WO2016155313A1 - High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor - Google Patents

High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor Download PDF

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WO2016155313A1
WO2016155313A1 PCT/CN2015/093824 CN2015093824W WO2016155313A1 WO 2016155313 A1 WO2016155313 A1 WO 2016155313A1 CN 2015093824 W CN2015093824 W CN 2015093824W WO 2016155313 A1 WO2016155313 A1 WO 2016155313A1
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lithium ion
cobalt
solution
sintering
preparation
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Chinese (zh)
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李兴翠
池田一崇
张永虎
宋文锋
李巧玲
许国干
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南通瑞翔新材料有限公司
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Priority to KR1020177025871A priority Critical patent/KR20170119691A/en
Publication of WO2016155313A1 publication Critical patent/WO2016155313A1/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
    • H01M4/48—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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/36—Aluminium phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • 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 relates to a cathode material of a lithium ion battery, in particular to a cathode material of a high-capacity nickel-cobalt-based lithium ion battery and a preparation method thereof.
  • Lithium-ion battery has the advantages of light weight, small size, high discharge platform, large capacity, long cycle life and no memory effect. It is widely used in mobile electronic devices such as mobile phones and notebook computers, and is also used in satellites and electrics. In the fields of automobiles, aerospace and aviation.
  • LiNi x Co 1-x O 2 (0.6 ⁇ x ⁇ 1) cathode material has the advantages of lithium cobaltate and lithium nickelate, high discharge specific capacity, good cycle performance, low cost and low environmental pollution, but due to its high Nickel material is difficult to completely oxidize Ni 2+ into Ni 3+ , which leads to cation mixing between Ni 2+ and Ni 3+ during high temperature crystallization, which leads to defects such as poor thermal stability and low initial charge and discharge efficiency. .
  • LiNi x Co 1-x O 2 (0.6 ⁇ x ⁇ 1) cathode material has the advantages of lithium cobaltate and lithium nickelate, high discharge specific capacity, good cycle performance, low cost and low environmental pollution, but due to its high Nickel material is difficult to completely oxidize Ni 2+ into Ni 3+ , which leads to cation mixing between Ni 2+ and Ni 3+ during high temperature crystallization, which leads to defects such as poor thermal stability and low initial charge and discharge efficiency. .
  • Li p Ni x Co 1-x O 2 is modified by doping and coating, and through a series of preparation methods, not only can the layer structure be stabilized, but also the phase transition during charge and discharge can be suppressed. It can provide its electrochemical performance and high temperature storage properties.
  • the present invention provides a high-capacity nickel-cobalt-based lithium ion cathode material and a preparation method thereof, which have uniform element mixing, sufficient reaction, favorable shape control, continuous production, improved production efficiency, and more granularity. Consistent.
  • a high-capacity nickel-cobalt-based lithium ion cathode material having a chemical formula of Li p Ni x Co 1-x M m O 2 , wherein 0.95 ⁇ p ⁇ 1.25, 0.6 ⁇ x ⁇ 1 , 0.01 ⁇ m ⁇ 0.12, M is a dopant, and the coating material is N, N accounts for 0.01-10% by weight of the total mass of the substrate;
  • the cathode material of the lithium ion secondary battery is a secondary particle obtained by agglomerating primary particles or Primary particles, or mixed particles of primary particles and secondary particles.
  • the preparation method of the high-capacity nickel-cobalt-based lithium ion cathode material comprises the following steps:
  • the first step is the preparation of a positive electrode material precursor for a lithium ion secondary battery:
  • Preparation of the initial liquid inject pure water into the reaction vessel, adjust the pH value of the solution with an alkali solution, and keep the temperature in the reaction vessel at 40-80 ° C, while introducing an inert gas and running through the entire reaction process;
  • Precursor reaction Add A1 solution to the reaction vessel, control the flow rate to 3-20 L/min, and slowly add appropriate amount of complexing agent and alkali solution to keep the temperature in the reaction vessel at 40-80 °C, adjust the stirring speed. 200 ⁇ 950r/min;
  • step c solid-liquid separation: the surface of the material in step c is treated, the synthesized binary cathode material precursor is transferred to a mature tank for solid-liquid separation, and the binary cathode material precursor obtained by solid-liquid separation is washed with deionized water, and dried. That is, the desired binary precursor A2, A2 has the chemical formula Ni x Co 1-x (OH) 2 ;
  • the second step is the preparation of a positive electrode material for a lithium ion secondary battery:
  • sintering mixing lithium source material, A2 and dopant M substance according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , wherein 0.95 ⁇ p ⁇ 1.25, 0.6 ⁇ x ⁇ 1, 0.01 ⁇ m ⁇ 0.12, M is a dopant, control sintering temperature is 400 ⁇ 1050°C, sintering time is 4 ⁇ 40h, air or oxygen is introduced into the sintering process, and the sintered materials are processed by crushing, grading and iron removal. , obtaining material A;
  • the material A is washed with water to reduce the alkali content, the ratio of the substance A to water is in the range of 1:1 to 1:6, and the material is dried and sieved after washing;
  • the material or substance A treated with f is used as a matrix, and the N substance is coated on the substrate, and the coating method is dry coating, wet coating or coprecipitation coating method, wherein N accounts for 0.01 to 10% by weight of the total mass of the material;
  • the g-coated material is sintered, the main temperature of the sintering is controlled at 400-1000 ° C, the sintering time in the main temperature zone is 3-35 h, and air or oxygen is required during the sintering process.
  • the sintering conditions are the same as the second sintering; the sintered materials are crushed, classified, sieved, iron removed and other processes as needed.
  • the alkali solution in the step a is a mixed solution of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide;
  • the complexing agent is ammonia water, ammonium hydrogencarbonate, ammonium sulfate, ammonium carbonate, One or more mixed solutions of citric acid and disodium edetate.
  • the nickel salt and the cobalt salt solution in the step a are one or more mixed solutions of a sulfate, a nitrate and a chloride.
  • the pH value in the step b is adjusted to 8.5 to 13.5.
  • the pH value in the step c is adjusted to 9.5 to 13.5.
  • the D50 of the precursor A2 ranges from 5 to 22 ⁇ m.
  • the lithium source material is selected from the group consisting of one or more of lithium hydroxide, lithium carbonate, and lithium oxalate.
  • the dopant M is an oxide or a halide of Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm. a mixture of hydroxide, metalorganic, nitrate, sulfate, carbonate, phosphate, oxalate or a composite oxide or metal fluoride with other metal elements.
  • the coating material N is a P-based substance, and includes a phosphate, a hypophosphite, a halide of P, an oxide of P, and a phospholipid, and an F-type substance, including a metal fluoride, a carbide of F, and an organic Compounds and composite oxides with other metals, B-based materials, including borate, B oxide, Al, Ti, Zr, Mo, Y, Tb, V, Mg-based substances, including Al, Ti, Zr, Mo, Y, Tb, V, Mg a mixture of one or more of hydroxides, oxides, chlorides, metalorganics, nitrates, sulfates, carbonates, phosphates, oxalates.
  • B-based materials including borate, B oxide, Al, Ti, Zr, Mo, Y, Tb, V
  • Mg-based substances including Al, Ti, Zr, Mo, Y, Tb, V, Mg a mixture of one or more of
  • the nickel-cobalt binary precursor is a continuous coprecipitation reaction, the elements are uniformly mixed, the reaction is sufficient, the morphology is controlled, and the continuous production is carried out, the production efficiency is improved, and the particle size is more uniform.
  • the binary high-nickel material reduces the cation mixing phenomenon by doping the appropriate elements, stabilizes the structure, improves the electrochemical performance of the battery, and improves the safety performance and high-temperature performance of the battery material.
  • the pH of the initial solution was adjusted to 8.5 with 1.5 mol/L sodium hydroxide solution, the temperature in the reaction vessel was adjusted to 40 ° C, the rotation speed was 200 r / min, and nitrogen gas was introduced; the flow rate of the A1 solution was adjusted to be 20 L/min, and the temperature was slow.
  • Sodium hydroxide and ammonium sulfate were added dropwise, and when the particle size reached the required level, solid-liquid separation was carried out and dried to obtain the desired precursor A2.
  • the sintering temperature is 1050 ° C
  • the sintering time is 40 h
  • the sintering process is introduced into the air
  • the sintered material is processed by crushing, grading, iron removal and the like to obtain the material A;
  • Coating The above-mentioned treated sample is used as a substrate, and the aluminum phosphate is coated on the substrate, and the coating method is dry coating, and N accounts for 0.01% of the total mass of the substrate.
  • Secondary sintering The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 450 ° C, the sintering time in the main temperature zone is 35 h, and air is introduced into the sintering process, and the aeration amount is 30 m 3 /h.
  • the pH of the initial solution adjusted by L sodium hydroxide solution is 13.5, the temperature in the reaction vessel is adjusted to 80 ° C, the rotation speed is 200 r / min, nitrogen gas is introduced; the flow rate of the A1 solution is adjusted to 3 L / min, and the hydroxide is slowly added dropwise.
  • Sodium and ammonium sulfate when the particle size is required, solid-liquid separation and drying to obtain the desired precursor A2.
  • the sintering temperature is 400 ° C
  • the sintering time is 4 h
  • the sintering process is introduced with oxygen
  • the sintered material is processed by crushing, grading, iron removal, etc. to obtain material A;
  • Coating The above-mentioned treated sample is used as a substrate, and the aluminum phosphate is coated on the substrate, and the coating method is dry coating, and N accounts for 0.12% of the total mass of the substrate.
  • Secondary sintering The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 1000 ° C, the sintering time in the main temperature zone is 3 h, and air is introduced during the sintering process.
  • the sintering temperature is 400 ° C
  • the sintering time is 4 h
  • the sintering process is introduced with oxygen
  • the sintered material is processed by crushing, grading, iron removal, etc. to obtain material A;
  • a substrate is coated with aluminum phosphate on the substrate, and the coating method is dry coating, and N accounts for 0.08% of the total mass of the substrate.
  • Secondary sintering The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 750 ° C, the sintering time in the main temperature zone is 6 h, and air is introduced during the sintering process.

Abstract

Disclosed is a high-capacity nickel-cobalt-based lithium ion positive electrode material. The lithium ion secondary battery positive electrode material is composed of secondary particles, which are formed by aggregating primary particles, or the primary particles, or mixed particles of the primary particles and the secondary particles. The preparation method therefor is as follows: the preparation of a precursor of the lithium ion secondary battery positive electrode material and the preparation of the lithium ion secondary battery positive electrode material. In the present invention, a nickel-cobalt binary precursor is formed by a continuous co-precipitation reaction, wherein the elements are uniformly mixed and fully reacted, which is beneficial for controlling the morphology; and continuous production is performed, wherein the production efficiency is improved, and the particle size tends to be more uniform. The cation mixing phenomenon is reduced in the binary high-nickel material by doping and coating with a suitable element, such that the structure is stabilized, the electrochemical performance of the battery is improved, and at the same time, the safety performance and high-temperature performance of the battery material are improved.

Description

一种高容量镍钴基锂离子正极材料及其制备方法High-capacity nickel-cobalt-based lithium ion cathode material and preparation method thereof 技术领域Technical field
本发明具体涉及一种锂离子电池正极材料，特别涉及一种高容量镍钴基锂离子电池正极材料及其制备方法。The invention relates to a cathode material of a lithium ion battery, in particular to a cathode material of a high-capacity nickel-cobalt-based lithium ion battery and a preparation method thereof.
背景技术Background technique
锂离子电池具有重量轻、体积小、放电平台高、容量大、循环寿命长、无记忆效应等优点，从而被广泛应用到手机、笔记本电脑等移动电子设备，同时也被应用于人造卫星、电动汽车、航天航空等领域。Lithium-ion battery has the advantages of light weight, small size, high discharge platform, large capacity, long cycle life and no memory effect. It is widely used in mobile electronic devices such as mobile phones and notebook computers, and is also used in satellites and electrics. In the fields of automobiles, aerospace and aviation.
LiNixCo1-xO2(0.6＜x＜1)正极材料具备了钴酸锂和镍酸锂的优点，放电比容量高、循环性能好、成本低和环境污染小等优点，但是由于高镍材料存在着Ni2+难以完全氧化成Ni3+，而导致高温结晶过程中Ni2+与Ni3+之间出现阳离子混排现象，从而会出现热稳定性差以及首次充放电效率低等缺陷。为了解决上述问题，LiNi x Co 1-x O 2 (0.6<x<1) cathode material has the advantages of lithium cobaltate and lithium nickelate, high discharge specific capacity, good cycle performance, low cost and low environmental pollution, but due to its high Nickel material is difficult to completely oxidize Ni 2+ into Ni 3+ , which leads to cation mixing between Ni 2+ and Ni 3+ during high temperature crystallization, which leads to defects such as poor thermal stability and low initial charge and discharge efficiency. . In order to solve the above problems,
本文通过对LipNixCo1-xO2进行掺杂包覆对其进行改性，并通过一系列的制备方法，不仅可以稳定其层状结构，抑制充放电过程中的相变，而且可以提供其电化学性能和高温保存性能。In this paper, Li p Ni x Co 1-x O 2 is modified by doping and coating, and through a series of preparation methods, not only can the layer structure be stabilized, but also the phase transition during charge and discharge can be suppressed. It can provide its electrochemical performance and high temperature storage properties.
发明内容Summary of the invention
发明目的：本发明提供一种高容量镍钴基锂离子正极材料及其制备方法，元素混合均匀，反应充分，有利于形貌的控制，且实行连续生产，提高了生产效率，并且粒度更趋于一致。OBJECT OF THE INVENTION The present invention provides a high-capacity nickel-cobalt-based lithium ion cathode material and a preparation method thereof, which have uniform element mixing, sufficient reaction, favorable shape control, continuous production, improved production efficiency, and more granularity. Consistent.
技术方案：一种高容量镍钴基锂离子正极材料，化学通式为：LipNixCo1-xMmO2，其中0.95≤p≤1.25，0.6≤x＜1，0.01≤m＜0.12，M为掺杂剂，包覆材料为N，N所占基材总质量的0.01～10wt％；所述的锂离子二次电池的正极材料是为一次粒子聚集而成的二次粒子或一次粒子，或一次粒子与二次粒子的混合粒子构成。Technical Solution: A high-capacity nickel-cobalt-based lithium ion cathode material having a chemical formula of Li p Ni x Co 1-x M m O 2 , wherein 0.95 ≤ p ≤ 1.25, 0.6 ≤ x < 1 , 0.01 ≤ m < 0.12, M is a dopant, and the coating material is N, N accounts for 0.01-10% by weight of the total mass of the substrate; the cathode material of the lithium ion secondary battery is a secondary particle obtained by agglomerating primary particles or Primary particles, or mixed particles of primary particles and secondary particles.
所述的高容量镍钴基锂离子正极材料的制备方法，包括如下步骤：The preparation method of the high-capacity nickel-cobalt-based lithium ion cathode material comprises the following steps:
第一步，锂离子二次电池正极材料前驱体的制备：The first step is the preparation of a positive electrode material precursor for a lithium ion secondary battery:
a、溶液的配制：按摩尔比Ni：Co＝x：1-x配制成混合盐溶液A1，使该盐溶液中金属离子浓度为0.5～3mol/L；配制浓度为1.5～12mol/L的碱溶液，配制浓度为0.5～5mol/L的络合剂溶液，其中0.6≤x＜1；a, the preparation of the solution: the molar ratio Ni: Co = x: 1-x is formulated into a mixed salt solution A1, the metal ion concentration in the salt solution is 0.5 ~ 3mol / L; the preparation of the concentration of 1.5 ~ 12mol / L of alkali a solution, a concentration of 0.5 to 5 mol / L of a complexing agent solution, wherein 0.6 ≤ x < 1;
b、初液的配制：在反应容器中注入纯水，并用碱溶液调节溶液的pH值，并保持反应容器内的温度为40～80℃，同时通入惰性气体，并贯穿整个反应过程；b. Preparation of the initial liquid: inject pure water into the reaction vessel, adjust the pH value of the solution with an alkali solution, and keep the temperature in the reaction vessel at 40-80 ° C, while introducing an inert gas and running through the entire reaction process;
c、前驱体的反应：向反应容器内加入A1溶液，控制流速为3～20L/min，同时缓慢加入适量络合剂和碱溶液，保持反应容器内的温度为40～80℃，调节搅拌速度为200～950r/min；c. Precursor reaction: Add A1 solution to the reaction vessel, control the flow rate to 3-20 L/min, and slowly add appropriate amount of complexing agent and alkali solution to keep the temperature in the reaction vessel at 40-80 °C, adjust the stirring speed. 200~950r/min;
d、固液分离：将步骤c中物料进行表面处理，合成的二元正极材料前驱体转至熟成槽进行固液分离，用去离子水洗涤固液分离所得的二元正极材料前驱体，干燥即得所需的二元前驱体A2，A2的化学式为NixCo1-x(OH)2；d, solid-liquid separation: the surface of the material in step c is treated, the synthesized binary cathode material precursor is transferred to a mature tank for solid-liquid separation, and the binary cathode material precursor obtained by solid-liquid separation is washed with deionized water, and dried. That is, the desired binary precursor A2, A2 has the chemical formula Ni x Co 1-x (OH) 2 ;
第二步，锂离子二次电池正极材料的制备： The second step is the preparation of a positive electrode material for a lithium ion secondary battery:
e、烧结：将锂源物质、A2和掺杂剂M物质按照分子式LipNixCo1-xMmO2中的比例进行混合，其中0.95≤p≤1.25，0.6≤x＜1，0.01≤m＜0.12，M为掺杂剂，控制烧结温度为400～1050℃，烧结时间为4～40h，烧结过程通入空气或者氧气，将烧结后的物料经破碎、分级、除铁等工艺处理，得到材料A；e, sintering: mixing lithium source material, A2 and dopant M substance according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , wherein 0.95 ≤ p ≤ 1.25, 0.6 ≤ x < 1, 0.01 ≤m<0.12, M is a dopant, control sintering temperature is 400～1050°C, sintering time is 4～40h, air or oxygen is introduced into the sintering process, and the sintered materials are processed by crushing, grading and iron removal. , obtaining material A;
f、表面处理：将材料A进行水洗处理以降低碱含量，物质A与水的比例范围为1:1～1:6，水洗后将物料干燥过筛；f, surface treatment: the material A is washed with water to reduce the alkali content, the ratio of the substance A to water is in the range of 1:1 to 1:6, and the material is dried and sieved after washing;
g、包覆：以f处理后的物料或物质A为基体，在基体上包覆N物质，包覆方法为干式包覆、湿式包覆或共沉淀包覆法，其中，N所占基材总质量的0.01～10wt％；g, coating: the material or substance A treated with f is used as a matrix, and the N substance is coated on the substrate, and the coating method is dry coating, wet coating or coprecipitation coating method, wherein N accounts for 0.01 to 10% by weight of the total mass of the material;
h、二次或多次烧结：将经过g包覆好的物料进行烧结，烧结主温度控制在400～1000℃，主温区烧结时间为3～35h，烧结过程中需通入空气或者氧气，根据产品性能要求，可以进行三次以上烧结，烧结条件同二次烧结；烧结后的物料按照需要进行破碎、分级、过筛、除铁等工艺处理。h, secondary or multiple sintering: the g-coated material is sintered, the main temperature of the sintering is controlled at 400-1000 ° C, the sintering time in the main temperature zone is 3-35 h, and air or oxygen is required during the sintering process. According to the product performance requirements, more than three times of sintering can be carried out, the sintering conditions are the same as the second sintering; the sintered materials are crushed, classified, sieved, iron removed and other processes as needed.
作为优化：所述步骤a中碱溶液为氢氧化钠、氢氧化钾和氢氧化锂中的一种或一种以上的混合溶液；络合剂为氨水、碳酸氢氨、硫酸铵、碳酸铵、柠檬酸和乙二胺四二酸二钠中的一种或一种以上混合溶液。As an optimization, the alkali solution in the step a is a mixed solution of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is ammonia water, ammonium hydrogencarbonate, ammonium sulfate, ammonium carbonate, One or more mixed solutions of citric acid and disodium edetate.
作为优化：所述步骤a中镍盐、钴盐溶液为硫酸盐、硝酸盐和氯化盐中的一种或一种以上混合溶液。As an optimization, the nickel salt and the cobalt salt solution in the step a are one or more mixed solutions of a sulfate, a nitrate and a chloride.
作为优化：所述步骤b中PH值调节至8.5～13.5。As an optimization, the pH value in the step b is adjusted to 8.5 to 13.5.
作为优化：所述步骤c中PH值调节至9.5～13.5。As an optimization, the pH value in the step c is adjusted to 9.5 to 13.5.
作为优化：前驱体A2的D50范围为5～22μm。As an optimization: the D50 of the precursor A2 ranges from 5 to 22 μm.
作为优化：所述的锂源物质选自氢氧化锂、碳酸锂、草酸锂中的一种或多种的混合物。As an optimization: the lithium source material is selected from the group consisting of one or more of lithium hydroxide, lithium carbonate, and lithium oxalate.
作为优化：所述的掺杂剂M为Cr、La、Ce、Zr、Ni、Mg、Ti、Al、Ca、V、B、Be、Y、Mo、Tb、Ho、Tm的氧化物、卤化物、氢氧化物、金属有机物、硝酸盐、硫酸盐、碳酸盐、磷酸盐、草酸盐或与其他金属元素的复合氧化物或金属氟化物的一种或者多种的混合物。As an optimization: the dopant M is an oxide or a halide of Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, V, B, Be, Y, Mo, Tb, Ho, Tm. a mixture of hydroxide, metalorganic, nitrate, sulfate, carbonate, phosphate, oxalate or a composite oxide or metal fluoride with other metal elements.
作为优化：所述的包覆材料N为P系物质，包含磷酸盐、次磷酸盐、P的卤化物、P的氧化物和磷脂，F系物质，包含金属氟化物、F的碳化物、有机化合物以及与其他金属的复合氧化物，B系物质，包含硼酸盐、B氧化物，Al、Ti、Zr、Mo、Y、Tb、V、Mg系物质，包含Al、Ti、Zr、Mo、Y、Tb、V、Mg的氢氧化物、氧化物、氯化物、金属有机物、硝酸盐、硫酸盐、碳酸盐、磷酸盐、草酸盐的一种或者多种的混合物。As an optimization: the coating material N is a P-based substance, and includes a phosphate, a hypophosphite, a halide of P, an oxide of P, and a phospholipid, and an F-type substance, including a metal fluoride, a carbide of F, and an organic Compounds and composite oxides with other metals, B-based materials, including borate, B oxide, Al, Ti, Zr, Mo, Y, Tb, V, Mg-based substances, including Al, Ti, Zr, Mo, Y, Tb, V, Mg a mixture of one or more of hydroxides, oxides, chlorides, metalorganics, nitrates, sulfates, carbonates, phosphates, oxalates.
有益效果：本发明中镍钴二元前驱体为连续式共沉淀反应，元素混合均匀，反应充分，有利于形貌的控制，且实行连续生产，提高了生产效率，并且粒度更趋于一致。二元高镍材料通过掺杂包覆适宜的元素减少阳离子混排现象，稳定了结构，提高了电池的电化学性能的同时，提高了电池材料的安全性能和高温性能。Advantageous Effects: In the present invention, the nickel-cobalt binary precursor is a continuous coprecipitation reaction, the elements are uniformly mixed, the reaction is sufficient, the morphology is controlled, and the continuous production is carried out, the production efficiency is improved, and the particle size is more uniform. The binary high-nickel material reduces the cation mixing phenomenon by doping the appropriate elements, stabilizes the structure, improves the electrochemical performance of the battery, and improves the safety performance and high-temperature performance of the battery material.
具体实施方式 detailed description
下面结合具体实施例对本发明作进一步说明：The present invention will be further described below in conjunction with specific embodiments:
实施例1：Example 1:
前驱体的制备：Ni：Co＝0.6:0.4配制成0.5mol/L的混合溶液A1，配制1.5mol/L的氢氧化钠溶液和0.5mol/L硫酸铵溶液；在反应容器中注入纯水，并用1.5mol/L氢氧化钠溶液调节初液的pH值为8.5，调节反应容器内的温度为40℃，转速为200r/min，通入氮气；调节A1溶液的流速为20L/min，同时缓慢滴加氢氧化钠和硫酸铵，当粒度达到要求时，进行固液分离，干燥，得到所需的前驱体A2。Precursor preparation: Ni:Co=0.6:0.4 is formulated into 0.5 mol/L mixed solution A1, 1.5 mol/L sodium hydroxide solution and 0.5 mol/L ammonium sulfate solution are prepared; pure water is injected into the reaction vessel. The pH of the initial solution was adjusted to 8.5 with 1.5 mol/L sodium hydroxide solution, the temperature in the reaction vessel was adjusted to 40 ° C, the rotation speed was 200 r / min, and nitrogen gas was introduced; the flow rate of the A1 solution was adjusted to be 20 L/min, and the temperature was slow. Sodium hydroxide and ammonium sulfate were added dropwise, and when the particle size reached the required level, solid-liquid separation was carried out and dried to obtain the desired precursor A2.
正极材料的制备：将氢氧化锂、A2、以及氢氧化铝按照分子式LipNixCo1-xMmO2中的比例进行混合，其中p＝1.25，x＝0.6，m＝0.12，控制烧结温度为1050℃，烧结时间为40h，烧结过程通入空气，将烧结后的物料经破碎、分级、除铁等工艺处理，得到材料A；Preparation of positive electrode material: lithium hydroxide, A2, and aluminum hydroxide were mixed according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , where p=1.25, x=0.6, m=0.12, control The sintering temperature is 1050 ° C, the sintering time is 40 h, the sintering process is introduced into the air, and the sintered material is processed by crushing, grading, iron removal and the like to obtain the material A;
表面处理：按照A：水＝1:1的比例进行水洗，干燥、过筛；Surface treatment: water washing according to A: water = 1:1 ratio, drying, sieving;
包覆：以上述处理好的样品为基体，在基体上包覆磷酸铝，包覆方法为干式包覆，N所占基材总质量的0.01％。Coating: The above-mentioned treated sample is used as a substrate, and the aluminum phosphate is coated on the substrate, and the coating method is dry coating, and N accounts for 0.01% of the total mass of the substrate.
二次烧结：将上述处理好的物料进行二次烧结，烧结主温度控制在450℃，主温区的烧结时间为35h，烧结过程中通入空气，通气量为30m3/h。Secondary sintering: The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 450 ° C, the sintering time in the main temperature zone is 35 h, and air is introduced into the sintering process, and the aeration amount is 30 m 3 /h.
实施例2：Example 2:
前驱体的制备：Ni：Co＝0.85:0.15配制成3mol/L的混合溶液A1，配制12mol/L的氢氧化钠溶液和5mol/L硫酸铵溶液；在反应容器中注入纯水，并用8mol/L氢氧化钠溶液调节初液的pH值为13.5，调节反应容器内的温度为80℃，转速为200r/min，通入氮气；调节A1溶液的流速为3L/min，同时缓慢滴加氢氧化钠和硫酸铵，当粒度达到要求时，进行固液分离，干燥，得到所需的前驱体A2。Precursor preparation: Ni:Co=0.85:0.15 is formulated into a 3 mol/L mixed solution A1, and 12 mol/L sodium hydroxide solution and 5 mol/L ammonium sulfate solution are prepared; pure water is injected into the reaction vessel, and 8 mol/ is used. The pH of the initial solution adjusted by L sodium hydroxide solution is 13.5, the temperature in the reaction vessel is adjusted to 80 ° C, the rotation speed is 200 r / min, nitrogen gas is introduced; the flow rate of the A1 solution is adjusted to 3 L / min, and the hydroxide is slowly added dropwise. Sodium and ammonium sulfate, when the particle size is required, solid-liquid separation and drying to obtain the desired precursor A2.
正极材料的制备：将氢氧化锂、A2、以及氢氧化铝按照分子式LipNixCo1-xMmO2中的比例进行混合，其中p＝0.95，x＝0.85，m＝0.01，控制烧结温度为400℃，烧结时间为4h，烧结过程通入氧气，将烧结后的物料经破碎、分级、除铁等工艺处理，得到材料A；Preparation of positive electrode material: lithium hydroxide, A2, and aluminum hydroxide were mixed according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , where p=0.95, x=0.85, m=0.01, control The sintering temperature is 400 ° C, the sintering time is 4 h, the sintering process is introduced with oxygen, and the sintered material is processed by crushing, grading, iron removal, etc. to obtain material A;
表面处理：按照A：水＝1:6的比例进行水洗，干燥、过筛。Surface treatment: Washed in a ratio of A:water = 1:6, dried, and sieved.
包覆：以上述处理好的样品为基体，在基体上包覆磷酸铝，包覆方法为干式包覆，N所占基材总质量的0.12％。Coating: The above-mentioned treated sample is used as a substrate, and the aluminum phosphate is coated on the substrate, and the coating method is dry coating, and N accounts for 0.12% of the total mass of the substrate.
二次烧结：将上述处理好的物料进行二次烧结，烧结主温度控制在1000℃，主温区的烧结时间为3h，烧结过程中通入空气。Secondary sintering: The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 1000 ° C, the sintering time in the main temperature zone is 3 h, and air is introduced during the sintering process.
实施例3：Example 3:
前驱体的制备：Ni：Co＝0.80:0.20配制成2mol/L的混合溶液A1，配制2.5mol/L的氢氧化钠溶液和1.8mol/L硫酸铵溶液；在反应容器中注入纯水，并用2.5mol/L氢氧化钠溶液调节初液的pH值为12，调节反应容器内的温度为60℃，转速为500r/min，通入氮气；调节A1溶液的流速为10L/min，同时缓慢滴加氢氧化钠和硫酸铵，当粒度达到要求时，进行固液 分离，干燥，得到所需的前驱体A2。Precursor preparation: Ni:Co=0.80:0.20 is formulated into 2mol/L mixed solution A1, 2.5mol/L sodium hydroxide solution and 1.8mol/L ammonium sulfate solution are prepared; pure water is injected into the reaction vessel, and used 2.5mol / L sodium hydroxide solution to adjust the initial liquid pH of 12, adjust the temperature inside the reaction vessel is 60 ° C, the rotation speed is 500r / min, pass nitrogen; adjust the flow rate of A1 solution is 10L / min, while slowly dropping Add sodium hydroxide and ammonium sulfate, when the particle size meets the requirements, carry out solid-liquid Separate and dry to obtain the desired precursor A2.
正极材料的制备：将氢氧化锂、A2、以及氢氧化铝按照分子式LipNixCo1-xMmO2中的比例进行混合，其中p＝0.11，x＝0.80，m＝0.04，控制烧结温度为400℃，烧结时间为4h，烧结过程通入氧气，将烧结后的物料经破碎、分级、除铁等工艺处理，得到材料A；Preparation of positive electrode material: lithium hydroxide, A2, and aluminum hydroxide were mixed according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , where p=0.11, x=0.80, m=0.04, control The sintering temperature is 400 ° C, the sintering time is 4 h, the sintering process is introduced with oxygen, and the sintered material is processed by crushing, grading, iron removal, etc. to obtain material A;
包覆：以A为基体，在基体上包覆磷酸铝，包覆方法为干式包覆，N所占基材总质量的0.08％。Coating: A substrate is coated with aluminum phosphate on the substrate, and the coating method is dry coating, and N accounts for 0.08% of the total mass of the substrate.
二次烧结：将上述处理好的物料进行二次烧结，烧结主温度控制在750℃，主温区的烧结时间为6h，烧结过程中通入空气。 Secondary sintering: The above-mentioned treated materials are subjected to secondary sintering, the main temperature of the sintering is controlled at 750 ° C, the sintering time in the main temperature zone is 6 h, and air is introduced during the sintering process.

Claims (10)

  1. 一种高容量镍钴基锂离子正极材料，其特征在于：基材的化学通式为：LipNixCo1-xMmO2，其中0.95≤p≤1.25，0.6≤x＜1，0.01≤m＜0.12，M为掺杂剂，包覆材料为N，N所占基材总质量的0.01～10wt％；所述的锂离子二次电池的正极材料是为一次粒子聚集而成的二次粒子或一次粒子，或一次粒子与二次粒子的混合粒子构成。A high-capacity nickel-cobalt-based lithium ion cathode material characterized in that: the chemical formula of the substrate is: Li p Ni x Co 1-x M m O 2 , wherein 0.95 ≤ p ≤ 1.25, 0.6 ≤ x < 1, 0.01≤m<0.12, M is a dopant, and the coating material is N, N accounts for 0.01-10% by weight of the total mass of the substrate; the positive electrode material of the lithium ion secondary battery is formed by primary particles. A secondary particle or a primary particle, or a mixed particle of a primary particle and a secondary particle.
  2. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：包括如下步骤：The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, comprising the steps of:
    第一步，锂离子二次电池正极材料前驱体的制备：The first step is the preparation of a positive electrode material precursor for a lithium ion secondary battery:
    a、溶液的配制：按摩尔比Ni：Co＝x：1-x配制成混合盐溶液A1，使该盐溶液中金属离子浓度为0.5～3mol/L；配制浓度为1.5～12mol/L的碱溶液，配制浓度为0.5～5mol/L的络合剂溶液，其中0.6≤x＜1；a, the preparation of the solution: the molar ratio Ni: Co = x: 1-x is formulated into a mixed salt solution A1, the metal ion concentration in the salt solution is 0.5 ~ 3mol / L; the preparation of the concentration of 1.5 ~ 12mol / L of alkali a solution, a concentration of 0.5 to 5 mol / L of a complexing agent solution, wherein 0.6 ≤ x < 1;
    b、初液的配制：在反应容器中注入纯水，并用碱溶液调节溶液的pH值，并保持反应容器内的温度为40～80℃，同时通入惰性气体，并贯穿整个反应过程；b. Preparation of the initial liquid: inject pure water into the reaction vessel, adjust the pH value of the solution with an alkali solution, and keep the temperature in the reaction vessel at 40-80 ° C, while introducing an inert gas and running through the entire reaction process;
    c、前驱体的反应：向反应容器内加入A1溶液，控制流速为3～20L/min，同时缓慢加入适量络合剂和碱溶液，保持反应容器内的温度为40～80℃，调节搅拌速度为200～950r/min；c. Precursor reaction: Add A1 solution to the reaction vessel, control the flow rate to 3-20 L/min, and slowly add appropriate amount of complexing agent and alkali solution to keep the temperature in the reaction vessel at 40-80 °C, adjust the stirring speed. 200~950r/min;
    d、固液分离：将步骤c中物料进行表面处理，合成的二元正极材料前驱体转至熟成槽进行固液分离，用去离子水洗涤固液分离所得的二元正极材料前驱体，干燥即得所需的二元前驱体A2，A2的化学式为NixCo1-x(OH)2。d, solid-liquid separation: the surface of the material in step c is treated, the synthesized binary cathode material precursor is transferred to a mature tank for solid-liquid separation, and the binary cathode material precursor obtained by solid-liquid separation is washed with deionized water, and dried. That is, the desired binary precursor A2, A2 has the chemical formula Ni x Co 1-x (OH) 2 .
    第二步，锂离子二次电池正极材料的制备：The second step is the preparation of a positive electrode material for a lithium ion secondary battery:
    e、烧结：将锂源物质、A2和掺杂剂M物质按照分子式LipNixCo1-xMmO2中的比例进行混合，其中0.95≤p≤1.25，0.6≤x＜1，0.01≤m＜0.12，M为掺杂剂，控制烧结温度为400～1050℃，烧结时间为4～40h，烧结过程通入空气或者氧气，将烧结后的物料经破碎、分级、除铁等工艺处理，得到材料A；e, sintering: mixing lithium source material, A2 and dopant M substance according to the ratio of the formula Li p Ni x Co 1-x M m O 2 , wherein 0.95 ≤ p ≤ 1.25, 0.6 ≤ x < 1, 0.01 ≤m<0.12, M is a dopant, control sintering temperature is 400～1050°C, sintering time is 4～40h, air or oxygen is introduced into the sintering process, and the sintered materials are processed by crushing, grading and iron removal. , obtaining material A;
    f、表面处理：将材料A进行水洗处理以降低碱含量，物质A与水的比例范围为1:1～1:6，水洗后将物料干燥过筛；f, surface treatment: the material A is washed with water to reduce the alkali content, the ratio of the substance A to water is in the range of 1:1 to 1:6, and the material is dried and sieved after washing;
    g、包覆：以f处理后的物料或物质A为基体，在基体上包覆N物质，包覆方法为干式包覆、湿式包覆或共沉淀包覆法，其中，N所占基材总质量的0.01～10wt％。g, coating: the material or substance A treated with f is used as a matrix, and the N substance is coated on the substrate, and the coating method is dry coating, wet coating or coprecipitation coating method, wherein N accounts for The total mass of the material is 0.01 to 10% by weight.
    h、二次或多次烧结：将经过g包覆好的物料进行烧结，烧结主温度控制在400～1000℃，主温区烧结时间为3～35h，烧结过程中需通入空气或者氧气，根据产品性能要求，可以进行三次以上烧结，烧结条件同二次烧结。烧结后的物料按照需要进行破碎、分级、过筛、除铁等工艺处理。h, secondary or multiple sintering: the g-coated material is sintered, the main temperature of the sintering is controlled at 400-1000 ° C, the sintering time in the main temperature zone is 3-35 h, and air or oxygen is required during the sintering process. According to the product performance requirements, more than three times of sintering can be performed, and the sintering conditions are the same as the second sintering. The sintered material is processed according to the requirements of crushing, classification, sieving, and iron removal.
  3. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述步骤a中碱溶液为氢氧化钠、氢氧化钾和氢氧化锂中的一种或一种以上的混合溶液；络合剂为氨水、碳酸氢氨、硫酸铵、碳酸铵、柠檬酸和乙二胺四二酸二钠中的一种或一种以上混合 溶液。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the alkali solution in the step a is one or a kind of sodium hydroxide, potassium hydroxide and lithium hydroxide. The above mixed solution; the complexing agent is one or more of ammonia water, ammonium hydrogencarbonate, ammonium sulfate, ammonium carbonate, citric acid and disodium edetate Solution.
  4. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述步骤a中镍盐、钴盐溶液为硫酸盐、硝酸盐和氯化盐中的一种或一种以上混合溶液。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the nickel salt and the cobalt salt solution in the step a are one of a sulfate, a nitrate and a chloride salt or More than one mixed solution.
  5. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述步骤b中PH值调节至8.5～13.5。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the pH value in the step b is adjusted to 8.5 to 13.5.
  6. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述步骤c中PH值调节至9.5～13.5。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the pH value in the step c is adjusted to 9.5 to 13.5.
  7. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：前驱体A2的D50范围为5～22μm。The method for preparing a high-capacity nickel-cobalt-based lithium ion positive electrode material according to claim 1, wherein the precursor A2 has a D50 ranging from 5 to 22 μm.
  8. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述的锂源物质选自氢氧化锂、碳酸锂、草酸锂中的一种或多种的混合物。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the lithium source material is selected from the group consisting of lithium hydroxide, lithium carbonate, and lithium oxalate. .
  9. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述的掺杂剂M为Cr、La、Ce、Zr、Ni、Mg、Ti、Al、Ca、V、B、Be、Y、Mo、Tb、Ho、Tm的氧化物、卤化物、氢氧化物、金属有机物、硝酸盐、硫酸盐、碳酸盐、磷酸盐、草酸盐或与其他金属元素的复合氧化物或金属氟化物的一种或者多种的混合物。The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the dopant M is Cr, La, Ce, Zr, Ni, Mg, Ti, Al, Ca, Oxides, halides, hydroxides, metalorganics, nitrates, sulfates, carbonates, phosphates, oxalates or other metallic elements of V, B, Be, Y, Mo, Tb, Ho, Tm a mixture of one or more of a composite oxide or a metal fluoride.
  10. 根据权利要求1所述的高容量镍钴基锂离子正极材料的制备方法，其特征在于：所述的包覆材料N为P系物质，包含磷酸盐、次磷酸盐、P的卤化物、P的氧化物和磷脂，F系物质，包含金属氟化物、F的碳化物、有机化合物以及与其他金属的复合氧化物，B系物质，包含硼酸盐、B氧化物，Al、Ti、Zr、Mo、Y、Tb、V、Mg系物质，包含Al、Ti、Zr、Mo、Y、Tb、V、Mg的氢氧化物、氧化物、氯化物、金属有机物、硝酸盐、硫酸盐、碳酸盐、磷酸盐、草酸盐的一种或者多种的混合物。 The method for preparing a high-capacity nickel-cobalt-based lithium ion cathode material according to claim 1, wherein the coating material N is a P-based substance, and comprises a phosphate, a hypophosphite, a halide of P, and a P. Oxides and phospholipids, F-based substances, including metal fluorides, carbides of F, organic compounds and composite oxides with other metals, B-based substances, including borate, B oxide, Al, Ti, Zr, Mo, Y, Tb, V, Mg-based substances, including hydroxides, oxides, chlorides, metal organics, nitrates, sulfates, carbonates of Al, Ti, Zr, Mo, Y, Tb, V, Mg a mixture of one or more of a salt, a phosphate, or an oxalate.
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CN107516730A (en) * 2016-06-17 2017-12-26 珠海泰坦储能科技有限公司 A kind of preparation of the lithium sulfur battery anode material of phosphoric acid iron and the lithium-sulfur cell containing this positive electrode
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CN112038588A (en) * 2019-06-03 2020-12-04 贝特瑞（江苏）新材料科技有限公司 Ternary material, preparation method and application thereof
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CN112279310A (en) * 2020-10-26 2021-01-29 合肥国轩高科动力能源有限公司 Preparation method of ternary cathode material precursor
CN114570370A (en) * 2022-02-15 2022-06-03 清华大学 Nickel-based multi-component alloy catalyst and preparation method thereof
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CN115893512A (en) * 2022-11-23 2023-04-04 荆门市格林美新材料有限公司 Doped cobalt carbonate and preparation method and application thereof

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104733724A (en) * 2015-03-31 2015-06-24 南通瑞翔新材料有限公司 Positive electrode material for high-nickel lithium ionic secondary battery and preparation method thereof
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CN106058230A (en) * 2016-08-11 2016-10-26 合肥国轩高科动力能源有限公司 Preparation method of aluminum-doped and surface-modified co-modified high-nickel positive electrode material
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KR102051714B1 (en) * 2017-12-27 2019-12-04 (주)이엠티 A Method for Preparing Precursor of Cathod Active Material for Lithium Ion Secondary Battery Using Polyamine as A Complex Agent
WO2019132080A1 (en) * 2017-12-29 2019-07-04 주식회사 엘 앤 에프 Cathode active material for lithium secondary battery, and lithium secondary battery comprising same
CN108807969A (en) * 2018-04-24 2018-11-13 合肥国轩高科动力能源有限公司 A method of reducing layered cathode material of lithium ion battery surface residual alkali
CN111029536A (en) * 2018-10-09 2020-04-17 北大先行科技产业有限公司 Lithium ion battery anode material and preparation method thereof
KR102557304B1 (en) * 2018-11-16 2023-07-18 충북대학교 산학협력단 Multicomponent Precursor For Lithium Ion Battery Using An Organic Acid, Cathode Active Material Using The Same, And Method For Producing The Same.
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CN110137487A (en) * 2019-05-24 2019-08-16 隆能科技(南通)有限公司 A kind of lithium ion secondary battery anode material and preparation method thereof of W compound cladding
CN112018341A (en) * 2019-05-28 2020-12-01 天津国安盟固利新材料科技股份有限公司 High-capacity high-nickel cathode material and preparation method thereof
CN111755692B (en) * 2020-05-28 2021-07-09 北京理工大学 High-nickel anode material with reconstructed primary particle surface layer and preparation method thereof
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CN114744188B (en) * 2022-06-13 2022-09-09 河南科隆新能源股份有限公司 Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800861A (en) * 2011-05-27 2012-11-28 日立金属株式会社 Positive electrode active material for lithium ion battery, method for producing the same, positive electrode for lithium ion battery, and lithium ion battery
CN103474647A (en) * 2013-09-12 2013-12-25 南通瑞翔新材料有限公司 Preparation method of modified spinel lithium manganese oxide cathode material
CN103823280A (en) * 2012-11-16 2014-05-28 日立金属株式会社 Signal transmission device
CN103943822A (en) * 2014-05-13 2014-07-23 南通瑞翔新材料有限公司 Nickel-based positive active material of lithium ion secondary battery and preparation method thereof
CN104752714A (en) * 2015-03-31 2015-07-01 南通瑞翔新材料有限公司 High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103872328B (en) * 2014-03-12 2017-01-25 南通瑞翔新材料有限公司 Positive electrode active material for lithium ion secondary battery and preparation method for positive electrode active material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800861A (en) * 2011-05-27 2012-11-28 日立金属株式会社 Positive electrode active material for lithium ion battery, method for producing the same, positive electrode for lithium ion battery, and lithium ion battery
CN103823280A (en) * 2012-11-16 2014-05-28 日立金属株式会社 Signal transmission device
CN103474647A (en) * 2013-09-12 2013-12-25 南通瑞翔新材料有限公司 Preparation method of modified spinel lithium manganese oxide cathode material
CN103943822A (en) * 2014-05-13 2014-07-23 南通瑞翔新材料有限公司 Nickel-based positive active material of lithium ion secondary battery and preparation method thereof
CN104752714A (en) * 2015-03-31 2015-07-01 南通瑞翔新材料有限公司 High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method thereof

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CN107768666B (en) * 2017-11-14 2023-12-22 北京圣比和科技有限公司 Method for preparing lithium nickel manganese cobalt oxide by using thermal cyclone type mechanochemical cladding method
CN107768666A (en) * 2017-11-14 2018-03-06 北京圣比和科技有限公司 The rotating mechanical force and chemical cladding process of hot gas prepares the device and method of nickel manganese cobalt acid lithium
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CN112158893A (en) * 2020-08-27 2021-01-01 荆门市格林美新材料有限公司 Preparation method of lithium-rich manganese-based positive electrode material precursor
CN112158893B (en) * 2020-08-27 2023-09-26 荆门市格林美新材料有限公司 Preparation method of lithium-rich manganese-based positive electrode material precursor
CN112279310A (en) * 2020-10-26 2021-01-29 合肥国轩高科动力能源有限公司 Preparation method of ternary cathode material precursor
CN114570370A (en) * 2022-02-15 2022-06-03 清华大学 Nickel-based multi-component alloy catalyst and preparation method thereof
CN114570370B (en) * 2022-02-15 2023-09-26 清华大学 Nickel-based multi-component alloy catalyst and preparation method thereof
CN114824193A (en) * 2022-03-17 2022-07-29 合肥国轩高科动力能源有限公司 alpha-Fe 2 O 3 Lithium ion ternary cathode material coated with initiation conductive polymer and preparation method thereof
CN114824193B (en) * 2022-03-17 2023-12-29 合肥国轩高科动力能源有限公司 alpha-Fe 2 O 3 Lithium ion ternary positive electrode material coated by initiating conductive polymer and preparation method thereof
CN115092978B (en) * 2022-07-20 2024-01-19 上海兰钧新能源科技有限公司 Coated nickel cobalt boron precursor, nickel cobalt boron positive electrode material and preparation method thereof
CN115092978A (en) * 2022-07-20 2022-09-23 上海兰钧新能源科技有限公司 Coated nickel-cobalt-boron precursor, nickel-cobalt-boron positive electrode material and preparation method thereof
CN115353156A (en) * 2022-08-29 2022-11-18 陕西红马科技有限公司 Short-process nickel-based cathode material preparation process based on waste lithium battery recovery
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