CN110112393A - A kind of positive electrode, and its preparation method and application - Google Patents
A kind of positive electrode, and its preparation method and application Download PDFInfo
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- CN110112393A CN110112393A CN201910412939.1A CN201910412939A CN110112393A CN 110112393 A CN110112393 A CN 110112393A CN 201910412939 A CN201910412939 A CN 201910412939A CN 110112393 A CN110112393 A CN 110112393A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 415
- 239000011257 shell material Substances 0.000 claims abstract description 89
- 239000012792 core layer Substances 0.000 claims abstract description 77
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000012798 spherical particle Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 138
- 239000007788 liquid Substances 0.000 claims description 88
- 238000009938 salting Methods 0.000 claims description 85
- 238000005245 sintering Methods 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 50
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 28
- 239000000908 ammonium hydroxide Substances 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 229910052712 strontium Inorganic materials 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 229910052738 indium Inorganic materials 0.000 claims description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- 229910052727 yttrium Inorganic materials 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007790 solid phase Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 18
- 239000010936 titanium Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 229910012820 LiCoO Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PHQIAQCZFCLYKL-UHFFFAOYSA-N sulfuric acid;tungsten Chemical compound [W].OS(O)(=O)=O PHQIAQCZFCLYKL-UHFFFAOYSA-N 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- DCGQUTJLMIWWSV-UHFFFAOYSA-N [W].[N+](=O)(O)[O-] Chemical compound [W].[N+](=O)(O)[O-] DCGQUTJLMIWWSV-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- -1 ternary Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc 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
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of positive electrode, and its preparation method and application.The present invention passes through the core layer material A and single crystal grain core layer material B surface that form in secondary spherical particle, surface coats Shell Materials forming material A and B respectively, materials A and material B are mixed again, to significantly improve the energy density of positive electrode, high rate performance, high temperature circulation and security performance.The present invention coats core layer material using Shell Materials, and the residual alkali of positive electrode can be significantly reduced, and reduces positive electrode to the oxygenolysis of electrolyte, promotes the high temperature circulation and security performance of positive electrode.Compared with the existing technology, the lithium ion battery that the present invention obtains can be in higher voltage (>=4.2V vs (Li+/ Li)) under play good energy density, cycle performance and security performance.Due to the raising of charge cutoff voltage, battery of the invention energy density also with higher can satisfy the demand that people are thinned lithium ion battery.
Description
Technical field
The invention belongs to battery material technical fields, and in particular to a kind of positive electrode, and its preparation method and application.
Background technique
The common positive electrode of lithium ion battery has cobalt acid lithium, ternary, LiMn2O4 and LiFePO4 etc., with electronic product
The positive electrode of the increase of lightening development and electric car course continuation mileage, higher energy density becomes Study on Li-ion batteries
Hot spot.
For ternary material, Ni content is higher, and the energy density of ternary material is higher, but Ni content is higher, ternary material
More serious to electrolyte oxidation decomposition, the high temperature storage, high temperature circulation and security performance for corresponding to ternary material battery are also poorer, especially
It is even more serious to nickelic ternary material.Under normal circumstances, ternary material is secondary spherical particle, and discharge-rate is good, electric discharge
Gram volume is high, but the compacted density of respective material is small, and high temperature circulation is poor, and thermal stability is poor, especially to short grained secondary spherical
Particle；But for monocrystalline ternary material, compacted density is big, and high temperature circulation is good, and thermal stability is good, but the gram volume that discharges is low,
Discharge-rate is poor.
CN107482204A discloses nickelic tertiary cathode material of a kind of metal solid solution modification and preparation method thereof.It is described
Material is core-shell structure, from inside to outside successively includes nickelic tertiary cathode material matrix, transition zone and clad, the packet
Coating includes that metal lithium salts and one or more dissimilar metal forerunners and nickelic tertiary cathode material forerunner react consolidating for generation
Solution positive active material, the transition zone are the nickelic tertiary cathode material of dissimilar metal element doping.The positive electrode
Preparation method the following steps are included: (1) uniformly mixes nickelic tertiary cathode material forerunner, dissimilar metal forerunner, lithium salts, shape
Resulting mixture；(2) high-temperature calcination is carried out to mixture and obtains the nickelic tertiary cathode material of the metal solid solution modification.It is described just
The chemical property of pole material is unable to satisfy the demand of excellent nickelic tertiary cathode material.
CN108298599A discloses a kind of nickelic ternary material precursor of monocrystalline, is core-shell structure, the materials chemistry of core
Formula is NixCoyM1(1-x-y)CO3, the materials chemistry formula of shell is NixCoyM1(1-x-y-z)M2z(OH)2, 0.6≤x < 0.9,0.1≤y≤
0.25,0≤z≤0.1,0 < 1-x-y-z≤0.25, M1 are selected from Mn, Al, and M2 is in Ti, Ba, Sr, Mg, Cr, Zn, V, Cu
It is at least one.By will have the persursor material of core-shell structure to be sintered, the nickelic of monocrystalline is can be obtained in abjection shell structure
Ternary material.The nickelic ternary material electric discharge gram volume of the monocrystalline is low, and discharge-rate is poor.
In view of this, it is necessory to provide a kind of nickelic positive electrode, the positive electrode has energy density high, hot
The advantages such as stability is good, good rate capability, high temperature circulation and safety are excellent, and preparation process is simple, it can industrialized production.
Summary of the invention
The purpose of the present invention is to provide a kind of positive electrode, and its preparation method and application, the positive electrode be height
The positive electrode of nickel, can be in higher voltage (>=4.2V vs (Li+/ Li)) under, the high, thermostabilization with excellent energy density
Property, high rate performance, high temperature cyclic performance and security performance, and preparation process is simple, it can industrialized production.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of positive electrode, the positive electrode includes materials A and material B, institute
Stating materials A and material B is all core-shell structure；
The core layer material chemical formula of the materials A and material B independently are Li1+aNibCocMndM1-b-c-dO2, 0≤a≤
It is any one in 0.15,0.8≤b≤0.95,0≤c≤0.2,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y
Kind or at least two combination；Value of a such as 0,0.05,0.1,0.11,0.12,0.13 or 0.14 etc.；The b's takes
Value is such as 0.81,0.82,0.83,0.85,0.86,0.88,0.9,0.92 or 0.94；The value of the c such as 0.05,0.1,
0.11,0.12,0.13,0.14,0.15,0.16,0.18 or 0.19 etc.；The value of the d such as 0.05,0.1,0.11,0.12,
0.13,0.14,0.15,0.16,0.18 or 0.19 etc.；
The core layer material of the materials A is secondary spherical particle, and the core layer material of the material B is single crystal grain；
The Shell Materials chemical formula of the materials A and material B independently are LixCoyAlzRsO2, wherein 0.05≤x≤1.0,
0 < s≤z < y < 1, y+z+s=1, in R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；Institute
State the value such as 0.06,0.08,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8 or 0.9 etc. of x；The value of the s is for example
0.01,0.05,0.1,0.2 or 0.3 etc.；Value of the z such as 0.01,0.05,0.1,0.2 or 0.3 etc.；The value of the y
Such as 0.4,0.5,0.6,0.7,0.8 or 0.9 etc..
Positive electrode of the invention includes materials A and material B, and the core layer material of the materials A is secondary spherical particle, institute
The core layer material for stating material B is single crystal grain, and secondary spherical particle and single crystal grain with clad cooperate, and collaboration is made
With energy density, high rate performance, high temperature circulation and the security performance of positive electrode can be obviously improved.
In addition to this, the present invention uses LixCoyAlzRsO2As Shell Materials, the residual of positive electrode can be significantly reduced
Alkali reduces positive electrode to the oxygenolysis of electrolyte, promotes the high temperature circulation and security performance of positive electrode.Specific mechanism
Are as follows: core layer material surface coats LixCoyAlzRsO2The LiCoO for mixing aluminium can be formed afterwards2Material, LixCoyAlzRsO2Shell is coating
In the process with the residual alkali (Li of core layer material2CO3And LiOH) effective association reaction is carried out, the cobalt acid lithium for mixing aluminium is formed, is not only consumed
Residual alkali in positive electrode, and surface formed mix aluminium cobalt acid lithium and can play effective gram volume, promote discharge voltage
Platform, to further promote the energy density of ternary material；Meanwhile it being formed and mixing the surface coating layer of aluminium and can further be promoted again
The high temperature circulation and thermal stability (security performance) of ternary material battery.
Preferably, the mass ratio of the materials A and material B be 0.1~20:1, preferably 3~20:1, such as 3:1,4:1,
5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18:1 or 19:1 etc..
The mass ratio of materials A of the present invention and the material B are that 0.1~20:1 can make if materials A ratio is excessive
The compacted density of material is lower, and if the ratio of material B is excessive, the specific discharge capacity of material can be made lower.
Preferably, the core layer material of the materials A and material B are identical or different.
Preferably, the Shell Materials of the materials A and material B are identical or different.
Preferably, the D50 of the materials A is 4~20 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μ
M, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm or 19 μm etc..
Preferably, the D50 of the material B is 1~10 μm, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm
Deng.
Preferably, the partial size of the materials A > material B partial size.
The partial size of heretofore described materials A > material B partial size, size particles mutual cooperation can be obviously improved positive material
Energy density, high rate performance, high temperature circulation and the security performance of material.
Preferably, in the materials A Shell Materials accounting be 0.1~10wt%, preferably 0.2~2.0wt%, such as
0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or 9wt% etc..
Preferably, in the material B Shell Materials accounting be 0.1~10wt%, preferably 0.2~2.0wt%, such as
0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or 9wt% etc..
The second object of the present invention is to provide a kind of preparation method of positive electrode as described in the first purpose, the preparation
Method includes the following steps:
(1) preparation of materials A:
(a) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, soluble in water
To the stratum nucleare salting liquid of materials A, the stratum nucleare salting liquid of the materials A is mixed with the first alkaline solution, it is molten to obtain the first mixing
Liquid；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,
In 0≤c≤0.20,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two group
It closes；
(b) first mixed solution is mixed with complexing agent, the first hydro-thermal reaction is then carried out, before obtaining materials A
Drive body；
(c) presoma of the materials A is mixed with the source Li, obtains the core layer material of materials A after the first sintering；
(d) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in alcohol
Obtain the shell salting liquid of materials A；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+
In s=1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(e) the shell salting liquid of the materials A is mixed with the core layer material of materials A, then carries out the second sintering, obtains
Materials A；
(2) preparation of material B:
(f) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, soluble in water
To the stratum nucleare salting liquid of material B, the stratum nucleare salting liquid of the material B is mixed with the second alkaline solution, it is molten to obtain the second mixing
Liquid；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,
In 0≤c≤0.20,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two group
It closes；
(g) second mixed solution is mixed with complexing agent, the second hydro-thermal reaction is then carried out, before obtaining material B
Drive body；
(h) presoma of the material B is mixed with the source Li, obtains the core layer material of material B after third sintering；
(i) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in alcohol
Obtain the shell salting liquid of material B；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+
In s=1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(j) the shell salting liquid of the material B is mixed with the core layer material of material B, then carries out the 4th sintering, obtains
Material B；
(3) preparation of positive electrode:
(k) materials A and material B are mixed, obtains positive electrode.
Step (1) and step (2) out-of-order limit in the present invention, i.e., first prepare materials A or material B indistinction.
Preferably, step (a) first alkaline solution is NaOH solution, the preferably NaOH solution of 1~5mol/L, example
Such as 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L.
Preferably, metallic element always rubs in the mole of NaOH and the stratum nucleare salting liquid of materials A in the NaOH solution
The ratio between your amount is 1~3:1, such as 1.2:1,1.5:1,1.8:1,2:1,2.2:1,2.5:1 or 2.8:1 etc..
Preferably, step (a) source Ni, the source Co, the source Mn and the source M include appointing in sulfate, nitrate and chlorate
It anticipates a kind of or at least two combinations.
Preferably, step (b) complexing agent is ammonium hydroxide.
Preferably, the ratio between the integral molar quantity of metallic element is in the stratum nucleare salting liquid of the mole and materials A of the ammonium hydroxide
0.2~1:1, such as 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1 or 0.9:1 etc..
Preferably, the product pH that step (b) first mixed solution and complexing agent are mixed to get is 11~12, such as
11.1,11.2,11.3,11.4,11.5,11.6,11.7,11.8 or 11.9 etc..
Preferably, the temperature of step (b) first hydro-thermal reaction is 50~70 DEG C, such as 52 DEG C, 55 DEG C, 58 DEG C, 60
DEG C, 62 DEG C, 65 DEG C, 66 DEG C or 68 DEG C etc..
Preferably, the time of step (b) first hydro-thermal reaction be 2~48h, such as 5h, 10h, 12h, 15h, 20h,
For 24 hours, 25h, 30h, 35h, 40h or 45h etc..
Preferably, step (c) source Li includes Li2CO3And/or LiOH.
Preferably, step (c) the mixed mode is solid-phase ball milling mixing.
Preferably, step (c) it is described first sintering temperature be 650~800 DEG C, such as 660 DEG C, 680 DEG C, 700 DEG C,
720 DEG C, 740 DEG C, 750 DEG C, 760 DEG C or 780 DEG C etc..
Preferably, step (c) it is described first sintering time be 5~for 24 hours, such as 6h, 8h, 10h, 12h, 14h, 15h,
16h, 18h, 20h or 22h etc..
Preferably, the atmosphere of step (c) first sintering is oxygen atmosphere.
Preferably, step (d) alcohol is ethyl alcohol and/or isopropanol.
Preferably, step (e) it is described second sintering temperature be 500~800 DEG C, such as 520 DEG C, 550 DEG C, 580 DEG C,
600 DEG C, 650 DEG C, 680 DEG C, 700 DEG C, 750 DEG C or 780 DEG C etc..
Preferably, step (e) it is described second sintering time be 2~for 24 hours, such as 3h, 5h, 6h, 8h, 10h, 12h, 14h,
15h, 16h, 18h, 20h or 22h etc..
Preferably, the atmosphere of step (e) second sintering is oxygen atmosphere.
Preferably, step (f) second alkaline solution is NaOH solution, the preferably NaOH solution of 1~5mol/L, example
Such as 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L.
Preferably, the mole of NaOH is always rubbed with metallic element in the stratum nucleare salting liquid of material B in the NaOH solution
The ratio between your amount is 1~3:1, such as 1.2:1,1.5:1,1.8:1,2:1,2.2:1,2.5:1 or 2.8:1 etc..
Preferably, step (f) source Ni, the source Co, the source Mn and the source M include appointing in sulfate, nitrate and chlorate
It anticipates a kind of or at least two combinations.
Preferably, step (g) complexing agent is ammonium hydroxide.
Preferably, the mole of the ammonium hydroxide and the ratio between the integral molar quantity of metallic element in the stratum nucleare salting liquid of material B are
0.2~1:1, such as 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1,0.8:1 or 0.9:1 etc..
Preferably, the product pH that step (g) second mixed solution and complexing agent are mixed to get is 10~12, such as
10.2,10.5,10.6,10.8,11,11.2,11.5,11.6 or 11.8 etc..
Preferably, the temperature of step (g) second hydro-thermal reaction is 40~70 DEG C, such as 42 DEG C, 45 DEG C, 50 DEG C, 55
DEG C, 60 DEG C, 65 DEG C or 68 DEG C etc..
Preferably, the time of step (g) second hydro-thermal reaction be 2~48h, such as 5h, 10h, 12h, 15h, 20h,
For 24 hours, 25h, 30h, 35h, 40h or 45h etc..
Preferably, step (h) source Li includes Li2CO3And/or LiOH.
Preferably, step (h) the mixed mode is solid-phase ball milling mixing.
Preferably, the temperature of step (h) third sintering is 750~950 DEG C, for example, 760 DEG C, 780 DEG C, 800 DEG C,
820 DEG C, 850 DEG C, 880 DEG C, 900 DEG C or 920 DEG C etc..
Preferably, the time of step (h) third sintering is 4~36h, for example, 6h, 8h, 10h, 12h, 15h, 20h,
For 24 hours, 26h, 30h or 35h etc..
Preferably, the atmosphere of step (h) the third sintering is oxygen atmosphere.
Preferably, step (i) alcohol is ethyl alcohol and/or isopropanol.
Preferably, step (j) it is described 4th sintering temperature be 600~950 DEG C, such as 650 DEG C, 680 DEG C, 700 DEG C,
750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C or 920 DEG C etc..
Preferably, step (j) it is described 4th sintering time be 2~for 24 hours, such as 3h, 5h, 6h, 8h, 10h, 12h, 14h,
15h, 16h, 18h, 20h or 22h etc..
Preferably, the atmosphere of step (j) the 4th sintering is oxygen atmosphere.
Preferably, the mass ratio of step (k) materials A and material B be 0.1~20:1, preferably 3~20:1, such as
0.5:1、0.8:1、1:1、2:1、3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1、12:1、13:1、14:1、15:
1,16:1,17:1,18:1 or 19:1 etc..
Preferably, step (k) the mixed mode is solid-phase ball milling mixing.
As optimal technical scheme, a kind of preparation method of positive electrode of the present invention includes the following steps:
(1) preparation of materials A:
(a) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, soluble in water
To the stratum nucleare salting liquid of materials A, the stratum nucleare salting liquid of the materials A is mixed with the NaOH solution of 1~5mol/L, the NaOH
The ratio between integral molar quantity of metallic element is 1~3:1 in the stratum nucleare salting liquid of the mole and materials A of NaOH in solution, obtains the
One mixed solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,
In 0≤c≤0.20,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two group
It closes；
(b) first mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of materials A
The ratio between integral molar quantity of metallic element is 0.2~1:1, and mix products pH is 11~12, and then carrying out temperature is 50~70 DEG C
First hydro-thermal reaction 2~48h time, obtain the presoma of materials A；
(c) presoma of the materials A is mixed with the source Li, under oxygen atmosphere, temperature is the first of 650~800 DEG C
Sintering 5~for 24 hours, obtain the core layer material of materials A；
(d) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in ethyl alcohol
And/or the shell salting liquid of materials A is obtained in isopropanol；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+
In s=1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(e) the shell salting liquid of the materials A is mixed by metering ratio with the core layer material of materials A, then in oxygen gas
Under atmosphere, 500~800 DEG C of second sintering 2 of progress~for 24 hours, obtain the materials A that Shell Materials accounting is 0.2~2wt%；
(2) preparation of material B:
(f) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, soluble in water
To the stratum nucleare salting liquid of material B, the stratum nucleare salting liquid of the material B is mixed with mass concentration for the NaOH solution of 1~5mol/L
Close, in the NaOH solution in the mole of NaOH and the stratum nucleare salting liquid of material B the ratio between integral molar quantity of metallic element for 1~
3:1 obtains the second mixed solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,
In 0≤c≤0.20,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two group
It closes；
(g) second mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of material B
The ratio between integral molar quantity of metallic element is 0.2~1:1, and mix products pH is 10~12, and then carrying out temperature is 40~70 DEG C
Second hydro-thermal reaction 2~48h time, obtain the presoma of material B；
(h) presoma of the material B is mixed with the source Li solid-phase ball milling, under oxygen atmosphere, temperature is 750~950
DEG C third be sintered 4~36h, obtain the core layer material of material B；
(i) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in ethyl alcohol
And/or the shell salting liquid of material B is obtained in isopropanol；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+
In s=1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(j) the shell salting liquid of the material B is mixed by metering ratio with the core layer material of material B, then in oxygen gas
Under atmosphere, carry out temperature be 600~950 DEG C the 4th sintering 2~for 24 hours, obtain Shell Materials accounting be 0.2~2wt% material
B；
(3) preparation of positive electrode:
(k) in mass ratio it is that 3~20:1 carries out solid-phase ball milling mixing by the materials A and material B, obtains positive electrode.
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery includes described in the first purpose
Positive electrode.
Compared with the existing technology, lithium ion battery of the present invention can be in higher voltage (>=4.2V vs (Li+/ Li)) it issues
Wave good energy density, cycle performance and security performance.Due to the raising of charge cutoff voltage, battery of the invention also has
Higher energy density can satisfy the demand that people are thinned lithium ion battery.
Compared with prior art, the invention has the following beneficial effects:
(1) positive electrode of the invention includes materials A and material B, and the core layer material of the materials A is secondary spherical
Grain, the core layer material of the material B are single crystal grain, and secondary spherical particle and single crystal grain with clad cooperate,
Synergistic effect, can be obviously improved energy density, high rate performance, high temperature circulation and the security performance of positive electrode.
(2) present invention uses LixCoyAlzRsO2As Shell Materials, the residual alkali of positive electrode can be significantly reduced, reduce
Positive electrode promotes the high temperature circulation and security performance of positive electrode to the oxygenolysis of electrolyte.Specific mechanism are as follows: stratum nucleare material
Expect that surface coats LixCoyAlzRsO2The LiCoO for mixing aluminium can be formed afterwards2Material, LixCoyAlzRsO2Shell is during cladding and core
Residual alkali (the Li of layer material2CO3And LiOH) effective association reaction is carried out, the cobalt acid lithium for mixing aluminium is formed, positive electrode is not only consumed
In residual alkali, and surface formed mix aluminium cobalt acid lithium and can play effective gram volume, promote discharge voltage plateau, thus into
The energy density of one step promotion ternary material；Meanwhile it being formed and mixing the surface coating layer of aluminium can further to promote ternary material again electric
The high temperature circulation and thermal stability (security performance) in pond.
(3) compared with the existing technology, lithium ion battery of the present invention can be in higher voltage (>=4.2V vs (Li+/ Li)) under
Play good energy density, cycle performance and security performance.Due to the raising of charge cutoff voltage, battery of the invention also has
There is higher energy density, can satisfy the demand that people are thinned lithium ion battery.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of positive electrode includes the following steps:
(1) preparation of materials A:
(a) nickel sulfate, cobaltous sulfate, manganese sulfate and aluminum sulfate are pressed into core layer material chemical formula Li1.04Ni0.88Co0.05Mn0.05
Al0.02O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining materials A, by the stratum nucleare salting liquid of the materials A with
The NaOH solution of 3mol/L mixes, metallic element in the mole of NaOH and the stratum nucleare salting liquid of materials A in the NaOH solution
The ratio between integral molar quantity be 2.1:1, obtain the first mixed solution；
(b) first mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of materials A
The ratio between integral molar quantity of metallic element is 0.5:1, and mix products pH is 11.5, and it is anti-then to carry out the first hydro-thermal that temperature is 60 DEG C
The 12h time is answered, the presoma of materials A is obtained；
(c) presoma of the materials A is mixed with LiOH, under oxygen atmosphere, temperature be 700 DEG C first sintering
12h, obtains the core layer material of materials A, and the core layer material of the materials A is made of second particle；
(d) LiOH, cobaltous sulfate, aluminum sulfate and sulfuric acid tungsten are pressed into Shell Materials chemical formula Li0.9Co0.7Al0.25W0.05O2Ratio
Example is configured, and the shell salting liquid that materials A is obtained in ethyl alcohol is dissolved in；
(e) the shell salting liquid of the materials A is mixed with the core layer material of materials A, then under oxygen atmosphere, is carried out
700 DEG C of second sintering 12h, obtains D50For 12 μm of materials A, the materials A is core-shell structure, and Shell Materials accounting is 2wt%；
(2) preparation of material B:
(f) nickel sulfate, cobaltous sulfate, manganese sulfate, aluminum sulfate and zirconium sulfate are pressed into core layer material chemical formula Li1.01Ni0.83
Co0.03Mn0.12Zr0.01Al0.01O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining material B, by the material B
Stratum nucleare salting liquid mixed with the NaOH solution of 4mol/L, the stratum nucleare salt of the mole of NaOH and material B in the NaOH solution
The ratio between integral molar quantity of GOLD FROM PLATING SOLUTION category element is 2.3:1, obtains the second mixed solution；
(g) second mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of material B
The ratio between integral molar quantity of metallic element is 0.3:1, and mix products pH is 11.6, and it is anti-then to carry out the second hydro-thermal that temperature is 50 DEG C
The 12h time is answered, the presoma of material B is obtained；
(h) presoma of the material B is mixed with LiOH solid-phase ball milling, under oxygen atmosphere, temperature is the of 870 DEG C
Three sintering 15h, obtain the core layer material of material B, the core layer material of the material B is made of single crystal grain；
(i) LiOH, cobaltous sulfate, aluminum sulfate, strontium sulfate and titanium sulfate are pressed into Shell Materials chemical formula
Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Ratio configured, be dissolved in the shell salting liquid that material B is obtained in isopropanol；
(j) the shell salting liquid of the material B is mixed with the core layer material of material B, then under oxygen atmosphere, is carried out
The 4th sintering 10h that temperature is 800 DEG C, obtains D50It is core-shell structure, Shell Materials accounting for 3 μm of material B, the material B
For 1wt%；
(3) preparation of positive electrode:
(k) in mass ratio it is that 85:15 carries out solid-phase ball milling mixing by the materials A and material B, obtains positive electrode.
Embodiment 2
A kind of preparation method of positive electrode includes the following steps:
(1) preparation of materials A:
(a) nickel nitrate, manganese nitrate, nitric acid tungsten and aluminum sulfate are pressed into core layer material chemical formula
Li1.01Ni0.92Mn0.04W0.01Al0.03O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining materials A, by the material
The stratum nucleare salting liquid of material A is mixed with the NaOH solution of 1mol/L, the stratum nucleare of the mole and materials A of NaOH in the NaOH solution
The ratio between integral molar quantity of metallic element is 2.5:1 in salting liquid, obtains the first mixed solution；
(b) first mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of materials A
The ratio between integral molar quantity of metallic element is 0.9:1, and mix products pH is 12, then carries out the first hydro-thermal reaction that temperature is 70 DEG C
The 36h time obtains the presoma of materials A；
(c) presoma of the materials A is mixed with LiOH, under oxygen atmosphere, temperature be 800 DEG C first sintering
10h, obtains the core layer material of materials A, and the core layer material of the materials A is made of second particle；
(d) LiOH, cobalt nitrate, aluminum nitrate and magnesium nitrate are pressed into Shell Materials chemical formula Li0.5Co0.7Al0.2Mg0.1O2Ratio
Example is configured, and the shell salting liquid that materials A is obtained in isopropanol is dissolved in；
(e) the shell salting liquid of the materials A is mixed with the core layer material of materials A, then under oxygen atmosphere, is carried out
800 DEG C of second sintering 8h, obtains D50For 9 μm of materials A, the materials A is core-shell structure, and Shell Materials accounting is 5wt%；
(2) preparation of material B:
(f) nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and zirconium nitrate are pressed into core layer material chemical formula Li1.01Ni0.89
Co0.02Mn0.07Zr0.01Al0.01O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining material B, by the material B
Stratum nucleare salting liquid mixed with the NaOH solution of 5mol/L, the stratum nucleare salt of the mole of NaOH and material B in the NaOH solution
The ratio between integral molar quantity of GOLD FROM PLATING SOLUTION category element is 1.8:1, obtains the second mixed solution；
(g) second mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of material B
The ratio between integral molar quantity of metallic element is 1:1, and mix products pH is 10.9, then carries out the second hydro-thermal reaction that temperature is 70 DEG C
The 10h time obtains the presoma of material B；
(h) presoma of the material B is mixed with LiOH solid-phase ball milling, under oxygen atmosphere, temperature is the of 820 DEG C
Three sintering for 24 hours, obtain the core layer material of material B, the core layer material of the material B is made of single crystal grain；
(i) LiOH, cobalt nitrate, aluminum nitrate and zirconium nitrate are pressed into Shell Materials chemical formula Li0.3Co0.8Al0.1Zr0.1O2Ratio
Example is configured, and the shell salting liquid that material B is obtained in ethyl alcohol is dissolved in；
(j) the shell salting liquid of the material B is mixed with the core layer material of material B, then under oxygen atmosphere, is carried out
The 4th sintering 8h that temperature is 930 DEG C, obtains D50It is core-shell structure for 3 μm of material B, the material B, Shell Materials accounting is
0.5wt%；
(3) preparation of positive electrode:
(k) in mass ratio it is that 95:5 carries out solid-phase ball milling mixing by the materials A and material B, obtains positive electrode.
Embodiment 3
The difference from embodiment 1 is that the mass ratio of step (k) materials A and material B are 0.1:1.
Embodiment 4
The difference from embodiment 1 is that the mass ratio of step (k) materials A and material B are 20:1.
Embodiment 5
The difference from embodiment 1 is that the mass ratio of step (k) materials A and material B are 0.05:1.
Embodiment 6
The difference from embodiment 1 is that the mass ratio of step (k) materials A and material B are 30:1.
Embodiment 7
A kind of preparation method of positive electrode includes the following steps:
(1) preparation of materials A:
(a) nickel sulfate, cobaltous sulfate, manganese sulfate and aluminum sulfate are pressed into core layer material chemical formula Li1.04Ni0.88Co0.05Mn0.05
Al0.02O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining materials A, by the stratum nucleare salting liquid of the materials A with
The NaOH solution of 2mol/L mixes, metallic element in the mole of NaOH and the stratum nucleare salting liquid of materials A in the NaOH solution
The ratio between integral molar quantity be 1.9:1, obtain the first mixed solution；
(b) first mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of materials A
The ratio between integral molar quantity of metallic element is 0.6:1, and mix products pH is 11, then carries out the first hydro-thermal reaction that temperature is 50 DEG C
The 16h time obtains the presoma of materials A；
(c) presoma of the materials A is mixed with LiOH, under oxygen atmosphere, temperature be 650 DEG C first sintering
For 24 hours, the core layer material of materials A is obtained, the core layer material of the materials A is made of second particle；
(d) LiOH, cobaltous sulfate, aluminum sulfate and sulfuric acid tungsten are pressed into Shell Materials chemical formula Li0.9Co0.7Al0.25W0.05O2Ratio
Example is configured, and the shell salting liquid that materials A is obtained in ethyl alcohol is dissolved in；
(e) the shell salting liquid of the materials A is mixed with the core layer material of materials A, then under oxygen atmosphere, is carried out
650 DEG C of second sintering for 24 hours, obtains D50For 11 μm of materials A, the materials A is core-shell structure, and Shell Materials accounting is
1.8wt%；
(2) preparation of material B:
(f) nickel sulfate, cobaltous sulfate, manganese sulfate, aluminum sulfate and zirconium sulfate are pressed into core layer material chemical formula Li1.01Ni0.83
Co0.03Mn0.12Zr0.01Al0.01O2Ratio configured, the stratum nucleare salting liquid soluble in water for obtaining material B, by the material B
Stratum nucleare salting liquid mixed with the NaOH solution of 3mol/L, the stratum nucleare salt of the mole of NaOH and material B in the NaOH solution
The ratio between integral molar quantity of GOLD FROM PLATING SOLUTION category element is 2.6:1, obtains the second mixed solution；
(g) second mixed solution is mixed with ammonium hydroxide, in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of material B
The ratio between integral molar quantity of metallic element is 0.3:1, and mix products pH is 11.8, and it is anti-then to carry out the second hydro-thermal that temperature is 68 DEG C
The 10h time is answered, the presoma of material B is obtained；
(h) presoma of the material B is mixed with LiOH solid-phase ball milling, under oxygen atmosphere, temperature is the of 920 DEG C
Three sintering 8h, obtain the core layer material of material B, the core layer material of the material B is made of single crystal grain；
(i) LiOH, cobaltous sulfate, aluminum sulfate, strontium sulfate and titanium sulfate are pressed into Shell Materials chemical formula
Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Ratio configured, be dissolved in the shell salting liquid that material B is obtained in isopropanol；
(j) the shell salting liquid of the material B is mixed with the core layer material of material B, then under oxygen atmosphere, is carried out
The 4th sintering 18h that temperature is 750 DEG C, obtains D50It is core-shell structure, Shell Materials accounting for 3 μm of material B, the material B
For 1.1wt%；
(3) preparation of positive electrode:
(k) in mass ratio it is that 80:20 carries out solid-phase ball milling mixing by the materials A and material B, obtains positive electrode.
Comparative example 1
The difference from embodiment 1 is that respectively by the shell salt of materials A and material B described in step (e) and step (j)
Solution replaces with aluminum nitrate, and Shell Materials are all Al in obtained materials A and material B2O3。
Comparative example 2
The difference from embodiment 1 is that the core layer material of materials A described in step (e) directly carry out second sintering, not with
The shell salting liquid of materials A mixes, and obtaining materials A does not have Shell Materials；The core layer material of material B directly carries out in step (j)
4th sintering, does not mix, obtaining material B does not have Shell Materials, i.e. materials A and material B does not all have with the shell salting liquid of material B
Shell Materials.
Comparative example 3
The difference from embodiment 1 is that the core layer material of materials A described in step (e) directly carry out second sintering, not with
The shell salting liquid of materials A mixes, and obtaining materials A does not have Shell Materials.
Comparative example 4
The difference from embodiment 1 is that in step (j) core layer material of material B directly carry out the 4th sintering, not with material
The shell salting liquid of B mixes, and obtaining material B does not have Shell Materials.
Comparative example 5
The difference from embodiment 1 is that get the positive electrode arrived being materials A without step (2) and step (3).
Comparative example 6
The difference from embodiment 1 is that get the positive electrode arrived being material B without step (1) and step (3).
Performance test:
Using the positive electrode being prepared as positive active material, conductive black is conductive agent, and Kynoar is bonding
Three is the ratio mixing of 96.6:2:1.4, is uniformly mixed, is starched by solvent of N-Methyl pyrrolidone by agent in mass ratio
Then the slurry is coated in current collector aluminum foil by material；Using artificial graphite as negative electrode active material, conductive black is conduction
Agent, CMC are dispersing agent, and SBR is bonding agent, mix according to the ratio of mass ratio 97.1:0.5:1.1:1.3, are with deionized water
Solvent is uniformly mixed, and obtains slurry, and then above-mentioned slurry is coated on copper foil of affluxion body；Above-mentioned positive and negative anodes pole plate is passed through respectively
It is wound together with common process after overbaking, roll-in and cutting with diaphragm, then by terminal welding, packaging foil encapsulation, note
Liquid, encapsulation chemical conversion, pumping form and 454261 (length/width/thickness is respectively 61/42/4.5mm) type flexible packing lithium ions are made
Battery, charge cutoff voltage are that (anodic potentials are with Li by 4.25V+About 4.35V on the basis of/Li), design capacity 2000mAh, into
Row charge-discharge test.
(1) energy density (ED) is tested: in normal temperature condition, with the rate of charge constant-current charge of 0.5C to 4.25V, then with
Then the rate of charge constant-voltage charge of 0.05C is discharged to 3.0V with the discharge-rate of 0.2C to 4.25V, obtain discharge capacity and
Average discharge volt platform；Then according to battery actual size (length and width, thickness),
(2) high rate performance is tested: in normal temperature condition, with the rate of charge constant-current charge of 0.5C to 4.25V, then with 0.05C
Rate of charge constant-voltage charge to 4.25V, 3.0V is then discharged to the discharge-rate of 0.2C, obtains 0.2C discharge capacity C5；
In normal temperature condition, with the rate of charge constant-current charge of 0.5C to 4.25V, then extremely with the rate of charge constant-voltage charge of 0.05C
Then 4.25V is discharged to 3.0V with the discharge-rate of 1C, obtain 1C discharge capacity C1；
(3) high-temperature storage performance: in normal temperature condition, with the rate of charge constant-current charge of 0.5C to 4.25V, then with 0.05C
Rate of charge constant-voltage charge to 4.25V, after standing 1h, test the original depth T of battery1, voltage U2With internal resistance R1, then
Battery, which is put into 70 DEG C of baking ovens, stores 48h, and cooling 10min tests the thickness T of battery2, voltage U2With internal resistance R2；
(4) cycle performance is tested: in normal temperature condition, with the rate of charge constant-current charge of 0.7C to 4.25V, then with 0.05C
Rate of charge constant-voltage charge to 4.25V, 3.0V is then discharged to the discharge-rate of 1C, 400 this charge and discharge follow repeatedly
Ring measures the discharge capacity when discharge capacity and the 400th circulation when recycling for the first time, the capacity holding after finding out circulation
Rate；
(5) security performance is tested: in normal temperature condition, with the rate of charge constant-current charge of 0.5C to 4.25V, then with 0.05C
Rate of charge constant-voltage charge to 4.25V, after standing 1h, test voltage and the internal resistance of battery, battery be then put into air blast and is dried
In case.Set oven temperature: 30min is warming up to 150 DEG C, then persistently toasts 6 hours at 150 DEG C, and record battery and toasting
The variation of temperature and voltage in the process.The superiority and inferiority of battery safety is measured so that whether battery in baking process burns, if electric
Pond is burnt, then security performance test does not pass through；Conversely, then passing through.
Table 1
1, embodiment 5 and the comparison discovery of embodiment 6 through the embodiment of the present invention, if materials A ratio is excessive, Gao Wencun
Storage, high temperature circulation and security performance are lower, although the compacted density of material is lower, keeps ED slightly lower in addition, electric discharge gram volume is high；
And if the ratio of material B is excessive, and the specific discharge capacity of material can be made lower, energy density (ED) is low, and discharge-rate is poor.
1, comparative example 1-4 comparison discovery through the embodiment of the present invention, compared with uncoated positive electrode, cladding Al2O3's
Positive electrode has better high temperature storage and cycle performance；With cladding Al2O3Than coating Li0.9Co0.7Al0.25W0.05O2With
Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Positive electrode have higher energy density, high rate performance, high temperature storage and cyclicity
Energy；The second particle material of shell is lacked, high temperature storage, high temperature circulation and security performance are insufficient, lack the monocrystalline material of shell
Material, high temperature storage and high temperature cyclic performance obviously want poor.This is because residual alkali (the Li on ternary material surface2CO3And LiOH)
Very much (pH value is up to 12) coats Al2O3The oxidisability for reducing ternary material is only played, it is basic without reducing in ternary material
The residual alkali (Li of lithium battery2CO3It is easy to happen side reaction at high temperature with LiOH, generates gas, interface impedance is caused to become larger, dislikes
Change circulation), and the present invention uses Li0.9Co0.7Al0.25W0.05O2And Li0.5Co0.6Al0.3Sr0.05Ti0.05O2After cladding, surface
Li0.9Co0.7Al0.25W0.05O2And Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Effectively knot can occur with the residual alkali on ternary material surface
It closes, generates the similar LiCoO for mixing Al2, that is, the clad generated not only consumes the residual alkali in ternary, moreover it is possible to play effective gram
Capacity and discharge platform (discharge platform of cobalt acid lithium about 0.1V higher than ternary), promote the energy density of ternary material；The oxygen of Co
The property changed is far smaller than Ni, therefore coats Li0.9Co0.7Al0.25W0.05O2And Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Ternary material
Battery has good high temperature storage, high temperature circulation and security performance, simultaneously as Surface L i0.9Co0.7Al0.25W0.05O2With
Li0.5Co0.6Al0.3Sr0.05Ti0.05O2Middle Al also further improves high temperature storage, cycle performance and the peace of ternary material battery
Full performance.
Through the embodiment of the present invention 1, comparative example 5 and the comparison discovery of comparative example 6, only with the materials A of secondary spherical particle,
Its discharge-rate is although good, but the compacted density of respective material is smaller, and corresponding ED is slightly lower, in addition, its high temperature circulation is poor, heat is steady
Qualitative difference, especially to short grained secondary spherical particle；Only with the material B of monocrystalline, high temperature circulation is good, thermal stability
Good, although compacted density is big, because the electric discharge gram volume of material is low, corresponding ED is lower, and discharge-rate is also poor.
Method detailed of the invention that the present invention is explained by the above embodiments, but the invention is not limited to it is above-mentioned in detail
Method, that is, do not mean that the invention must rely on the above detailed methods to implement.Person of ordinary skill in the field should
It is illustrated, any improvement in the present invention, addition, the concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Selection etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of positive electrode, which is characterized in that the positive electrode includes materials A and material B, and the materials A and material B are all
For core-shell structure；
The core layer material chemical formula of the materials A and material B independently are Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,
In 0.8≤b≤0.95,0≤c≤0.2,0≤d≤0.2, M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or extremely
Few two kinds of combination；
The core layer material of the materials A is secondary spherical particle, and the core layer material of the material B is single crystal grain；
The Shell Materials chemical formula of the materials A and material B independently are LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s
≤ z < y < 1, y+z+s=1, in R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination.
2. positive electrode as described in claim 1, which is characterized in that the mass ratio of the materials A and material B are 0.1~20:
1, preferably 3~20:1；
Preferably, the core layer material of the materials A and material B are identical or different；
Preferably, the Shell Materials of the materials A and material B are identical or different.
3. positive electrode as claimed in claim 1 or 2, which is characterized in that the D50 of the materials A is 4~20 μm；
Preferably, the D50 of the material B is 1~10 μm；
Preferably, the partial size of the materials A > material B partial size.
4. the positive electrode as described in one of claim 1-3, which is characterized in that Shell Materials accounting is 0.1 in the materials A
~10wt%, preferably 0.2~2wt%；
Preferably, Shell Materials accounting is 0.1~10wt%, preferably 0.2~2wt% in the material B.
5. a kind of preparation method of the positive electrode as described in one of claim 1-4, which is characterized in that the preparation method includes
Following steps:
(1) preparation of materials A:
(a) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, it is soluble in water to obtain material
The stratum nucleare salting liquid for expecting A, the stratum nucleare salting liquid of the materials A is mixed with the first alkaline solution, obtains the first mixed solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,0≤c
≤ 0.20,0≤d≤0.2, in M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(b) first mixed solution is mixed with complexing agent, then carries out the first hydro-thermal reaction, obtains the presoma of materials A；
(c) presoma of the materials A is mixed with the source Li, obtains the core layer material of materials A after the first sintering；
(d) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in alcohol and obtains
The shell salting liquid of materials A；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+s=
In 1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(e) the shell salting liquid of the materials A is mixed with the core layer material of materials A, then carries out the second sintering, obtains material
A；
(2) preparation of material B:
(f) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, it is soluble in water to obtain material
The stratum nucleare salting liquid for expecting B, the stratum nucleare salting liquid of the material B is mixed with the second alkaline solution, obtains the second mixed solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,0≤c
≤ 0.20,0≤d≤0.2, in M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(g) second mixed solution is mixed with complexing agent, then carries out the second hydro-thermal reaction, obtains the presoma of material B；
(h) presoma of the material B is mixed with the source Li, obtains the core layer material of material B after third sintering；
(i) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, is dissolved in alcohol and obtains
The shell salting liquid of material B；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+s=
In 1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(j) the shell salting liquid of the material B is mixed with the core layer material of material B, then carries out the 4th sintering, obtains material
B；
(3) preparation of positive electrode:
(k) materials A and material B are mixed, obtains positive electrode.
6. the preparation method as described in one of claim 1-5, which is characterized in that step (a) first alkaline solution is
NaOH solution, the preferably NaOH solution of 1~5mol/L；
Preferably, in the NaOH solution in the mole of NaOH and the stratum nucleare salting liquid of materials A metallic element integral molar quantity
The ratio between be 1~3:1；
Preferably, step (a) source Ni, the source Co, the source Mn and the source M include any one in sulfate, nitrate and chlorate
Kind or at least two combination；
Preferably, step (b) complexing agent is ammonium hydroxide；
Preferably, in the stratum nucleare salting liquid of the mole and materials A of the ammonium hydroxide the ratio between integral molar quantity of metallic element be 0.2~
1:1；
Preferably, the product pH that step (b) first mixed solution and complexing agent are mixed to get is 11~12；
Preferably, the temperature of step (b) first hydro-thermal reaction is 50~70 DEG C；
Preferably, the time of step (b) first hydro-thermal reaction is 2~48h；
Preferably, step (c) source Li includes Li2CO3And/or LiOH；
Preferably, step (c) the mixed mode is solid phase method ball milling mixing；
Preferably, the temperature of step (c) first sintering is 650~800 DEG C；
Preferably, step (c) it is described first sintering time be 5~for 24 hours；
Preferably, the atmosphere of step (c) first sintering is oxygen atmosphere；
Preferably, step (d) alcohol is ethyl alcohol and/or isopropanol；
Preferably, the temperature of step (e) second sintering is 500~800 DEG C；
Preferably, step (e) it is described second sintering time be 2~for 24 hours；
Preferably, the atmosphere of step (e) second sintering is oxygen atmosphere.
7. the preparation method as described in one of claim 1-6, which is characterized in that step (f) second alkaline solution is
NaOH solution, the preferably NaOH solution of 1~5mol/L；
Preferably, in the NaOH solution in the mole of NaOH and the stratum nucleare salting liquid of material B metallic element integral molar quantity
The ratio between be 1~3:1；
Preferably, step (f) source Ni, the source Co, the source Mn and the source M include any one in sulfate, nitrate and chlorate
Kind or at least two combination；
Preferably, step (g) complexing agent is ammonium hydroxide；
Preferably, in the stratum nucleare salting liquid of the mole of the ammonium hydroxide and material B the ratio between integral molar quantity of metallic element for 0.2~
1:1；
Preferably, the product pH that step (g) second mixed solution and complexing agent are mixed to get is 10~12；
Preferably, the temperature of step (g) second hydro-thermal reaction is 40~70 DEG C；
Preferably, the time of step (g) second hydro-thermal reaction is 2~48h；
Preferably, step (h) source Li includes Li2CO3And/or LiOH；
Preferably, step (h) the mixed mode is solid-phase ball milling mixing；
Preferably, the temperature of step (h) the third sintering is 750~950 DEG C；
Preferably, the time of step (h) the third sintering is 4~36h；
Preferably, the atmosphere of step (h) the third sintering is oxygen atmosphere；
Preferably, step (i) alcohol is ethyl alcohol and/or isopropanol；
Preferably, the temperature of step (j) the 4th sintering is 600~950 DEG C；
Preferably, step (j) it is described 4th sintering time be 2~for 24 hours；
Preferably, the atmosphere of step (j) the 4th sintering is oxygen atmosphere.
8. the preparation method as described in one of claim 1-7, which is characterized in that the matter of step (k) materials A and material B
Amount is than being 0.1~20:1, preferably 3~20:1；
Preferably, step (k) the mixed mode is solid-phase ball milling mixing.
9. preparation method as described in one of claim 1-8, which is characterized in that the preparation method includes the following steps:
(1) preparation of materials A:
(a) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, it is soluble in water to obtain material
The stratum nucleare salting liquid for expecting A, the stratum nucleare salting liquid of the materials A is mixed with the NaOH solution of 1~5mol/L, the NaOH solution
The ratio between integral molar quantity of metallic element is 1~3:1 in the mole of middle NaOH and the stratum nucleare salting liquid of materials A, and it is mixed to obtain first
Close solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,0≤c
≤ 0.20,0≤d≤0.2, in M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(b) first mixed solution is mixed with ammonium hydroxide, metal in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of materials A
The ratio between integral molar quantity of element is 0.2~1:1, and mix products pH is 11~12, then carries out first that temperature is 50~70 DEG C
Hydro-thermal reaction 2~48h time, obtain the presoma of materials A；
(c) presoma of the materials A is mixed with the source Li, under oxygen atmosphere, temperature be 650~800 DEG C first sintering 5
~for 24 hours, obtain the core layer material of materials A；
(d) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, be dissolved in ethyl alcohol and/or
The shell salting liquid of materials A is obtained in isopropanol；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+s=
In 1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(e) the shell salting liquid of the materials A is mixed by metering ratio with the core layer material of materials A, then under oxygen atmosphere,
500~800 DEG C of second sintering 2 of progress~for 24 hours, obtain the materials A that Shell Materials accounting is 0.2~2wt%；
(2) preparation of material B:
(f) source Ni, the source Co, the source Mn and the source M are configured in the ratio of the core layer material chemical formula, it is soluble in water to obtain material
The stratum nucleare salting liquid for expecting B mixes the stratum nucleare salting liquid of the material B with the NaOH solution that mass concentration is 1~5mol/L, institute
The ratio between the integral molar quantity for stating metallic element in the stratum nucleare salting liquid of the mole of NaOH and material B in NaOH solution is 1~3:1,
Obtain the second mixed solution；
Wherein, the core layer material chemical formula is Li1+aNibCocMndM1-b-c-dO2, 0≤a≤0.15,0.8≤b≤0.95,0≤c
≤ 0.20,0≤d≤0.2, in M Al, Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(g) second mixed solution is mixed with ammonium hydroxide, metal in the mole of the ammonium hydroxide and the stratum nucleare salting liquid of material B
The ratio between integral molar quantity of element is 0.2~1:1, and mix products pH is 10~12, then carries out second that temperature is 40~70 DEG C
Hydro-thermal reaction 2~48h time, obtain the presoma of material B；
(h) presoma of the material B is mixed with the source Li solid-phase ball milling, under oxygen atmosphere, temperature is 750~950 DEG C
Third is sintered 4~36h, obtains the core layer material of material B；
(i) source Li, the source Co, the source Al and the source R are configured in the ratio of the Shell Materials chemical formula, be dissolved in ethyl alcohol and/or
The shell salting liquid of material B is obtained in isopropanol；
Wherein, the Shell Materials chemical formula is LixCoyAlzRsO2, wherein 0.05≤x≤1.0,0 < s≤z < y < 1, y+z+s=
In 1, R Mg, Ti, Zr, W, Sr, La, In and Y any one or at least two combination；
(j) the shell salting liquid of the material B is mixed by metering ratio with the core layer material of material B, then under oxygen atmosphere,
Carry out temperature be 600~950 DEG C the 4th sintering 2~for 24 hours, obtain Shell Materials accounting be 0.2~2wt% material B；
(3) preparation of positive electrode:
(k) in mass ratio it is that 3~20:1 carries out solid-phase ball milling mixing by the materials A and material B, obtains positive electrode.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode described in one of claim 1-4
Material.
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| CN111370664B (en) * | 2020-03-18 | 2022-04-29 | 溧阳中科海钠科技有限责任公司 | Method for reducing residual alkali content on surface of layered positive electrode material of sodium-ion battery and application |
| CN112919551A (en) * | 2021-01-28 | 2021-06-08 | 桑顿新能源科技有限公司 | Cathode material, preparation method thereof, cathode and lithium ion battery |
| CN112919551B (en) * | 2021-01-28 | 2023-12-15 | 湖南桑瑞新材料有限公司 | Positive electrode material, preparation method thereof, positive electrode and lithium ion battery |
| CN113851607A (en) * | 2021-09-15 | 2021-12-28 | 蜂巢能源科技有限公司 | Positive electrode material, preparation method thereof, positive electrode including same, and lithium ion battery |
| WO2023122946A1 (en) * | 2021-12-28 | 2023-07-06 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method therefor, and secondary battery having same |
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