Concentration is maximum, and the concentration of nickel is gradually decreased by radial direction from core to particle surface, minimum or even can reach 0% in surface concentration,
So as to solve the deficiencies in the prior art, it is simple and practicable to provide one kind, can synthesize with excellent chemical property, superior processing
The preparation method of the lithium ion battery lithium nickel cobalt alumina positive electrode of performance and storge quality.
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the cobalt salt for preparing nickel salt and cobalt salt mixing respectively are molten
Liquid, sodium aluminate solution, sodium metaaluminate intermediate solution；
（2）By step（1）The cobalt salt solution of preparation is added to constant flow rate stream in the nickel cobalt mixing salt solution being stirred continuously,
Mixing speed is 10 ~ 1000 revs/min, and sodium aluminate solution is added to constant flow rate stream in the sodium metaaluminate being stirred continuously
Between in solution, mixing speed is 10 ~ 1000 revs/min, while by nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate
Intermediate solution is added to constant flow rate in the enveloping agent solution II being stirred continuously, and mixing speed is 10 ~ 1000 revs/min,
Under inert atmosphere protection, until nickel cobalt salt-mixture adds, reaction process control ph is 8 ~ 13, is obtained for 30 ~ 95 DEG C of reactions
Ball-shape nickel hydroxide cobalt aluminium precursor material；
（3）By step（2）With 20 ~ 80 DEG C, the sodium hydroxide that mass percent concentration is 2 ~ 10% after obtained precursor material ageing
10 ~ 60min of solution stirring and washing；It is precipitated 3 ~ 5 times using 20 ~ 80 DEG C of deionized water cleaning, until final ph is less than 10；It will be clear
Wet feed after washing is placed at 60 ~ 150 DEG C dry 6 ~ 60h；
（4）By step（3）Precursor material after drying is with lithium hydroxide according to the molar ratio (ratios of Ni+Co+Al) ︰ Li=1 ︰ 1 ~ 1.1
Example is uniformly mixed, and mixture calcines 10 ~ 30h in oxygen atmosphere stove in 650 ~ 850 DEG C, and nickel cobalt aluminium three is obtained after being cooled to room temperature
The nickel cobalt lithium aluminate cathode material of kind concentration of element distribution gradient.
The chemical general formula of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution is LiNi1-x- yCoxAlyO2, wherein 0.05≤x≤0.3,0.01≤y≤0.1.
Step（1）The molar ratio of nickel salt and cobalt salt is 3-100 ︰ 1, nickel cobalt mixing salt solution in the nickel cobalt mixing salt solution
The total concentration of middle nickel salt and cobalt salt is 0.2 ~ 2.5mol/L；The nickel salt is in nickel sulfate, nickel chloride, nickel acetate and nickel nitrate
One or more of arbitrary proportion mixing；The cobalt salt is that one or more of cobaltous sulfate, cobalt chloride, cobalt acetate and cobalt nitrate are appointed
Meaning ratio mixes.
Step（1）The enveloping agent solution I is identical with the complexing agent in enveloping agent solution II, in the enveloping agent solution I
A concentration of 2 ~ 14mol/L of complexing agent；A concentration of 0.1 ~ 4mol/L of II complexing agent of the enveloping agent solution, complexing agent are ammonia
One or more of water, triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate arbitrary proportion mixes.
Step（1）A concentration of 0.2 ~ 2.5mol/L of cobalt salt in the cobalt salt solution, the cobalt salt are cobaltous sulfate, chlorination
One or more of cobalt, cobalt acetate and cobalt nitrate arbitrary proportion mixes.
Step（1）A concentration of 0.1 ~ 2mol/L of aluminium element in the sodium aluminate solution.
Step（1）The pH value of the sodium metaaluminate intermediate solution is 10 ~ 13, is adjusted using sodium hydroxide solution, hydrogen
A concentration of 2 ~ 10mol/L of sodium hydroxide solution, sodium aluminate solution are added with constant flow rate, are obtained sodium metaaluminate concentration and are constantly become
Big sodium metaaluminate intermediate solution, sodium metaaluminate intermediate solution is added with constant current in enveloping agent solution II, in enveloping agent solution II
Aluminum concentration gradually increases.
Step（2）Enveloping agent solution is added in the nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate intermediate solution
II velocity ratio is（1~2）︰（0.05~0.8）The flow velocity of ︰ 1, nickel cobalt mixing salt solution are 2mL/min ~ 4400mL/min.
Step（2）The reaction process using sodium hydroxide solution regulate and control pH value, sodium hydroxide solution a concentration of 2 ~
10mol/L。
Step（2）The flow velocity that sodium metaaluminate intermediate solution is added in the sodium aluminate solution is 0.2mL/min ~ 400mL/
min；It is 0.2mL/min ~ 400mL/min that the cobalt salt solution, which is added to the flow velocity in nickel cobalt mixing salt solution,.
Step（2）The inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
The present invention is directed to Al3+Facile hydrolysis problem, it is proposed that it is silicon source, sodium aluminate solution individually to prepare sodium aluminate solution
It is gradually added into sodium metaaluminate intermediate solution so that the concentration of wherein aluminium gradually increases；Individually prepare cobalt salt solution, cobalt salt solution
It is gradually added into nickel cobalt mixing salt solution so that the concentration of wherein cobalt gradually increases；In the sodium metaaluminate that aluminum concentration is gradually increased
Between the nickel cobalt mixed salt solution that gradually increases of solution, cobalt concentration and enveloping agent solution I flow plus be added in enveloping agent solution II respectively
Successive reaction, to make aluminium and cobalt element in gained precursor material that there is the increased distribution of gradient from the centre of sphere to spherical surface.It should
In spherical nickel-cobalt aluminum material prepared by method, the concentration for adulterating aluminium element and cobalt element is increased continuously from core to spherical surface, surface
Nickel content even can drop to 0%, the LiNi that such presoma is prepared1-x-yCoxAlyO2Adulterate aluminium element and cobalt element concentration
It is increased continuously from core to spherical surface, greatly reduces the concentration of exposed Ni, it is in air and electric fundamentally to solve material
The problem for solving the stability difference in liquid, significantly improves kinetics of diffusion of the lithium ion in material bodies phase, and can reduce
Aluminum amount is mixed to improve the energy density of material.Method using the present invention is prepared for a series of Ni-based gradient and mixes aluminium composite material
Show high-energy density, high safety stability and superior processing performance.
The present invention has multiple advantageous effects：（1）Ball-shape nickel hydroxide cobalt aluminium prepared by method using the present invention
The concentration of precursor material and the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, aluminium element and cobalt element presses diameter
Gradually increase to from core to particle surface, maximum in most surface concentration, the sum of concentration of cobalt aluminium element can be up to 100%；
（2）The method of the present invention can be realized by stringent control system condition using the ball-shape nickel hydroxide cobalt alumina particles centre of sphere as origin
Preparation to cobalt surface, the uniform increased presoma of aluminium element；（3）The positive electrode of preparation, humidity resistance significantly improve, greatly
Moisture sensitivity of the material in preparation and application is reduced greatly, is conducive to the manufacture of NCA materials and associated batteries；（4）System
Standby obtained nickel cobalt lithium aluminate cathode material, have big stable electrochemical property, energy density, good rate capability, it is safe,
The features such as temperature, moisture sensitivity are low, processing performance is excellent can be used for preparing meeting needed for electronic product and electric vehicle
Power battery；（5）The method of the present invention is simple and practicable, and condition is easily controllable, green high-efficient.
Description of the drawings
Fig. 1 is precursor material preparation technology flow chart in embodiment 1, and MP is constant flow pump in figure, and M is stirring system.
Fig. 2 is 1 step of embodiment（3）SEM figures and the Uniform Doped NCA presoma SEM comparison diagrams of the precursor material of preparation；
Fig. 3 is 1 step of embodiment（3）The precursor material of preparation and Uniform Doped NCA presomas XRD comparison diagrams；
Fig. 4 is the three graded elemental LiNi of nickel cobalt aluminium that embodiment 1 obtains0.80Co0.15Al0.05O2The XRD spectrum of material；
Fig. 5 is the cycle performance curve of the nickel cobalt lithium aluminate cathode material for three graded elemental of the nickel cobalt aluminium difference that embodiment 1 obtains；
Fig. 6 is 2 step of embodiment（3）The SEM of the precursor material of preparation schemes；
Fig. 7 is the SEM sectional views of the nickel cobalt lithium aluminate cathode material of obtained three graded elemental of nickel cobalt aluminium of embodiment 2 respectively and cuts open
The corresponding electron probe microanalysis collection of illustrative plates in face；
Fig. 8 is 3 step of embodiment（3）The SEM figures of the nickel cobalt lithium aluminate presoma of three graded elemental of the nickel cobalt aluminium distribution of preparation；
Fig. 9 is the 0.2C cycle performances of the nickel cobalt lithium aluminate cathode material for three graded elemental of the nickel cobalt aluminium distribution that embodiment 3 obtains
Curve；
Figure 10 is 0.2C the and 1C charge and discharges of the nickel cobalt lithium aluminate cathode material for three graded elemental of the nickel cobalt aluminium distribution that embodiment 4 obtains
Electric curve；
Figure 11 is the cycle performance under the nickel cobalt lithium aluminate cathode material 1C for three graded elemental of the nickel cobalt aluminium distribution that embodiment 4 obtains
Curve.
Specific implementation mode
In order to better understand the technical means of the present invention, it can be implemented in accordance with the contents of the specification, and
It is special below to lift specific reality of the invention in order to which above and other objects of the present invention, feature and advantage can be clearer and more comprehensible
Apply mode.
Although hereinafter showing the illustrative embodiments of the disclosure, it being understood, however, that can be real in a variety of manners
The existing disclosure is to be able to more thoroughly without should be limited by embodiments set forth herein on the contrary, providing these embodiments
The present invention is understood thoroughly, and the scope of the present invention can be completely communicated to those skilled in the art, it should be understood that this
Field technology personnel it is contemplated that although not being expressly recited or recording but realize the present invention simultaneously in the present specification
And it is included in various methods, component and content in spirit of that invention, principle and range, all examples quoted from this specification
Son and conditional language are all for the purpose of explanation and introduction, and to help reader to understand, inventor contributes to the prior art
Principle and concept, and the example and condition for being not limited to that these are specifically quoted from are should be understood that, in addition, in order to more clearly
Illustrate, the detailed description for known method, component and content is omitted, not obscure description of the invention, it should be appreciated that remove
Non-specifically illustrate, the feature in each embodiment described herein can be combined with each other.
Embodiment 1
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the hydroxide of nickel salt and cobalt salt mixing are prepared respectively
Sodium solution, cobalt salt solution, sodium aluminate solution, sodium metaaluminate intermediate solution；Ni and Co is total wherein in nickel cobalt mixing salt solution
Ion concentration is 2mol/L and the molar ratio of Ni and Co is 95 ︰ 5, and nickel salt is nickel sulfate, and cobalt salt is cobaltous sulfate, and nickel cobalt salt-mixture is molten
Liquid is 2L, and the cobalt sulfate solution 0.3L of a concentration of 2mol/L is as cobalt salt solution, the sodium hydroxide solution 3L of a concentration of 2mol/L,
The ammonia spirit 1L of a concentration of 14mol/L is as enveloping agent solution I, and the ammonia spirit 3.6L of a concentration of 0.1mol/L is as complexing
Agent solution II, aluminium element content are the sodium aluminate solution 0.3L of 1mol/L, and the sodium hydroxide solution 2.019L of pH=12 is as inclined
Sodium aluminate intermediate solution；
（2）As shown in Figure 1, being previously added the ammonia spirit 3.6L of a concentration of 0.1mol/L in 10L reaction kettles as complexing agent
Solution II uses sodium hydroxide solution to adjust II pH value of enveloping agent solution as 8 ± 0.02, pH value is by pH controlled at 60 DEG C
Meter detection,（NH3·H2O+NH4 +）Concentration is detected by chemical titration；
By step（1）It is molten that the cobalt salt solution of preparation with the flow velocity stream of 0.227mL/min is added to the nickel cobalt salt-mixture being stirred continuously
In liquid, mixing speed be 400 revs/min, sodium aluminate solution be added to the flow velocity stream of 0.211mL/min be stirred continuously it is inclined
In sodium aluminate intermediate solution, mixing speed is 400 revs/min, while by nickel cobalt mixing salt solution, enveloping agent solution I, meta-aluminic acid
Sodium intermediate solution is added to constant flow rate in the enveloping agent solution II being stirred continuously, and mixing speed is 400 revs/min, nickel cobalt
The velocity ratio that enveloping agent solution II is added in mixing salt solution, enveloping agent solution I, sodium metaaluminate intermediate solution is 1 ︰, 0.05 ︰ 1, nickel
The flow velocity of cobalt mixing salt solution is 2mL/min, and under nitrogen atmosphere protection, 60 DEG C are reacted until nickel cobalt metal salt adds,
Reaction process uses step（1）II the inside of sodium hydroxide solution control enveloping agent solution of a concentration of 2mol/L prepared
PH value be 8.00 ± 0.02, strictly control enveloping agent solution II complexing agent concentration, pH value and each solution feed speed in the process
Degree, after charging starts, sodium aluminate solution is continuously added in sodium metaaluminate intermediate solution, and aluminium element concentration is higher and higher, to
The concentration of charging to aluminium element in the mixed solution in reaction kettle is also higher and higher, the aluminium member that precipitation particle surface touches
Plain concentration also increases, and is incrementally distributed thus to obtain along precipitation particle radial direction interface aluminium element gradient, likewise, charging is opened
After beginning, since cobalt sulfate solution is continuously added in nickel cobalt mixing salt solution container, the cobalt element in nickel cobalt mixing salt solution container
Concentration is higher and higher, to which the concentration of charging to cobalt element in the mixed solution in reaction kettle is also higher and higher, precipitation
The cobalt element concentration that grain surface touches also increases, and thus incrementally divides along precipitation particle radial direction interface cobalt element gradient
Cloth is realized in precursor material particle, and from core to surface, cobalt, aluminium element concentration are gradually incremented by and Ni concentration continuously decreases, reaction
Ball-shape nickel hydroxide cobalt aluminium precursor material is obtained after the completion；
（3）By step（2）After precursor material is aged 30min, filtrated stock, the hydrogen for being 5wt% with 60 DEG C, mass percent concentration
Sodium hydroxide solution stirring and washing 30min；It is precipitated 3 times using 60 DEG C of deionized water cleaning, until final ph is less than 10；It will cleaning
Acquisition surface aluminum atoms number percentage composition is 33at%, cobalt atom after wet feed afterwards is placed in 100 DEG C of air dry ovens dry 20h
Ni of the number percentage composition close to 67at%0.80Co0.15Al0.05(OH)2Precursor material, SEM figures, can be with from SEM figures referring to Fig. 2
Find out, precursor material pattern is spherical or spherical, and size distribution is concentrated；The XRD spectrum of precursor material is as shown in figure 3, comparison
The NCA of obtained Uniform Doped purchased in market, by Ni (OH)2Structure and Ni (OH)2·0.75H2O structure compositions；
（4）By step（3）Precursor material Ni after drying0.80Co0.15Al0.05(OH)2With lithium hydroxide according to molar ratio (Ni+Co
1.03 ratios of+Al) ︰ Li=1 ︰ are uniformly mixed, and the mole of Ni+Co+Al can pass through step（2）Used in material calculate
Come, mixture calcines 12h in oxygen atmosphere stove in 750 DEG C, and three kinds of concentration of element of nickel cobalt aluminium are obtained after being cooled to room temperature in ladder
Spend the nickel cobalt lithium aluminate cathode material LiNi of distribution0.80Co0.15Al0.05O2。
The nickel cobalt lithium aluminate cathode material of three kinds of concentration of element distribution gradients of nickel cobalt aluminium that the present embodiment is prepared
LiNi0.80Co0.15Al0.05O2XRD detect the material have single α-NaFeO3Structure, referring to Fig. 4；The positive electrode 2.8 ~
Discharge capacity is 201mAh/g for the first time under 4.3 voltage window charge and discharge 0.1C, and specific discharge capacity is maintained at 188mAh/g under 1C, follows
200 weeks capacity retention ratio ＞ 88% of ring, shown in Fig. 5.
Embodiment 2
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the hydroxide of nickel salt and cobalt salt mixing are prepared respectively
Sodium solution, cobalt salt solution, sodium aluminate solution, sodium metaaluminate intermediate solution；Wherein Ni in nickel cobalt mixing salt solution2+Ion and cobalt
The nickel cobalt mixing salt solution 40L that the molar ratio of the total a concentration of 0.2mol/L and Ni and Co of ion are 3 ︰ 1, nickel salt is chlorination
Nickel, cobalt salt are cobalt chloride, and the cobalt chloride solution 4L of a concentration of 0.2mol/L is as cobalt salt solution, the hydroxide of a concentration of 2mol/L
For the citric acid solution 20L of sodium solution 30L, a concentration of 2mol/L as enveloping agent solution I, the citric acid of a concentration of 0.2mol/L is molten
Liquid 36L is the sodium aluminate solution 2L of 0.1mol/L as enveloping agent solution II, aluminium element content, and the sodium hydroxide of pH=13 is molten
Liquid 41.78L is as sodium metaaluminate intermediate solution；
（2）The citric acid solution 36L of a concentration of 0.2mol/L is previously added in 150L reaction kettles as enveloping agent solution II, control
Temperature processed is 30 DEG C, uses sodium hydroxide solution to adjust II pH value of enveloping agent solution as 13 ± 0.02, pH value is detected by pH meter；
By step（1）It is molten that the cobalt salt solution of preparation with the flow velocity stream of 1.63mL/min is added to the nickel cobalt salt-mixture being stirred continuously
In liquid, mixing speed is 10 revs/min, and sodium aluminate solution is added to the inclined aluminium being stirred continuously with the flow velocity stream of 0.82mL/min
In sour sodium intermediate solution, mixing speed is 10 revs/min, while by nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate
Intermediate solution is added to constant flow rate in the enveloping agent solution II being stirred continuously, and mixing speed is 1000 revs/min, and nickel cobalt is mixed
It is 80 ︰, 21 ︰ 80, nickel cobalt to close salting liquid, enveloping agent solution I, sodium metaaluminate intermediate solution and the velocity ratio of enveloping agent solution II is added
The flow velocity of mixing salt solution be 20mL/min, inert atmosphere of nitrogen protection under, 30 DEG C reaction until nickel cobalt metal salt add for
Only, reaction process uses step（1）The sodium hydroxide solution of a concentration of 2mol/L prepared controls enveloping agent solution II
The pH value of the inside is 13 ± 0.02, strictly controls II complexing agent concentration of enveloping agent solution, pH value and each solution feed in the process
Speed, after charging starts, sodium aluminate solution is continuously added in sodium metaaluminate intermediate solution, and aluminium element concentration is higher and higher, from
And the concentration of charging to aluminium element in the mixed solution in reaction kettle is also higher and higher, the aluminium that precipitation particle surface touches
Concentration of element also increases, and is incrementally distributed thus to obtain along precipitation particle radial direction interface aluminium element gradient, likewise, charging
After beginning, since cobalt sulfate solution is continuously added in nickel cobalt mixing salt solution container, the cobalt member in nickel cobalt mixing salt solution container
Plain concentration is higher and higher, to which the concentration of charging to cobalt element in the mixed solution in reaction kettle is also higher and higher, precipitation
The cobalt element concentration that particle surface touches also increases, and thus incrementally divides along precipitation particle radial direction interface cobalt element gradient
Cloth is realized in precursor material particle, and from core to surface, cobalt, aluminium element concentration are gradually incremented by and Ni concentration continuously decreases, reaction
Ball-shape nickel hydroxide cobalt aluminium precursor material is obtained after the completion；
（3）By step（2）After precursor material is aged 30min, filtrated stock, the hydrogen for being 5wt% with 60 DEG C, mass percent concentration
Sodium hydroxide solution stirring and washing 40min；It is precipitated 4 times using 70 DEG C of deionized water cleaning, until final ph is less than 10；It will cleaning
Acquisition surface aluminum atoms number percentage composition is 30at%, cobalt atom number after wet feed afterwards is placed in 60 DEG C of air dry ovens dry 48h
Percentage composition is the Ni close to 70at%0.70Co0.28Al0.02(OH)2Presoma, SEM figures, can from SEM figures referring to Fig. 6
Go out, presoma pattern is spherical or spherical, and size distribution is concentrated；
（4）By step（3）Precursor material Ni after drying0.70Co0.28Al0.02(OH)2With lithium hydroxide according to 1 ︰ 1.03 of molar ratio
Ratio is uniformly mixed, and the mole of Ni+Co+Al can pass through step（2）Used in material calculate, mixture is placed in oxygen
850 DEG C of calcining 30h, obtain the nickel cobalt aluminic acid of three kinds of concentration of element distribution gradients of nickel cobalt aluminium in gas atmosphere furnace after being cooled to room temperature
Lithium anode material Li Ni0.70Co0.28Al0.02O2。
The Li Ni that the present embodiment obtains0.70Co0.28Al0.02O2The section electron probe microanalysis (EPMA) of positive electrode
The result shows that in material internal, cobalt, aluminium element concentration are from core to surface graded raising, and nickel content gradient is reduced, element point
Cloth is referring to Fig. 7, obtained material model and patent CN102214819 A, 103078109 CN A, CN 103715424 A and CN
The model of 201510233112.6 applications is different, which puts for the first time under 2.8 ~ 4.3V voltage window charge and discharge, 0.2 C
Capacitance is 185mAh/g, and specific discharge capacity is maintained at 172mAh/g under 1C, and cycle performance is excellent.
Embodiment 3
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the hydroxide of nickel salt and cobalt salt mixing are prepared respectively
Sodium solution, cobalt salt solution, sodium aluminate solution, sodium metaaluminate intermediate solution；Wherein Ni in nickel cobalt mixing salt solution2+Ion and cobalt
The nickel cobalt mixing salt solution 40L that the molar ratio of the total a concentration of 2.5mol/L and Ni and Co of ion are 50 ︰ 1, nickel salt is nitric acid
Nickel, cobalt salt are cobalt nitrate, and the cobalt sulfate solution 4L of a concentration of 2.5mol/L is as cobalt salt solution, the hydroxide of a concentration of 8mol/L
The sodium ethylene diamine tetracetate solution 20L of sodium solution 30L, a concentration of 2mol/L as enveloping agent solution I, a concentration of 0.1mol/L's
Sodium ethylene diamine tetracetate solution 36L as enveloping agent solution II, sodium aluminate solution 2L, pH that aluminium element content is 2mol/L=
10 sodium hydroxide solution and sodium aluminate solution 41.78L is as sodium metaaluminate intermediate solution, and wherein sodium aluminate solution is dense
Degree is 0.1mol/L；
（2）The sodium ethylene diamine tetracetate solution 36L of a concentration of 0.1mol/L is previously added in 150L reaction kettles as complexing agent
Solution II uses sodium hydroxide solution to adjust II pH value of enveloping agent solution as 11.50 ± 0.02, pH value controlled at 95 DEG C
It is detected by pH meter；
By step（1）It is molten that the cobalt salt solution of preparation with the flow velocity stream of 1.63mL/min is added to the nickel cobalt salt-mixture being stirred continuously
In liquid, mixing speed be 1000 revs/min, sodium aluminate solution be added to the flow velocity stream of 0.82ml/min be stirred continuously it is inclined
In sodium aluminate intermediate solution, mixing speed is 10 revs/min, while by nickel cobalt mixing salt solution, enveloping agent solution I, meta-aluminic acid
Sodium intermediate solution is added to constant flow rate in the enveloping agent solution II being stirred continuously, and mixing speed is 1000 revs/min, nickel cobalt
The velocity ratio that enveloping agent solution II is added in mixing salt solution, enveloping agent solution I, sodium metaaluminate intermediate solution is 20 ︰, 2.63 ︰ 20,
The flow velocity of nickel cobalt mixing salt solution be 20mL/min, argon gas atmosphere protection under, 95 DEG C reaction until nickel cobalt metal salt add for
Only, reaction process uses step（1）Prepare II the inside of the sodium hydroxide solution for being a concentration of 8mol/L control enveloping agent solution
PH value be 11.50 ± 0.02, strictly control enveloping agent solution II complexing agent concentration, pH value and each solution feed speed in the process
Degree, after charging starts, sodium aluminate solution is continuously added in sodium metaaluminate intermediate solution, and aluminium element concentration is higher and higher, to
The concentration of charging to aluminium element in the mixed solution in reaction kettle is also higher and higher, the aluminium member that precipitation particle surface touches
Plain concentration also increases, and is incrementally distributed thus to obtain along precipitation particle radial direction interface aluminium element gradient, likewise, charging is opened
After beginning, since cobalt sulfate solution is continuously added in nickel cobalt mixing salt solution container, the cobalt element in nickel cobalt mixing salt solution container
Concentration is higher and higher, to which the concentration of charging to cobalt element in the mixed solution in reaction kettle is also higher and higher, precipitation
The cobalt element concentration that grain surface touches also increases, and thus incrementally divides along precipitation particle radial direction interface cobalt element gradient
Cloth is realized in precursor material particle, and from core to surface, cobalt, aluminium element concentration are gradually incremented by and Ni concentration continuously decreases, reaction
Ball-shape nickel hydroxide cobalt aluminium precursor material is obtained after the completion；
（3）By step（2）After precursor material is aged 30min, filtrated stock, the hydrogen for being 2wt% with 80 DEG C, mass percent concentration
Sodium hydroxide solution stirring and washing 10min is precipitated 3 times using 80 DEG C of deionized water cleaning, until final ph is less than 10；It will cleaning
Acquisition surface aluminum atoms number percentage composition is 30at%, cobalt atom after wet feed afterwards is placed in 100 DEG C of air dry ovens dry 60h
Ni of the number percentage composition close to 70at%0.84Co0.09Al0.07(OH)2Precursor material, SEM figures, can be with from SEM figures referring to Fig. 8
Find out, presoma pattern is spherical or spherical, and size distribution is concentrated；
（4）By step（3）Precursor material Ni after drying0.84Co0.09Al0.07(OH)2With lithium hydroxide according to molar ratio (Ni+Co
1.1 ratios of+Al) ︰ Li=1 ︰ are uniformly mixed, and the mole of Ni+Co+Al can pass through step（2）Used in material calculate
Come, mixture is placed in 850 DEG C of calcining 10h in oxygen atmosphere stove, and three kinds of concentration of element of nickel cobalt aluminium are obtained after being cooled to room temperature in ladder
Spend the nickel cobalt lithium aluminate cathode material LiNi of distribution0.84Co0.09Al0.07O2。
Discharge capacity is the positive electrode that the present embodiment obtains for the first time at 2.8 ~ 4.3 voltage window charge and discharge 0.2C
209mAh/g, 0.2C cycle performance are highly stable, and chemical property is referring to Fig. 9.
Embodiment 4
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the hydroxide of nickel salt and cobalt salt mixing are prepared respectively
Sodium solution, cobalt salt solution, sodium aluminate solution, sodium metaaluminate intermediate solution；Wherein Ni in nickel cobalt mixing salt solution2+Ion and cobalt
The nickel cobalt mixing salt solution 4000L that the molar ratio of the total a concentration of 2mol/L and Ni and Co of ion are 100 ︰ 1, nickel salt is nitric acid
Nickel, cobalt salt are cobalt nitrate, and the cobalt nitrate solution 400L of a concentration of 2mol/L is as cobalt salt solution, the hydrogen-oxygen of a concentration of 10mol/L
Change the ammonia spirit 3000L of sodium solution 3000L, a concentration of 14mol/L as enveloping agent solution I, the ammonium hydroxide of a concentration of 4mol/L
For solution 3600L as enveloping agent solution II, aluminium element content is the sodium aluminate solution 200L of 1mol/L, the hydroxide of pH=11
The mixed solution 2100L of sodium solution and sodium aluminate solution is as sodium metaaluminate intermediate solution, and wherein sodium aluminate solution is dense
Degree is 0.0005mol/L；
（2）The ammonia spirit 3600L of a concentration of 4mol/L is previously added in 20000L reaction kettles as enveloping agent solution II, control
Temperature processed is 70 DEG C, uses sodium hydroxide solution to adjust II pH value of enveloping agent solution as 13 ± 0.02, pH value is detected by pH meter；
By step（1）The cobalt salt solution of preparation is added to the nickel cobalt mixing salt solution being stirred continuously with the flow velocity of 163mL/min
In, mixing speed is 500 revs/min, and sodium aluminate solution is added to the meta-aluminic acid being stirred continuously with the flow velocity stream of 82mL/min
In sodium intermediate solution, mixing speed is 1000 revs/min, while by nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate
Intermediate solution is added to constant flow rate in the enveloping agent solution II being stirred continuously, and mixing speed is 10 revs/min, nickel cobalt mixing
The velocity ratio that enveloping agent solution II is added in salting liquid, enveloping agent solution I, sodium metaaluminate intermediate solution is 2 ︰, 0.8 ︰ 1, nickel cobalt mixing
The flow velocity of salting liquid is 2000mL/min, and under inert argon atmosphere protection, 70 DEG C are reacted until nickel cobalt metal salt adds,
Reaction process uses step（1）In the sodium hydroxide solution control enveloping agent solution II of a concentration of 10mol/L prepared
The pH value in face is 13 ± 0.02, and strictly II complexing agent concentration of control enveloping agent solution, pH value and each solution feed are fast in the process
Degree, after charging starts, sodium aluminate solution is continuously added in sodium metaaluminate intermediate solution, and aluminium element concentration is higher and higher, to
The concentration of charging to aluminium element in the mixed solution in reaction kettle is also higher and higher, the aluminium member that precipitation particle surface touches
Plain concentration also increases, and is incrementally distributed thus to obtain along precipitation particle radial direction interface aluminium element gradient, likewise, charging is opened
After beginning, since cobalt sulfate solution is continuously added in nickel cobalt mixing salt solution container, the cobalt element in nickel cobalt mixing salt solution container
Concentration is higher and higher, to which the concentration of charging to cobalt element in the mixed solution in reaction kettle is also higher and higher, precipitation
The cobalt element concentration that grain surface touches also increases, and thus incrementally divides along precipitation particle radial direction interface cobalt element gradient
Cloth is realized in precursor material particle, and from core to surface, cobalt, aluminium element concentration are gradually incremented by and Ni concentration continuously decreases, reaction
Ball-shape nickel hydroxide cobalt aluminium precursor material is obtained after the completion；
（3）By step（2）After precursor material is aged 30min, filtrated stock, with 20 DEG C, the hydrogen-oxygen of mass percent concentration 10wt%
Change sodium solution stirring and washing 60min, is precipitated 5 times using 20 DEG C of deionized water cleaning, until final ph is less than 10；After cleaning
Wet feed be placed in 150 DEG C of air dry ovens after dry 6h that obtain surface aluminum atoms number percentage composition be 50at%, cobalt atom is hundreds of
Divide content close to the Ni of 50at%0.90Co0.08Al0.02(OH)2Precursor material；
（4）By step（3）Precursor material Ni after drying0.90Co0.08Al0.02(OH)2With lithium hydroxide according to molar ratio (Ni+Co
1 ratios of+Al) ︰ Li=1 ︰ are uniformly mixed, and the mole of Ni+Co+Al can pass through step（2）Used in material calculate,
Mixture is placed in 650 DEG C of calcinings in oxygen atmosphere stove, and for 24 hours, acquisition three kinds of concentration of element of nickel cobalt aluminium divide in gradient after being cooled to room temperature
The nickel cobalt lithium aluminate cathode material Li Ni of cloth0.90Co0.08Al0.02O2。
Discharge capacity is the positive electrode that the present embodiment obtains for the first time at 2.8 ~ 4.3 voltage window charge and discharge 0.2C
Specific discharge capacity is maintained at 209mAh/g under 223mAh/g, 1C, and 1C cycle performances are highly stable, chemical property referring to Figure 10 and
Figure 11.
Embodiment 5
A kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, is as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the hydroxide of nickel salt and cobalt salt mixing are prepared respectively
Sodium solution, cobalt salt solution, sodium aluminate solution, sodium metaaluminate intermediate solution；Wherein Ni in nickel cobalt mixing salt solution2+Ion and cobalt
The nickel cobalt mixing salt solution 8000L that the molar ratio of the total a concentration of 2mol/L and Ni and Co of ion are 100 ︰ 1（It is considered as Co2+From
The mixing salt solution of son a concentration of 0）, nickel salt is nickel nitrate, and cobalt salt is cobalt nitrate, the cobalt nitrate solution of a concentration of 0.976mol/L
800L is as cobalt salt solution, the sodium hydroxide solution 6000L of a concentration of 10mol/L, the ammonia spirit of a concentration of 10.5mol/L
6000L is as enveloping agent solution I, and the ammonia spirit 8000L of a concentration of 0.5mol/L is as enveloping agent solution II, aluminium element content
For the sodium aluminate solution 800L of 2mol/L, the sodium hydroxide solution of pH=11 and the mixed solution 8000L of sodium aluminate solution make
For sodium metaaluminate intermediate solution, the wherein a concentration of 0.0353mol/L of sodium aluminate solution；
（2）The ammonia spirit 8000L of a concentration of 0.5mol/L is previously added in 50000L reaction kettles as enveloping agent solution II,
Controlled at 50 DEG C, sodium hydroxide solution is used to adjust II pH value of enveloping agent solution as 11.5 ± 0.02, pH value is examined by pH meter
It surveys；
By step（1）The cobalt salt solution of preparation is added to the nickel cobalt mixing salt solution being stirred continuously with the flow velocity of 400mL/min
In, mixing speed is 200 revs/min, and sodium aluminate solution is added to the meta-aluminic acid being stirred continuously with the flow velocity stream of 400mL/min
In sodium intermediate solution, mixing speed is 100 revs/min, while will be in nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate
Between solution be added to constant flow rate in the enveloping agent solution II being stirred continuously, mixing speed be 300 revs/min, nickel cobalt mixing
The velocity ratio that enveloping agent solution II is added in salting liquid, enveloping agent solution I, sodium metaaluminate intermediate solution is 8.33 ︰, 1 ︰ 8.33, nickel cobalt
The flow velocity of mixing salt solution is 4400mL/min, and under inert argon atmosphere protection, 50 DEG C of reactions are until nickel cobalt metal salt adds
Until, reaction process uses step（1）The sodium hydroxide solution of a concentration of 10mol/L prepared controls enveloping agent solution
The pH value of II the inside is 11.5 ± 0.02, strictly controls II complexing agent concentration of enveloping agent solution, pH value and each solution in the process
Charging rate, after charging starts, sodium aluminate solution is continuously added in sodium metaaluminate intermediate solution, and aluminium element concentration is increasingly
Height, to which the concentration of charging to aluminium element in the mixed solution in reaction kettle is also higher and higher, precipitation particle surface contact
To aluminium element concentration also increase, be incrementally distributed thus to obtain along precipitation particle radial direction interface aluminium element gradient, equally
, after charging starts, since cobalt sulfate solution is continuously added in nickel cobalt mixing salt solution container, in nickel cobalt mixing salt solution container
Cobalt element concentration it is higher and higher, to charging to cobalt element in the mixed solution in reaction kettle concentration also increasingly
Height, the cobalt element concentration that precipitation particle surface touches also increase, thus along precipitation particle radial direction interface cobalt element ladder
The incremental distribution of degree realizes in precursor material particle, from core to surface, cobalt, aluminium element concentration are gradually incremented by and Ni concentration is gradual
It reduces, ball-shape nickel hydroxide cobalt aluminium precursor material is obtained after the completion of reaction；
（3）By step（2）After precursor material is aged 30min, filtrated stock, with 60 DEG C, the hydrogen-oxygen of mass percent concentration 3wt%
Change sodium solution stirring and washing 60min, is precipitated 5 times using 60 DEG C of deionized water cleaning, until final ph is less than 10；After cleaning
Wet feed be placed in 150 DEG C of air dry ovens after dry 6h that obtain surface aluminum atoms number percentage composition be 67at%, cobalt atom is hundreds of
Divide content close to the Ni of 33at%0.85Co0.05Al0.1(OH)2Precursor material；
（4）By step（3）Precursor material Ni after drying0.85Co0.05Al0.1 (OH)2With lithium hydroxide according to molar ratio (Ni+Co
1.03 ratios of+Al) ︰ Li=1 ︰ are uniformly mixed, and the mole of Ni+Co+Al can pass through step（2）Used in material calculate
Come, mixture is placed in 720 DEG C of calcining 15h in oxygen atmosphere stove, and three kinds of concentration of element of nickel cobalt aluminium are obtained after being cooled to room temperature in ladder
Spend the nickel cobalt lithium aluminate cathode material Li Ni of distribution0.85Co0.05Al0.1O2。
The positive electrode Li Ni that the present embodiment obtains0.85Co0.05Al0.1O2Show excellent chemical property.
Claims (10)
1. a kind of preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution, which is characterized in that specific
Steps are as follows：
（1）Nickel cobalt mixing salt solution, enveloping agent solution I, enveloping agent solution II, the cobalt salt for preparing nickel salt and cobalt salt mixing respectively are molten
Liquid, sodium aluminate solution, sodium metaaluminate intermediate solution；
（2）By step（1）The cobalt salt solution of preparation is added to constant flow rate stream in the nickel cobalt mixing salt solution being stirred continuously,
Sodium aluminate solution is added to constant flow rate stream in the sodium metaaluminate intermediate solution being stirred continuously, while nickel cobalt salt-mixture is molten
Liquid, enveloping agent solution I, sodium metaaluminate intermediate solution are added to constant flow rate in the enveloping agent solution II being stirred continuously, lazy
Property atmosphere protection under, 30 ~ 95 DEG C reaction until nickel cobalt salt-mixture adds, reaction process control ph be 8 ~ 13, obtain spherical shape
Nickel cobalt aluminum hydroxide precursor material, the mixing speed are 10 ~ 1000 revs/min；
（3）By step（2）With 20 ~ 80 DEG C, the sodium hydroxide that mass percent concentration is 2 ~ 10% after obtained precursor material ageing
10 ~ 60min of solution stirring and washing；It is precipitated 3 ~ 5 times using 20 ~ 80 DEG C of deionized water cleaning, until final ph is less than 10；It will be clear
Wet feed after washing is placed at 60 ~ 150 DEG C dry 6 ~ 60h；
（4）By step（3）Precursor material after drying is with lithium hydroxide according to the molar ratio (ratios of Ni+Co+Al) ︰ Li=1 ︰ 1 ~ 1.1
Example is uniformly mixed, and mixture calcines 10 ~ 30h under oxygen atmosphere in 650 ~ 850 DEG C, and three kinds of nickel cobalt aluminium is obtained after being cooled to room temperature
The nickel cobalt lithium aluminate cathode material of concentration of element distribution gradient.
2. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, the chemical general formula of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution is LiNi1-x- yCoxAlyO2, wherein 0.05≤x≤0.3,0.01≤y≤0.1.
3. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（1）The molar ratio of nickel salt and cobalt salt is 3-100 ︰ 1 in the nickel cobalt mixing salt solution, and nickel cobalt salt-mixture is molten
The total concentration of nickel salt and cobalt salt is 0.2 ~ 2.5mol/L in liquid；The nickel salt is in nickel sulfate, nickel chloride, nickel acetate and nickel nitrate
One or more of arbitrary proportions mixing；The cobalt salt is one or more of cobaltous sulfate, cobalt chloride, cobalt acetate and cobalt nitrate
Arbitrary proportion mixes.
4. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（1）The enveloping agent solution I is identical with the complexing agent in enveloping agent solution II, in the enveloping agent solution I
A concentration of 2 ~ 14mol/L of complexing agent；A concentration of 0.1 ~ 4mol/L of II complexing agent of the enveloping agent solution, complexing agent are ammonia
One or more of water, triethanolamine, ammonium fluoride, citric acid, oxalic acid, sodium ethylene diamine tetracetate arbitrary proportion mixes.
5. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（1）A concentration of 0.2 ~ 2.5mol/L of cobalt salt in the cobalt salt solution, the cobalt salt are cobaltous sulfate, chlorination
One or more of cobalt, cobalt acetate and cobalt nitrate arbitrary proportion mixes.
6. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（1）A concentration of 0.1 ~ 2mol/L of aluminium element in the sodium aluminate solution.
7. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（1）The pH value of the sodium metaaluminate intermediate solution is 10 ~ 13, is adjusted using sodium hydroxide solution, hydrogen
A concentration of 2 ~ 10mol/L of sodium hydroxide solution.
8. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（2）Enveloping agent solution is added in the nickel cobalt mixing salt solution, enveloping agent solution I, sodium metaaluminate intermediate solution
II velocity ratio is（1~2）︰（0.05~0.8）The flow velocity of ︰ 1, nickel cobalt mixing salt solution are 2mL/min ~ 4400mL/min.
9. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（2）The reaction process using sodium hydroxide solution regulate and control pH value, sodium hydroxide solution a concentration of 2 ~
10mol/L。
10. the preparation method of the nickel cobalt lithium aluminate cathode material of three graded elemental of nickel cobalt aluminium distribution according to claim 1,
It is characterized in that, step（2）The flow velocity that sodium metaaluminate intermediate solution is added in the sodium aluminate solution is 0.2mL/min ~ 400mL/
min；It is 0.2mL/min ~ 400mL/min that the cobalt salt solution, which is added to the flow velocity in nickel cobalt mixing salt solution,.
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