CN116425210B - High-nickel precursor, positive electrode material and preparation method of positive electrode material - Google Patents
High-nickel precursor, positive electrode material and preparation method of positive electrode material Download PDFInfo
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- CN116425210B CN116425210B CN202310139359.6A CN202310139359A CN116425210B CN 116425210 B CN116425210 B CN 116425210B CN 202310139359 A CN202310139359 A CN 202310139359A CN 116425210 B CN116425210 B CN 116425210B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002243 precursor Substances 0.000 title claims abstract description 64
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 63
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 68
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 52
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012266 salt solution Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000011572 manganese Substances 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 238000006138 lithiation reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 241000080590 Niso Species 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 41
- 239000002245 particle Substances 0.000 abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 3
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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Abstract
一种高镍前驱体、正极材料及其制备方法，属于锂离子电池材料技术领域，克服现有技术制备高镍前驱体时，掺杂元素在材料体相内分布不均的缺陷。本发明高镍前驱体的制备方法包括以下步骤：步骤1、配制含Al镍钴锰盐溶液、氨水溶液、碱液沉淀剂和氨水底液；含Al镍钴锰盐溶液中，Al/TM原子比为0.001‑0.01，TM为镍、钴、锰原子的物质的量之和；步骤2、将氨水底液加入反应釜中，并将氨水底液pH调节至10.7‑11.7，将含Al镍钴锰盐溶液、氨水溶液、碱液沉淀剂同时泵入反应釜内，进料过程中进行搅拌，进料结束后继续搅拌反应；步骤3、固液分离，洗涤、干燥后获得高镍前驱体。本发明可减少颗粒微裂纹的产生，提升材料的长循环稳定性。
A kind of high nickel precursor, positive electrode material and preparation method thereof, belong to the technical field of lithium ion battery materials, overcome the defect that doping elements are unevenly distributed in the material body when the prior art prepares high nickel precursor. The preparation method of the high nickel precursor of the present invention comprises the following steps: step 1, prepare Al-containing nickel cobalt manganese salt solution, ammonia solution, alkali solution precipitant and ammonia bottom liquid; in the Al-containing nickel cobalt manganese salt solution, the Al/TM atomic ratio is 0.001-0.01, and TM is the sum of the amount of substance of nickel, cobalt and manganese atoms; step 2, add the ammonia bottom liquid to the reactor, and adjust the pH of the ammonia bottom liquid to 10.7-11.7, pump the Al-containing nickel cobalt manganese salt solution, ammonia solution and alkali solution precipitant into the reactor at the same time, stir during the feeding process, and continue stirring reaction after the feeding ends; step 3, solid-liquid separation, washing, drying to obtain a high nickel precursor. The present invention can reduce the generation of particle microcracks and improve the long cycle stability of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-nickel precursor, a positive electrode material and a preparation method thereof.
Background
In order to relieve the shortage of petroleum and reduce the emission of CO 2, china is gradually moving to the new energy and electric appliance era. Along with the popularization of new energy automobiles, a lithium ion power battery serving as a main power source of the new energy automobiles has a broad development prospect. At present, the main commercial lithium ion power battery anode materials comprise nickel cobalt manganese ternary materials LiNi xCoyMnz(OH)2 (0 < x+y < 1) and lithium iron phosphate materials (LiFePO 4), because the low-nickel ternary materials LiNi xCoyMnz(OH)2 (x < 0.6) and LiFePO 4 materials have low energy densities (about 150-160 Wh/kg), the requirements of electric vehicles on the endurance mileage are difficult to meet, and the main bottleneck of development of the electric vehicles in the field of power batteries is formed, and the high-nickel ternary materials (LiNi xCoyMnz(OH)2, x is more than or equal to 0.6) can endow the materials with more reversible capacity due to the increase of Ni components, so that the high-nickel anode materials with excellent development performance become one of the main development directions of future power lithium battery materials.
At present, the production of high-nickel anode materials generally adopts a complex coprecipitation method to prepare a polycrystalline spherical precursor, and then the polycrystalline spherical precursor is sintered by mixing lithium to prepare the corresponding anode material. The high nickel material Ni component content increases, although the reversible capacity is improved, the structural stability and the safety of the material are also deteriorated, adverse Li/Ni mixed phase change, stress accumulation caused by surface residual alkali and lattice anisotropic expansion/expansion and the like are easy to form in the material preparation and circulation process, and further the capacity rapid decay, the charge transfer impedance increase, the interface side reaction aggravation and the serious particle crushing in the material circulation overcharging are caused, so that the potential safety hazard is brought to the long-term circulation use of the battery.
In order to stabilize the material structure, one effective method is to introduce a small amount of impurity elements into the material to stabilize and strengthen the structure, for example, common doping elements comprise Mg, al, zr, nb, ta and the like, wherein Al can obviously improve the circularity, multiplying power and thermal stability of the high-nickel material, and has a certain inhibition effect on surface residual alkali, but most researches generally introduce the doping elements in a precursor lithiation sintering stage and disperse the doping elements at each site of material crystal grains in a solid-phase thermal diffusion way, and the diffusion efficiency of the solid-phase sintering elements is low, so that the uneven distribution of the doping elements in the material bulk is easily caused, thereby causing inconsistent electrochemical behaviors among different sites of the material and poor doping effect.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect that the doping elements are unevenly distributed in the bulk phase of the material when the high-nickel precursor is prepared in the prior art, so as to provide the high-nickel precursor, the positive electrode material and the preparation method thereof.
For this purpose, the invention provides the following technical scheme.
In a first aspect, the invention provides a method for preparing a high nickel precursor, comprising the following steps:
step 1, preparing an Al-containing nickel-cobalt-manganese salt solution, an ammonia water solution, an alkali solution precipitant and an ammonia water bottom solution, wherein in the Al-containing nickel-cobalt-manganese salt solution, the Al/TM atomic ratio is 0.001-0.01, and TM is the sum of the amounts of substances of nickel, cobalt and manganese atoms;
step2, adding ammonia water base solution into a reaction kettle, regulating the pH value of the ammonia water base solution to 10.7-11.7, simultaneously pumping an Al-containing nickel cobalt manganese salt solution, an ammonia water solution and an alkali solution precipitant into the reaction kettle, stirring in the feeding process, and continuing stirring reaction after the feeding is finished;
and step 3, solid-liquid separation, washing and drying to obtain the high-nickel precursor.
Further, at least one of the following conditions is satisfied:
(1) In the feeding process, the feeding speed range of the Al-containing nickel cobalt manganese salt solution is 0.5-2.0mL/min;
preferably 0.5-0.9mL/min;
(2) In the feeding process, in order to ensure the cooperative coordination of the complexation and the precipitation reaction, the molar ratio of NH 3 in the aqueous ammonia solution fed in unit time to TM in the solution containing Al, nickel, cobalt and manganese is 1.0-1.4, preferably 1.1-1.3.
The feed rate of the aqueous ammonia solution was converted based on the aqueous ammonia concentration and the NH 3:TM feed molar ratio.
The flow rate of the alkali solution precipitant is used for adjusting the pH value of the feed solution in the reaction kettle, so that the pH value is always constant at the target pH value.
(3) In the solution containing Al, ni, co and Mn, the Al/TM atomic ratio is 0.005-0.01.
Further, the feeding speed of the Al-containing nickel cobalt manganese salt solution is 0.8-0.9mL/min or 0.5-0.6mL/min.
In the feeding process, all the reaction materials are fully dispersed and meet again for precipitation crystallization reaction under stirring, so as to maintain the supersaturation degree of the system to be stable and enable the structure crystal ions to be uniformly deposited, and the reaction pH, the feeding speed and the feed liquid temperature are kept constant in the process.
And after the reaction is finished, washing the precursor precipitate for 3-4 times by adopting low-concentration alkaline water and pure water, so that Na +、NH3、SO4 2- mixed in the precipitate product is washed out, and the washed precursor is placed in a vacuum drying oven and dried at 100-120 ℃ for 12-20 hours to obtain dry high-nickel precursor powder.
Further, at least one of the following conditions is satisfied in step 2:
(1) Adding ammonia water bottom solution into a reaction kettle, and heating the ammonia water bottom solution to 45-60 ℃;
(2) Ultrasonically dispersing dissolved oxygen in an Al-containing nickel cobalt manganese salt solution, an ammonia water solution and an alkali solution precipitant before pumping the solution into a reaction kettle;
(3) The stirring speed in the feeding process is 500-1000rpm;
Preferably, the feeding time is controlled within 10-50 h;
(4) After the feeding is finished, stirring and heating are continuously maintained for 10-12 hours, so that the reaction is fully carried out, and the crystal growth is more mature;
optionally, the stirring speed after the end of the feeding is adjusted to 100-500rpm.
Further, the step 1 satisfies at least one of the following conditions:
(1) The TM concentration in the Al-containing nickel cobalt manganese salt solution is 1.5-2.5mol/L;
Preparing Al-containing nickel-cobalt-manganese salt solution, namely taking soluble metal salts of nickel, cobalt, manganese and aluminum, and rapidly dissolving the soluble metal salts with hot water to obtain Al-containing nickel-cobalt-manganese salt solution with target concentration, or adopting an Al-containing nickel-cobalt-manganese leaching solution obtained by wet recovery of waste lithium ion batteries, and preparing the concentration of each metal element in the leaching solution to meet the material design proportion to serve as metal salt raw material liquid, thereby realizing the recycling of metal resources;
(2) Preparing an Al-containing nickel cobalt manganese salt solution according to Ni xCoyMn1-x-y(OH)2, wherein 0.6.ltoreq.x <1,0< x+y <1;
(3) The concentration of the ammonia water solution is 4.0-5.6mol/L;
(4) The concentration of the alkali solution precipitant is 4.0-8.0mol/L;
(5) The concentration of the ammonia water bottom solution is 1.0-1.4mol/L (the concentration of ammonia in the bottom solution (namely the ammonia water bottom solution) initially entering the reaction kettle is the concentration of ammonia after the ammonia water solution is diluted by the Al-containing nickel cobalt manganese salt solution and the alkali solution precipitant during feeding.
In the step 2, the adding amount of the ammonia water base solution is selected according to the bottom position of the stirring pitch reaction kettle, so that the stirring paddle can be used for beating the ammonia water base solution, alternatively, the adding amount of the ammonia water base solution is 1/4-1/2 of the volume of the reaction kettle, after the ammonia water base solution is added, the ammonia water base solution is preheated to 45-60 ℃, meanwhile, protective gas is continuously injected into the kettle to drive air, at the moment, the pH of the ammonia water base solution is generally lower than a reaction set value by 10.7-11.7, and an alkaline pump is started to adjust the pH of the ammonia water base solution to the reaction set value.
Further, at least one of the following conditions is satisfied:
(1) Preparing an Al-containing nickel-cobalt-manganese salt solution by adopting soluble metal salts of nickel, cobalt, manganese and aluminum, wherein the metal salts are one or more of hydrochloride, sulfate, nitrate or acetate;
(2) The alkali solution precipitant is one or more selected from LiOH, naOH, KOH.
In a second aspect, the present invention provides a high nickel precursor prepared by the above method.
In a third aspect, the invention provides a preparation method of a positive electrode material, and the high-nickel precursor prepared by the method is subjected to lithiation sintering to prepare the positive electrode material.
Optionally, after sintering, grinding and sieving the prepared positive electrode material (the ambient humidity is controlled below 30%), and then sealing and preserving the positive electrode material by using a vacuum sample bag. Illustratively, a 200 mesh screen is employed.
Further, the lithiation sintering comprises oxygen-enriched heat preservation sintering after mixing a high nickel precursor with a lithium source;
optionally, the lithium source is LiOH-H 2 O micron-sized powder;
The sintering is carried out in a tubular furnace, and the sagger is made of corundum alumina.
Optionally, the heat-preserving sintering is divided into two sections, wherein the first section is pre-sintered for 4-6 hours at 450-550 ℃ and the second section is heat-preserving for 8-16 hours at 700-800 ℃. The higher the Ni content is, the lower the temperature is in the second-stage heat preservation sintering.
In one possible design, the rate of temperature rise is 3-5C/min and the rate of temperature reduction is 3-5C/min during sintering.
In a fourth aspect, the present invention provides a positive electrode material prepared according to the above method.
The technical scheme of the invention has the following advantages:
1. The preparation method of the high-nickel precursor comprises the following steps of 1, preparing an Al-containing nickel-cobalt-manganese salt solution, an ammonia water solution, an alkali solution precipitant and an ammonia water base solution, wherein the Al/TM atomic ratio in the Al-containing nickel-cobalt-manganese salt solution is 0.001-0.01, TM is the sum of the amounts of substances of nickel, cobalt and manganese atoms, 2, adding the ammonia water base solution into a reaction kettle, regulating the pH of the ammonia water base solution to 10.7-11.7, pumping the Al-containing nickel-cobalt-manganese salt solution, the ammonia water solution and the alkali solution precipitant into the reaction kettle at the same time, stirring in the feeding process, continuing stirring for reaction after the feeding is finished, and 3, carrying out solid-liquid separation, washing and drying to obtain the high-nickel precursor.
According to the invention, al element and other elements are used for coprecipitation reaction in-situ doping, and Al 3+ is uniformly migrated into precursor particles, so that element distribution non-uniformity caused by solid phase sintering diffusion is effectively avoided, lattice contraction/expansion difference in a material charging and discharging process caused by non-uniformity of doping is reduced, generation of particle microcracks is reduced, and long-cycle stability of the material is improved.
In order to improve the structural instability of the high-nickel positive electrode material and improve the circularity, a proper amount of impurity Al 3+ is introduced into a nickel-cobalt-manganese metal salt solution, so that the high-nickel positive electrode material is uniformly doped into a high-nickel spherical precursor in the nickel-cobalt-manganese coprecipitation process, and the high-nickel positive electrode material with Al uniformly doped is formed after lithiation and sintering. Al occupies transition metal positions in the material, and the doping of Al has a stabilizing effect on the bulk phase structure of the material because the bond energy of Al-O (512 kJ/mol) is higher than that of other TM-O bonds (Ni-O, 391.6kJ/mol; co-O,368kJ/mol; mn-O,402 kJ/mol), so that the collapse of the layered structure can be inhibited in the long-cycle process;
In the solution containing Al, ni, co and Mn, the atomic ratio of Al/TM is 0.001-0.01. By controlling the content of Al, the influence of the Al on the particle size and uniformity of the precursor is avoided, and the tap density of the precursor is improved, so that the energy density of the high-nickel positive electrode material is ensured.
2. The preparation method of the high-nickel precursor provided by the invention meets at least one of the following conditions that (1) in the feeding process, the feeding speed of the Al-containing nickel cobalt manganese salt solution ranges from 0.5 to 2.0mL/min, preferably from 0.5 to 0.9mL/min, (2) in the feeding process, the molar ratio of NH 3 in the ammonia water solution to TM in the Al-containing nickel cobalt manganese salt solution ranges from 1.0 to 1.4, preferably from 1.1 to 1.3 (3) in the Al-containing nickel cobalt manganese salt solution, and the Al/TM atomic ratio ranges from 0.005 to 0.01.
According to the invention, after aluminum is introduced into the liquid phase, a product with good particle size consistency, namely a precursor product with narrower particle size distribution can be obtained by controlling the Al/TM atomic ratio and the NH 3:TM atomic ratio and adopting a lower feeding speed of the Al-containing nickel-cobalt-manganese salt solution. Since the solubility product constant K sp(～10-33) of Al 3+ is far lower than that of Ni 2+、Co2+、Mn2+, the introduction of Al 3+ can increase the reaction supersaturation degree of a solution system, so that new agglomeration sites are formed continuously in the continuous feeding reaction, thereby inhibiting continuous growth of primary grains and secondary grains on the original basis, and finally causing shrinkage of the size and uneven particle size distribution of precursor products. However, the invention reduces the reaction feed rate (especially the feed rate of the Al-containing nickel cobalt manganese salt solution is in the range of 0.5-0.9 mL/min), so that the number of the configurational crystal ions entering the reaction system in unit time is reduced, the reaction supersaturation degree can be reduced, the adverse effect on the morphology of the precursor caused by the introduction of Al 3+ can be improved to a certain extent, and the invention provides necessary conditions for further improving the cycle life and energy density of the product.
3. According to the preparation method of the high-nickel precursor, the feeding speed of the Al-containing nickel cobalt manganese salt solution is controlled to be 0.5-0.6 mL/min, so that higher cycle performance can be obtained.
4. The nickel-cobalt-manganese metal solution obtained in the wet leaching process inevitably contains impurity Al 3+ because the Al foil cannot be thoroughly separated from the anode material in the pretreatment sorting of the waste lithium battery, and the impurity Al 3+ does not need to be removed in a certain concentration range, so that the structure of the regenerated anode material can be directly stabilized and strengthened as a doping element, the production cost is greatly reduced, and the recycling of metal resources is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a high nickel precursor sample of example 1;
FIG. 2 is an SEM image of a high nickel precursor sample of example 2;
FIG. 3 is an SEM image of a high nickel precursor sample of example 3;
FIG. 4 is an SEM image of a high nickel precursor sample of example 4;
FIG. 5 is an SEM image of a high nickel precursor sample of comparative example 3;
FIG. 6 is an SEM image of a high nickel precursor sample of comparative example 4;
fig. 7 is an SEM picture of (a) a positive electrode material sample of example 1, (b) example 2, (c) example 3, (d) example 4, (e) comparative example 3;
fig. 8 shows discharge capacity decay curves of example 1, example 2, example 3, example 4, comparative example 1, and comparative example 2.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a positive electrode material, wherein the Al/TM atomic ratio=0.005, and the preparation method comprises the following steps:
(1) Preparing a high nickel precursor:
And 1, preparing an Al-containing nickel-cobalt-manganese salt solution, namely accurately weighing soluble NiSO 4·6H2O、CoSO4·7H2 O and MnSO 4·H2 O salt according to the mass ratio of Ni to Co to Mn=0.9 to 0.05, placing the soluble NiSO 4·6H2O、CoSO4·7H2 O and the MnSO 4·H2 O salt in a beaker, adding a certain amount of Al 2(SO4)3·18H2 O serving as an Al source, adding a certain amount of hot pure water, stirring, ultrasonically dissolving, cooling to normal temperature, and transferring to a volumetric flask to fix volume to obtain the Al-containing nickel-cobalt-manganese salt solution, wherein the total metal concentration of nickel-cobalt-manganese is 2.0mol/L, and the molar ratio of Al to TM is 0.005.
Preparing ammonia water solution, namely accurately measuring a certain volume of concentrated ammonia water in a volumetric flask by using a pipette, and adding pure water to a certain volume to obtain 4.8mol/L ammonia water solution.
Preparing an alkali solution precipitant, namely weighing a certain amount of NaOH in a beaker, adding cold pure water, performing ultrasonic dissolution in a cold water bath, and then rapidly transferring to a volumetric flask for constant volume to obtain the alkali solution precipitant with the concentration of 8.0 mol/L.
Preparing ammonia water bottom solution, namely accurately measuring a certain volume of concentrated ammonia water in a volumetric flask by using a pipette, adding pure water into the volumetric flask to obtain the ammonia water bottom solution with the concentration of 1.2mol/L, wherein the volume of the ammonia water bottom solution is 1.5L.
And 2, carrying out two-point calibration on a pH meter before the experiment starts, adding ammonia water base solution into a reaction kettle, pumping circulating water into an interlayer of the reaction kettle through a water bath kettle to heat the temperature in the kettle, continuously introducing nitrogen into the kettle to exhaust air (the nitrogen is introduced below the liquid level), and adjusting the pH of the ammonia water base solution to 11.5 after the temperature in the kettle rises to 50 ℃.
The preparation process comprises the steps of stopping three feed pumps after the three feed pumps are connected to the tail end of a feed inlet (ensuring that three feed liquids enter a kettle at the same time), setting the flow rate of the three feed pumps, wherein the pump 1 is used for pumping Al-containing nickel cobalt manganese salt solution, the flow rate is controlled to be 0.9mL/min, the feed time is about 24 hours, and the pumps 2 and 3 are respectively used for pumping ammonia water solution and alkali solution precipitant, and the flow rates are respectively set to be 0.45mL/min and 0.7mL/min according to the feed rate conversion of the Al-containing nickel cobalt manganese salt solution of the pump 1.
After the preparation process is finished, three feeding pumps are started and timing is started, in the reaction process, the temperature in the kettle is controlled to be 50 ℃, the pH value of the feed liquid is kept constant at 11.5, the stirring speed is 600rpm, and the molar ratio of NH 3 to TM is ensured to be 1.2 in the feeding process.
And continuously maintaining heating and stirring for 12 hours after the feeding is finished, wherein the stirring speed is 600rpm, discharging and collecting precursor feed liquid, washing the precursor for 4 times by using alkaline water and pure water, vacuum filtering, transferring a filter cake to a vacuum drying oven for drying at 100 ℃ for 24 hours to obtain a high-nickel precursor, grinding, and filling the high-nickel precursor into a sealing bag for drying and preserving, wherein the particle morphology is shown in figure 1, and the tap density is 1.93g/cm 3.
(2) Carrying out lithiation sintering on the high-nickel precursor to prepare a positive electrode material:
The precursor and micron-sized LiOH.H 2 O are uniformly mixed and ground by using ethanol as a dispersing agent (the atomic ratio of Li: TM=1.04), then the mixture is put into a sagger, oxygen is introduced into a tube furnace for sintering, the temperature rising rate is 3 ℃ per minute, the calcination is divided into two sections, the first section is subjected to heat preservation at 500 ℃ for 5 hours, the second section is subjected to heat preservation at 700 ℃ for 12 hours, then the mixture is taken out after cooling at 5 ℃ per minute, and the mixture is ground and screened by a 200-mesh sieve to obtain the Al-doped LiNi 0.9Co0.05Mn0.05O2 high-nickel anode material (Al/TM=0.005), and the particle morphology of the material is shown in a figure 7 (a).
Example 2
This example is substantially the same as example 1 except that the Al/TM atomic ratio of this example=0.01.
The morphology of the high-nickel precursor particles prepared in the embodiment is shown in figure 2, and the tap density is 1.87g/cm 3.
The morphology of the positive electrode material prepared in this example is shown in fig. 7 (b).
Example 3
This example is substantially the same as example 2, except that the feed rate of the Al-containing Ni-Co-Mn salt solution of this example is 0.5mL/min (the feed time is correspondingly prolonged), and the feed rate of ammonia water is also reduced by a corresponding ratio (0.25 mL/min).
The morphology of the high nickel precursor and the morphology of the positive electrode material prepared in the embodiment are shown in fig. 3 and fig. 7 (c), respectively. The tap density of the precursor was 1.94g/cm 3. The sample of example 3 had slightly increased particle size and significantly improved particle uniformity compared to example 2.
Example 4
This example is substantially the same as example 3 except that the feed rate of the Al-containing Ni-Co-Mn salt solution of this example is 0.7mL/min, and the feed rate of ammonia water is adjusted to a corresponding ratio (0.35 mL/min).
The morphology of the high nickel precursor and the morphology of the positive electrode material prepared in this example are shown in fig. 4 and fig. 7 (d), respectively. The tap density of the precursor is 1.90g/cm 3. The high nickel precursor particles of example 4 were slightly reduced in size and uniformity compared to example 3, but were superior to the sample of example 2.
Comparative example 1
This comparative example is substantially the same as example 1 except that no Al was added for doping, i.e., al/tm=0.
Comparative example 2
This comparative example is substantially the same as example 1 except that aluminum is not contained in the nickel cobalt manganese salt solution in this comparative example, and a certain amount of Al (OH) 3 is added to perform aluminum doping during the precursor lithiation sintering process, wherein the atomic ratio Al: tm=0.005.
Comparative example 3
This comparative example is substantially the same as example 1 except that this comparative example has an Al/TM atomic ratio=0.02.
The morphology of the high nickel precursor and the morphology of the positive electrode material prepared in the comparative example are shown in fig. 5 and fig. 7 (e), respectively. Compared with examples 1 and 2, the sample particle size of the comparative example is further reduced, the uniformity of particle morphology is poor, the lower tap density can bring about the reduction of the energy density of the material, and the requirement of a commercial power lithium ion battery is difficult to meet.
Comparative example 4
The comparative example is basically the same as comparative example 3, except that the feed rate of the Al-containing Ni-Co-Mn salt solution of the comparative example is 0.5mL/min, and the feed rate of ammonia water is also reduced by a corresponding ratio (about 0.25 mL/min).
The morphology of the high nickel precursor particles prepared in the comparative example is shown in figure 6, and the tap density is 1.77g/cm 3.
Test examples
The positive electrode materials prepared in examples 1-4 and comparative examples 1 and 2, a binder PVDF and an acetylene black conductive agent are mixed and ground according to a mass ratio of 8:1:1, NMP solvent is added, stirring and mixing are carried out for 3 hours to obtain positive electrode slurry, the positive electrode slurry is uniformly coated on aluminum foil, the temperature is 90 ℃ and baking is carried out for 12 hours to obtain a positive electrode plate, the positive electrode plate is sheared into a wafer with the diameter of 12mm through a punching machine, a metal lithium plate is adopted as a negative electrode, a button cell is assembled in an argon glove box, and the charge and discharge performance test of the cell is carried out on a blue electric test system.
The test system is that the charge and discharge cycles are 100 circles under the current density of 1C (1 C=200 mAh/g) and the temperature is 25 ℃ and the voltage range is 2.8-4.3V, and the test results are shown in Table 1 and FIG. 8.
TABLE1 Positive electrode Material electrical Properties
As can be seen from Table 1, the increase in the amount of Al doped in example 2 compared with example 1 promotes the material cycle performance.
The cycle performance of comparative example 1 is significantly deteriorated compared with examples 1 and 2, and it is seen that the electrochemical stability of the material can be improved by doping a proper amount of Al into the high nickel positive electrode material by the method.
Example 3 the capacity retention exceeding 100% is due to the fact that the material has not been fully activated at the beginning of the cycle, resulting in a lower initial capacity. Compared with the embodiment 2, the feeding speed of the embodiment 3 is reduced, the supersaturation degree increase caused by the introduction of Al 3+ is reduced, the primary crystal grains and the secondary grains of the precursor slowly grow, the spherical grains are more compact, the contact area of the material and the electrolyte is reduced, and the interface side reaction is inhibited, so that the material cycle performance is enhanced.
Example 4 has a feed rate between examples 2 and 3, and the prepared precursor particle size and tap density are also between the two, so that the material cycle stability is also between the two. Therefore, the particle morphology of the Al-doped precursor can be regulated and controlled by controlling the feeding speed, so that the corresponding electrochemical performance is affected.
Compared with the examples 1 and 2, the particle size of the comparative example 3 is reduced and the morphology uniformity is poor, so that the tap density of the material is obviously reduced, and the practical key parameters such as the energy density of the material are affected.
The comparative example 4 has a higher Al content, and the precursor particle size is increased after the feed rate is reduced, and the tap density is increased as compared with the product of comparative example 3, but the product is still lower than that of examples 1 and 2, so that the requirement of the high nickel material on the tap density is difficult to meet. Therefore, the Al/TM atomic ratio in the solution containing the Al-nickel-cobalt-manganese salt is limited to be 0.001-0.01.
The solid phase Al doped product of comparative example 2 has improved cycle performance, but the effect of improving cycle performance is not as obvious as in-situ coprecipitation Al doping because of the fact that Al element possibly exists in the bulk of the material and the Al content on the surface of the particles is high and the content of Al in the particles is low, so that the stabilization effect of Al element on the material is lacked in the inner regions of the particles.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (2)
1. The preparation method of the positive electrode material is characterized by comprising the following steps of:
(1) Preparing a high nickel precursor:
Preparing an Al-containing nickel cobalt manganese salt solution, namely weighing NiSO 4·6H2O、CoSO4·7H2 O and MnSO 4·H2 O according to the mass ratio of element substances Ni to Co, mn=0.9:0.05:0.05, placing the Ni, mn=0.9:0.05 and Mn in a beaker, adding a certain amount of Al 2(SO4)3·18H2 O as an Al source, adding a certain amount of hot pure water, stirring and ultrasonically dissolving, and transferring the mixture into a volumetric flask to constant volume after cooling to normal temperature to obtain the Al-containing nickel cobalt manganese salt solution, wherein the total metal concentration of nickel, cobalt and manganese is 2.0mol/L, and the molar ratio of Al to TM is 0.01;
preparing an ammonia water solution, namely accurately measuring a certain volume of concentrated ammonia water in a volumetric flask by using a pipette, and adding pure water to a certain volume to obtain a 4.8mol/L ammonia water solution;
preparing an alkali solution precipitant, namely weighing a certain amount of NaOH in a beaker, adding cold pure water, performing ultrasonic dissolution in a cold water bath, and then transferring the solution into a volumetric flask for constant volume to obtain the alkali solution precipitant with the concentration of 8.0 mol/L;
Preparing ammonia water bottom solution, namely measuring a certain volume of concentrated ammonia water in a volumetric flask by using a pipette, adding pure water into the volumetric flask to fix the volume to obtain the ammonia water bottom solution with the concentration of 1.2mol/L, wherein the volume of the ammonia water bottom solution is 1.5L;
Step 2, firstly performing two-point calibration on a pH meter before the experiment starts, adding ammonia water base solution into a reaction kettle, pumping circulating water into an interlayer of the reaction kettle through a water bath kettle to heat the temperature in the kettle, continuously introducing nitrogen into the kettle to exhaust air, and adjusting the pH of the ammonia water base solution to 11.5 after the temperature in the kettle is increased to 50 ℃ of the reaction temperature;
the preparation process comprises stopping three feed pumps after the three feed pumps are connected to the tail end of a feed inlet, and setting the flow rate of the three feed pumps, wherein the pump 1 is used for pumping Al-containing nickel cobalt manganese salt solution, the flow rate is controlled at 0.5mL/min, and the feed time is correspondingly prolonged on the basis of 24 hours;
After the preparation process is finished, three feeding pumps are started and timing is started, in the reaction process, the temperature in the kettle is controlled to be 50 ℃, the pH value of the feed liquid is kept constant at 11.5, the stirring speed is 600rpm, and the molar ratio of NH 3 to TM is ensured to be 1.2 in the feeding process;
Continuously maintaining heating and stirring for 12 hours after the feeding is finished, wherein the stirring speed is 600rpm, discharging and collecting precursor feed liquid, washing the precursor for 4 times by using alkaline water and pure water, vacuum filtering, transferring a filter cake to a vacuum drying oven for drying at 100 ℃ for 24 hours to obtain a high-nickel precursor, and filling the high-nickel precursor into a sealing bag for drying and storing after grinding;
(2) Carrying out lithiation sintering on the high-nickel precursor to prepare a positive electrode material:
Uniformly mixing and grinding a high-nickel precursor and micron-sized LiOH-H 2 O by using ethanol as a dispersing agent, wherein the atomic ratio Li is TM=1.04, then placing the mixture into a sagger, placing the sagger into a tube furnace, introducing oxygen for sintering, wherein the temperature rising rate is 3 ℃ per minute, dividing the calcination into two sections, preserving heat for 5H at 500 ℃ in the first section and preserving heat for 12H at 700 ℃ in the second section, taking out the mixture after cooling at 5 ℃ per minute, grinding and sieving the mixture by a 200-mesh sieve, and obtaining the Al-doped LiNi 0.9Co0.05Mn0.05O2 high-nickel anode material.
2. A positive electrode material, characterized by being produced according to the production method of claim 1.
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