WO2024031911A1 - Gradient ternary positive electrode material, preparation method therefor and use thereof - Google Patents

Gradient ternary positive electrode material, preparation method therefor and use thereof Download PDF

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WO2024031911A1
WO2024031911A1 PCT/CN2022/140379 CN2022140379W WO2024031911A1 WO 2024031911 A1 WO2024031911 A1 WO 2024031911A1 CN 2022140379 W CN2022140379 W CN 2022140379W WO 2024031911 A1 WO2024031911 A1 WO 2024031911A1
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optionally
solution
cobalt
source
preparation
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PCT/CN2022/140379
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French (fr)
Chinese (zh)
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李聪
张坤
华文超
许开华
薛晓斐
范亮姣
李雪倩
贾冬鸣
贡正杰
杨幸
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荆门市格林美新材料有限公司
格林美股份有限公司
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Publication of WO2024031911A1 publication Critical patent/WO2024031911A1/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
    • 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
    • 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

  • This application belongs to the field of lithium-ion batteries and relates to a gradient ternary cathode material and its preparation method and application.
  • High-nickel and low-cobalt ternary materials have high energy density and low cobalt content, which can reduce raw material costs, making them popular materials for commercial cathodes.
  • problems such as thermal stability and structural stability become particularly prominent.
  • the main function of the coating is to serve as a protective layer to isolate the direct contact between the electrolyte and the active electrode material, which greatly reduces a series of side reactions, such as reducing the precipitation of transition metals, forming a thinner SEI film, reducing The precipitation of oxygen atoms, etc., thereby improving electrochemical stability.
  • a series of side reactions such as reducing the precipitation of transition metals, forming a thinner SEI film, reducing The precipitation of oxygen atoms, etc., thereby improving electrochemical stability.
  • CN110311136A discloses a graphene-coated ternary cathode material for lithium-ion batteries.
  • the graphene is evenly dispersed between the particles of the ternary cathode material.
  • the graphene on the surface of the ternary cathode "fixes" the O atoms on the surface of the material. function to stabilize the material structure.
  • CN112002896A discloses a method for preparing a lithium-ion battery electrode containing a graphene-coated single crystal cathode material. The steps include mixing the graphene-coated single crystal cathode material with a conductive agent and a binder and then adding N-methyl. It is prepared by adjusting the solid content with pyrrolidone and then coating it on the current collector.
  • the thickness controllability of the coated graphene described in the above solution is small, the cobalt content is large, the cost is high, and the capacity is low, which greatly limits the application of ternary cathode materials.
  • the purpose of this application is to provide a gradient ternary cathode material and its preparation method and application.
  • the cobalt metal concentration in the gradient ternary cathode material gradually increases from the inside out to improve the rate performance and structural stability of the material.
  • Single layer Graphene coating maximizes the rate performance and cycle performance of the material.
  • this application provides a method for preparing a gradient ternary cathode material.
  • the preparation method includes the following steps:
  • This application forms a ternary material with gradient distribution of cobalt element concentration through late-stage sintering and diffusion, effectively solving the problem of poor consistency in the production of gradient materials. Moreover, the gradient distribution of cobalt element is conducive to improving the rate performance of the material.
  • the atomic layer deposition method is used to coat the surface of the material. A layer of graphene, the atomic layer deposition method can achieve single-layer graphene coating, greatly improving the conductivity, rate performance and cycle performance of the material.
  • the nickel source in step (1) includes any one or a combination of at least two of nickel sulfate, nickel chloride or nickel nitrate.
  • the manganese source includes any one or a combination of at least two of manganese sulfate, manganese chloride or manganese nitrate.
  • the cobalt source includes any one or a combination of at least two of cobalt sulfate, cobalt chloride or cobalt nitrate.
  • the molar ratio of nickel ions and manganese ions in the solution A is (90-98): (2-10), for example: 90:10, 92:8, 95:5, 96:4 or 98: 2 etc.
  • the mass concentration of the liquid caustic soda in step (1) is 30-35%, for example: 30%, 31%, 32%, 33%, 34% or 35%, etc.
  • the mass concentration of the ammonia water is 12% to 18%, such as: 12%, 14%, 16% or 18%, etc.
  • the pH of the bottom liquid in step (1) is 11 to 13, for example: 11, 11.5, 12, 12.5 or 13, etc., preferably 11.6 to 11.8.
  • the ammonia concentration of the bottom liquid is 5-20g/L, for example: 5g/L, 8g/L, 10g/L, 15g/L or 20g/L, etc., preferably 10-12g/L.
  • the reaction temperature is 40-80°C, such as: 40°C, 50°C, 60°C, 70°C or 80°C, etc.
  • reaction is performed while stirring.
  • the stirring speed is 100 to 500 rpm, for example: 100 rpm, 200 rpm, 300 rpm, 400 rpm or 500 rpm, etc.
  • the flow rate of the solution A is 200-400L/h, for example: 200L/h, 250L/h, 300L/h, 350L/h or 400L/h, etc.
  • the flow rate of the liquid alkali is 80-120L/h, for example: 80L/h, 90L/h, 100L/h, 110L/h or 120L/h, etc.
  • the flow rate of the ammonia water is 50-80L/h, for example: 50L/h, 55L/h, 60L/h, 70L/h or 80L/h, etc.
  • the temperature of the sintering treatment in step (2) is 600-1000°C, for example: 600°C, 700°C, 800°C, 900°C or 1000°C, etc.
  • the sintering treatment time is 10 to 20 hours, such as: 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, etc.
  • the liquid organic matter in step (2) includes any one or a combination of at least two of nitrobenzene, bromobenzene, carbon tetrachloride, chloroform, brominated hydrocarbons, ethylene glycol or glycerol.
  • the present application provides a gradient ternary cathode material, which is prepared by the method described in the first aspect.
  • the gradient ternary cathode material includes a core and a single-layer graphene coating layer covering the surface of the core.
  • the gradient of cobalt element in the core increases from the inside to the outside.
  • the cobalt metal concentration in the gradient ternary cathode material described in this application gradually increases from the inside out, improving the rate performance and structural stability of the material.
  • the single-layer graphene coating maximizes the rate performance and cycle performance of the material.
  • the present application provides a positive electrode sheet, which contains the gradient ternary positive electrode material as described in the second aspect.
  • the present application provides a lithium-ion battery, which includes a positive electrode plate as described in the first aspect.
  • This application forms a ternary material with a gradient distribution of cobalt element concentration through late-stage sintering and diffusion, which effectively solves the problem of poor consistency in the production of gradient materials. Moreover, the gradient distribution of cobalt element is conducive to improving the rate performance of the material.
  • the atomic layer deposition method is used in the material. The surface is coated with a layer of graphene. The atomic layer deposition method can achieve single-layer graphene coating, which greatly improves the conductivity, rate performance and cycle performance of the material.
  • the structural stability of the material after coating with cobalt is improved.
  • the electronic conductivity of the material after graphene coating is significantly improved, but the ionic conductivity is not reduced (compared to coating inert substances such as Al, Zr and Ti) , and because there is no damage to the surface structure by water washing, the NiO rock salt phase is thinner in the surface area, reducing side reactions, which is more conducive to the deintercalation of lithium ions, thereby improving cycle performance.
  • the charge specific capacity of the battery made of the ternary cathode material described in this application can reach more than 250mAh/g, the discharge specific capacity can reach more than 229.4mAh/g, the first efficiency can reach more than 91.6%, and the 1C rate performance can reach 218mAh. /g or above, the 5C rate performance can reach above 180mAh/g, and the capacity retention rate can reach above 97%.
  • This embodiment provides a gradient ternary cathode material.
  • the preparation method of the gradient ternary cathode material is as follows:
  • Complexing agent add 3000L pure water to the reaction kettle and pass in N 2 as a protective gas, add liquid caustic soda to adjust the pH to 12.0, add ammonia water to adjust the ammonia concentration to 10g/L, control the temperature at 80°C, and control the stirring speed at 450rpm, add solution A, liquid alkali and ammonia water to the reaction kettle at the same time at the speed of 300L/h, 100L/h, 60L/h, keep the pH at 11.6-11.8, the ammonia concentration at 10-12g/L, the temperature is 80°C, and the rotation speed 450 rpm, after D50 reaches 6 ⁇ m, replace solution A with solution B, adjust the reaction pH to 11.0-11.2, continue the reaction for 2 hours and then stop feeding, wash, dry, screen, remove iron, and package the slurry obtained from the reaction , obtaining a cobalt-coated NM95/5 nickel-manganese binary precursor;
  • This embodiment provides a gradient ternary cathode material.
  • the preparation method of the gradient ternary cathode material is as follows:
  • Complexing agent add 3000L pure water to the reaction kettle and pass in N 2 as a protective gas, add liquid caustic soda to adjust the pH to 12.2, add ammonia water to adjust the ammonia concentration to 10g/L, control the temperature at 80°C, and control the stirring speed at 480rpm, add solution A, liquid alkali and ammonia water to the reaction kettle at the same time at the speed of 300L/h, 100L/h, 60L/h, keep the pH at 12.0-12.2, the ammonia concentration at 10-12g/L, the temperature is 80°C, and the rotation speed 450 rpm, after D50 reaches 6 ⁇ m, replace solution A with solution B, adjust the reaction pH to 11.0-11.2, continue the reaction for 2 hours and then stop feeding, wash, dry, screen, remove iron, and package the slurry obtained from the reaction , obtaining a cobalt-coated NM95/5 nickel-manganese binary precursor;
  • reaction pH in step (1) is 11.2-11.4, and other conditions and parameters are exactly the same as in Example 1.
  • reaction pH in step (1) is 11.0-11.2, and other conditions and parameters are exactly the same as in Example 1.
  • ammonia concentration in step (1) is 14-16g/L, and other conditions and parameters are exactly the same as in Example 1.
  • ammonia concentration in step (1) is 6-8g/L, and other conditions and parameters are exactly the same as in Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that solution B is added when D50 reaches 4 ⁇ m. Other conditions and parameters are exactly the same as Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that solution B is added when D50 reaches 10 ⁇ m, and other conditions and parameters are exactly the same as Example 1.
  • Example 1 The only difference between this comparative example and Example 1 is that conventional solid-phase mixed sintering coating is used to coat graphene on the core surface. Other conditions and parameters are exactly the same as Example 1.
  • the prepared cathode material was mixed evenly with the conductive agent acetylene carbon black and the binder PVDF according to the mass ratio of 92:4:4, and an appropriate amount of 1-methyl-2-pyrrolidone was added and ball milled for 1 hour to form a slurry that was evenly coated on the aluminum sheet. , dried and pressed into sheets to make positive electrode sheets.
  • a 2032 button battery is assembled with metal lithium sheets as the negative electrode, and the blue battery test system is used for electrical performance testing.
  • the charge and discharge voltage is 2.5-4.25V.
  • the first cycle is tested according to 0.2/0.2C charge and discharge, and then cycled at 0.5C/1C for 50 lock up.
  • the charge specific capacity of the battery made of the ternary cathode material described in the present application can reach more than 250mAh/g, and the discharge specific capacity can reach more than 229.4mAh/g.
  • the efficiency can reach more than 91.6%
  • the 1C rate performance can reach more than 218mAh/g
  • the 5C rate performance can reach more than 180mAh/g
  • the capacity retention rate can reach more than 97%
  • the precursor reaction pH is high
  • the discharge specific capacity is high
  • the rate performance is good , excellent cycle performance.
  • Example 1 it can be seen from the comparison between Example 1 and Example 3-4 that during the preparation process of the gradient ternary cathode material described in this application, the pH of the precursor reaction will affect the performance of the cathode material.
  • the reaction pH is controlled at 11.6-11.8. , the cathode material obtained has better performance. If the pH is too high, a large amount of micro-powder will be generated, and the cycle performance will become poor; if the pH is too low, the primary particles will be too coarse, and the pores will be reduced, affecting the deintercalation of lithium ions.
  • Example 1 It can be seen from the comparison between Example 1 and Examples 5-6 that the concentration of ammonia in the precursor reaction process during the preparation process of the gradient ternary cathode material described in this application will affect the performance of the prepared cathode material.
  • the ammonia concentration is controlled at 10- 12g/L, the prepared cathode material has better performance. If the ammonia concentration is too high, the metal precipitation will be incomplete; if the ammonia concentration is too low, the electrochemical performance of the finished product will be affected.
  • Example 1 Comparative Examples 1-2 that during the preparation process of the gradient ternary cathode material described in this application, the timing of adding solution B will affect the performance of the cathode material.
  • the addition time of solution B will affect the performance of the cathode material.
  • Solution B produces a positive electrode material with better performance. If the addition time is too early, the cobalt coating layer will be too thick and it will be difficult to fully diffuse during later sintering. If the addition time is too late, the cobalt coating layer will be too thin and the cobalt content will be insufficient. It is difficult for the above to bring out the best performance of the material.
  • Example 1 uses atomic layer deposition to coat a layer of graphene on the surface of the material.
  • the atomic layer deposition method can achieve single-layer graphene coating and greatly improve the conductivity of the material. , rate performance and cycle performance.

Abstract

Provided in the present application are a gradient ternary positive electrode material, a preparation method therefor and the use thereof. The preparation method comprises the following steps: (1) mixing a nickel source and a manganese source with a solvent to obtain a solution A, mixing a cobalt source and a solvent to obtain a solution B, adding the solution A, liquid caustic soda and ammonia water into a base solution at the same time for a reaction, and after the particle D50 reaches 5-8 μm, changing solution A to solution B and continuing the reaction to obtain a cobalt-coated nickel-manganese binary precursor; and (2) mixing the cobalt-coated nickel-manganese binary precursor with a lithium source, then carrying out sintering treatment to obtain an inner-core material, and by means of taking a liquid organic matter as a carbon source, coating the surface of the inner-core material with graphene by using an atomic layer deposition method, so as to obtain the gradient ternary positive electrode material. The concentration of cobalt metal in the gradient ternary positive electrode material gradually increases from inside to outside, so that the rate capability and structural stability of the material are improved; the single-layer graphene coating improves the rate capability and cycle performance of the material to the maximum extent.

Description

一种梯度三元正极材料及其制备方法和应用A gradient ternary cathode material and its preparation method and application 技术领域Technical field
本申请属于锂离子电池领域，涉及一种梯度三元正极材料及其制备方法和应用。This application belongs to the field of lithium-ion batteries and relates to a gradient ternary cathode material and its preparation method and application.
背景技术Background technique
随着新能源汽车的发展，锂离子动力电池作为最热门的电动车动力电池而备受关注。高镍低钴三元材料拥有较高的能量密度，同时钴含量低可以降低原料成本，从而成为商业正极的热门材料。但是随着镍含量的提高，其热稳定性、结构稳定性等问题显得尤为突出。With the development of new energy vehicles, lithium-ion power batteries have attracted much attention as the most popular power batteries for electric vehicles. High-nickel and low-cobalt ternary materials have high energy density and low cobalt content, which can reduce raw material costs, making them popular materials for commercial cathodes. However, as the nickel content increases, problems such as thermal stability and structural stability become particularly prominent.
包覆的主要作用是作为一个保护层隔绝电解液和活性电极材料的直接接触，很大程度上地降低了一系列的副反应，比如，减少过渡金属的析出、形成更薄的SEI膜、降低氧原子的析出等，从而提高电化学稳定性。石墨烯由于自身的超高导电性，大比表面积，强机械性能等等优点，在众多领域，如锂电、钠电、超级电容器等得到了广泛应用。作为包覆层材料，石墨烯能够很好地改善电子导电性能，弥补钴含量低带来的电池阻抗高、循环失效快等负面影响。The main function of the coating is to serve as a protective layer to isolate the direct contact between the electrolyte and the active electrode material, which greatly reduces a series of side reactions, such as reducing the precipitation of transition metals, forming a thinner SEI film, reducing The precipitation of oxygen atoms, etc., thereby improving electrochemical stability. Due to its ultra-high conductivity, large specific surface area, strong mechanical properties and other advantages, graphene has been widely used in many fields, such as lithium batteries, sodium batteries, supercapacitors, etc. As a coating material, graphene can well improve electronic conductivity and make up for the negative effects of high battery impedance and rapid cycle failure caused by low cobalt content.
CN110311136A公开了一种石墨烯包覆锂离子电池三元正极材料，其通过石墨烯均匀分散于三元正极材料颗粒之间，三元正极表面的石墨烯对材料表面的O原子起到“固定”作用，从而稳定材料结构。CN110311136A discloses a graphene-coated ternary cathode material for lithium-ion batteries. The graphene is evenly dispersed between the particles of the ternary cathode material. The graphene on the surface of the ternary cathode "fixes" the O atoms on the surface of the material. function to stabilize the material structure.
CN112002896A公开了一种含石墨烯包覆单晶正极材料的锂离子电池电极的制备方法，步骤包括将含石墨烯包覆单晶正极材料与导电剂和粘结剂混合后再加入N-甲基吡咯烷酮调节固含量后涂布在集流体上制备得到。CN112002896A discloses a method for preparing a lithium-ion battery electrode containing a graphene-coated single crystal cathode material. The steps include mixing the graphene-coated single crystal cathode material with a conductive agent and a binder and then adding N-methyl. It is prepared by adjusting the solid content with pyrrolidone and then coating it on the current collector.
上述方案所述包覆石墨烯的厚度可控性小且钴含量较大，成本较高，容量 较低，大大限制了三元正极材料的应用。The thickness controllability of the coated graphene described in the above solution is small, the cobalt content is large, the cost is high, and the capacity is low, which greatly limits the application of ternary cathode materials.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请的目的在于提供一种梯度三元正极材料及其制备方法和应用，所述梯度三元正极材料中钴金属浓度由内而外逐渐增加，提高材料的倍率性能和结构稳定性，单层石墨烯包覆，最大程度提高材料的倍率性能和循环性能。The purpose of this application is to provide a gradient ternary cathode material and its preparation method and application. The cobalt metal concentration in the gradient ternary cathode material gradually increases from the inside out to improve the rate performance and structural stability of the material. Single layer Graphene coating maximizes the rate performance and cycle performance of the material.
为达到此申请目的，本申请采用以下技术方案：In order to achieve the purpose of this application, this application adopts the following technical solutions:
第一方面，本申请提供了一种梯度三元正极材料的制备方法，所述制备方法包括以下步骤：In a first aspect, this application provides a method for preparing a gradient ternary cathode material. The preparation method includes the following steps:
(1)将镍源和锰源与溶剂混合得到溶液A，将钴源和溶剂混合得到溶液B，将溶液A、液碱和氨水同时加入底液进行反应，颗粒D50达到5～8μm后将溶液A换成溶液B继续反应得到钴包覆镍锰二元前驱体；(1) Mix the nickel source and manganese source with the solvent to obtain solution A. Mix the cobalt source and the solvent to obtain solution B. Add solution A, liquid alkali and ammonia water to the bottom liquid at the same time for reaction. After the particle D50 reaches 5~8 μm, the solution A is replaced with solution B and the reaction continues to obtain a cobalt-coated nickel-manganese binary precursor;
(2)将钴包覆镍锰二元前驱体和锂源混合后进行烧结处理，得到内核材料，以液态有机物为碳源，采用原子层沉积法在内核材料表面包覆石墨烯，得到所述梯度三元正极材料。(2) Mix the cobalt-coated nickel-manganese binary precursor and the lithium source and then perform sintering treatment to obtain the core material. Using liquid organic matter as the carbon source, use atomic layer deposition method to coat graphene on the surface of the core material to obtain the above Gradient ternary cathode material.
本申请通过后期烧结扩散形成钴元素浓度梯度分布的三元材料，有效解决梯度材料生产一致性差的难题，并且钴元素梯度分布有利于提高材料的倍率性能，采用原子层沉积法在材料表面包覆一层石墨烯，所述原子层沉积法可以实现单层石墨烯包覆，大幅提高材料的导电性、倍率性能和循环性能。This application forms a ternary material with gradient distribution of cobalt element concentration through late-stage sintering and diffusion, effectively solving the problem of poor consistency in the production of gradient materials. Moreover, the gradient distribution of cobalt element is conducive to improving the rate performance of the material. The atomic layer deposition method is used to coat the surface of the material. A layer of graphene, the atomic layer deposition method can achieve single-layer graphene coating, greatly improving the conductivity, rate performance and cycle performance of the material.
本申请所述梯度三元正极材料的制备方法中，在烧结处理结束后立即进行石墨烯包覆，无需水洗及二次烧结，降低加工成本。In the preparation method of the gradient ternary cathode material described in this application, graphene coating is performed immediately after the sintering process is completed, eliminating the need for water washing and secondary sintering, thereby reducing processing costs.
可选地，步骤(1)所述镍源包括硫酸镍、氯化镍或硝酸镍中的任意一种或至少两种的组合。Optionally, the nickel source in step (1) includes any one or a combination of at least two of nickel sulfate, nickel chloride or nickel nitrate.
可选地，所述锰源包括硫酸锰、氯化锰或硝酸锰中的任意一种或至少两种的组合。Optionally, the manganese source includes any one or a combination of at least two of manganese sulfate, manganese chloride or manganese nitrate.
可选地，所述钴源包括硫酸钴、氯化钴或硝酸钴中的任意一种或至少两种的组合。Optionally, the cobalt source includes any one or a combination of at least two of cobalt sulfate, cobalt chloride or cobalt nitrate.
可选地，所述溶液A中镍离子和锰离子的摩尔比为(90～98):(2～10)，例如：90:10、92:8、95:5、96:4或98:2等。Alternatively, the molar ratio of nickel ions and manganese ions in the solution A is (90-98): (2-10), for example: 90:10, 92:8, 95:5, 96:4 or 98: 2 etc.
可选地，步骤(1)所述液碱的质量浓度为30～35％，例如：30％、31％、32％、33％、34％或35％等。Optionally, the mass concentration of the liquid caustic soda in step (1) is 30-35%, for example: 30%, 31%, 32%, 33%, 34% or 35%, etc.
可选地，所述氨水的质量浓度为12～18％，例如：12％、14％、16％或18％等。Optionally, the mass concentration of the ammonia water is 12% to 18%, such as: 12%, 14%, 16% or 18%, etc.
可选地，步骤(1)所述底液的pH为11～13，例如：11、11.5、12、12.5或13等，优选为11.6～11.8。Optionally, the pH of the bottom liquid in step (1) is 11 to 13, for example: 11, 11.5, 12, 12.5 or 13, etc., preferably 11.6 to 11.8.
可选地，所述底液的氨浓度为5～20g/L，例如：5g/L、8g/L、10g/L、15g/L或20g/L等，优选为10～12g/L。Optionally, the ammonia concentration of the bottom liquid is 5-20g/L, for example: 5g/L, 8g/L, 10g/L, 15g/L or 20g/L, etc., preferably 10-12g/L.
可选地，所述反应的温度为40～80℃，例如：40℃、50℃、60℃、70℃或80℃等。Optionally, the reaction temperature is 40-80°C, such as: 40°C, 50°C, 60°C, 70°C or 80°C, etc.
可选地，所述反应的同时进行搅拌。Optionally, the reaction is performed while stirring.
可选地，所述搅拌的速度为100～500rpm，例如：100rpm、200rpm、300rpm、400rpm或500rpm等。Optionally, the stirring speed is 100 to 500 rpm, for example: 100 rpm, 200 rpm, 300 rpm, 400 rpm or 500 rpm, etc.
可选地，所述溶液A的流速为200～400L/h，例如：200L/h、250L/h、300 L/h、350L/h或400L/h等。Optionally, the flow rate of the solution A is 200-400L/h, for example: 200L/h, 250L/h, 300L/h, 350L/h or 400L/h, etc.
可选地，所述液碱的流速为80～120L/h，例如：80L/h、90L/h、100L/h、110L/h或120L/h等。Optionally, the flow rate of the liquid alkali is 80-120L/h, for example: 80L/h, 90L/h, 100L/h, 110L/h or 120L/h, etc.
可选地，所述氨水的流速为50～80L/h，例如：50L/h、55L/h、60L/h、70L/h或80L/h等。Optionally, the flow rate of the ammonia water is 50-80L/h, for example: 50L/h, 55L/h, 60L/h, 70L/h or 80L/h, etc.
可选地，步骤(2)所述烧结处理的温度为600～1000℃，例如：600℃、700℃、800℃、900℃或1000℃等。Optionally, the temperature of the sintering treatment in step (2) is 600-1000°C, for example: 600°C, 700°C, 800°C, 900°C or 1000°C, etc.
可选地，所述烧结处理的时间为10～20h，例如：10h、12h、15h、18h或20h等。Optionally, the sintering treatment time is 10 to 20 hours, such as: 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, etc.
可选地，步骤(2)所述液态有机物包括硝基苯、溴苯、四氯化碳、氯仿、溴代烃、乙二醇或丙三醇中的任意一种或至少两种的组合。Optionally, the liquid organic matter in step (2) includes any one or a combination of at least two of nitrobenzene, bromobenzene, carbon tetrachloride, chloroform, brominated hydrocarbons, ethylene glycol or glycerol.
第二方面，本申请提供了一种梯度三元正极材料，所述梯度三元正极材料通过如第一方面所述方法制得。In a second aspect, the present application provides a gradient ternary cathode material, which is prepared by the method described in the first aspect.
可选地，所述梯度三元正极材料包括内核和包覆在所述内核表面的单层石墨烯包覆层。Optionally, the gradient ternary cathode material includes a core and a single-layer graphene coating layer covering the surface of the core.
可选地，所述内核中钴元素由内向外梯度增加。Optionally, the gradient of cobalt element in the core increases from the inside to the outside.
本申请所述梯度三元正极材料中钴金属浓度由内而外逐渐增加，提高材料的倍率性能和结构稳定性，单层石墨烯包覆，最大程度提高材料的倍率性能和循环性能。The cobalt metal concentration in the gradient ternary cathode material described in this application gradually increases from the inside out, improving the rate performance and structural stability of the material. The single-layer graphene coating maximizes the rate performance and cycle performance of the material.
第三方面，本申请提供了一种正极极片，所述正极极片包含如第二方面所述的梯度三元正极材料。In a third aspect, the present application provides a positive electrode sheet, which contains the gradient ternary positive electrode material as described in the second aspect.
第四方面，本申请提供了一种锂离子电池，所述锂离子电池包含如第一方 面所述的正极极片In a fourth aspect, the present application provides a lithium-ion battery, which includes a positive electrode plate as described in the first aspect.
相对于现有技术，本申请具有以下有益效果：Compared with the existing technology, this application has the following beneficial effects:
(1)本申请通过后期烧结扩散形成钴元素浓度梯度分布的三元材料，有效解决梯度材料生产一致性差的难题，并且钴元素梯度分布有利于提高材料的倍率性能，采用原子层沉积法在材料表面包覆一层石墨烯，所述原子层沉积法可以实现单层石墨烯包覆，大幅提高材料的导电性、倍率性能和循环性能。(1) This application forms a ternary material with a gradient distribution of cobalt element concentration through late-stage sintering and diffusion, which effectively solves the problem of poor consistency in the production of gradient materials. Moreover, the gradient distribution of cobalt element is conducive to improving the rate performance of the material. The atomic layer deposition method is used in the material. The surface is coated with a layer of graphene. The atomic layer deposition method can achieve single-layer graphene coating, which greatly improves the conductivity, rate performance and cycle performance of the material.
(2)包钴后的材料结构稳定性得到提高，经过石墨烯包覆后的材料，其电子导电性明显提高，而离子导电性没有降低(相比包覆惰性物质如Al、Zr和Ti)，同时由于没有水洗对表面结构的破坏，NiO类岩盐相在表面区域更薄，副反应发生减少，更有利于锂离子的脱嵌，从而改善循环性能。(2) The structural stability of the material after coating with cobalt is improved. The electronic conductivity of the material after graphene coating is significantly improved, but the ionic conductivity is not reduced (compared to coating inert substances such as Al, Zr and Ti) , and because there is no damage to the surface structure by water washing, the NiO rock salt phase is thinner in the surface area, reducing side reactions, which is more conducive to the deintercalation of lithium ions, thereby improving cycle performance.
(3)本申请所述三元正极材料制得电池的充电比容量可达250mAh/g以上，放电比容量可达229.4mAh/g以上，首效可达91.6％以上，1C倍率性能可达218mAh/g以上，5C倍率性能可达180mAh/g以上，容量保持率可达97％以上。(3) The charge specific capacity of the battery made of the ternary cathode material described in this application can reach more than 250mAh/g, the discharge specific capacity can reach more than 229.4mAh/g, the first efficiency can reach more than 91.6%, and the 1C rate performance can reach 218mAh. /g or above, the 5C rate performance can reach above 180mAh/g, and the capacity retention rate can reach above 97%.
在阅读并理解了详细描述后，可以明白其他方面。Other aspects will become apparent after reading and understanding the detailed description.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。The technical solutions of the present application will be further described below through specific implementations. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.
实施例1Example 1
本实施例提供了一种梯度三元正极材料，所述梯度三元正极材料的制备方法如下：This embodiment provides a gradient ternary cathode material. The preparation method of the gradient ternary cathode material is as follows:
(1)将硫酸镍、硫酸锰金属摩尔比95:5配制成2mol/L的水溶液A，将硫酸钴配制成2mol/L的水溶液B，采用32％工业液碱作为沉淀剂，16％氨水作为 络合剂，在反应釜中加入3000L纯水并通入N 2作为保护气体，加入液碱将pH调制12.0，加入氨水将氨浓度调整至10g/L，温度控制在80℃，搅拌速度控制在450rpm，将溶液A，液碱以及氨水同时以300L/h，100L/h，60L/h的速度加入反应釜，保持pH在11.6-11.8，氨浓度在10-12g/L，温度80℃，转速450rpm，D50达到6μm后，将溶液A换成溶液B，调整反应pH至11.0-11.2，继续反应2h后停止进料，将反应得到的浆料进行洗涤，烘干，筛分，除铁，包装，得到钴包覆NM95/5镍锰二元前驱体； (1) Prepare nickel sulfate and manganese sulfate metal molar ratio 95:5 into 2 mol/L aqueous solution A, prepare cobalt sulfate into 2 mol/L aqueous solution B, use 32% industrial liquid alkali as the precipitant, and 16% ammonia water as the precipitant. Complexing agent, add 3000L pure water to the reaction kettle and pass in N 2 as a protective gas, add liquid caustic soda to adjust the pH to 12.0, add ammonia water to adjust the ammonia concentration to 10g/L, control the temperature at 80°C, and control the stirring speed at 450rpm, add solution A, liquid alkali and ammonia water to the reaction kettle at the same time at the speed of 300L/h, 100L/h, 60L/h, keep the pH at 11.6-11.8, the ammonia concentration at 10-12g/L, the temperature is 80°C, and the rotation speed 450 rpm, after D50 reaches 6 μm, replace solution A with solution B, adjust the reaction pH to 11.0-11.2, continue the reaction for 2 hours and then stop feeding, wash, dry, screen, remove iron, and package the slurry obtained from the reaction , obtaining a cobalt-coated NM95/5 nickel-manganese binary precursor;
(2)将钴包覆的NM95/5二元前躯体与单水氢氧化锂混合，在氧气气氛下680℃烧结12h，得到钴元素梯度分布的内核材料，以乙二醇为碳源，采用原子层沉积的方法在内核材料表面包覆一层石墨烯，得到石墨烯包覆的梯度NCM90/5/5三元材料。(2) Mix the cobalt-coated NM95/5 binary precursor with lithium hydroxide monohydrate, and sinter it at 680°C for 12 hours in an oxygen atmosphere to obtain a core material with gradient distribution of cobalt element. Using ethylene glycol as the carbon source, use The atomic layer deposition method is used to coat a layer of graphene on the surface of the core material to obtain a graphene-coated gradient NCM90/5/5 ternary material.
实施例2Example 2
本实施例提供了一种梯度三元正极材料，所述梯度三元正极材料的制备方法如下：This embodiment provides a gradient ternary cathode material. The preparation method of the gradient ternary cathode material is as follows:
(1)将硫酸镍、硫酸锰金属摩尔比96:4配制成2mol/L的水溶液A，将硫酸钴配制成2mol/L的水溶液B，采用32％工业液碱作为沉淀剂，17％氨水作为络合剂，在反应釜中加入3000L纯水并通入N 2作为保护气体，加入液碱将pH调制12.2，加入氨水将氨浓度调整至10g/L，温度控制在80℃，搅拌速度控制在480rpm，将溶液A，液碱以及氨水同时以300L/h，100L/h，60L/h的速度加入反应釜，保持pH在12.0-12.2，氨浓度在10-12g/L，温度80℃，转速450rpm，D50达到6μm后，将溶液A换成溶液B，调整反应pH至11.0-11.2，继续反应2h后停止进料，将反应得到的浆料进行洗涤，烘干，筛分，除铁，包装，得到钴包 覆NM95/5镍锰二元前驱体； (1) Prepare nickel sulfate and manganese sulfate metal molar ratio 96:4 into 2 mol/L aqueous solution A, prepare cobalt sulfate into 2 mol/L aqueous solution B, use 32% industrial liquid alkali as the precipitant, and 17% ammonia water as the precipitant. Complexing agent, add 3000L pure water to the reaction kettle and pass in N 2 as a protective gas, add liquid caustic soda to adjust the pH to 12.2, add ammonia water to adjust the ammonia concentration to 10g/L, control the temperature at 80°C, and control the stirring speed at 480rpm, add solution A, liquid alkali and ammonia water to the reaction kettle at the same time at the speed of 300L/h, 100L/h, 60L/h, keep the pH at 12.0-12.2, the ammonia concentration at 10-12g/L, the temperature is 80°C, and the rotation speed 450 rpm, after D50 reaches 6 μm, replace solution A with solution B, adjust the reaction pH to 11.0-11.2, continue the reaction for 2 hours and then stop feeding, wash, dry, screen, remove iron, and package the slurry obtained from the reaction , obtaining a cobalt-coated NM95/5 nickel-manganese binary precursor;
(2)将钴包覆的NM95/5二元前躯体与单水氢氧化锂混合，在氧气气氛下690℃烧结12h，得到钴元素梯度分布的内核材料，以乙二醇为碳源，采用原子层沉积的方法在内核材料表面包覆一层石墨烯，得到石墨烯包覆的梯度NCM96/4/5三元材料。(2) Mix the cobalt-coated NM95/5 binary precursor with lithium hydroxide monohydrate, and sinter it at 690°C for 12 hours in an oxygen atmosphere to obtain a core material with gradient distribution of cobalt element. Using ethylene glycol as the carbon source, use The atomic layer deposition method is used to coat a layer of graphene on the surface of the core material to obtain a graphene-coated gradient NCM96/4/5 ternary material.
实施例3Example 3
本实施例与实施例1区别仅在于，步骤(1)所述反应pH为11.2-11.4，其他条件与参数与实施例1完全相同。The only difference between this example and Example 1 is that the reaction pH in step (1) is 11.2-11.4, and other conditions and parameters are exactly the same as in Example 1.
实施例4Example 4
本实施例与实施例1区别仅在于，步骤(1)所述反应pH为11.0-11.2，其他条件与参数与实施例1完全相同。The only difference between this example and Example 1 is that the reaction pH in step (1) is 11.0-11.2, and other conditions and parameters are exactly the same as in Example 1.
实施例5Example 5
本实施例与实施例1区别仅在于，步骤(1)所述氨浓度为14-16g/L，其他条件与参数与实施例1完全相同。The only difference between this embodiment and Example 1 is that the ammonia concentration in step (1) is 14-16g/L, and other conditions and parameters are exactly the same as in Example 1.
实施例6Example 6
本实施例与实施例1区别仅在于，步骤(1)所述氨浓度为6-8g/L，其他条件与参数与实施例1完全相同。The only difference between this embodiment and Example 1 is that the ammonia concentration in step (1) is 6-8g/L, and other conditions and parameters are exactly the same as in Example 1.
对比例1Comparative example 1
本对比例与实施例1区别仅在于，D50达到4μm加入溶液B，其他条件与参数与实施例1完全相同。The only difference between this comparative example and Example 1 is that solution B is added when D50 reaches 4 μm. Other conditions and parameters are exactly the same as Example 1.
对比例2Comparative example 2
本对比例与实施例1区别仅在于，D50达到10μm加入溶液B，其他条件与参数与实施例1完全相同。The only difference between this comparative example and Example 1 is that solution B is added when D50 reaches 10 μm, and other conditions and parameters are exactly the same as Example 1.
对比例3Comparative example 3
本对比例与实施例1区别仅在于，采用常规固相混合烧结包覆，将石墨烯包覆在内核表面，其他条件与参数与实施例1完全相同。The only difference between this comparative example and Example 1 is that conventional solid-phase mixed sintering coating is used to coat graphene on the core surface. Other conditions and parameters are exactly the same as Example 1.
性能测试：Performance Testing:
制备的正极材料分别与导电剂乙炔炭黑，粘结剂PVDF按照质量比92：4：4比例混合均匀，加入适量的1-甲基-2吡咯烷酮球磨1小时配成浆料均匀涂在铝片上，烘干、压片制成正极片。以金属锂片为负极组装成2032扣式电池，采用蓝电测试***进行电性能测试，充放电电压2.5-4.25V，首圈按照0.2/0.2C充放电测试，再以0.5C/1C循环50圈。The prepared cathode material was mixed evenly with the conductive agent acetylene carbon black and the binder PVDF according to the mass ratio of 92:4:4, and an appropriate amount of 1-methyl-2-pyrrolidone was added and ball milled for 1 hour to form a slurry that was evenly coated on the aluminum sheet. , dried and pressed into sheets to make positive electrode sheets. A 2032 button battery is assembled with metal lithium sheets as the negative electrode, and the blue battery test system is used for electrical performance testing. The charge and discharge voltage is 2.5-4.25V. The first cycle is tested according to 0.2/0.2C charge and discharge, and then cycled at 0.5C/1C for 50 lock up.
测试结果如表1所示：The test results are shown in Table 1:
表1Table 1
Figure PCTCN2022140379-appb-000001
Figure PCTCN2022140379-appb-000001
Figure PCTCN2022140379-appb-000002
Figure PCTCN2022140379-appb-000002
由表1可以看出，由实施例1-2可得，本申请所述三元正极材料制得电池的充电比容量可达250mAh/g以上，放电比容量可达229.4mAh/g以上，首效可达91.6％以上，1C倍率性能可达218mAh/g以上，5C倍率性能可达180mAh/g以上，容量保持率可达97％以上，前驱体反应pH高，放电比容量高，倍率性能好，循环性能优异。It can be seen from Table 1 that according to Examples 1-2, the charge specific capacity of the battery made of the ternary cathode material described in the present application can reach more than 250mAh/g, and the discharge specific capacity can reach more than 229.4mAh/g. First of all, The efficiency can reach more than 91.6%, the 1C rate performance can reach more than 218mAh/g, the 5C rate performance can reach more than 180mAh/g, the capacity retention rate can reach more than 97%, the precursor reaction pH is high, the discharge specific capacity is high, and the rate performance is good , excellent cycle performance.
由实施例1和实施例3-4对比可得，本申请所述梯度三元正极材料的制备过程中，前驱体反应的pH会影响制得正极材料的性能，将反应pH控制在11.6-11.8，制得正极材料性能较好，若pH过高，会生成大量微粉，循环性能变差；若pH过低一次颗粒过粗，孔隙减少影响锂离子脱嵌。It can be seen from the comparison between Example 1 and Example 3-4 that during the preparation process of the gradient ternary cathode material described in this application, the pH of the precursor reaction will affect the performance of the cathode material. The reaction pH is controlled at 11.6-11.8. , the cathode material obtained has better performance. If the pH is too high, a large amount of micro-powder will be generated, and the cycle performance will become poor; if the pH is too low, the primary particles will be too coarse, and the pores will be reduced, affecting the deintercalation of lithium ions.
由实施例1和实施例5-6对比可得，本申请所述梯度三元正极材料的制备过程中前驱体反应过程氨的浓度会影响制得正极材料的性能，将氨浓度控制在 10-12g/L，制得正极材料性能较好，若氨浓度过高，金属沉淀不完全；若氨浓度过低，会影响成品的电化学性能。It can be seen from the comparison between Example 1 and Examples 5-6 that the concentration of ammonia in the precursor reaction process during the preparation process of the gradient ternary cathode material described in this application will affect the performance of the prepared cathode material. The ammonia concentration is controlled at 10- 12g/L, the prepared cathode material has better performance. If the ammonia concentration is too high, the metal precipitation will be incomplete; if the ammonia concentration is too low, the electrochemical performance of the finished product will be affected.
由实施例1和对比例1-2对比可得，本申请所述梯度三元正极材料的制备过程中，溶液B的加入时机会影响制得正极材料的性能，在颗粒D50达到5～8μm加入溶液B，制得正极材料性能较好，若加入时间过早，钴包覆层过厚，后期烧结难以扩散完全；若加入时间过晚，钴包覆层过薄，钴含量不足。以上均难以发挥材料的最佳性能。It can be seen from the comparison between Example 1 and Comparative Examples 1-2 that during the preparation process of the gradient ternary cathode material described in this application, the timing of adding solution B will affect the performance of the cathode material. When the particle D50 reaches 5 to 8 μm, the addition time of solution B will affect the performance of the cathode material. Solution B produces a positive electrode material with better performance. If the addition time is too early, the cobalt coating layer will be too thick and it will be difficult to fully diffuse during later sintering. If the addition time is too late, the cobalt coating layer will be too thin and the cobalt content will be insufficient. It is difficult for the above to bring out the best performance of the material.
由实施例1和对比例3对比可得，本申请采用原子层沉积法在材料表面包覆一层石墨烯，所述原子层沉积法可以实现单层石墨烯包覆，大幅提高材料的导电性、倍率性能和循环性能。It can be seen from the comparison between Example 1 and Comparative Example 3 that this application uses atomic layer deposition to coat a layer of graphene on the surface of the material. The atomic layer deposition method can achieve single-layer graphene coating and greatly improve the conductivity of the material. , rate performance and cycle performance.
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。The applicant declares that the above are only specific implementation modes of the present application, but the protection scope of the present application is not limited thereto. Persons skilled in the technical field should understand that any person skilled in the technical field will not disclose any information disclosed in this application. Within the technical scope, changes or substitutions that can be easily imagined fall within the protection scope and disclosure scope of this application.

Claims (11)

  1. 一种梯度三元正极材料的制备方法，其中，所述制备方法包括以下步骤：A method for preparing gradient ternary cathode materials, wherein the preparation method includes the following steps:
    (1)将镍源和锰源与溶剂混合得到溶液A，将钴源和溶剂混合得到溶液B，将溶液A、液碱和氨水同时加入底液进行反应，颗粒D50达到5～8μm后将溶液A换成溶液B继续反应得到钴包覆镍锰二元前驱体；(1) Mix the nickel source and manganese source with the solvent to obtain solution A. Mix the cobalt source and the solvent to obtain solution B. Add solution A, liquid alkali and ammonia water to the bottom liquid at the same time for reaction. After the particle D50 reaches 5~8 μm, the solution A is replaced with solution B and the reaction continues to obtain a cobalt-coated nickel-manganese binary precursor;
    (2)将钴包覆镍锰二元前驱体和锂源混合后进行烧结处理，得到内核材料，以液态有机物为碳源，采用原子层沉积法在内核材料表面包覆石墨烯，得到所述梯度三元正极材料。(2) Mix the cobalt-coated nickel-manganese binary precursor and the lithium source and then perform sintering treatment to obtain the core material. Using liquid organic matter as the carbon source, use atomic layer deposition method to coat graphene on the surface of the core material to obtain the above Gradient ternary cathode material.
  2. 如权利要求1所述的制备方法，其中，步骤(1)所述镍源包括硫酸镍、氯化镍或硝酸镍中的任意一种或至少两种的组合；The preparation method according to claim 1, wherein the nickel source in step (1) includes any one or a combination of at least two of nickel sulfate, nickel chloride or nickel nitrate;
    可选地，所述锰源包括硫酸锰、氯化锰或硝酸锰中的任意一种或至少两种的组合；Optionally, the manganese source includes any one or a combination of at least two of manganese sulfate, manganese chloride or manganese nitrate;
    可选地，所述钴源包括硫酸钴、氯化钴或硝酸钴中的任意一种或至少两种的组合；Optionally, the cobalt source includes any one or a combination of at least two of cobalt sulfate, cobalt chloride or cobalt nitrate;
    可选地，所述溶液A中镍离子和锰离子的摩尔比为(90～98):(2～10)；Optionally, the molar ratio of nickel ions and manganese ions in the solution A is (90~98): (2~10);
    可选地，所述溶液B的摩尔浓度为1.5～2.5mol/L。Optionally, the molar concentration of solution B is 1.5-2.5 mol/L.
  3. 如权利要求1或2所述的制备方法，其中，步骤(1)所述液碱的质量浓度为30～35％；The preparation method according to claim 1 or 2, wherein the mass concentration of the liquid caustic soda in step (1) is 30-35%;
    可选地，所述氨水的质量浓度为12～18％。Optionally, the mass concentration of the ammonia water is 12 to 18%.
  4. 如权利要求1-3任一项所述的制备方法，其中，步骤(1)所述底液的pH为11～13，优选为11.6～11.8；The preparation method according to any one of claims 1 to 3, wherein the pH of the bottom liquid in step (1) is 11 to 13, preferably 11.6 to 11.8;
    可选地，所述底液的氨浓度为5～20g/L；Optionally, the ammonia concentration of the bottom liquid is 5-20g/L;
    可选地，所述反应的温度为40～80℃；Optionally, the reaction temperature is 40 to 80°C;
    可选地，所述反应的同时进行搅拌；Optionally, the reaction is carried out while stirring;
    可选地，所述搅拌的速度为100～500rpm；Optionally, the stirring speed is 100 to 500 rpm;
    可选地，所述溶液A的流速为200～400L/h；Optionally, the flow rate of solution A is 200-400L/h;
    可选地，所述液碱的流速为80～120L/h；Optionally, the flow rate of the liquid alkali is 80-120L/h;
    可选地，所述氨水的流速为50～80L/h。Optionally, the flow rate of the ammonia water is 50-80L/h.
  5. 如权利要求4所述的制备方法，其中，所述底液的氨浓度为10～12g/LThe preparation method according to claim 4, wherein the ammonia concentration of the bottom liquid is 10-12g/L
  6. 如权利要求1-5任一项所述的制备方法，其中，步骤(2)所述烧结处理的温度为600～1000℃；The preparation method according to any one of claims 1 to 5, wherein the temperature of the sintering treatment in step (2) is 600-1000°C;
    可选地，所述烧结处理的时间为10～20h。Optionally, the sintering treatment time is 10 to 20 hours.
  7. 如权利要求1-6任一项所述的制备方法，其中，步骤(2)所述液态有机物包括硝基苯、溴苯、四氯化碳、氯仿、溴代烃、乙二醇或丙三醇中的任意一种或至少两种的组合。The preparation method according to any one of claims 1 to 6, wherein the liquid organic matter in step (2) includes nitrobenzene, bromobenzene, carbon tetrachloride, chloroform, brominated hydrocarbons, ethylene glycol or glycerol. Any one or a combination of at least two alcohols.
  8. 一种梯度三元正极材料，其通过如权利要求1-7任一项所述方法制得。A gradient ternary cathode material prepared by the method according to any one of claims 1-7.
  9. 如权利要求8所述的梯度三元正极材料，其中，所述梯度三元正极材料包括内核和包覆在所述内核表面的单层石墨烯包覆层；The gradient ternary cathode material according to claim 8, wherein the gradient ternary cathode material includes a core and a single-layer graphene coating layer covering the surface of the core;
    可选地，所述内核中钴元素由内向外梯度增加。Optionally, the gradient of cobalt element in the core increases from the inside to the outside.
  10. 一种正极极片，其包含如权利要求8或9所述的梯度三元正极材料。A cathode plate comprising the gradient ternary cathode material as claimed in claim 8 or 9.
  11. 一种锂离子电池，其包含如权利要求10所述的正极极片。A lithium-ion battery comprising the positive electrode sheet as claimed in claim 10.
PCT/CN2022/140379 2022-08-09 2022-12-20 Gradient ternary positive electrode material, preparation method therefor and use thereof WO2024031911A1 (en)

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