WO2024259622A1 - 一种三元正极材料及其制备方法 - Google Patents

一种三元正极材料及其制备方法 Download PDF

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WO2024259622A1
WO2024259622A1 PCT/CN2023/101627 CN2023101627W WO2024259622A1 WO 2024259622 A1 WO2024259622 A1 WO 2024259622A1 CN 2023101627 W CN2023101627 W CN 2023101627W WO 2024259622 A1 WO2024259622 A1 WO 2024259622A1
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positive electrode
electrode material
ternary
particle
ternary positive
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French (fr)
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余海军
李爱霞
谢英豪
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380009556.4A priority Critical patent/CN117015864A/zh
Priority to PCT/CN2023/101627 priority patent/WO2024259622A1/zh
Publication of WO2024259622A1 publication Critical patent/WO2024259622A1/zh
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present application belongs to the technical field of lithium-ion battery positive electrode materials, and in particular, relates to a ternary positive electrode material and a preparation method thereof.
  • Lithium-ion batteries are widely used in many fields such as 3C electronic products, power vehicles and chemical energy storage due to their high energy density and long cycle life. They are a hot research topic in the new energy field. With the rapid development of new energy vehicles, higher requirements are placed on the energy density of lithium-ion batteries.
  • the key to improving the energy density of power batteries lies in the development of high-capacity positive electrode materials.
  • Nickel-cobalt-manganese-oxide lithium ternary positive electrode materials have the advantages of high specific capacity, high energy density, low price and environmental friendliness, and have good application prospects in the field of power batteries. With the increase of nickel content, the specific capacity of ternary positive electrode materials gradually increases, but the cycle stability and safety become weaker. Therefore, how to improve the capacity of positive electrode materials without increasing the Ni content has become a hot topic of research.
  • tap density of their positive electrode materials An important indicator that affects the capacity of lithium-ion batteries is the tap density of their positive electrode materials.
  • the increase in tap density can be achieved by methods such as the selection of precursors, the adjustment of sintering temperature, and the grading of large and small particles.
  • Chinese patent CN104724763A uses precursors of different particle sizes to mix with lithium salts to synthesize large single crystal particles at a temperature above 900°C, and then dopes the large particle size material with particles smaller than it.
  • Chinese patent CN109516509A also mixes small-particle single crystal ternary oxides, large-particle single crystal ternary oxides and lithium salts in a preset ratio, then sinters, and cools to obtain a high-density single crystal ternary positive electrode material.
  • the conductivity of the positive electrode material is closely related to the particle size, there is a difference in conductivity between large and small particles, resulting in conductivity mismatch and rapid capacity decay in the early stage of the cycle.
  • the slurry is very likely to form a jelly-like state, resulting in uneven coating, which can easily cause capacity Residual alkali reacts easily with electrolyte at high temperature to generate gas, which causes battery bloating and poses serious safety hazards.
  • the purpose of the present application is to overcome the deficiencies of the above-mentioned prior art and to provide a ternary positive electrode material with low residual alkali content, high tap density, good conductivity and excellent cycle performance and a preparation method thereof.
  • the technical solution adopted in the present application is: a method for preparing a ternary positive electrode material, the preparation method comprising the following steps:
  • ternary composite cathode material Preparation of ternary composite cathode material: adding silicon source to the aqueous solution of small-particle ternary cathode material and reacting, separating solid and liquid after the reaction, collecting solid and drying, sintering and cooling to obtain ternary composite cathode material with silicon dioxide coated on the surface;
  • the ternary composite cathode material and the large-particle ternary cathode material are mixed and ball-milled, calcined at 500-900° C. for 1-10 hours, cooled, ground and sieved to obtain the ternary cathode material;
  • the median particle size D 50 of the small-particle ternary positive electrode material is less than 10 ⁇ m, and the median particle size D 50 of the large-particle ternary positive electrode material is greater than or equal to 10 ⁇ m;
  • the molar ratio of the small particle ternary positive electrode material to the silicon source is 1:(0.015-0.075).
  • a ternary positive electrode material provided in the present application, small-particle ternary positive electrode materials and large-particle ternary positive electrode materials with different median particle sizes D50 are used as raw materials for grading, and before calcination, the small-particle ternary positive electrode material is reacted with a silicon source so that the surface of the small-particle ternary positive electrode material is coated with silicon dioxide to form a fully coated core-shell structured ternary composite positive electrode material, thereby significantly improving the conductivity, cycle stability and tap density of the ternary positive electrode material, and reducing the residual alkali content on the surface of the ternary positive electrode material.
  • reacting a small-particle ternary cathode material with a silicon source at a specific molar ratio can obtain a ternary composite cathode material whose surface is coated with silicon dioxide at a specific mass ratio.
  • the obtained ternary composite cathode material can, on the one hand, improve the cycle stability of the small-particle ternary cathode material in the core layer and reduce the conductivity of the core layer; on the other hand, it can react with the residual alkali on the surface of the large-particle ternary cathode material at a subsequent specific calcination temperature and time to generate conductive lithium silicate, thereby increasing the conductivity of the large-particle ternary cathode material; thereby narrowing the conductivity difference between the small-particle ternary cathode material and the large-particle ternary cathode material with different median particle sizes D50 .
  • the small-particle ternary cathode material and the large-particle ternary cathode material with different median particle sizes D50 have a higher conductivity than the large-particle ternary cathode material.
  • the grading of the electrode material as a raw material can avoid the problem of low tap density caused by the gap between the ternary positive electrode materials with the same median particle size D 50. That is, the ternary positive electrode material obtained by adopting the technical solution of the present application improves the tap density while making the conductivity of the ternary positive electrode materials with different median particle sizes D 50 values more matched, thereby improving the problem of capacity attenuation during the cycle process and improving the cycle stability of the product.
  • the median particle size D 50 of the small-particle ternary positive electrode material is 0.5 ⁇ D 50 ⁇ 10 ⁇ m, and the median particle size D 50 of the large-particle ternary positive electrode material is 10 ⁇ D 50 ⁇ 30 ⁇ m.
  • the median particle size D 50 of the small-particle ternary positive electrode material is 2-7 ⁇ m, and the median particle size D 50 of the large-particle ternary positive electrode material is 10-20 ⁇ m.
  • the median particle size D 50 of the small-particle ternary positive electrode material is 4-5 ⁇ m, and the median particle size D 50 of the large-particle ternary positive electrode material is 14-16 ⁇ m.
  • the median particle size D50 of the small-particle ternary positive electrode material and the large-particle ternary positive electrode material is further selected to be 2-7 ⁇ m and 10-20 ⁇ m, respectively, especially when it is 4-5 ⁇ m and 14-16 ⁇ m, respectively. This can make the conductivity difference between the small-particle ternary positive electrode material and the large-particle ternary positive electrode material smaller, and the ternary composite positive electrode material can better enter the gaps of the large-particle ternary positive electrode material, further improving the tap density.
  • the inventors have found that the mass ratio of the ternary composite positive electrode material and the large-particle ternary positive electrode material in the ternary positive electrode material will have a significant impact on the performance of the product.
  • the amount of the ternary composite positive electrode material added is too little, there will not be enough ternary composite positive electrode material to contact and react with the residual alkali on the surface of the large-particle ternary positive electrode material, which will lead to the inability to effectively reduce the difference in conductivity between the small-particle ternary positive electrode material and the large-particle ternary positive electrode material, and the tap density cannot be effectively improved; when the amount of the ternary composite positive electrode material added is too much, because it is coated with silicon dioxide, it will cause the overall conductivity of the product to decrease.
  • the mass ratio of the ternary composite positive electrode material and the large-particle ternary positive electrode material is further selected to be (1-2): (2-8), especially 1: (2-5), and further 1: 3, the comprehensive performance of the obtained product is more excellent.
  • the molar ratio of the small particle ternary cathode material to the silicon source is 1:(0.025-0.047).
  • the inventors have found that when the molar ratio of the small-particle ternary positive electrode material to the silicon source is 1:(0.015-0.075), the mass ratio of silicon dioxide on the surface of the ternary composite positive electrode material formed after the reaction to the small-particle ternary positive electrode material can be between (0.02-0.1):1, especially when the molar ratio of the small-particle ternary positive electrode material to the silicon source is 1:(0.025-0.047), the mass ratio of silicon dioxide to the small-particle ternary positive electrode material can be between (0.038-0.061):1; the molar ratio or mass ratio is controlled within the above range because At the contact position between the ternary composite positive electrode material and the large-particle ternary positive electrode material, the silicon dioxide on the surface of the ternary composite positive electrode material can react with the residual alkali on the surface of the large-particle ternary positive electrode material.
  • the mass of silicon dioxide on the surface of the ternary composite positive electrode material is too small, the residual alkali on the surface of the large-particle ternary positive electrode material cannot be completely removed, resulting in the inability to effectively reduce the difference in conductivity between the small-particle ternary positive electrode material and the large-particle ternary positive electrode material; if the mass of silicon dioxide on the surface of the ternary composite positive electrode material is too much, its own conductivity will be greatly reduced, thereby affecting the rate performance of the final product.
  • the molar ratio of the small-particle ternary positive electrode material to the silicon source is further selected within the above range, the comprehensive performance of the obtained product is more excellent.
  • the calcination temperature is 700-800° C.
  • the calcination time is 2-6 hours.
  • the inventors have found that during the calcination process, the silicon dioxide coated on the surface of the ternary composite positive electrode material will react with the residual alkali on the surface of the large-particle ternary positive electrode material. Within the calcination temperature and time range given in this application, it can ensure to the greatest extent that the residual alkali on the surface is reacted as completely as possible, reduce the residual alkali amount of the final product, and improve the conductivity and cycle stability of the product.
  • the temperature of the aqueous solution of the small particle ternary cathode material is 40-80°C.
  • the reaction is: firstly stirred at 40-80° C. for 15-30 min, and then allowed to stand for 10-20 h.
  • the inventors have found that the above-mentioned preparation method can ensure that the silicon source is well coated on the surface of the ternary positive electrode material A.
  • the silicon source is a silicate compound.
  • the silicon source is at least one of ethyl orthosilicate and methyl silicate.
  • the mass concentration of the small-particle ternary cathode material is (5-15) g/100 mL.
  • the sintering temperature is 500-900° C.
  • the sintering time is 2-3 hours.
  • the ball milling speed is 800-1000 rpm, and the ball milling time is 30-120 min.
  • the structural formula of the small-particle ternary cathode material is LiNi x Co y Mn (1-xy) O 2 , wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.2;
  • the structural formula of the large-particle ternary cathode material is LiNi x Co y Mn (1-xy) O 2 , wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 0.2.
  • the inventors have found that the solution provided in this application is applicable to any ternary positive electrode material.
  • the cycle stability of small-particle ternary positive electrode materials can be increased, the residual alkali on the surface of large-particle ternary positive electrode materials can be reduced, and the conductivity difference between large and small particles can be reduced, thereby improving the cycle stability of the positive electrode material.
  • Further selecting the ternary positive electrode material as a substance with the above structural formula can more significantly improve the cycle stability of the product.
  • the present invention also provides a ternary positive electrode material, which is prepared by the preparation method of the present application.
  • a ternary positive electrode material provided by the present application, by using small-particle ternary positive electrode materials and large-particle ternary positive electrode materials with different median particle sizes D 50 as raw materials for grading, and reacting the small-particle ternary positive electrode material with a silicon source before calcination so that the surface of the small-particle ternary positive electrode material is coated with silicon dioxide to form a fully coated core-shell structured ternary composite positive electrode material, the conductivity, cycle stability and tap density of the ternary positive electrode material can be significantly improved, and the residual alkali content on the surface of the ternary positive electrode material can be reduced.
  • the lithium carbonate content in the product obtained by the technical solution of the present application is less than 0.27%
  • the lithium hydroxide content is less than 0.25%
  • the tap density is more than 2.72g/m 3
  • the 0.1C discharge capacity is more than 211.1mAh/g
  • the capacity retention rate after 100 cycles of 1C is more than 92.1%.
  • the preparation method of the ternary positive electrode material provided by the present application is simple to operate, the raw materials are easy to obtain, and it is suitable for actual production applications.
  • reagents, methods and equipment used in this application are conventional reagents, methods and equipment in the art.
  • the present invention provides a ternary positive electrode material.
  • the preparation method of the ternary positive electrode material comprises: follow these steps:
  • ternary composite cathode material small - particle ternary cathode material (median particle size D50 is 5 ⁇ m, structural formula is LiNi0.8Co0.1Mn0.1O2 , mass is 20 g, molar weight is 0.125 mol) is dissolved in 200 mL of deionized water to form an aqueous solution of small-particle ternary cathode material, the aqueous solution is heated in a 40 ° C water bath and stirred, 0.0466 equivalents of ethyl orthosilicate (1.3 mL, 0.00582 mol) is added dropwise during the stirring process, stirring is continued for 30 min after the addition is completed, and then the mixture is allowed to stand for 15 h.
  • ethyl orthosilicate 1.3 mL, 0.00582 mol
  • the solid and liquid are separated, the solid is collected and dried, and then sintered at 700°C for 2 h. Finally, the mixture is cooled to room temperature to obtain a ternary composite cathode material with silicon dioxide coated on the surface; wherein the mass ratio of silicon dioxide to small-particle ternary cathode material is 0.061:1;
  • the present invention provides a ternary cathode material, and the preparation method of the ternary cathode material comprises the following steps:
  • ternary composite cathode material small particle ternary cathode material (median particle size D50 is 4 ⁇ m, structural formula is LiNi0.8Co0.1Mn0.1O2 , mass is 20 g, molar weight is 0.125 mol) is dissolved in 200 mL of deionized water to form an aqueous solution of small particle ternary cathode material, the aqueous solution is heated in a water bath at 80 ° C and stirred, 0.0466 equivalent of ethyl orthosilicate (1.3 mL, 0.00582 mol) is added dropwise during stirring, stirring is continued for 15 min after the addition is completed, and then the mixture is allowed to stand for 10 h.
  • ethyl orthosilicate 1.3 mL, 0.00582 mol
  • the present application embodiment provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and the embodiment 1 is that the median particle size D 50 of the small particle ternary positive electrode material is 2 ⁇ m, and the large particle ternary positive electrode material The median particle size D50 of the material is 10 ⁇ m.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and embodiment 1 is that the median particle size D50 of the small-particle ternary positive electrode material is 7 ⁇ m, and the median particle size D50 of the large-particle ternary positive electrode material is 20 ⁇ m.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and embodiment 1 is that the median particle size D50 of the small-particle ternary positive electrode material is 9 ⁇ m, and the median particle size D50 of the large-particle ternary positive electrode material is 25 ⁇ m.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and embodiment 1 is that the median particle size D50 of the small-particle ternary positive electrode material is 0.5 ⁇ m, and the median particle size D50 of the large-particle ternary positive electrode material is 30 ⁇ m.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the embodiment of the present application provides a ternary positive electrode material.
  • An embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that 0.0256 times the equivalent of ethyl orthosilicate is added, and the mass ratio of silicon dioxide to small-particle ternary positive electrode material in the obtained ternary composite positive electrode material with a surface coated with silicon dioxide is 0.038:1.
  • An embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that 0.0192 times the equivalent of ethyl orthosilicate is added, and in the obtained ternary composite positive electrode material with a surface coated with silicon dioxide, the mass ratio of silicon dioxide to small-particle ternary positive electrode material is 0.024:1.
  • the embodiment of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that 0.0716 times the equivalent of ethyl orthosilicate is added, and the mass ratio of silicon dioxide to small-particle ternary positive electrode material in the obtained ternary composite positive electrode material with a surface coated with silicon dioxide is 0.094:1.
  • the embodiment of the present application provides a ternary cathode material.
  • the only difference between the ternary cathode material and the embodiment 1 is that the structural formula of the large-particle ternary cathode material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 , and the structural formula of the small-particle ternary cathode material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 .
  • the comparative example of the present application provides a ternary positive electrode material, wherein the ternary positive electrode material comprises the following preparation raw materials: a small-particle ternary positive electrode material and a large-particle ternary positive electrode material, wherein the mass ratio of the small-particle ternary positive electrode material to the large-particle ternary positive electrode material is 1:3;
  • the structural formula of the large-particle ternary cathode material B is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the median particle size D 50 is 15 ⁇ m;
  • the structural formula of the small-particle ternary cathode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the median particle size D 50 is 5 ⁇ m;
  • the preparation method of the ternary positive electrode material comprises the following steps:
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that the median particle size D50 of the small-particle ternary positive electrode material is 10 ⁇ m, and the median particle size D50 of the large-particle ternary positive electrode material B is 10 ⁇ m.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that 0.009 times the equivalent of ethyl orthosilicate is added, and in the obtained ternary composite positive electrode material with a surface coated with silicon dioxide, the mass ratio of silicon dioxide to small particle ternary positive electrode material is 0.011:1.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that 0.118 times the equivalent of ethyl orthosilicate is added, and the mass ratio of silicon dioxide to small-particle ternary positive electrode material in the obtained ternary composite positive electrode material with a surface coated with silicon dioxide is 0.15:1.
  • the comparative example of the present application provides a ternary positive electrode material, the ternary positive electrode material is different from the only One difference is that during the preparation of the ternary composite positive electrode material, sintering is performed at 400°C for 2 hours.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that during the preparation of the ternary composite positive electrode material, it is sintered at 1000° C. for 2 hours.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that during the preparation process, after ball milling, it is calcined at 300° C. for 2 hours.
  • the comparative example of the present application provides a ternary positive electrode material.
  • the only difference between the ternary positive electrode material and Example 1 is that during the preparation process, after ball milling, it is calcined at 1200° C. for 2 hours.
  • the test method for the residual alkali content is as follows: the residual alkali content of the ternary positive electrode material prepared in the embodiment and the comparative example is tested by a potentiometric titrator;
  • the tap density test method is as follows: the tap density of the prepared ternary cathode material is measured using a JZ-7 powder tap density instrument. The material mass used in the measurement process is 7 g, and the vibration frequency is set to 3,000 rpm.
  • the electrochemical performance test method is as follows: the ternary cathode materials prepared in Examples 1-14 and Comparative Examples 1-10 are dissolved in NMP with a binder PVDF and a conductive agent SP at a mass ratio of 8:1:1, stirred to form a slurry, coated on an aluminum foil, dried, assembled into a button cell, and subjected to 0.2C and 1C charge-discharge and cycle tests in a voltage range of 3.0 to 4.3V, respectively;
  • Example 1 and Comparative Example 2 it can be seen from Example 1 and Comparative Example 2 that when the ternary positive electrode material grading of the large and small median particle size D 50 is not used in Comparative Example 2, the tap density of the obtained product is significantly lower, and the cycle stability is also significantly reduced. Compared with Example 1, the tap density is reduced by 9.15%, the 0.1C discharge capacity is reduced by 5.26%, and the capacity retention rate after 100 cycles of 1C is reduced by 9.52%; It can be seen from Example 1 and Examples 3-4 that the value of the large and small median particle size D 50 selected by the grading will also affect the performance of the product;
  • Example 1 It can be seen from Example 1, Examples 5-8 and Comparative Examples 3-4 that the mass ratio of the ternary composite positive electrode material to the large-particle ternary positive electrode material will also affect the performance of the product. When the mass ratio of the ternary composite positive electrode material to the large-particle ternary positive electrode material is not within the range given in this application, the comprehensive performance of the product is significantly reduced;
  • Example 1 Examples 9-10 and Comparative Examples 5-6 that in the ternary composite positive electrode material, the molar ratio of the silicon source to the small-particle ternary positive electrode material will also affect the performance of the product.
  • the molar ratio of the silicon source to the small-particle ternary positive electrode material is not within the range given in this application, the comprehensive performance of the product is significantly reduced;
  • Example 1 It can be seen from Example 1 and Comparative Examples 7-10 that the parameters in the preparation process of the ternary positive electrode material will also have an impact on the performance of the product.

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Abstract

本文公开了一种三元正极材料及其制备方法，属于锂离子电池正极材料技术领域；本申请提供的一种三元正极材料通过采用不同中值粒径D50的小颗粒三元正极材料和大颗粒三元正极材料作为原料进行级配，并且在煅烧之前将小颗粒三元正极材料与硅源进行反应使小颗粒三元正极材料表面上包覆二氧化硅形成核壳结构的三元复合正极材料，能够明显的提升三元正极材料的导电性、循环稳定性和振实密度，并且能降低三元正极材料表面的残碱含量。

Description

一种三元正极材料及其制备方法 技术领域
本申请属于锂离子电池正极材料技术领域，尤其涉及一种三元正极材料及其制备方法。
背景技术
锂离子电池因其高的能量密度、较长的循环寿命等优点而被广泛应用于3C电子产品、动力汽车和化学储能等众多领域，是当下新能领域的研究热点。随着新能源汽车的高速发展，对锂离子电池的能量密度提出了更高的要求，提高动力电池能量密度核心就在于高容量的正极材料的开发。镍钴锰酸锂三元正极材料具有比容量高、能量密度高、价格低、环境友好等优点，在动力电池领域具有良好的应用前景。随着镍含量的升高，三元正极材料的比容量逐渐升高，但循环稳定性和安全性变弱。因此，如何在不提高Ni含量的前提下提升正极材料容量，成为了研究的热点。
影响锂离子电池容量的重要指标是其正极材料的振实密度，振实密度越高，同体积下正极材料越多，锂离子电池储能越多。所以通过提高正极材料的振实密度可提升其能量密度，改善其性能。振实密度的提高可以通过前驱体的选型、烧结温度的调整以及大小粒子的级配等方法来实现。中国专利CN104724763A采用不同粒度前驱体与锂盐混合后在高于900℃的温度合成大单晶颗粒，然后在大粒径材料中掺杂了粒径与之相比更小的颗粒，大颗粒之间的间隙就可以被小的颗粒所填充，空间得到了充分的利用，提高了压实密度，使得能量密度更高。中国专利CN109516509A也是将小颗粒单晶三元氧化物、大颗粒单晶三元氧化物和锂盐按预设的比例混合，再烧结，经冷却得到高压实单晶三元正极材料。然而，由于正极材料的导电性跟颗粒大小密切相关，因此大小颗粒之间导电性存在差异，导致电导不匹配，在循环过程中前期容量衰减迅速。同时三元正极材料表面有含量较高的残碱，在电池制作的匀浆、涂布过程中料浆极易形成果冻状，导致涂布不均匀，容易造成容 量衰减。残碱在高温下易与电解液发生反应生成气体，导致电池胀气，带来严重的安全隐患。
因此，亟需寻找一种低残碱含量的高振实密度三元正极材料的制备方法，能够提高材料的能量密度并且减缓容量衰减。
发明内容
本申请的目的在于克服上述现有技术的不足之处而提供一种残碱含量低、振实密度高、导电性良好且循环性能优异的三元正极材料及其制备方法。
为实现上述目的，本申请采取的技术方案为：一种三元正极材料的制备方法，所述制备方法包括以下步骤：
三元复合正极材料的制备：往小颗粒三元正极材料的水溶液中滴加硅源并反应，反应结束后固液分离，收集固体并烘干、烧结、冷却，得表面包覆有二氧化硅的三元复合正极材料；
将三元复合正极材料和大颗粒三元正极材料混合球磨、500-900℃下煅烧1-10h、冷却、研磨筛分，得三元正极材料；
所述小颗粒三元正极材料的中值粒径D50＜10μm，大颗粒三元正极材料的中值粒径D50≥10μm；
所述小颗粒三元正极材料与硅源的摩尔比为1：(0.015-0.075)。
本申请提供的一种三元正极材料中，通过采用不同中值粒径D50的小颗粒三元正极材料和大颗粒三元正极材料作为原料进行级配，并且在煅烧之前将小颗粒三元正极材料与硅源进行反应使小颗粒三元正极材料表面上包覆二氧化硅形成全包覆的核壳结构的三元复合正极材料，从而能够明显提升三元正极材料的导电性、循环稳定性和振实密度，并且能降低三元正极材料表面的残碱含量。具体地，将小颗粒三元正极材料与硅源在特定的摩尔比下进行反应能够得到表面包覆有特定质量比的二氧化硅的三元复合正极材料，得到的三元复合正极材料一方面能够提高核层小颗粒三元正极材料的循环稳定性，降低核层的导电性；另一方面在后续特定的煅烧温度和时间下能够与大颗粒三元正极材料表面的残碱发生反应，生成具有导电性的硅酸锂，增加大颗粒三元正极材料的导电性；从而缩小不同中值粒径D50的小颗粒三元正极材料和大颗粒三元正极材料之间的导电性差异。同时，不同中值粒径D50的小颗粒三元正极材料和大颗粒三元正 极材料作为原料的级配能够避免完全使用相同中值粒径D50的三元正极材料之间存在的间隙导致的振实密度低的问题。即采用本申请的技术方案得到的三元正极材料在提升振实密度的同时，使得不同中值粒径D50数值的三元正极材料电导更匹配，进而改善循环过程容量衰减的问题，提升产品的循环稳定性。
在一实施例中，所述小颗粒三元正极材料的中值粒径D50为0.5≤D50＜10μm，所述大颗粒三元正极材料的中值粒径D50为10≤D50＜30μm。
在一实施例中，所述小颗粒三元正极材料的中值粒径D50为2-7μm，所述大颗粒三元正极材料的中值粒径D50为10-20μm。
在一实施例中，所述小颗粒三元正极材料的中值粒径D50为4-5μm，所述大颗粒三元正极材料的中值粒径D50为14-16μm。
发明人研究发现，采用本申请的技术方案时，进一步选择小颗粒三元正极材料和大颗粒三元正极材料的中值粒径D50分别为2-7μm和10-20μm，尤其是分别为4-5μm和14-16μm时，能够使得小颗粒三元正极材料和大颗粒三元正极材料之间的电导性差异更小，且三元复合正极材料能够更好的进入大颗粒三元正极材料的间隙内，进一步提升振实密度。
在一实施例中，所述三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝(1-2)：(2-8)。
在一实施例中，所述三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：(2-5)。
在一实施例中，所述三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：3。
发明人研究发现，三元正极材料中三元复合正极材料和大颗粒三元正极材料的质量比会对产品的性能带来明显的影响，当三元复合正极材料的添加量过少时，会导致没有足够的三元复合正极材料与大颗粒三元正极材料表面的残碱进行接触反应，进而导致小颗粒三元正极材料和大颗粒三元正极材料之间的导电性差异无法有效的缩小，并且振实密度也无法得到有效的提升；当三元复合正极材料的添加量过多时，则由于其本身包覆有二氧化硅，则会导致产品整体的导电性下降。当进一步选择三元复合正极材料和大颗粒三元正极材料的质量比为(1-2)：(2-8)，尤其是1：(2-5)，更进一步是1:3时，得到的产品综合性能更优异。
在一实施例中，所述小颗粒三元正极材料与硅源的摩尔比为1：(0.025-0.047)。
发明人研究发现，当小颗粒三元正极材料与硅源的摩尔比为1：(0.015-0.075)时，能够使得反应后形成的三元复合正极材料表面上的二氧化硅与小颗粒三元正极材料的质量比在(0.02-0.1)：1之间，尤其是当小颗粒三元正极材料与硅源的摩尔比为1：(0.025-0.047)时，能够使得二氧化硅与小颗粒三元正极材料的质量比在(0.038-0.061)：1之间；控制摩尔比或者说质量比在上述范围内是由于在三元复合正极材料和大颗粒三元正极材料的接触的位置，三元复合正极材料表面的二氧化硅能够与大颗粒三元正极材料表面的残碱发生反应，因此，若三元复合正极材料表面的二氧化硅的质量过少，则不能使得大颗粒三元正极材料表面的残碱完全去除，导致小颗粒三元正极材料和大颗粒三元正极材料之间的导电性差异无法有效的缩小；若三元复合正极材料表面的二氧化硅的质量过多，则其本身的导电性会大幅降低，从而影响最终产品的倍率性能。当进一步选择小颗粒三元正极材料与硅源的摩尔比在上述范围内时，得到的产品的综合性能更为优异。
在一实施例中，所述煅烧的温度为700-800℃，煅烧的时间为2-6h。
发明人研究发现，煅烧的过程三元复合正极材料表面包覆的二氧化硅会与大颗粒三元正极材料表面的残碱反应，在本申请给出的煅烧温度和时间范围内，能极大程度保证表面的残碱尽可能的反应完毕，减少最终产品的残碱量，提升产品的导电性和循环稳定性。
在一实施例中，所述小颗粒三元正极材料的水溶液的温度为40-80℃。
在一实施例中，所述反应为：先于40-80℃下搅拌15-30min，随后静置10-20h。
发明人研究发现，采用上述方法进行制备，能够确保硅源良好的包覆到三元正极材料A的表面上。
在一实施例中，所述硅源为硅酸酯类化合物。
在一实施例中，所述硅源为正硅酸乙酯、硅酸甲酯中的至少一种。
在一实施例中，小颗粒三元正极材料的水溶液中，小颗粒三元正极材料的质量浓度为(5-15)g/100mL。
在一实施例中，所述烧结的温度为500-900℃，烧结的时间为2-3h。
在一实施例中，所述球磨的速度为800-1000rpm，球磨时间为30-120min。
在一实施例中，所述筛分为采用200-400目的筛网进行筛分。
在一实施例中，所述小颗粒三元正极材料的结构式为LiNixCoyMn(1-x-y)O2，其中0.6≤x＜1，0＜y≤0.2；所述大颗粒三元正极材料的结构式为LiNixCoyMn(1-x-y)O2，其中0.6≤x＜1，0＜y≤0.2。
发明人研究发现，本申请提供的方案对任意的三元正极材料都适用，通过提供不同中值粒径D50的三元正极材料，能够增加小颗粒三元正极材料的循环稳定性、降低大颗粒三元正极材料表面的残碱，还能降低大小颗粒之间的电导率差异，进而提高正极材料的循环稳定性。进一步选择三元正极材料为上述结构式的物质能够更为显著的提升产品的循环稳定性。
另外，本发明还提供了一种三元正极材料，所述三元正极材料采用本申请的制备方法制备而成。
与现有技术相比，本申请的有益效果为：
本申请提供的一种三元正极材料中，通过采用不同中值粒径D50的小颗粒三元正极材料和大颗粒三元正极材料作为原料进行级配，并且在煅烧之前将小颗粒三元正极材料与硅源进行反应使小颗粒三元正极材料表面上包覆二氧化硅形成全包覆的核壳结构的三元复合正极材料，能够明显的提升三元正极材料的导电性、循环稳定性和振实密度，并且能降低三元正极材料表面的残碱含量。具体地，采用本申请的技术方案得到的产品中碳酸锂含量在0.27％以下，氢氧化锂含量在0.25％以下，振实密度在2.72g/m3以上，0.1C放电容量在211.1mAh/g以上，1C循环100圈后容量保持率在92.1％以上。并且本申请提供的三元正极材料的制备方法操作简单、原料易得，适合实际生产应用。
具体实施方式
为更好的说明本申请的目的、技术方案和优点，下面将结合具体实施例对本申请作进一步说明。
本申请所采用的试剂、方法和设备，如无特殊说明，均为本领域常规试剂、方法和设备。
实施例1
本申请实施例提供一种三元正极材料，所述三元正极材料的制备方法包括 以下步骤：
(1)三元复合正极材料的制备：将小颗粒三元正极材料(中值粒径D50为5μm，结构式为LiNi0.8Co0.1Mn0.1O2，质量为20g，摩尔量为0.125mol)溶于200mL去离子水中形成小颗粒三元正极材料的水溶液，40℃水浴加热该水溶液并搅拌，搅拌的过程中滴加0.0466倍当量的正硅酸乙酯(1.3mL，0.00582mol)，滴加结束后，继续搅拌30min，随后静置15h，静置结束后固液分离，收集固体并烘干，接着于700℃下烧结2h，最后冷却至室温，得表面包覆有二氧化硅的三元复合正极材料；其中二氧化硅与小颗粒三元正极材料的质量比为0.061：1；
(2)将15g三元复合正极材料和5g大颗粒三元正极材料(中值粒径D50为15μm，结构式为LiNi0.8Co0.1Mn0.1O2)混合后于1000rpm的球磨速度下球磨60min，球磨结束后于800℃下煅烧2h，随后冷却至室温，接着研磨，过200目筛网，收集筛下物，得三元正极材料。
实施例2
本申请实施例提供一种三元正极材料，所述三元正极材料的制备方法包括以下步骤：
(1)三元复合正极材料的制备：将小颗粒三元正极材料(中值粒径D50为4μm，结构式为LiNi0.8Co0.1Mn0.1O2，质量为20g，摩尔量为0.125mol)溶于200mL去离子水中形成小颗粒三元正极材料的水溶液，80℃水浴加热该水溶液并搅拌，搅拌的过程中滴加0.0466倍当量的正硅酸乙酯(1.3mL，0.00582mol)，滴加结束后，继续搅拌15min，随后静置10h，静置结束后固液分离，收集固体并烘干，接着于500℃下烧结3h，最后冷却至室温，得三元复合正极材料；其中二氧化硅与小颗粒三元正极材料的质量比为0.061：1；
(2)将15g三元复合正极材料和5g大颗粒三元正极材料(中值粒径D50为14μm，结构式为LiNi0.8Co0.1Mn0.1O2)混合后于800rpm的球磨速度下球磨120min，球磨结束后于700℃下煅烧6h，随后冷却至室温，接着研磨，过400目筛网，收集筛下物，得三元正极材料。
实施例3
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于小颗粒三元正极材料的中值粒径D50为2μm，所述大颗粒三元正极材 料的中值粒径D50为10μm。
实施例4
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于小颗粒三元正极材料的中值粒径D50为7μm，所述大颗粒三元正极材料的中值粒径D50为20μm。
实施例5
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于小颗粒三元正极材料的中值粒径D50为9μm，所述大颗粒三元正极材料的中值粒径D50为25μm。
实施例6
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于小颗粒三元正极材料的中值粒径D50为0.5μm，所述大颗粒三元正极材料的中值粒径D50为30μm。
实施例7
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：2。
实施例8
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：5。
实施例9
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：1。
实施例10
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：8。
实施例11
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于滴加0.0256倍当量的正硅酸乙酯，得到的表面包覆有二氧化硅的三元复合正极材料中，二氧化硅与小颗粒三元正极材料的质量比为0.038：1。
实施例12
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于滴加0.0192倍当量的正硅酸乙酯，得到的表面包覆有二氧化硅的三元复合正极材料中，二氧化硅与小颗粒三元正极材料的质量比为0.024：1。
实施例13
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于滴加0.0716倍当量的正硅酸乙酯，得到的表面包覆有二氧化硅的三元复合正极材料中，二氧化硅与小颗粒三元正极材料的质量比为0.094：1。
实施例14
本申请实施例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于大颗粒三元正极材料的结构式为LiNi0.6Co0.2Mn0.2O2，小颗粒三元正极材料的结构式为LiNi0.6Co0.2Mn0.2O2。
对比例1
本申请对比例提供一种三元正极材料，所述三元正极材料包括如下制备原料：小颗粒三元正极材料和大颗粒三元正极材料，两者的质量比为小颗粒三元正极材料：大颗粒三元正极材料＝1：3；
其中，大颗粒三元正极材料B的结构式为LiNi0.8Co0.1Mn0.1O2，中值粒径D50为15μm；小颗粒三元正极材料的结构式为LiNi0.8Co0.1Mn0.1O2，中值粒径D50为5μm；
所述三元正极材料的制备方法包括以下步骤：
将15g小颗粒三元正极材料(中值粒径D50为5μm，结构式为LiNi0.8Co0.1Mn0.1O2)和5g大颗粒三元正极材料(中值粒径D50为15μm，结构式为LiNi0.8Co0.1Mn0.1O2)混合后于1000rpm的球磨速度下球磨60min，球磨结束后于800℃下煅烧2h，随后冷却至室温，接着研磨，过200目筛网，收集筛下物，得三元正极材料。
对比例2
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于小颗粒三元正极材料的中值粒径D50为10μm，所述大颗粒三元正极材料B的中值粒径D50为10μm。
对比例3
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：10。
对比例4
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝2：1。
对比例5
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于滴加0.009倍当量的正硅酸乙酯，得到的表面包覆有二氧化硅的三元复合正极材料中，二氧化硅与小颗粒三元正极材料的质量比为0.011：1。
对比例6
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于滴加0.118倍当量的正硅酸乙酯，得到的表面包覆有二氧化硅的三元复合正极材料中，二氧化硅与小颗粒三元正极材料的质量比为0.15：1。
对比例7
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯 一差别在于制备三元复合正极材料过程中，于400℃下烧结2h。
对比例8
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于制备三元复合正极材料过程中，于1000℃下烧结2h。
对比例9
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于制备过程中，球磨结束后于300℃下煅烧2h。
对比例10
本申请对比例提供一种三元正极材料，所述三元正极材料与实施例1的唯一差别在于制备过程中，球磨结束后于1200℃下煅烧2h。
效果例
本效果例验证实施例1-14和对比例1-10制备得到的三元正极材料的残碱含量、振实密度以及电化学性能；
其中残碱含量的测试方法为：通过电位滴定仪对实施例及对比例制备得到的三元正极材料进行残碱测试；
振实密度的测试方法为：采用JZ-7型粉体振实密度仪测量所制备三元正极材料的振实密度，测量过程中所用材料质量为7g，振动次数设定为3,000转/分；
电化学性能的测试方法为：将实施例1-14和对比例1-10制备得到的三元正极材料分别与粘结剂PVDF和导电剂SP按8:1:1的质量比溶于NMP中，搅拌形成浆料，将浆料涂布在铝箔上，烘干，组装成扣式电池，在3.0～4.3V电压范围内，分别进行0.2C和1C充放电和循环测试；
得到的测试结果如表1所示；
表1

从表1中可以看出，当采用本申请的技术方案时，得到的三元正极材料中，残碱含量低、振实密度高、导电性好、循环稳定性优异；具体地，碳酸锂含量在0.27％以下，氢氧化锂含量在0.25％以下，振实密度在2.72g/m3以上，0.1C放电容量在211.1mAh/g以上，1C循环100圈后容量保持率在92.1％以上；尤其是进一步选择小颗粒三元正极材料和大颗粒三元正极材料的中值粒径D50分别为4-5μm和14-16μm、三元复合正极材料：大颗粒三元正极材料＝1：(2-5)以及二氧化硅：小颗粒三元正极材料＝(0.038-0.061)：1时，得到的产品的综合性 能更为优异，碳酸锂含量在0.23％以下，氢氧化锂含量在0.20％以下，振实密度在2.79g/m3以上，0.1C放电容量在212.0mAh/g以上，1C循环100圈后容量保持率在92.4％以上；与对比例1中没有在小颗粒三元正极材料的表面包覆二氧化硅相比，得到的碳酸锂含量下降了39.47％以上，氢氧化锂含量下降了42.86％以上，振实密度提升了2.20％以上，0.1C放电容量提升了5.74％以上，1C循环100圈后容量保持率提升了12.41％以上；
从实施例1和对比例2中可以看出，当对比例2中不采用大小中值粒径D50的三元正极材料级配时，得到的产品的振实密度明显偏低，且循环稳定性也明显下降，与实施例1相比，振实密度下降了9.15％，0.1C放电容量下降了5.26％，1C循环100圈后容量保持率下降了9.52％；从实施例1和实施例3-4中可以看出，级配选择的大小中值粒径D50的数值也会对产品的性能带来影响；
从实施例1、实施例5-8和对比例3-4中可以看出，三元复合正极材料和大颗粒三元正极材料的质量比也会对产品的性能带来影响，当三元复合正极材料和大颗粒三元正极材料的质量比不在本申请给出的范围内时，产品的综合性能明显下降；
从实施例1、实施例9-10和对比例5-6中可以看出，三元复合正极材料中，硅源与小颗粒三元正极材料的摩尔比也会对产品的性能带来影响，当硅源与小颗粒三元正极材料的摩尔比不在本申请给出的范围内时，产品的综合性能明显下降；
从实施例1和对比例7-10中可以看出，三元正极材料的制备过程中的参数也会对产品的性能带来影响。

Claims (15)

  1. 一种三元正极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    三元复合正极材料的制备：往小颗粒三元正极材料的水溶液中滴加硅源并反应，反应结束后固液分离，收集固体并烘干、烧结、冷却，得表面包覆有二氧化硅的三元复合正极材料；
    将三元复合正极材料和大颗粒三元正极材料混合球磨、500-900℃下煅烧1-10h、冷却、研磨筛分，得三元正极材料；
    所述小颗粒三元正极材料的中值粒径D50＜10μm，大颗粒三元正极材料的中值粒径D50≥10μm；
    所述小颗粒三元正极材料与硅源的摩尔比为1：(0.015-0.075)。
  2. 根据权利要求1所述的制备方法，其特征在于，所述小颗粒三元正极材料的中值粒径D50为2-7μm，所述大颗粒三元正极材料的中值粒径D50为10-20μm。
  3. 根据权利要求2所述的制备方法，其特征在于，所述小颗粒三元正极材料的中值粒径D50为4-5μm，所述大颗粒三元正极材料的中值粒径D50为14-16μm。
  4. 根据权利要求1所述的制备方法，其特征在于，所述三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝(1-2)：(2-8)。
  5. 根据权利要求4所述的制备方法，其特征在于，所述三元复合正极材料和大颗粒三元正极材料的质量比为三元复合正极材料：大颗粒三元正极材料＝1：(2-5)。
  6. 根据权利要求1所述的制备方法，其特征在于，所述小颗粒三元正极材料与硅源的摩尔比为1：(0.025-0.047)。
  7. 根据权利要求1所述的制备方法，其特征在于，所述煅烧的温度为700-800℃，煅烧的时间为2-6h。
  8. 根据权利要求1所述的制备方法，其特征在于，所述小颗粒三元正极材料的水溶液的温度为40-80℃。
  9. 根据权利要求1所述的制备方法，其特征在于，所述反应为：先于40-80℃下搅拌15-30min，随后静置10-20h。
  10. 根据权利要求1所述的制备方法，其特征在于，所述硅源为硅酸酯类化合物。
  11. 根据权利要求1所述的制备方法，其特征在于，所述硅源为正硅酸乙酯、硅酸甲酯中的至少一种。
  12. 根据权利要求1所述的制备方法，其特征在于，所述烧结的温度为500-900℃，烧结的时间为2-3h。
  13. 根据权利要求1所述的制备方法，其特征在于，所述球磨的速度为800-1000rpm，球磨时间为30-120min。
  14. 根据权利要求1所述的制备方法，其特征在于，所述小颗粒三元正极材料的结构式为LiNixCoyMn(1-x-y)O2，其中0.6≤x＜1，0＜y≤0.2；
    所述大颗粒三元正极材料的结构式为LiNixCoyMn(1-x-y)O2，其中0.6≤x＜1，0＜y≤0.2。
  15. 一种三元正极材料，其特征在于，所述三元正极材料采用如权利要求1-14任一项所述的制备方法制备而成。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104724763A (zh) * 2015-02-11 2015-06-24 江苏科捷锂电池有限公司 高压实三元正极材料的制备方法
CN106159244A (zh) * 2016-09-27 2016-11-23 宁德时代新能源科技股份有限公司 一种锂电池正极材料其制备方法及动力用锂离子电池
CN108172825A (zh) * 2017-12-07 2018-06-15 格林美（无锡）能源材料有限公司 一种高电压高压实低成本钴酸锂正极材料及其制备方法
US20190386293A1 (en) * 2016-12-20 2019-12-19 Byd Company Limited Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery
CN111384393A (zh) * 2018-12-28 2020-07-07 天津国安盟固利新材料科技股份有限公司 一种高振实密度高镍正极材料及其制备方法
CN112194200A (zh) * 2020-08-27 2021-01-08 浙江美都海创锂电科技有限公司 一种低残碱、高压实、包覆层均匀的高镍正极材料的制备方法
CN113036115A (zh) * 2021-02-07 2021-06-25 东莞市创明电池技术有限公司 级配高镍三元复合材料及其制备方法、锂二次电池
CN116190604A (zh) * 2023-02-16 2023-05-30 宁夏中化锂电池材料有限公司 一种混合高镍正极材料及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104724763A (zh) * 2015-02-11 2015-06-24 江苏科捷锂电池有限公司 高压实三元正极材料的制备方法
CN106159244A (zh) * 2016-09-27 2016-11-23 宁德时代新能源科技股份有限公司 一种锂电池正极材料其制备方法及动力用锂离子电池
US20190386293A1 (en) * 2016-12-20 2019-12-19 Byd Company Limited Ternary material and preparation method thereof, battery slurry, positive electrode and lithium battery
CN108172825A (zh) * 2017-12-07 2018-06-15 格林美（无锡）能源材料有限公司 一种高电压高压实低成本钴酸锂正极材料及其制备方法
CN111384393A (zh) * 2018-12-28 2020-07-07 天津国安盟固利新材料科技股份有限公司 一种高振实密度高镍正极材料及其制备方法
CN112194200A (zh) * 2020-08-27 2021-01-08 浙江美都海创锂电科技有限公司 一种低残碱、高压实、包覆层均匀的高镍正极材料的制备方法
CN113036115A (zh) * 2021-02-07 2021-06-25 东莞市创明电池技术有限公司 级配高镍三元复合材料及其制备方法、锂二次电池
CN116190604A (zh) * 2023-02-16 2023-05-30 宁夏中化锂电池材料有限公司 一种混合高镍正极材料及其制备方法

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