WO2022268022A1 - High-nickel positive electrode material and preparation method therefor - Google Patents

High-nickel positive electrode material and preparation method therefor Download PDF

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WO2022268022A1
WO2022268022A1 PCT/CN2022/099799 CN2022099799W WO2022268022A1 WO 2022268022 A1 WO2022268022 A1 WO 2022268022A1 CN 2022099799 W CN2022099799 W CN 2022099799W WO 2022268022 A1 WO2022268022 A1 WO 2022268022A1
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stage
reaction system
growth reaction
positive electrode
electrode material
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French (fr)
Chinese (zh)
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公伟伟
孟立君
黄承焕
喻时顺
张海艳
周新东
郭忻
胡志兵
周友元
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湖南长远锂科股份有限公司
湖南长远锂科新能源有限公司
金驰能源材料有限公司
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Publication of WO2022268022A1 publication Critical patent/WO2022268022A1/en

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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Definitions

  • the invention belongs to the technical field of lithium-ion battery materials, and in particular relates to a high-nickel cathode material with high particle strength and a preparation method thereof.
  • Lithium-ion battery cathode materials are an important part of new energy electric vehicle batteries. At present, new energy electric vehicle batteries still have problems such as high temperature, flammability, and fast cycle decay. The reason is mainly due to the unstable structure of the positive and negative electrode materials, and the severe side reactions between the electrolyte and the positive and negative electrode materials.
  • the structural stability of cathode materials has a critical impact on the safety and cycle performance of lithium-ion batteries. In order to improve the structural stability of positive electrode materials, researchers usually use doping and coating to improve their structure.
  • element doping, coating and other means are usually used for modification, but in the process of element doping, there is a risk of uneven segregation of doping elements in the positive electrode material, and this segregation will cause structural instability; and after coating As the cycle progresses, the electrolyte continues to erode the positive electrode material, resulting in the failure of the coating process; and in the process of making the battery from the positive electrode material, it is necessary to mix the positive electrode material with additives such as conductive agents and binders, and then coat, Rolling. During the rolling process, some particles will be deformed or even cracked.
  • the deformation or cracking will cause part of the surface of the material to be exposed, forming a site for side reactions during the charge-discharge cycle, and increasing the structural instability of the material. Therefore, regardless of doping and/or coating, the negative impact caused by the rolling process cannot be effectively solved, and even the rolling process will cause the coating to fail.
  • the invention provides a high-nickel cathode material with high particle strength and a preparation method thereof.
  • the present invention is specifically realized through the following technical solutions.
  • the present invention provides a high-nickel cathode material with high particle strength, which includes an inner core and an outer shell with an intermediate layer between the inner core and the outer shell.
  • the inner core is spherical or spheroidal, which is obtained by the accumulation of spherical or spheroidal particles I.
  • the middle layer is composed of cylindrical particles II, and the particles II radially accumulate on the surface of the inner core.
  • the outer shell is composed of spherical or spherical particles III, and the particles III are accumulated on the outer surface of the middle layer.
  • the content of element M in granule I and granule II is lower than the content of element M in granule III.
  • the average particle diameter of the positive electrode material is 0.1 ⁇ m-40 ⁇ m, and the specific surface area is 0.15 m 2 /g-1.5 m 2 /g.
  • the average particle diameter of particle I is 0.1 ⁇ m-2 ⁇ m; the width of particle II is ⁇ 20 nm, and the aspect ratio is >1.5.
  • the particle III is accumulated on the outer surface of the particle II, and is distributed in a dot-like manner.
  • particle III includes M oxide or M lithium oxide.
  • the high-nickel cathode material provided by the invention has a three-layer structure of an inner core, an intermediate layer and an outer shell, and can significantly improve the particle strength of the cathode material. Moreover, the particles in the inner core are evenly dispersed, and the middle layer is distributed radially, which can further increase the particle strength. Generally speaking, the particle strength of the cathode material provided by the present invention is ⁇ 60 MPa.
  • the content of the element M in the particles located in the outer layer is relatively high, because the M element is introduced after mixing with the precursor powder and sintering. During the sintering process, the concentration of M element diffuses from the particle surface to the interior of the particle, so the M content on the surface is relatively high. From the structural point of view, the bond energy strength of M-O is greater than that of Ni-O and Co-O. After forming a shell on the surface, like egg shells, the strength of the particles increases.
  • the present invention further provides a method for preparing the above-mentioned positive electrode material.
  • the present invention provides a method for preparing the precursor of the above-mentioned positive electrode material, which specifically includes the following steps:
  • Step S1 solution preparation: prepare nickel-cobalt mixed salt solution according to the content of nickel and cobalt in the positive electrode material; prepare precipitant solution and complexing agent solution;
  • Step S2 co-precipitation reaction: respectively pass nickel-cobalt mixed salt solution, precipitant solution and complexing agent solution into the reaction kettle, stir, adjust the pH of the reaction system to 8-13, and co-precipitation reaction occurs;
  • Step S3 the growth reaction of the first stage: After the co-precipitation reaction is completed, continue to feed the nickel-cobalt mixed salt solution, the precipitant solution and the complexing agent solution into the reaction kettle, and maintain the concentration of the complexing agent in the reaction system Compared with the concentration of the complexing agent solution in the step S2 reaction system, the concentration is reduced by 20%-80%, and the pH of the reaction system is adjusted so that it is reduced by 0.1-1 relative to step S2; the stirring speed of the reaction system is adjusted to make it relatively The stirring speed in step S2 is reduced by 1%-30%. When the average particle diameter D50 of the reaction slurry reaches the set particle size, the growth reaction of the first stage is stopped, and the growth reaction of the second stage is started.
  • Step S4 the growth reaction of the second stage: continue to feed the nickel-cobalt mixed salt solution, the precipitating agent solution and the complexing agent solution into the reaction kettle respectively, and keep the concentration of the complexing agent in the reaction system compared with the reaction system in step S3
  • the concentration of the complexing agent solution in the solution increases by 30%-200%; adjust the pH of the reaction system to increase it by 0.1-3 relative to step S3; adjust the stirring speed of the reaction system to make it relative to the stirring speed in step S3 Reduce 1%-50%. After the average particle diameter D50 of the reaction slurry reaches the target particle size, stop the reaction.
  • step S5 the reaction slurry obtained in step S4 is separated from solid to liquid, aged, washed and dried to obtain the precursor.
  • the nickel-cobalt mixed salt solution, the precipitating agent solution, and the complexing agent solution are continuously added until the end of the reaction in each stage, and the next stage begins.
  • the present invention mainly forms different structures by regulating different reaction conditions (mainly pH, stirring speed, temperature) in each stage.
  • step S1 when preparing the nickel-cobalt mixed salt solution, the nickel salt is selected from NiSO 4 , Ni(NO 3 ) 2 , NiF 2 , NiCl 2 , NiBr 2 or NiI 2 One or more of; the cobalt salt is selected from one or more of CoSO 4 , Co(NO 3 ) 2 , or CoCl 2 .
  • step S1 the concentration of the prepared nickel-cobalt mixed salt solution is 0.2 mol/L-15 mol/L.
  • the precipitating agent is NaOH or KOH
  • the complexing agent is one or more selected from ammonia water, ammonium sulfate and EDTA.
  • step S1 the solubility of the precipitation agent is 3 mol/L-15 mol/L, and the concentration of ammonia in the complexing agent is 0.1 mol/L-1 mol/L.
  • step S2 the temperature of the co-precipitation reaction is 40°C-60°C, the reaction time is 20min-5h, and the stirring speed is 100rpm-1000rpm.
  • the time for the growth reaction of the first stage and the growth reaction of the second stage is 1h-10h.
  • step S3 the set particle size is 2 ⁇ m-10 ⁇ m.
  • the target particle size is 10 ⁇ m-20 ⁇ m.
  • the precursor prepared by the above method is mixed with the lithium salt and the M-containing compound and then sintered to obtain a high-nickel positive electrode material with high particle strength.
  • the M element forms concentration diffusion, which diffuses from the area with high element content to the area with low element content. Therefore, there will be M element in the inner core, middle layer and shell layer, but due to the existence of concentration gradient, the content of M element in the shell layer is high. .
  • the sintering atmosphere is oxygen, and the concentration of oxygen in the atmosphere is greater than 85%; the sintering temperature is 650°C-800°C.
  • Ni 3+ is easily reduced to Ni 2+ ions in the air, and the radius of Ni 2+ and Li + is similar, which can easily cause Li/Ni mixed row, resulting in crystallization properties Difference.
  • the higher the concentration of oxygen the more inhibited the formation of Li/Ni mixed row. Too high oxygen concentration, high production cost. Generally controlled above 85%.
  • the sintering temperature is also a key consideration for R&D personnel. If it is lower than the above-mentioned sintering temperature, a complete crystal will not be formed. If it is higher than the highest temperature, the material will have the problem of over-burning and decomposition, resulting in a sharp deterioration in material performance.
  • the precursor of a specific structure is prepared by controlling the synthesis parameters. After the precursor is mixed and sintered with the lithium salt, a core layer in which the primary particles are uniformly dispersed and an outer layer in which the primary particles are radially distributed can be formed, thereby improving particle strength.
  • M can form a shell layer rich in M-O or Li-M-O compounds on the surface of secondary particles.
  • the shell can further increase particle strength.
  • the formation of the shell layer is carried out simultaneously with the calcination preparation process of the positive electrode material, which can effectively improve the structural stability of the high-nickel positive electrode material.
  • FIG. 1 is a schematic structural view of the positive electrode material prepared in Example 1 of the present invention.
  • FIG. 2 is a SEM image of the cross-section of the positive electrode material prepared in Example 1 of the present invention.
  • Fig. 3 is an elemental line scan diagram of the section of the positive electrode material prepared in Example 1 of the present invention.
  • FIG. 4 is a micro-pressure deformation curve of the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 1.
  • FIG. 4 is a micro-pressure deformation curve of the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 1.
  • FIG. 5 is a discharge cycle diagram of a lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 1.
  • FIG. 6 is a high-temperature discharge cycle diagram of a lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 2.
  • FIG. 6 is a high-temperature discharge cycle diagram of a lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 2.
  • 1 represents the shell
  • 2 represents the middle layer
  • 3 represents the inner core
  • Ni 0.9 Co 0.1 (OH) 2 precursor is prepared.
  • the specific operation process includes:
  • Co-precipitation reaction stage nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 2mol/L, the molar ratio of nickel and cobalt is 9:1, and the industrial sodium hydroxide solution is diluted into a 4mol/L solution.
  • Prepare 0.5mol/L ammonia solution Add 50L of deionized water to the 300L reaction kettle as the bottom liquid, add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 11, start stirring at 400rpm, maintain the reaction temperature at 45°C, and use a metering pump to feed nickel-cobalt solution, ammonia Aqueous solution with a flow ratio of 10:1.
  • a metering pump is used to pump the sodium hydroxide solution, and an online pH meter is used to control the flow of the sodium hydroxide solution.
  • the flow rate of the aqueous solution is 80%, the stirring speed is reduced by 15%, and the reaction is maintained until the particle size reaches 15 ⁇ m.
  • a Ni 0.9 Co 0.1 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
  • Lithium hydroxide was mechanically mixed with the Ni 0.9 Co 0.1 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1.03:0.95:0.05, and then sintered in a high-temperature furnace after mixing evenly.
  • the oxygen mass concentration during the sintering process was 85%, the sintering temperature is 770°C, and the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with a chemical formula of Li 1.03 Ni 0.855 Co 0.095 Al 0.05 O 2 .
  • the specific operation process includes:
  • nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 2mol/L, the molar ratio of nickel to cobalt is 0.855:0.095, and metaaluminic acid with a metal ion concentration of 2mol/L is prepared Sodium solution, dilute industrial sodium hydroxide solution to 4mol/L solution, and prepare 0.5mol/L ammonia solution.
  • the flow ratio of sodium aluminate solution and ammonia solution is 10:0.5:1.
  • the metering pump is used to pump the sodium hydroxide solution
  • the online pH is used to control the flow of the sodium hydroxide solution.
  • a Ni 0.855 Co 0.095 Al 0.05 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
  • Lithium hydroxide was mechanically mixed with the Ni 0.855 Co 0.095 Al 0.05 (OH) 2 precursor synthesized above according to the molar ratio of 1.03:1, and then sintered in a high-temperature furnace after mixing evenly. During the sintering process, the oxygen mass concentration was 85%. The temperature is 770°C and the temperature is kept for 12 hours. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with a chemical formula of Li 1.03 Ni 0.855 Co 0.095 Al 0.05 O 2 .
  • the synthesis method of the precursor is the same as in Example 1, and the final synthesis product is the Ni 0.9 Co 0.1 (OH) 2 precursor.
  • Lithium hydroxide and the Ni 0.9 Co 0.1 (OH) 2 precursor synthesized above were mechanically mixed according to the molar ratio of 1.03:1, and then sintered in a high-temperature furnace after mixing evenly.
  • the oxygen mass concentration was 85%, and the sintering temperature was 770°C, keep warm for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with the chemical formula Li 1.03 Ni 0.9 Co 0.1 O 2 .
  • FIG. 1 is a schematic structural view of the cathode material prepared in Example 1.
  • FIG. 2 is an SEM image of a section of the positive electrode material prepared in Example 1.
  • FIG. 2 It can be clearly seen from FIG. 2 that the positive electrode material prepared in Example 1 has three layers: an inner core, an intermediate layer and an outer shell.
  • Figure 3 is an element line scan diagram of the section of the positive electrode material prepared in Example 1, showing three wavy element distribution curves at the top, middle and bottom, the upper line represents the content of Ni element in different positions in the particle, and the middle line represents the content of Al element in the particle The content of different positions, the lower line represents the content of Co element in different positions in the particle.
  • the Al content curve is higher on the particle surface, indicating that the Al element has a higher concentration on the surface, forming an Al-rich shell.
  • FIG. 4 is a micro-pressure deformation curve of the positive electrode material prepared in Example 1 and the positive electrode material prepared in Comparative Example 1. FIG. It can be seen from FIG. 4 that the positive electrode material prepared in Example 1 has higher particle strength.
  • Figure 5 is the discharge cycle diagram of the lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 and the positive electrode material prepared in Comparative Example 1
  • Figure 6 is the positive electrode material prepared in Example 1 and the positive electrode prepared in Comparative Example 2 High-temperature discharge cycle diagram of material-assembled Li-ion half-cells.
  • Ni 0.8 Co 0.2 (OH) 2 precursor is prepared.
  • the specific operation process includes:
  • Co-precipitation reaction stage nickel nitrate and cobalt nitrate are prepared into a mixed metal salt solution with a total metal ion concentration of 3mol/L, the molar ratio of nickel to cobalt is 8:2, and the industrial sodium hydroxide solution is diluted into a 4.5mol/L solution , prepare 0.8mol/L ammonia solution.
  • Add 50L of deionized water to the 300L reactor as the bottom liquid add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 12, start stirring at 500rpm, maintain the reaction temperature at 50°C, and use a metering pump to feed nickel-cobalt solution, ammonia Aqueous solution with a flow ratio of 10:1.
  • a metering pump is used to pump the sodium hydroxide solution, and an online pH meter is used to control the flow of the sodium hydroxide solution.
  • the flow rate of the aqueous solution is 100%, the stirring speed is reduced by 20%, and the reaction is maintained until the particle size reaches 15 ⁇ m.
  • a Ni 0.8 Co 0.2 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
  • Lithium hydroxide was mechanically mixed with the Ni 0.8 Co 0.2 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1.05:0.95:0.05. After mixing evenly, they were sintered in a high-temperature furnace. During the sintering process, the oxygen mass concentration was 85%, the sintering temperature is 770°C, and the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium-ion battery with a chemical formula of Li 1.05 Ni 0.76 Co 0 x 19 Al 0.05 O 2 .
  • Ni 0.85 Co 0.15 (OH) 2 precursor is prepared.
  • the specific operation process includes:
  • Co-precipitation reaction stage nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 4mol/L, the molar ratio of nickel to cobalt is 0.85:0.15, and the industrial sodium hydroxide solution is diluted into a 4mol/L solution. Prepare 1mol/L ammonia solution.
  • a Ni 0.85 Co 0.15 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
  • Lithium hydroxide was mechanically mixed with the Ni 0.85 Co 0.15 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1:0.95:0.05, and then sintered in a high-temperature furnace after mixing evenly.
  • the oxygen mass concentration was 85%
  • the sintering temperature is 770°C
  • the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a lithium-ion battery cathode material with the chemical formula LiNi 0.8075 Co 0.1425 Al 0.05 O 2 .

Abstract

The present invention belongs to the technical field of lithium ion battery materials. Particularly disclosed are a high-nickel positive electrode material and a preparation method therefor. The high-nickel positive electrode material provided in the present invention has a three-layer structure comprising an inner core, a middle layer and an outer shell, wherein particles of the inner core are uniformly dispersed, the middle layer is distributed in a radial shape, and the particle strength is greater than or equal to 60 MPa. A preparation method for a precursor of the high-nickel positive electrode material of the present invention comprises three reaction stages of a co-precipitation reaction, a first-stage growth reaction and a second-stage growth reaction. Different structures are mainly formed by regulating and controlling different reaction conditions of each stage, said conditions mainly being pH, the stirring speed, the temperature, etc. After the precursor, a lithium salt and an M-containing compound are mixed and sintered, a core layer, in which primary particles are uniformly dispersed, and an outer layer, in which primary particles are distributed in a radial shape, can be formed, such that the particle strength is improved.

Description

一种高镍正极材料及其制备方法A kind of high-nickel positive electrode material and preparation method thereof 技术领域technical field
本发明属于锂离子电池材料技术领域，具体涉及一种高粒子强度的高镍正极材料及其制备方法。The invention belongs to the technical field of lithium-ion battery materials, and in particular relates to a high-nickel cathode material with high particle strength and a preparation method thereof.
背景技术Background technique
锂离子电池正极材料是新能源电动汽车电池的重要组成部分。目前新能源电动汽车电池依然存在高温易燃、循环衰减快等问题。究其原因，主要是因为正负极材料结构不稳定、电解液与正负极材料副反应剧烈导致。而正极材料的结构稳定性对锂离子电池的安全和循环性能具有关键性影响。为提高正极材料的结构稳定性，研究者通常用掺杂和包覆的方式对其进行结构改善。Lithium-ion battery cathode materials are an important part of new energy electric vehicle batteries. At present, new energy electric vehicle batteries still have problems such as high temperature, flammability, and fast cycle decay. The reason is mainly due to the unstable structure of the positive and negative electrode materials, and the severe side reactions between the electrolyte and the positive and negative electrode materials. The structural stability of cathode materials has a critical impact on the safety and cycle performance of lithium-ion batteries. In order to improve the structural stability of positive electrode materials, researchers usually use doping and coating to improve their structure.
随着新能源汽车的发展，消费者对汽车的续航能力要求越来越高。提高电动汽车的续航，只有提高电池容量，提高电池容量的主要途径是使用容量更高的正极材料，而提高正极材料中的Ni含量是提高正极材料容量的最主要的方法。但是，随着Ni含量的提高，由于Ni-O的本征结构不稳定，会造成正极材料结构更加失稳。因此，对于高镍正极材料结构稳定性的改善是本行业亟待解决的问题。With the development of new energy vehicles, consumers have higher and higher requirements for the battery life of vehicles. To improve the battery life of electric vehicles, the only way to increase battery capacity is to use cathode materials with higher capacity, and increasing the Ni content in cathode materials is the most important way to increase the capacity of cathode materials. However, as the Ni content increases, the structure of the positive electrode material will become more unstable due to the instability of the intrinsic structure of Ni-O. Therefore, improving the structural stability of high-nickel cathode materials is an urgent problem to be solved in this industry.
目前通常采用元素掺杂、包覆等手段进行改性，但是元素掺杂过程中，存在掺杂元素在正极材料中不均匀偏析的风险，这种偏析会造成结构的不稳定；而包覆后的材料，随着循环的进行，电解液不断侵蚀正极材料，造成包覆工艺失效；且正极材料制作电池的过程中，需要将正极材料与导电剂、粘结剂等添加剂混合，然后涂布、辊压。辊压过程中，会造成部分颗粒的变形甚至破裂，变形或破裂导致材料部分表面裸露，形成充放电循环过程中副反应的发生地，增加材料的结构不稳定性。所以，无论掺杂和/或包覆，都不能有效解决辊压过程造成的负面影响，甚至辊压过程会造成包覆的失效。At present, element doping, coating and other means are usually used for modification, but in the process of element doping, there is a risk of uneven segregation of doping elements in the positive electrode material, and this segregation will cause structural instability; and after coating As the cycle progresses, the electrolyte continues to erode the positive electrode material, resulting in the failure of the coating process; and in the process of making the battery from the positive electrode material, it is necessary to mix the positive electrode material with additives such as conductive agents and binders, and then coat, Rolling. During the rolling process, some particles will be deformed or even cracked. The deformation or cracking will cause part of the surface of the material to be exposed, forming a site for side reactions during the charge-discharge cycle, and increasing the structural instability of the material. Therefore, regardless of doping and/or coating, the negative impact caused by the rolling process cannot be effectively solved, and even the rolling process will cause the coating to fail.
发明内容Contents of the invention
针对现有技术存在的缺陷，本发明提供一种高粒子强度的高镍正极材料及其制备方法。Aiming at the defects in the prior art, the invention provides a high-nickel cathode material with high particle strength and a preparation method thereof.
本发明具体通过以下技术方案实现。The present invention is specifically realized through the following technical solutions.
首先，本发明提供一种高粒子强度的高镍正极材料，包括内核和外壳，且内核和外壳之间具有中间层。内核为球形或类球形，由球形或类球形的颗粒Ⅰ堆积得到。中间层由类圆柱形的颗粒Ⅱ构成，颗粒Ⅱ径向堆积于内核表面。外壳由类球形或球形的颗粒Ⅲ构成，颗粒Ⅲ堆积于中间层外表面。Firstly, the present invention provides a high-nickel cathode material with high particle strength, which includes an inner core and an outer shell with an intermediate layer between the inner core and the outer shell. The inner core is spherical or spheroidal, which is obtained by the accumulation of spherical or spheroidal particles I. The middle layer is composed of cylindrical particles II, and the particles II radially accumulate on the surface of the inner core. The outer shell is composed of spherical or spherical particles III, and the particles III are accumulated on the outer surface of the middle layer.
颗粒Ⅰ、Ⅱ和Ⅲ的化学通式为Li aNi xCo yM zO 2，其中0.95≤a≤1.2，0.8≤x≤1，0＜y≤0.2，0＜z≤0.05，x+y+z＝1，M选自Mn、Al、Zr、Mg、Ti中的一种或两种以上。 The general chemical formula of particles I, II and III is Li a Ni x Co y M z O 2 , where 0.95≤a≤1.2, 0.8≤x≤1, 0<y≤0.2, 0<z≤0.05, x+y +z=1, M is selected from one or more of Mn, Al, Zr, Mg and Ti.
此外，颗粒Ⅰ和颗粒Ⅱ中元素M的含量低于颗粒Ⅲ中元素M的含量。Furthermore, the content of element M in granule I and granule II is lower than the content of element M in granule III.
进一步的，所述正极材料的平均粒径为0.1μm～40μm，比表面积为0.15m 2/g-1.5m 2/g。 Further, the average particle diameter of the positive electrode material is 0.1 μm-40 μm, and the specific surface area is 0.15 m 2 /g-1.5 m 2 /g.
进一步的，所述正极材料中，颗粒Ⅰ的平均粒径为0.1μm～2μm；颗粒Ⅱ的宽度≥20nm，长径比＞1.5。Further, in the positive electrode material, the average particle diameter of particle I is 0.1 μm-2 μm; the width of particle II is ≥20 nm, and the aspect ratio is >1.5.
进一步的，所述正极材料中，颗粒Ⅲ堆积于颗粒Ⅱ的外表面，呈点状分布。Further, in the positive electrode material, the particle III is accumulated on the outer surface of the particle II, and is distributed in a dot-like manner.
进一步的，所述正极材料中，颗粒Ⅲ包括M的氧化物或者M的锂氧化物。Further, in the positive electrode material, particle III includes M oxide or M lithium oxide.
本发明提供的高镍正极材料具有内核、中间层和外壳三层结构，可以显著提高正极材料的粒子强度。而且，内核的颗粒均匀分散，中间层呈放射状分布，可进一步提高粒子强度。总的来说，本发明提供的正极材料的粒子强度≥60MPa。此外，位于外层的颗粒中的元素M的含量相对较高，这是因为M元素是与前驱体粉末混合烧结后引入。在烧结过程中，M元素在颗粒表面向颗粒内部形成浓度扩散，因此表面的M含量较高。从结构上看，M-O的键能强度比Ni-O和Co-O键能大，在表面形成壳层后，像鸡蛋壳一样，颗粒粒子强度提高。The high-nickel cathode material provided by the invention has a three-layer structure of an inner core, an intermediate layer and an outer shell, and can significantly improve the particle strength of the cathode material. Moreover, the particles in the inner core are evenly dispersed, and the middle layer is distributed radially, which can further increase the particle strength. Generally speaking, the particle strength of the cathode material provided by the present invention is ≥60 MPa. In addition, the content of the element M in the particles located in the outer layer is relatively high, because the M element is introduced after mixing with the precursor powder and sintering. During the sintering process, the concentration of M element diffuses from the particle surface to the interior of the particle, so the M content on the surface is relatively high. From the structural point of view, the bond energy strength of M-O is greater than that of Ni-O and Co-O. After forming a shell on the surface, like egg shells, the strength of the particles increases.
基于同样的发明构思，本发明另提供上述的正极材料的制备方法。Based on the same inventive concept, the present invention further provides a method for preparing the above-mentioned positive electrode material.
首先，本发明提供上述的正极材料的前驱体的制备方法，具体包括以下步骤：First of all, the present invention provides a method for preparing the precursor of the above-mentioned positive electrode material, which specifically includes the following steps:
步骤S1，溶液配制:根据正极材料中镍、钴的含量配制镍钴混合盐溶液；配制沉淀剂溶液和络合剂溶液；Step S1, solution preparation: prepare nickel-cobalt mixed salt solution according to the content of nickel and cobalt in the positive electrode material; prepare precipitant solution and complexing agent solution;
步骤S2，共沉淀反应：在反应釜中分别通入镍钴混合盐溶液、沉淀剂溶液和络合剂溶液，搅拌，调节反应体系的pH为8～13，发生共沉淀反应；Step S2, co-precipitation reaction: respectively pass nickel-cobalt mixed salt solution, precipitant solution and complexing agent solution into the reaction kettle, stir, adjust the pH of the reaction system to 8-13, and co-precipitation reaction occurs;
步骤S3，第一阶段的生长反应：待共沉淀反应结束后，继续向反应釜中分别通入镍钴混合盐溶液、沉淀剂溶液和络合剂溶液，并保持反应体系中络合剂的浓度相较于步骤S2反应体系中的络合剂溶液的浓度降低20％-80％，且调节反应体系的pH，使其相对于步骤S2降低0.1-1；调节反应体系的搅拌转速，使其相对于步骤S2中的搅拌转速降低1％-30％。当反应浆料的颗粒平均粒径D50达到设定粒度后，停止第一阶段的生长反应，开始第二阶段的生长反应。Step S3, the growth reaction of the first stage: After the co-precipitation reaction is completed, continue to feed the nickel-cobalt mixed salt solution, the precipitant solution and the complexing agent solution into the reaction kettle, and maintain the concentration of the complexing agent in the reaction system Compared with the concentration of the complexing agent solution in the step S2 reaction system, the concentration is reduced by 20%-80%, and the pH of the reaction system is adjusted so that it is reduced by 0.1-1 relative to step S2; the stirring speed of the reaction system is adjusted to make it relatively The stirring speed in step S2 is reduced by 1%-30%. When the average particle diameter D50 of the reaction slurry reaches the set particle size, the growth reaction of the first stage is stopped, and the growth reaction of the second stage is started.
步骤S4，第二阶段的生长反应：继续向反应釜中分别通入镍钴混合盐溶液、沉淀剂溶液和络合剂溶液，并保持反应体系中络合剂的浓度相较于步骤S3反应体系中的络合剂溶液的浓度升高30％-200％；调节反应体系的pH，使其相对于步骤S3提高0.1-3；调节反应体系 的搅拌转速，使其相对于步骤S3中的搅拌转速降低1％-50％。当反应浆料的颗粒平均粒径D50达到目标粒度后，停止反应。Step S4, the growth reaction of the second stage: continue to feed the nickel-cobalt mixed salt solution, the precipitating agent solution and the complexing agent solution into the reaction kettle respectively, and keep the concentration of the complexing agent in the reaction system compared with the reaction system in step S3 The concentration of the complexing agent solution in the solution increases by 30%-200%; adjust the pH of the reaction system to increase it by 0.1-3 relative to step S3; adjust the stirring speed of the reaction system to make it relative to the stirring speed in step S3 Reduce 1%-50%. After the average particle diameter D50 of the reaction slurry reaches the target particle size, stop the reaction.
步骤S5，将步骤S4得到的反应浆料固液分离、陈化、洗涤和烘干，得到所述的前驱体。In step S5, the reaction slurry obtained in step S4 is separated from solid to liquid, aged, washed and dried to obtain the precursor.
上述制备方法在反应的几个阶段中，镍钴混合盐溶液、沉淀剂溶液、络合剂溶液是持续加入的，直至每一个阶段的反应终点，并开始下一个阶段。本发明主要通过调控每个阶段的不同的反应条件(主要是pH、搅拌速度、温度)形成不同结构。In the several stages of the reaction of the above preparation method, the nickel-cobalt mixed salt solution, the precipitating agent solution, and the complexing agent solution are continuously added until the end of the reaction in each stage, and the next stage begins. The present invention mainly forms different structures by regulating different reaction conditions (mainly pH, stirring speed, temperature) in each stage.
进一步的，在上述的前驱体的制备方法中，步骤S1中，配制镍钴混合盐溶液时，镍盐选自NiSO 4、Ni(NO 3) 2、NiF 2、NiCl 2、NiBr 2或NiI 2中的一种或多种；钴盐选自CoSO 4、Co(NO 3) 2、或CoCl 2中的一种或多种。 Further, in the preparation method of the above precursor, in step S1, when preparing the nickel-cobalt mixed salt solution, the nickel salt is selected from NiSO 4 , Ni(NO 3 ) 2 , NiF 2 , NiCl 2 , NiBr 2 or NiI 2 One or more of; the cobalt salt is selected from one or more of CoSO 4 , Co(NO 3 ) 2 , or CoCl 2 .
进一步的，在上述的前驱体的制备中，步骤S1中，配制的镍钴混合盐溶液浓度为0.2mol/L-15mol/L。Further, in the preparation of the above-mentioned precursor, in step S1, the concentration of the prepared nickel-cobalt mixed salt solution is 0.2 mol/L-15 mol/L.
进一步的，在上述的前驱体的制备方法中，步骤S1中，沉淀剂为NaOH或KOH，络合剂为选自氨水、硫酸铵和EDTA中的一种或多种。Further, in the above precursor preparation method, in step S1, the precipitating agent is NaOH or KOH, and the complexing agent is one or more selected from ammonia water, ammonium sulfate and EDTA.
进一步的，在上述的前驱体的制备方法中，步骤S1中，沉淀剂的溶度为3mol/L-15mol/L，络合剂中氨的浓度0.1mol/L-1mol/L。Further, in the above-mentioned preparation method of the precursor, in step S1, the solubility of the precipitation agent is 3 mol/L-15 mol/L, and the concentration of ammonia in the complexing agent is 0.1 mol/L-1 mol/L.
进一步的，在上述的前驱体的制备方法中，步骤S2中，所述共沉淀反应的温度为40℃-60℃，反应时间为20min-5h，搅拌的转速为100rpm～1000rpm。Further, in the preparation method of the above precursor, in step S2, the temperature of the co-precipitation reaction is 40°C-60°C, the reaction time is 20min-5h, and the stirring speed is 100rpm-1000rpm.
进一步的，在上述的前驱体的制备方法中，第一阶段的生长反应和第二阶段的生长反应的时间为1h-10h。Further, in the preparation method of the above-mentioned precursor, the time for the growth reaction of the first stage and the growth reaction of the second stage is 1h-10h.
进一步的，在上述的前驱体的制备方法中，步骤S3中，所述设定粒度为2μm-10μm。Further, in the above method for preparing the precursor, in step S3, the set particle size is 2 μm-10 μm.
进一步的，在上述的前驱体的制备方法中，步骤S4中，所述目标粒度为10μm-20μm。Further, in the above method for preparing the precursor, in step S4, the target particle size is 10 μm-20 μm.
将通过上述方法制备得到的前驱体与锂盐和含M的化合物混合后烧结，即得高粒子强度的高镍正极材料。The precursor prepared by the above method is mixed with the lithium salt and the M-containing compound and then sintered to obtain a high-nickel positive electrode material with high particle strength.
烧结过程中，M元素形成浓度扩散，由元素含量高的区域向元素含量低的区域扩散，因此内核、中间层、壳层都会有M元素，但是由于浓度梯度的存在，壳层M元素含量高。During the sintering process, the M element forms concentration diffusion, which diffuses from the area with high element content to the area with low element content. Therefore, there will be M element in the inner core, middle layer and shell layer, but due to the existence of concentration gradient, the content of M element in the shell layer is high. .
进一步的，所述烧结气氛为氧气，所述气氛中氧气的浓度大于85％；所述烧结的温度为650℃-800℃。Further, the sintering atmosphere is oxygen, and the concentration of oxygen in the atmosphere is greater than 85%; the sintering temperature is 650°C-800°C.
高Ni材料在烧结过程中，由于Ni含量高，在空气中，Ni 3+容易还原成Ni 2+离子，Ni 2+与Li +的半径相近，极易造成Li/Ni混排，导致结晶性能差。烧结气氛中，氧气的浓度越高，越抑制Li/Ni混排的形成。太高的氧气浓度，生产成本高。一般控制在85％以上。 During the sintering process of high-Ni materials, due to the high Ni content, Ni 3+ is easily reduced to Ni 2+ ions in the air, and the radius of Ni 2+ and Li + is similar, which can easily cause Li/Ni mixed row, resulting in crystallization properties Difference. In the sintering atmosphere, the higher the concentration of oxygen, the more inhibited the formation of Li/Ni mixed row. Too high oxygen concentration, high production cost. Generally controlled above 85%.
烧结温度也是研发人员重点考虑的问题，低于上述的烧结温度，将不能形成完整结晶体，高于最高的温度，材料有过烧分解问题，造成材料性能的急剧变差。The sintering temperature is also a key consideration for R&D personnel. If it is lower than the above-mentioned sintering temperature, a complete crystal will not be formed. If it is higher than the highest temperature, the material will have the problem of over-burning and decomposition, resulting in a sharp deterioration in material performance.
相比于现有技术，本发明带来以下技术效果：Compared with the prior art, the present invention brings the following technical effects:
1、在制备前驱体的过程中，通过控制合成参数，制备特定结构的前驱体。所述前驱体与锂盐混合烧结后，可以形成一次颗粒均匀分散的核心层和一次颗粒放射状分布的外层，提高粒子强度。1. In the process of preparing the precursor, the precursor of a specific structure is prepared by controlling the synthesis parameters. After the precursor is mixed and sintered with the lithium salt, a core layer in which the primary particles are uniformly dispersed and an outer layer in which the primary particles are radially distributed can be formed, thereby improving particle strength.
2、前驱体的合成过程中，只沉淀含Ni、Co的盐溶液，因为Ni 2+、Co 2+的溶度积系数相近，保证了Ni、Co沉淀分布的均匀性，同时便于生成特定结构的前驱体。 2. During the synthesis of the precursor, only the salt solution containing Ni and Co is precipitated, because the solubility product coefficients of Ni 2+ and Co 2+ are similar, which ensures the uniformity of Ni and Co precipitation distribution and facilitates the formation of specific structures precursors.
3、在与锂盐混合中，加入含M的化合物一起混合，节省了工序，提高生产效率，降低了能耗。3. When mixing with lithium salt, add M-containing compound to mix together, which saves procedures, improves production efficiency, and reduces energy consumption.
4、经过与锂盐、含M的化合物混合烧结后，M可以在二次颗粒表面形成富含M-O或Li-M-O化合物的壳层。所述壳层可以进一步提高粒子强度。并且所述壳层的形成与正极材料的煅烧制备过程同时进行，可有效改善高镍正极材料结构稳定性。4. After mixing and sintering with lithium salts and M-containing compounds, M can form a shell layer rich in M-O or Li-M-O compounds on the surface of secondary particles. The shell can further increase particle strength. Moreover, the formation of the shell layer is carried out simultaneously with the calcination preparation process of the positive electrode material, which can effectively improve the structural stability of the high-nickel positive electrode material.
附图说明Description of drawings
图1为本发明实施例1制备得到的正极材料的结构示意图。FIG. 1 is a schematic structural view of the positive electrode material prepared in Example 1 of the present invention.
图2为本发明实施例1制备得到的正极材料的剖面的SEM图。FIG. 2 is a SEM image of the cross-section of the positive electrode material prepared in Example 1 of the present invention.
图3为本发明实施例1制备得到的正极材料的剖面的元素线扫描图。Fig. 3 is an elemental line scan diagram of the section of the positive electrode material prepared in Example 1 of the present invention.
图4为本发明实施例1制备得到的正极材料与对比例1制备得到的正极材料的微压形变曲线图。4 is a micro-pressure deformation curve of the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 1. FIG.
图5为本发明实施例1制备得到的正极材料与对比例1制备得到的正极材料组装的锂离子半电池的放电循环图。5 is a discharge cycle diagram of a lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 1.
图6为本发明实施例1制备得到的正极材料与对比例2制备得到的正极材料组装的锂离子半电池的高温放电循环图。6 is a high-temperature discharge cycle diagram of a lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 of the present invention and the positive electrode material prepared in Comparative Example 2. FIG.
图中，1表示外壳，2表示中间层，3表示内核。In the figure, 1 represents the shell, 2 represents the middle layer, and 3 represents the inner core.
具体实施方式detailed description
下面结合附图对本发明进行详细描述，本部分的描述仅是示范性和解释性，不应对本发明的保护范围有任何的限制作用。The present invention will be described in detail below in conjunction with the accompanying drawings. The description in this part is only exemplary and explanatory, and should not have any limiting effect on the protection scope of the present invention.
需要注意的是，除非另有说明，本申请使用的技术术语或者科学术语应当为本发明所属领域技术人员所理解的通常意义。It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application shall have the usual meanings understood by those skilled in the art to which the present invention belongs.
实施例1Example 1
首先制备Ni 0.9Co 0.1(OH) 2前驱体。具体操作过程包括： Firstly, the Ni 0.9 Co 0.1 (OH) 2 precursor is prepared. The specific operation process includes:
共沉淀反应阶段：将硫酸镍、硫酸钴配制成总金属离子浓度为2mol/L的混合金属盐溶液，镍钴的摩尔比为9：1，将工业氢氧化钠溶液稀释成4mol/L溶液，准备0.5mol/L的氨水溶液。在300L反应釜中加入50L去离子水做底液，加入5L氨水溶液，加入氢氧化钠溶液调整pH为11，开启搅拌400rpm，维持反应温度为45℃，使用计量泵通入镍钴溶液、氨水溶液，流量比10：1，同时使用计量泵泵入氢氧化钠溶液，采用在线pH计控制氢氧化钠溶液的流量。维持反应釜内pH为11，沉淀反应进行1h，将pH降低0.5至10.5，将氨水溶液降低流量30％，搅拌速度降低10％，维持反应直到粒度达到8μm，提高pH1.5至12.0，提高氨水溶液流量80％，降低搅拌速度15％，维持反应直到粒度达到15μm。将反应得到的沉淀经固液分离、陈化、洗涤以及烘干后，得到Ni 0.9Co 0.1(OH) 2前驱体。 Co-precipitation reaction stage: nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 2mol/L, the molar ratio of nickel and cobalt is 9:1, and the industrial sodium hydroxide solution is diluted into a 4mol/L solution. Prepare 0.5mol/L ammonia solution. Add 50L of deionized water to the 300L reaction kettle as the bottom liquid, add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 11, start stirring at 400rpm, maintain the reaction temperature at 45°C, and use a metering pump to feed nickel-cobalt solution, ammonia Aqueous solution with a flow ratio of 10:1. At the same time, a metering pump is used to pump the sodium hydroxide solution, and an online pH meter is used to control the flow of the sodium hydroxide solution. Maintain the pH in the reactor at 11, carry out the precipitation reaction for 1 hour, reduce the pH by 0.5 to 10.5, reduce the flow rate of the ammonia solution by 30%, reduce the stirring speed by 10%, maintain the reaction until the particle size reaches 8 μm, increase the pH from 1.5 to 12.0, and increase the ammonia The flow rate of the aqueous solution is 80%, the stirring speed is reduced by 15%, and the reaction is maintained until the particle size reaches 15 μm. A Ni 0.9 Co 0.1 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
将氢氧化锂与上述合成的Ni 0.9Co 0.1(OH) 2前驱体、纳米氧化铝按照摩尔比1.03：0.95：0.05进行机械混合，混合均匀后在高温炉中烧结，烧结过程中氧气质量浓度为85％，烧结温度为770℃，保温12h。烧结完成后，自然冷却并过筛，得到化学式为Li 1.03Ni 0.855Co 0.095Al 0.05O 2的锂离子电池正极材料。 Lithium hydroxide was mechanically mixed with the Ni 0.9 Co 0.1 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1.03:0.95:0.05, and then sintered in a high-temperature furnace after mixing evenly. The oxygen mass concentration during the sintering process was 85%, the sintering temperature is 770°C, and the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with a chemical formula of Li 1.03 Ni 0.855 Co 0.095 Al 0.05 O 2 .
对比例1Comparative example 1
首先制备Ni 0.855Co 0.095Al 0.05(OH) 2前驱体。具体操作过程包括： Firstly, the Ni 0.855 Co 0.095 Al 0.05 (OH) 2 precursor was prepared. The specific operation process includes:
共沉淀反应阶段，将硫酸镍、硫酸钴配制成总金属离子浓度为2mol/L的混合金属盐溶液，镍钴的摩尔比为0.855：0.095，并配制金属离子浓度为2mol/L的偏铝酸钠溶液，将工业氢氧化钠溶液稀释成4mol/L溶液，准备0.5mol/L的氨水溶液。在300L反应釜中加入50L去离子水做底液，加入5L氨水溶液，加入氢氧化钠溶液调整pH为11，开启搅拌400rpm，维持反应温度为45℃，使用计量泵通入镍钴溶液、偏铝酸钠溶液、氨水溶液，流量比10：0.5：1，同时使用计量泵泵入氢氧化钠溶液，采用在线pH及控制氢氧化钠溶液的流量。维持反应釜内pH为11，沉淀反应进行1h，将pH降低0.5，将氨水溶液降低流量30％，搅拌速度降低10％，维持反应直到粒度达到8μm，提高pH1.5，提高氨水溶液流量80％，降低搅拌速度15％，维持反应直到粒度达到15μm。将反应得到的沉淀经固液分离、陈化、洗涤以及烘干后，得到Ni 0.855Co 0.095Al 0.05(OH) 2前驱体。 In the co-precipitation reaction stage, nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 2mol/L, the molar ratio of nickel to cobalt is 0.855:0.095, and metaaluminic acid with a metal ion concentration of 2mol/L is prepared Sodium solution, dilute industrial sodium hydroxide solution to 4mol/L solution, and prepare 0.5mol/L ammonia solution. Add 50L of deionized water into the 300L reactor as the bottom liquid, add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 11, start stirring at 400rpm, and maintain the reaction temperature at 45°C. The flow ratio of sodium aluminate solution and ammonia solution is 10:0.5:1. At the same time, the metering pump is used to pump the sodium hydroxide solution, and the online pH is used to control the flow of the sodium hydroxide solution. Maintain the pH in the reactor at 11, carry out the precipitation reaction for 1 hour, reduce the pH by 0.5, reduce the flow rate of the ammonia solution by 30%, reduce the stirring speed by 10%, maintain the reaction until the particle size reaches 8 μm, increase the pH to 1.5, and increase the flow rate of the ammonia solution by 80% , reduce the stirring speed by 15%, and maintain the reaction until the particle size reaches 15 μm. A Ni 0.855 Co 0.095 Al 0.05 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
将氢氧化锂与上述合成的Ni 0.855Co 0.095Al 0.05(OH) 2前驱体按照摩尔比1.03：1进行机械混 合，混合均匀后在高温炉中烧结，烧结过程中氧气质量浓度为85％，烧结温度为770℃，保温12h。烧结完成后，自然冷却并过筛，得到化学式为Li 1.03Ni 0.855Co 0.095Al 0.05O 2的锂离子电池正极材料。 Lithium hydroxide was mechanically mixed with the Ni 0.855 Co 0.095 Al 0.05 (OH) 2 precursor synthesized above according to the molar ratio of 1.03:1, and then sintered in a high-temperature furnace after mixing evenly. During the sintering process, the oxygen mass concentration was 85%. The temperature is 770°C and the temperature is kept for 12 hours. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with a chemical formula of Li 1.03 Ni 0.855 Co 0.095 Al 0.05 O 2 .
对比例2Comparative example 2
前驱体的合成方式与实施例1相同，最终合成产物为Ni 0.9Co 0.1(OH) 2前驱体。 The synthesis method of the precursor is the same as in Example 1, and the final synthesis product is the Ni 0.9 Co 0.1 (OH) 2 precursor.
将氢氧化锂与上述合成的Ni 0.9Co 0.1(OH) 2前驱体按照摩尔比1.03：1进行机械混合，混合均匀后在高温炉中烧结，烧结过程中氧气质量浓度为85％，烧结温度为770℃，保温12h。烧结完成后，自然冷却并过筛，得到化学式为Li 1.03Ni 0.9Co 0.1O 2的锂离子电池正极材料。 Lithium hydroxide and the Ni 0.9 Co 0.1 (OH) 2 precursor synthesized above were mechanically mixed according to the molar ratio of 1.03:1, and then sintered in a high-temperature furnace after mixing evenly. During the sintering process, the oxygen mass concentration was 85%, and the sintering temperature was 770°C, keep warm for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium ion battery with the chemical formula Li 1.03 Ni 0.9 Co 0.1 O 2 .
图1为实施例1制备得到的正极材料的结构示意图。图2为实施例1制备得到的正极材料的剖面的SEM图。从图2可以明显看出，实施例1制备得到的正极材料具备内核、中间层和外壳三层。FIG. 1 is a schematic structural view of the cathode material prepared in Example 1. FIG. 2 is an SEM image of a section of the positive electrode material prepared in Example 1. FIG. It can be clearly seen from FIG. 2 that the positive electrode material prepared in Example 1 has three layers: an inner core, an intermediate layer and an outer shell.
图3为本实施例1制备得到的正极材料的剖面的元素线扫描图，显示上中下三条波浪形元素分布曲线，上线代表Ni元素在颗粒中不同位置的含量，中线代表Al元素在颗粒中不同位置的含量，下线代表Co元素在颗粒中不同位置的含量。Al含量曲线在颗粒表面含量更高，说明Al元素在表面的浓度更高，形成富含Al的壳层。Figure 3 is an element line scan diagram of the section of the positive electrode material prepared in Example 1, showing three wavy element distribution curves at the top, middle and bottom, the upper line represents the content of Ni element in different positions in the particle, and the middle line represents the content of Al element in the particle The content of different positions, the lower line represents the content of Co element in different positions in the particle. The Al content curve is higher on the particle surface, indicating that the Al element has a higher concentration on the surface, forming an Al-rich shell.
图4为实施例1制备得到的正极材料与对比例1制备得到的正极材料的微压形变曲线图。从图4可以看出，实施例1制备得到的正极材料具有更高的粒子强度。FIG. 4 is a micro-pressure deformation curve of the positive electrode material prepared in Example 1 and the positive electrode material prepared in Comparative Example 1. FIG. It can be seen from FIG. 4 that the positive electrode material prepared in Example 1 has higher particle strength.
图5为实施例1制备得到的正极材料与对比例1制备得到的正极材料组装的锂离子半电池的放电循环图，图6为实施例1制备得到的正极材料与对比例2制备得到的正极材料组装的锂离子半电池的高温放电循环图。Figure 5 is the discharge cycle diagram of the lithium-ion half-cell assembled with the positive electrode material prepared in Example 1 and the positive electrode material prepared in Comparative Example 1, and Figure 6 is the positive electrode material prepared in Example 1 and the positive electrode prepared in Comparative Example 2 High-temperature discharge cycle diagram of material-assembled Li-ion half-cells.
从图5和图6可以明确得到，实施例1制备得到的正极材料相对于对比例1和2制备得到的正极材料，循环性能更加优越。It can be clearly obtained from Fig. 5 and Fig. 6 that the positive electrode material prepared in Example 1 has better cycle performance than the positive electrode materials prepared in Comparative Examples 1 and 2.
实施例2Example 2
首先制备Ni 0.8Co 0.2(OH) 2前驱体。具体操作过程包括： Firstly, the Ni 0.8 Co 0.2 (OH) 2 precursor is prepared. The specific operation process includes:
共沉淀反应阶段：将硝酸镍、硝酸钴配制成总金属离子浓度为3mol/L的混合金属盐溶液，镍钴的摩尔比为8：2，将工业氢氧化钠溶液稀释成4.5mol/L溶液，准备0.8mol/L的氨水溶液。在300L反应釜中加入50L去离子水做底液，加入5L氨水溶液，加入氢氧化钠溶液调整pH为12，开启搅拌500rpm，维持反应温度为50℃，使用计量泵通入镍钴溶液、氨水溶液，流量比10：1，同时使用计量泵泵入氢氧化钠溶液，采用在线pH计控制氢氧化钠 溶液的流量。维持反应釜内pH为12，沉淀反应进行2h，将pH降低0.5至11.5，将氨水溶液降低流量40％，搅拌速度降低15％，维持反应直到粒度达到5μm，提高pH1.5至13.0，提高氨水溶液流量100％，降低搅拌速度20％，维持反应直到粒度达到15μm。将反应得到的沉淀经固液分离、陈化、洗涤以及烘干后，得到Ni 0.8Co 0.2(OH) 2前驱体。 Co-precipitation reaction stage: nickel nitrate and cobalt nitrate are prepared into a mixed metal salt solution with a total metal ion concentration of 3mol/L, the molar ratio of nickel to cobalt is 8:2, and the industrial sodium hydroxide solution is diluted into a 4.5mol/L solution , prepare 0.8mol/L ammonia solution. Add 50L of deionized water to the 300L reactor as the bottom liquid, add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 12, start stirring at 500rpm, maintain the reaction temperature at 50°C, and use a metering pump to feed nickel-cobalt solution, ammonia Aqueous solution with a flow ratio of 10:1. At the same time, a metering pump is used to pump the sodium hydroxide solution, and an online pH meter is used to control the flow of the sodium hydroxide solution. Maintain the pH in the reactor at 12, carry out the precipitation reaction for 2 hours, reduce the pH by 0.5 to 11.5, reduce the flow rate of the ammonia solution by 40%, reduce the stirring speed by 15%, maintain the reaction until the particle size reaches 5 μm, increase the pH from 1.5 to 13.0, and increase the ammonia The flow rate of the aqueous solution is 100%, the stirring speed is reduced by 20%, and the reaction is maintained until the particle size reaches 15 μm. A Ni 0.8 Co 0.2 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
将氢氧化锂与上述合成的Ni 0.8Co 0.2(OH) 2前驱体、纳米氧化铝按照摩尔比1.05∶0.95∶0.05进行机械混合，混合均匀后在高温炉中烧结，烧结过程中氧气质量浓度为85％，烧结温度为770℃，保温12h。烧结完成后，自然冷却并过筛，得到化学式为Li 1.05Ni 0.76Co 0x 19Al 0.05O 2锂离子电池正极材料。 Lithium hydroxide was mechanically mixed with the Ni 0.8 Co 0.2 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1.05:0.95:0.05. After mixing evenly, they were sintered in a high-temperature furnace. During the sintering process, the oxygen mass concentration was 85%, the sintering temperature is 770°C, and the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a positive electrode material for a lithium-ion battery with a chemical formula of Li 1.05 Ni 0.76 Co 0 x 19 Al 0.05 O 2 .
实施例3Example 3
首先制备Ni 0.85Co 0.15(OH) 2前驱体。具体操作过程包括： Firstly, the Ni 0.85 Co 0.15 (OH) 2 precursor is prepared. The specific operation process includes:
共沉淀反应阶段：将硫酸镍、硫酸钴配制成总金属离子浓度为4mol/L的混合金属盐溶液，镍钴的摩尔比为0.85∶0.15，将工业氢氧化钠溶液稀释成4mol/L溶液，准备1mol/L的氨水溶液。在300L反应釜中加入50L去离子水做底液，加入5L氨水溶液，加入氢氧化钠溶液调整pH为10，开启搅拌600rpm，维持反应温度为50℃，使用计量泵通入镍钴溶液、氨水溶液，流量比10∶1，同时使用计量泵泵入氢氧化钠溶液，采用在线pH计控制氢氧化钠溶液的流量。维持反应釜内pH为10，沉淀反应进行1h，将pH降低0.8至9.2，将氨水溶液降低流量50％，搅拌速度降低20％，维持反应直到粒度达到8μm，提高pH1.5至10.7，提高氨水溶液流量120％，降低搅拌速度15％，维持反应直到粒度达到15μm。将反应得到的沉淀经固液分离、陈化、洗涤以及烘干后，得到Ni 0.85Co 0.15(OH) 2前驱体。 Co-precipitation reaction stage: nickel sulfate and cobalt sulfate are prepared into a mixed metal salt solution with a total metal ion concentration of 4mol/L, the molar ratio of nickel to cobalt is 0.85:0.15, and the industrial sodium hydroxide solution is diluted into a 4mol/L solution. Prepare 1mol/L ammonia solution. Add 50L of deionized water to the 300L reactor as the bottom liquid, add 5L of ammonia solution, add sodium hydroxide solution to adjust the pH to 10, start stirring at 600rpm, maintain the reaction temperature at 50°C, and use a metering pump to feed nickel-cobalt solution, ammonia Aqueous solution, flow ratio 10: 1, use metering pump to pump in sodium hydroxide solution simultaneously, adopt online pH meter to control the flow of sodium hydroxide solution. Maintain the pH in the reactor at 10, carry out the precipitation reaction for 1 hour, reduce the pH by 0.8 to 9.2, reduce the flow rate of the ammonia solution by 50%, reduce the stirring speed by 20%, maintain the reaction until the particle size reaches 8 μm, increase the pH from 1.5 to 10.7, and increase the ammonia The flow rate of the aqueous solution is 120%, the stirring speed is reduced by 15%, and the reaction is maintained until the particle size reaches 15 μm. A Ni 0.85 Co 0.15 (OH) 2 precursor is obtained by subjecting the precipitate obtained from the reaction to solid-liquid separation, aging, washing and drying.
将氢氧化锂与上述合成的Ni 0.85Co 0.15(OH) 2前驱体、纳米氧化铝按照摩尔比1∶0.95∶0.05进行机械混合，混合均匀后在高温炉中烧结，烧结过程中氧气质量浓度为85％，烧结温度为770℃，保温12h。烧结完成后，自然冷却并过筛，得到化学式为LiNi 0.8075Co 0.1425Al 0.05O 2锂离子电池正极材料。 Lithium hydroxide was mechanically mixed with the Ni 0.85 Co 0.15 (OH) 2 precursor synthesized above, and nano-alumina at a molar ratio of 1:0.95:0.05, and then sintered in a high-temperature furnace after mixing evenly. During the sintering process, the oxygen mass concentration was 85%, the sintering temperature is 770°C, and the temperature is kept for 12h. After the sintering is completed, it is naturally cooled and sieved to obtain a lithium-ion battery cathode material with the chemical formula LiNi 0.8075 Co 0.1425 Al 0.05 O 2 .
进一步测试实施例1-3制备得到的正极材料的粒子强度，结果如表1所示。The particle strength of the positive electrode materials prepared in Examples 1-3 was further tested, and the results are shown in Table 1.
表1实施例1-3制备得到的正极材料的离子强度The ionic strength of the positive electrode material that table 1 embodiment 1-3 prepares
正极材料Cathode material 粒子强度MpaParticle strength Mpa
实施例1Example 1 8080
实施例2Example 2 8585
实施例3Example 3 9595
从表1可以看出，通过本发明提供的技术方案制备得到的正极材料的离子强度都在80MPa以上。It can be seen from Table 1 that the ionic strength of the positive electrode materials prepared by the technical scheme provided by the present invention is above 80 MPa.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (14)

  1. 一种高镍正极材料，其特征在于，包括内核和外壳，且内核和外壳之间具有中间层；A high-nickel positive electrode material is characterized in that it includes a core and a shell, and there is an intermediate layer between the core and the shell;
    所述内核为球形或类球形，由球形或类球形的颗粒Ⅰ堆积得到；The inner core is spherical or spheroidal, and is obtained by stacking spherical or spheroidal particles I;
    所述中间层由类圆柱形的颗粒Ⅱ构成，颗粒Ⅱ径向堆积于内核表面；The middle layer is composed of cylindrical-like particles II, and the particles II are radially deposited on the surface of the inner core;
    所述外壳由类球形或球形的颗粒Ⅲ构成，颗粒Ⅲ堆积于中间层外表面；The shell is composed of spherical or spherical particles III, and the particles III are accumulated on the outer surface of the middle layer;
    所述颗粒Ⅰ、Ⅱ和Ⅲ的化学通式为Li aNi xCo yM zO 2，其中0.95≤a≤1.2，0.8≤x≤1，0＜y≤0.2，0＜z≤0.05，x+y+z＝1，M选自Mn、Al、Zr、Mg、Ti中的一种或两种以上； The general chemical formula of the particles I, II and III is Li a Ni x Co y M z O 2 , where 0.95≤a≤1.2, 0.8≤x≤1, 0<y≤0.2, 0<z≤0.05, x +y+z=1, M is selected from one or more of Mn, Al, Zr, Mg, Ti;
    所述颗粒Ⅰ和颗粒Ⅱ中元素M的含量低于所述颗粒Ⅲ中元素M的含量；The content of element M in the particles I and II is lower than the content of element M in the particle III;
    所述正极材料的粒子强度≥60MPa。The particle strength of the positive electrode material is ≥60 MPa.
  2. 如权利要求1所述的高镍正极材料，其特征在于，所述正极材料的平均粒径为0.1μm～40μm，比表面积为0.15m 2/g-1.5m 2/g。 The high-nickel positive electrode material according to claim 1, characterized in that, the average particle diameter of the positive electrode material is 0.1 μm-40 μm, and the specific surface area is 0.15 m 2 /g-1.5 m 2 /g.
  3. 如权利要求1所述的高镍正极材料，其特征在于，所述颗粒Ⅰ的平均粒径为0.1μm～2μm；所述颗粒Ⅱ的宽度≥20nm，长径比＞1.5。The high-nickel positive electrode material according to claim 1, characterized in that, the average particle diameter of the particles I is 0.1 μm-2 μm; the width of the particles II is ≥20 nm, and the aspect ratio is >1.5.
  4. 如权利要求1所述的高镍正极材料，其特征在于，所述颗粒Ⅲ堆积于颗粒Ⅱ的外表面，呈点状分布。The high-nickel positive electrode material according to claim 1, characterized in that, the particles III are accumulated on the outer surface of the particles II in a dot-like distribution.
  5. 如权利要求1所述的高镍正极材料，其特征在于，所述颗粒Ⅲ包括M的氧化物或者M的锂氧化物。The high-nickel positive electrode material according to claim 1, wherein the particle III includes M oxide or M lithium oxide.
  6. 如权利要求1-5任一项所述的高镍正极材料的前驱体的制备方法，其特征在于，包括共沉淀反应、第一阶段的生长反应和第二阶段的生长反应三个反应阶段；The preparation method of the precursor of high-nickel positive electrode material as claimed in any one of claims 1-5, is characterized in that, comprises coprecipitation reaction, the growth reaction of the first stage and the growth reaction of the second stage three reaction stages;
    所述共沉淀反应阶段的pH为8～13；The pH of the co-precipitation reaction stage is 8-13;
    所述第一阶段的生长反应体系中的络合剂的浓度低于共沉淀反应体系的络合剂的浓度，所述第一阶段的生长反应体系的pH低于共沉淀反应体系的pH，所述第一阶段的生长反应体系的搅拌转速低于共沉淀反应体系的搅拌转速；The concentration of the complexing agent in the growth reaction system of the first stage is lower than the concentration of the complexing agent in the coprecipitation reaction system, and the pH of the growth reaction system of the first stage is lower than the pH of the coprecipitation reaction system, so The stirring speed of the growth reaction system in the first stage is lower than the stirring speed of the coprecipitation reaction system;
    所述第二阶段的生长反应体系中的络合剂的浓度高于第一阶段的生长反应体系的络合剂的浓度，所述第二阶段的生长反应体系的pH高于第一阶段的生长反应体系的pH，所述第二阶段的生长反应体系的搅拌转速低于第一阶段的生长反应体系的搅拌转速。The concentration of the complexing agent in the growth reaction system of the second stage is higher than the concentration of the complexing agent in the growth reaction system of the first stage, and the pH of the growth reaction system of the second stage is higher than that of the growth reaction system of the first stage The pH of the reaction system, the stirring speed of the growth reaction system in the second stage is lower than the stirring speed of the growth reaction system in the first stage.
  7. 如权利要求6所述的制备方法，其特征在于，preparation method as claimed in claim 6, is characterized in that,
    所述的第一阶段的生长反应体系中络合剂的浓度相较于共沉淀反应体系中的络合剂溶液的浓度降低20％-80％，所述的第一阶段的生长反应体系的pH相对于共沉淀反应体系降低0.1-1，所述的第一阶段的生长反应体系的搅拌转速相对于共沉淀反应体系的搅拌转速降低1％-30％；Compared with the concentration of the complexing agent solution in the co-precipitation reaction system, the concentration of the complexing agent in the growth reaction system of the first stage is reduced by 20%-80%, and the pH of the growth reaction system of the first stage is Compared with the co-precipitation reaction system, the stirring speed of the growth reaction system in the first stage is reduced by 1%-30% relative to the stirring speed of the coprecipitation reaction system;
    所述的第二阶段的生长反应体系中络合剂的浓度相较于第一阶段的生长反应体系中的络合剂溶液的浓度升高30％-200％，所述的第二阶段的生长反应体系的pH相对于第一阶段的生长反应体系的pH提高0.1-3，所述的第二阶段的生长反应体系的搅拌转速相对于第一阶段的生长反应体系的搅拌转速降低1％-50％。Compared with the concentration of the complexing agent solution in the growth reaction system of the first stage, the concentration of the complexing agent in the growth reaction system of the second stage is increased by 30%-200%. The pH of the reaction system is increased by 0.1-3 relative to the pH of the growth reaction system in the first stage, and the stirring speed of the growth reaction system in the second stage is reduced by 1%-50 relative to the stirring speed of the growth reaction system in the first stage. %.
  8. 如权利要求6或7所述的制备方法，其特征在于，所述共沉淀反应、第一阶段的生长反应和第二阶段的生长反应是镍钴混合盐溶液、沉淀剂溶液和络合剂溶液三者之间的反应。The preparation method according to claim 6 or 7, characterized in that, the coprecipitation reaction, the growth reaction of the first stage and the growth reaction of the second stage are nickel-cobalt mixed salt solution, precipitant solution and complexing agent solution reactions among the three.
  9. 如权利要求6或7所述的制备方法，其特征在于，所述共沉淀反应的温度为40℃-60℃，反应时间为20min-5h，搅拌的转速为100rpm～1000rpm；所述第一阶段的生长反应和第二阶段的生长反应的时间为1h-10h。The preparation method according to claim 6 or 7, wherein the temperature of the co-precipitation reaction is 40°C-60°C, the reaction time is 20min-5h, and the stirring speed is 100rpm-1000rpm; the first stage The time of the growth reaction of the first phase and the growth reaction of the second stage is 1h-10h.
  10. 如权利要求6或7所述的制备方法，其特征在于，当第一阶段的生长反应的浆料的颗粒平均粒径D50达到设定粒度后，停止第一阶段的生长反应，开始第二阶段的生长反应；所述设定粒度为2μm-10μm。The preparation method according to claim 6 or 7, wherein, when the average particle size D50 of the slurry of the growth reaction in the first stage reaches the set particle size, the growth reaction in the first stage is stopped, and the second stage is started. growth reaction; the set particle size is 2 μm-10 μm.
  11. 如权利要求6或7所述的制备方法，其特征在于，当第二阶段的生长反应的浆料的颗粒平均粒径D50达到目标粒度后，停止反应；所述目标粒度为10μm-20μm。The preparation method according to claim 6 or 7, characterized in that, when the average particle diameter D50 of the slurry of the growth reaction in the second stage reaches the target particle size, the reaction is stopped; the target particle size is 10 μm-20 μm.
  12. 如权利要求8所述的制备方法，其特征在于，所述镍钴混合盐溶液中的镍盐选自NiSO 4、Ni(NO 3) 2、NiF 2、NiCl 2、NiBr 2、NiI 2中的一种或多种，钴盐选自CoSO 4、Co(NO 3) 2、CoCl 2中的一种或多种；沉淀剂为NaOH或KOH，络合剂选自氨水、硫酸铵和EDTA中的一种或多种。 The preparation method according to claim 8, wherein the nickel salt in the nickel-cobalt mixed salt solution is selected from NiSO 4 , Ni(NO 3 ) 2 , NiF 2 , NiCl 2 , NiBr 2 , NiI 2 One or more, the cobalt salt is selected from one or more of CoSO 4 , Co(NO 3 ) 2 , CoCl 2 ; the precipitating agent is NaOH or KOH, and the complexing agent is selected from ammonia water, ammonium sulfate and EDTA one or more.
  13. 如权利要求1-5任一项所述的高镍正极材料的制备方法，其特征在于，将通过权利要求7-13任一项所述的制备方法制备得到的前驱体与锂盐和含M的化合物混合后烧结，即得。The method for preparing a high-nickel positive electrode material as claimed in any one of claims 1-5, wherein the precursor prepared by the preparation method described in any one of claims 7-13 is mixed with a lithium salt and a M-containing The compounds are mixed and then sintered to obtain.
  14. 如权利要求13所述的制备方法，其特征在于，所述烧结气氛为氧气，所述气氛中氧气的浓度大于85％；所述烧结的温度为650℃-800℃。The preparation method according to claim 13, wherein the sintering atmosphere is oxygen, and the concentration of oxygen in the atmosphere is greater than 85%; the sintering temperature is 650°C-800°C.
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