CN114180648A - Preparation method of lithium ion battery anode material - Google Patents
Preparation method of lithium ion battery anode material Download PDFInfo
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- CN114180648A CN114180648A CN202111491120.2A CN202111491120A CN114180648A CN 114180648 A CN114180648 A CN 114180648A CN 202111491120 A CN202111491120 A CN 202111491120A CN 114180648 A CN114180648 A CN 114180648A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000010405 anode material Substances 0.000 title abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 61
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 18
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical group [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 23
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- 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 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 16
- 229910013716 LiNi Inorganic materials 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- JOMNYEIYSNJMSL-UHFFFAOYSA-N [O].[Zr].[Li] Chemical compound [O].[Zr].[Li] JOMNYEIYSNJMSL-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- -1 lithium zirconium oxide compound Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910012623 LiNi0.5Co0.2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- WYDJZNNBDSIQFP-UHFFFAOYSA-N [O-2].[Zr+4].[Li+] Chemical compound [O-2].[Zr+4].[Li+] WYDJZNNBDSIQFP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZTWBEOCMVOSCSU-UHFFFAOYSA-N lithium;oxotitanium Chemical compound [Li].[Ti]=O ZTWBEOCMVOSCSU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
Abstract
The invention discloses a preparation method of a lithium ion battery anode material, relates to the technical field of lithium ion batteries, and particularly relates to a preparation method of a lithium ion battery anode materialaNixCoyMnzMmO2，Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.33 and less than or equal to 0.7, y is more than or equal to 0 and less than or equal to 0.33, z is more than or equal to 0 and less than or equal to 0.5, M is more than or equal to 0 and less than or equal to 0.1, x + y + z + M is 1, M is Zr, Ti, Al, Ti, and Ti, or a,One or more of Ta or F elements, wherein the component A accounts for 85-99% by weight; the component B is lithium manganese iron phosphate with a chemical formula of LiaMnxFeyPO4Wherein a is more than or equal to 0.9 and less than or equal to 1.1, x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.7, x + y is 1, and the mass ratio of the component B is 1-15%. According to the invention, through modification of the nickel cobalt lithium manganate material, the high-voltage electrochemical performance of the material is improved, so that the material has high capacity and high cycling stability; on the other hand, the nickel content is reduced, and a high-stability lithium manganese iron phosphate material is introduced, so that the multi-component material has high thermal stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a lithium ion battery anode material.
Background
At present, the main anode materials of the lithium battery comprise lithium iron phosphate and ternary materials (nickel cobalt manganese oxide)Lithium), the lithium iron phosphate material has excellent thermal stability but low energy density. Ternary materials have higher energy density but poorer thermal stability. The ternary material mainly comprises metal elements of lithium, nickel, cobalt and manganese according to a certain proportion, and the specific capacity of the ternary material is increased along with the increase of the content of nickel, while the thermal stability is reduced. At present, in view of the demand of people for energy density of lithium batteries, a ternary material LiNi with high nickel content0.8Co0.1Mn0.1O2The material is applied to new energy automobile power batteries, but the thermal stability of the material is poor, so that the safety of the power batteries is reduced. On the other hand, LiNi0.6Co0.2Mn0.2O2The nickel content of the iso-ternary material is lower than that of LiNi0.8Co0.1Mn0.1O2The material has higher thermal stability and LiNi can be obtained at high voltage0.8Co0.1Mn0.1O2The capacity of the material, but the high voltage can cause the side reaction between the interface of the anode material and the electrolyte, thereby reducing the electrochemical cycling stability of the material and limiting the application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a lithium ion battery anode material, which solves the existing problems in the background technology.
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of a lithium ion battery anode material is compounded by a component A and a component B, wherein the component A is modified nickel cobalt lithium manganate with a chemical formula of LiaNixCoyMnzMmO2，Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.33 and less than or equal to 0.7, y is more than or equal to 0 and less than or equal to 0.33, z is more than or equal to 0 and less than or equal to 0.5, M is more than or equal to 0 and less than or equal to 0.1, x + y + z + M is 1, M is one or more of Zr, Ti, Ta or F elements, and the mass of the component A accounts for 85-99%;
the component B is lithium manganese iron phosphate with a chemical formula of LiaMnxFeyPO4Wherein a is more than or equal to 0.9 and less than or equal to 1.1, x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.7, x + y is 1, and the mass ratio of the component B is 1-15%.
Optionally, the particle size of the modified nickel cobalt lithium manganate material is 1-15 μm, and the modified nickel cobalt lithium manganate material can be a single crystal or polycrystalline material.
Optionally, the particle size of the lithium iron manganese phosphate material is 50-300 nm.
A preparation method of a lithium ion battery anode material comprises the following steps:
s1, preparing modified nickel cobalt lithium manganate;
s2, carrying out physical compounding on the components A and B.
Optionally, the preparation method of modified nickel cobalt lithium manganate in step S1 includes the following steps:
s101, mixing four or three solutions of nickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfate at 55 ℃ in a nitrogen atmosphere to form a mixed solution with the total metal ion concentration of 2 mol/L;
s102, adding ammonia water and sodium hydroxide into the mixed salt solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution;
s103, heating to 65 ℃ and reacting for 2h to obtain a coprecipitate;
s104, performing solid-liquid separation in a centrifugal mode, wherein the centrifugal rotating speed is 8000rmp/min, and performing vacuum drying on the obtained solid at 80 ℃ to obtain a precursor of the nickel cobalt lithium manganate;
s105, uniformly mixing the precursor of the lithium nickel cobalt manganese oxide and LiOH, putting the mixture into a sagger, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain the lithium nickel cobalt manganese oxide product.
Optionally, in the step S2, the method further includes the following steps:
s201, weighing the component A and the component B, and mixing for 3 hours in a ball mill at the rotating speed of 300 rpm/min;
s202, transferring the mixture into a sagger, heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping for 10 hours;
s203, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and sieving with a 400-mesh sieve to obtain the multielement cathode material product.
The invention provides a preparation method of a lithium ion battery anode material, which has the following beneficial effects:
according to the invention, through modification of the nickel cobalt lithium manganate material, the high-voltage electrochemical performance of the material is improved, so that the material has high capacity and high cycling stability; on the other hand, the nickel content is reduced, and a high-stability lithium manganese iron phosphate material is introduced, so that the multi-component material has high thermal stability;
the conventional lithium nickel cobalt manganese oxide material is modified and then compounded with lithium manganese iron phosphate to obtain the multi-element cathode material, and the material has excellent high-voltage stability and can realize LiNi with the conventional high-capacity cathode material0.8Co0.1Mn0.1O2The equivalent energy density, more importantly, because the proportion of Ni element is reduced and Fe and Mn elements with high stability are added in the multi-element material, the thermal stability of the material is greatly improved, so that the multi-element anode material has high safety;
the invention improves the ionic conductivity of the surface of the material by introducing the lithium zirconium oxygen or lithium titanium oxygen fast ion conductor on the surface of the nickel cobalt lithium manganate particles, because the compounding of the lithium manganese iron phosphate and the lithium nickel cobalt manganese oxide adopts mechanical physical compounding, the surface of the lithium nickel cobalt manganese oxide is not completely coated by the lithium manganese iron phosphate, exposed sites of fast ion conductors such as lithium zirconium oxide exist, the sites can provide fast channels for the transmission of lithium ions, so that the problem of poor rate performance of conventional lithium manganese iron phosphate or lithium nickel cobalt manganese oxide composite anode materials is solved, on the other hand, the lithium zirconium oxide compound on the surface can provide a high-voltage interface stable layer for lithium nickel cobalt manganese oxide particles in combination with the lithium manganese iron phosphate compound, the side reaction with electrolyte is reduced, the cycle life of the material under high voltage is prolonged, the lithium manganese iron phosphate has excellent thermal stability, and the thermal decomposition stability of the composite anode material can be improved.
Drawings
FIG. 1 is a schematic diagram of the electrochemical rate performance of the present invention;
FIG. 2 is a schematic diagram of the performance of the electrochemical cycle of the present invention;
fig. 3 is a schematic view of the thermal decomposition temperature of the positive electrode material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
A positive electrode material of lithium ion battery is compounded by a component A and a component B, wherein the component A is modified nickel cobalt lithium manganate with a chemical formula of LiaNixCoyMnzMmO2，Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.33 and less than or equal to 0.7, y is more than or equal to 0 and less than or equal to 0.33, z is more than or equal to 0 and less than or equal to 0.5, M is more than or equal to 0 and less than or equal to 0.1, x + y + z + M is 1, M is one or more of Zr, Ti, Ta or F elements, the particle size of the modified nickel cobalt lithium manganate material is between 1 and 15 mu M, the modified nickel cobalt lithium manganate material can be a single crystal or polycrystalline material, and the mass of the component A accounts for 85 to 99 percent;
the component B is lithium manganese iron phosphate with a chemical formula of LiaMnxFeyPO4Wherein a is more than or equal to 0.9 and less than or equal to 1.1, x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.7, x + y is 1, the particle size of the lithium iron manganese phosphate material is 50-300 nm, and the mass ratio of the component B is 1-15%.
Example 1 (preparation of modified lithium nickel cobalt manganese oxide precursor)
Mixing four solutions of nickel sulfate (93g, 0.6mol), cobalt sulfate (31g, 0.2mol), manganese sulfate (27.2g, 0.18mol) and zirconium sulfate (5.67g, 0.02mol) at 55 ℃ in a nitrogen atmosphere according to the molar ratio of Ni to Co to Mn to Zr being 60:20:18:2 to form a mixed solution with the total metal ion concentration of 2mol/L, adding ammonia water (0.36mol/L) and sodium hydroxide (2mol/L) into the mixed solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution, heating to 65 ℃ for reaction for 2h to obtain a coprecipitate, carrying out solid-liquid separation in a centrifugal mode, carrying out centrifugal rotation speed of 8000rmp/min, carrying out vacuum drying on the obtained solid at 80 ℃ to obtain a precursor 1 of the nickel cobalt lithium manganate with the chemical formula of Ni0.6Co0.2Mn0.18Zr0.02(OH)2。
Example 2 (preparation of modified lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 1, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain a nickel cobalt lithium manganate product 1 with the chemical formula of LiNi0.6Co0.2Mn0.18Zr0.02O2。
Example 3 (preparation of Nickel cobalt lithium manganate precursor)
Mixing three solutions of nickel sulfate (93g, 0.6mol), cobalt sulfate (31g, 0.2mol) and manganese sulfate (30.2g, 0.18mol) at 55 ℃ in a nitrogen atmosphere according to the molar ratio of Ni to Co to Mn of 60:20:20 to form a mixed solution with the total metal ion concentration of 2mol/L, then adding ammonia water (0.36mol/L) and sodium hydroxide (2mol/L) into the mixed salt solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution, heating to 65 ℃ for reaction for 2 hours to obtain a coprecipitate, carrying out solid-liquid separation in a centrifugal mode, carrying out vacuum drying at 8000rmp/min to obtain a solid of 80 ℃ to obtain a precursor 2 of the nickel cobalt lithium manganate with the chemical formula of Ni0.6Co0.2Mn0.2(OH)2。
Example 4 (preparation of modified lithium nickel cobalt manganese oxide precursor)
Dispersing (92g, 1mol) precursor 2 into a solution of ethanol and deionized water (90:10 mass ratio), stirring and heating to 60 ℃, slowly adding (6.54g, 0.02mol) ethanol solution of zirconium isopropoxide, and continuously stirring for hydrolysis reaction for 1 h. And (3) performing solid-liquid separation in a centrifugal mode, wherein the centrifugal rotating speed is 8000rmp/min, and performing vacuum drying on the obtained solid at the temperature of 80 ℃ to obtain a precursor 3 of the nickel cobalt lithium manganate.
Example 5 (preparation of modified lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 3, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, and reducing the temperature at the heating rate of 3 ℃/minCooling to 300 ℃, mechanically crushing the mixture, and sieving with a 300-mesh sieve to obtain a lithium nickel cobalt manganese oxide product 2 with a chemical formula of LiNi0.6Co0.2Mn0.18Zr0.02O2。
Example 6 (preparation of modified lithium nickel cobalt manganese oxide precursor)
Mixing four solutions of nickel sulfate (77.4g, 0.5mol), cobalt sulfate (31g, 0.2mol), manganese sulfate (42.3g, 0.28mol) and zirconium sulfate (5.67g, 0.02mol) according to the molar ratio of Ni to Co to Mn to Zr being equal to 50:20:28:2 under the atmosphere of nitrogen and at 55 ℃ to form a mixed solution with the total metal ion concentration of 2mol/L, then adding ammonia water (0.36mol/L) and sodium hydroxide (2mol/L) into the mixed salt solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution, heating to 65 ℃ for reaction for 2h to obtain a coprecipitate, carrying out solid-liquid separation in a centrifugal mode, wherein the centrifugal speed is 8000rmp/min, and carrying out vacuum drying on the obtained solid at 80 ℃ to obtain a lithium manganate precursor 4 of nickel cobalt, wherein the chemical formula is Ni0.5Co0.2Mn0.28Zr0.02(OH)2。
Example 7 (preparation of modified lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 1, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 950 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain a nickel cobalt lithium manganate product 3 with the chemical formula of LiNi0.5Co0.2Mn0.28Zr0.02O2。
Example 8 (preparation of modified lithium nickel cobalt manganese oxide precursor)
Mixing four solutions of nickel sulfate (108.3g, 0.7mol), cobalt sulfate (23.3g, 0.15mol), manganese sulfate (19.6g, 0.13mol) and zirconium sulfate (5.67g, 0.02mol) according to the molar ratio of Ni: Co: Mn: Zr equal to 70:15:13:2 under the nitrogen atmosphere at 55 ℃ to form a mixed solution with the total metal ion concentration of 2mol/L, then adding ammonia water (0.36mol/L) and sodium hydroxide (2mol/L) into the mixed salt solution until the pH of the solution reaches 11 to obtain a coprecipitation mixed solution, and raising the pH to 11Heating to 65 ℃ for reaction for 2h to obtain a coprecipitate, performing solid-liquid separation in a centrifugal mode, wherein the centrifugal speed is 8000rmp/min, and performing vacuum drying on the obtained solid at 80 ℃ to obtain a precursor 5 of the nickel cobalt lithium manganate with the chemical formula of Ni0.7Co0.15Mn0.13Zr0.02(OH)2。
Example 9 (preparation of modified lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 1, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 840 ℃ at the heating rate of 5 ℃/min, keeping for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain a nickel cobalt lithium manganate product 4 with the chemical formula of LiNi0.7Co0.15Mn0.13Zr0.02O2。
Example 10 (preparation of multielement positive electrode material)
Weighing (95g) nickel cobalt lithium manganate product 1 (LiNi)0.6Co0.2Mn0.18Zr0.02O2) With (5g) LiMn0.6Fe0.4O4The materials are mixed in a ball mill at the rotating speed of 300rpm/min for 3h, transferred into a sagger, heated to 600 ℃ at the heating rate of 5 ℃/min, kept for 10 h, cooled to 300 ℃ at the heating rate of 3 ℃/min, naturally cooled to room temperature, mechanically crushed, and sieved by a 400-mesh sieve to obtain the multielement anode material product 1.
Example 11 (preparation of a multielement positive electrode material)
Weighing (90g) nickel cobalt lithium manganate product 1 (LiNi)0.6Co0.2Mn0.18Zr0.02O2) With (10g) LiMn0.6Fe0.4O4The materials are mixed in a ball mill at the rotating speed of 300rpm/min for 3h, transferred into a sagger, heated to 600 ℃ at the heating rate of 5 ℃/min, kept for 10 hours, cooled to 300 ℃ at the heating rate of 3 ℃/min, naturally cooled to room temperature, mechanically crushed, and sieved by a 400-mesh sieve to obtain the multielement anode material product 2.
Example 12 (preparation of a multielement positive electrode material)
Weighing (90g) NiCoMn acid lithium product 3 (LiNi)0.5Co0.2Mn0.28Zr0.02O2) With (10g) LiMn0.6Fe0.4O4Mixing the materials in a ball mill at the rotating speed of 300rpm/min for 3h, transferring the materials into a sagger, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 10 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and sieving by a 400-mesh sieve to obtain the multielement anode material product 3.
Example 13 (preparation of a multielement positive electrode material)
Weighing (90g) nickel cobalt lithium manganate product 4 (LiNi)0.7Co0.15Mn0.13Zr0.02O2) With (10g) LiMn0.6Fe0.4O4The materials are mixed in a ball mill at the rotating speed of 300rpm/min for 3h, transferred into a sagger, heated to 600 ℃ at the heating rate of 5 ℃/min, kept for 10 h, cooled to 300 ℃ at the heating rate of 3 ℃/min, naturally cooled to room temperature, mechanically crushed, and sieved by a 400-mesh sieve to obtain a multielement anode material product 4.
Example 14 (preparation of multielement positive electrode material)
Weighing (85g) nickel cobalt lithium manganate product 4 (LiNi)0.7Co0.15Mn0.13Zr0.02O2) With (15g) LiMn0.6Fe0.4O4The materials are mixed in a ball mill at the rotating speed of 300rpm/min for 3h, transferred into a sagger, heated to 600 ℃ at the heating rate of 5 ℃/min, kept for 10 hours, cooled to 300 ℃ at the heating rate of 3 ℃/min, naturally cooled to room temperature, mechanically crushed, and sieved by a 400-mesh sieve to obtain the multielement anode material product 5.
Example 15
0.9g of the nickel cobalt lithium manganate product 1, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, uniformly mixed, coated on an aluminum foil, dried at 80 ℃ for 2 hours and dried at 120 ℃ for 6 hours. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Example 16
0.9g of the multielement positive electrode material product 1, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, evenly mixed, coated on an aluminum foil, dried for 2 hours at 80 ℃ and dried for 6 hours at 120 ℃. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Example 17
0.9g of multi-element anode material product 2, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, evenly mixed, coated on aluminum foil, dried for 2 hours at 80 ℃ and dried for 6 hours at 120 ℃. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Example 18
0.9g of multi-element anode material product 4, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, evenly mixed, coated on aluminum foil, dried for 2 hours at 80 ℃ and dried for 6 hours at 120 ℃. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Example 19
0.9g of multi-element anode material product 5, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, evenly mixed, coated on aluminum foil, dried for 2 hours at 80 ℃ and dried for 6 hours at 120 ℃. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Comparative example 1 (preparation of lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 2 of nickel cobalt lithium manganate, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and sieving by a 300-mesh sieve to obtain a nickel cobalt lithium manganate product 5 with the chemical formula of LiNi0.6Co0.2Mn0.2O2。
Comparative example 2 (preparation of lithium nickel cobalt manganese oxide precursor)
Mixing three solutions of nickel sulfate (123.8g, 0.8mol), cobalt sulfate (15.5g, 0.1mol) and manganese sulfate (15.1g, 0.1mol) at 55 ℃ in a nitrogen atmosphere according to the molar ratio of Ni to Co to Mn to Zr being 80:10:10 to form a mixed solution with the total metal ion concentration of 2mol/L, then adding ammonia water (0.36mol/L) and sodium hydroxide (2mol/L) into the mixed salt solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution, heating to 65 ℃ for reaction for 2h to obtain a coprecipitate, carrying out solid-liquid separation in a centrifugal mode, carrying out vacuum drying at 80 ℃ on the obtained solid to obtain a precursor 6 of nickel cobalt, wherein the chemical formula is Ni lithium manganate0.8Co0.1Mn0.1(OH)2。
Comparative example 3 (preparation of lithium nickel cobalt manganese oxide)
Uniformly mixing (92g, 1mol) precursor 6, (25.13g, 1.05mol) LiOH, putting the mixture into a sagger, heating to 780 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain a nickel cobalt lithium manganate product 6 with the chemical formula of LiNi0.8Co0.1Mn0.1O2。
Comparative example 4
0.9g of nickel cobalt lithium manganate product 5, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, uniformly mixed, coated on an aluminum foil, dried at 80 ℃ for 2 hours and dried at 120 ℃ for 6 hours. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Comparative example 5
0.9g of the lithium nickel cobalt manganese oxide product 6, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, mixed uniformly, coated on an aluminum foil, dried at 80 ℃ for 2 hours and dried at 120 ℃ for 6 hours. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Comparative example 6 (preparation of multielement positive electrode material)
Weighing (95g) nickel cobalt lithium manganate product 5 (LiNi)0.6Co0.2Mn0.2O2) With (5g) LiMn0.6Fe0.4O4The materials are mixed in a ball mill at the rotating speed of 300rpm/min for 3h, transferred into a sagger, heated to 600 ℃ at the heating rate of 5 ℃/min, kept for 10 h, cooled to 300 ℃ at the heating rate of 3 ℃/min, naturally cooled to room temperature, mechanically crushed, and sieved by a 400-mesh sieve to obtain the multielement anode material product 6.
Comparative example 7
0.9g of the multielement positive electrode material product 6, 0.05g of acetylene black and 0.05g of PVDF are dissolved in NMP solvent, evenly mixed, coated on an aluminum foil, dried for 2 hours at 80 ℃ and dried for 6 hours at 120 ℃. Making into a circular pole piece with diameter of 1cm, using metal lithium as counter electrode, and electrolyte (EC/EMC: 3/7 volume ratio, 1 MLiPF)6) A 2032 button cell is assembled.
Electrochemical testing
(1) Multiplying power test
Testing the electrochemical performance of the material by adopting a constant current charge-discharge instrument; the loading capacity of all positive active materials is 6-8 mgcm-2(ii) a Discharge specific capacity test conditions: the voltage range is 2.8-4.3V (considering that the high voltage of 4.5V can cause the surface of the comparative example 7 to be degraded and influence the multiplying factor authenticity of the comparative example, the test is uniformly carried out under 2.8-4.3V), the 0.1C is circulated for 1 time, and then the 0.2C, 0.5C, 1C, 2C, 3C, 5C, 10C and 20C are circulated for 5 times respectively;
as can be seen from FIG. 1, the modification with the lithium zirconium oxygen fast ion conductor is example 16 (95% LiNi)0.6Co0.2Mn0.18Zr0.02O2+5％LiMn0.6Fe0.4O4) The rate capability of (2) is obviously better than that of comparative example 7 (95% LiNi)0.6Co0.2Mn0.2O2+5％LiMn0.6Fe0.4O4) Especially at high magnifications above 5C, this difference is significantly increased.
(2) Capacity and cycle Performance testing
Using constant current charge-discharge instrument pairsTesting the electrochemical performance of the material; the loading capacity of all positive active substances is 6-8 mg cm-2(ii) a Discharge specific capacity test conditions: the voltage range is 2.8-4.3V or 2.8-4.5V, and the charge/discharge current is 0.1C/0.1C multiplying power; cycling test conditions: the voltage range is 2.8-4.3V or 2.8-4.5V, the charge/discharge current is 1C/1C multiplying power, and the cycle is 200 times.
TABLE 1 electrochemical comparison Table (units (mAh/g))
As can be seen from Table 1 and FIG. 2, conventional LiNi0.6Co0.2Mn0.2O2The specific capacity of the material (comparative example 4) at 4.3V was 177mAhg-1Lower than conventional LiNi0.8Co0.1Mn0.1O2Material (192mAhg-1) (comparative examples 4, 4.3V); when conventional LiNi is used0.6Co0.2Mn0.2O2When the voltage of the material (comparative example 4) is raised to 4.5V for circulation, the specific capacity exceeds that of the conventional LiNi0.8Co0.1Mn0.1O2Material (comparative example 4, 4.3V), but the cycle capacity retention at 200 cycles dropped to 71%, while zirconium-modified LiNi0.6Co0.2Mn0.18Zr0.02O2The specific capacity of the material (example 15) and the multielement material (example 16) under 4.5V not only reaches or exceeds that of the conventional LiNi0.8Co0.1Mn0.1O2The capacity of the material (comparative example 4, 4.3V) and more excellent cycle capacity retention.
(3) Thermal stability test
Differential Scanning Calorimeter (DSC) test conditions: for the example cell, the cell was pre-cycled three times at 0.1C rate under 2.8-4.5V, then charged to 4.5V at 0.1C rate, disassembled in an argon atmosphere glove box, and the positive electrode was removedWashing off residual electrolyte on the surface of the sheet by using dimethyl carbonate, drying, separating the active substance coating from the current collector, and separating the active substance coating from the electrolyte (1 MLiPF)6EC/EMC: 3/7 volume ratio) 10:1 mass ratio, and sealing in an Au high-pressure crucible. For the battery of comparative example 5, the battery was pre-cycled three times at 0.1C rate under 2.8-4.3V, then charged to 4.3V at 0.1C rate, the battery was disassembled in an argon atmosphere glove box, the positive electrode plate was taken out, the residual electrolyte on the surface was washed away with dimethyl carbonate, after drying, the active material coating was separated from the current collector, mixed in an Au high-pressure crucible with a mass ratio of electrolyte 10:1, and sealed for testing.
TABLE 2DSC exothermic peak comparison table (in. (. degree. C.))
As can be seen from Table 2 and FIG. 3, conventional LiNi0.8Co0.1Mn0.1O2The material (comparative example 5, 4.3V) had a thermal decomposition temperature of 218 ℃ in the 4.3V charged state under the electrolyte-charged condition, while the zirconium-modified LiNi0.6Co0.2Mn0.18Zr0.02O2The material (example 15) has a thermal decomposition temperature of 261 ℃ in the charged state of 4.5V in the presence of electrolyte, which is significantly higher than that of comparative example 5; the thermal decomposition temperatures of the multielement material (example 16) in the charged state of 4.5V with electrolyte are 273 c and 276 c higher than in example 15.
In summary, the present invention provides a multi-element cathode material suitable for a lithium ion battery, which has the characteristics of high capacity, high cycle capacity retention rate and high safety; for example, the capacity of the multielement material (example 16) is 195mAhg-1(4.5V), a capacity retention ratio of 95% at 200 cycles, and a thermal decomposition stability of 273 ℃ compared to a conventional LiNi of similar capacity0.8Co0.1Mn0.1O2The thermal runaway temperature of the material (comparative example 4, 4.3V) increased by 55 ℃.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (6)
1. A positive electrode material of lithium ion battery is compounded by a component A and a component B, wherein the component A is modified nickel cobalt lithium manganate with a chemical formula of LiaNixCoyMnzMmO2，Wherein a is more than or equal to 1.0 and less than or equal to 1.1, x is more than or equal to 0.33 and less than or equal to 0.7, y is more than or equal to 0 and less than or equal to 0.33, z is more than or equal to 0 and less than or equal to 0.5, M is more than or equal to 0 and less than or equal to 0.1, x + y + z + M is 1, M is one or more of Zr, Ti, Ta or F elements, and the mass of the component A accounts for 85-99%;
the component B is lithium manganese iron phosphate with a chemical formula of LiaMnxFeyPO4Wherein a is more than or equal to 0.9 and less than or equal to 1.1, x is more than or equal to 0.3 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.7, x + y is 1, and the mass ratio of the component B is 1-15%.
2. The positive electrode material of the lithium ion battery according to claim 1, wherein: the particle size of the modified nickel cobalt lithium manganate material is 1-15 mu m, and the modified nickel cobalt lithium manganate material can be a single crystal or polycrystalline material.
3. The positive electrode material of the lithium ion battery according to claim 1, wherein: the particle size of the lithium iron manganese phosphate material is 50-300 nm.
4. A method for preparing a lithium ion battery cathode material based on any one of claims 1-3, comprising the following steps:
s1, preparing modified nickel cobalt lithium manganate;
s2, carrying out physical compounding on the components A and B.
5. The method for preparing the positive electrode material of the lithium ion battery according to claim 4, wherein the method for preparing the modified nickel cobalt lithium manganate in the step S1 comprises the following steps:
s101, mixing four or three solutions of nickel sulfate, cobalt sulfate, manganese sulfate and zirconium sulfate at 55 ℃ in a nitrogen atmosphere to form a mixed solution with the total metal ion concentration of 2 mol/L;
s102, adding ammonia water and sodium hydroxide into the mixed salt solution until the pH value of the solution reaches 11 to obtain a coprecipitation mixed solution;
s103, heating to 65 ℃ and reacting for 2h to obtain a coprecipitate;
s104, performing solid-liquid separation in a centrifugal mode, wherein the centrifugal rotating speed is 8000rmp/min, and performing vacuum drying on the obtained solid at 80 ℃ to obtain a precursor of the nickel cobalt lithium manganate;
s105, uniformly mixing the precursor of the lithium nickel cobalt manganese oxide and LiOH, putting the mixture into a sagger, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 15 hours, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and screening by using a 300-mesh screen to obtain the lithium nickel cobalt manganese oxide product.
6. The method for preparing the positive electrode material of the lithium ion battery according to claim 4, wherein in the step S2, the method further comprises the following steps:
s201, weighing the component A and the component B, and mixing for 3 hours in a ball mill at the rotating speed of 300 rpm/min;
s202, transferring the mixture into a sagger, heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping for 10 hours;
s203, cooling to 300 ℃ at the heating rate of 3 ℃/min, naturally cooling to room temperature, mechanically crushing the mixture, and sieving with a 400-mesh sieve to obtain the multielement cathode material product.
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