CN107681123A - Positive electrode material and preparation method thereof, positive electrode sheet and lithium ion battery - Google Patents

Positive electrode material and preparation method thereof, positive electrode sheet and lithium ion battery Download PDF

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CN107681123A
CN107681123A CN201610620230.7A CN201610620230A CN107681123A CN 107681123 A CN107681123 A CN 107681123A CN 201610620230 A CN201610620230 A CN 201610620230A CN 107681123 A CN107681123 A CN 107681123A
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lithium cobaltate
positive electrode
cathode material
lithium
cobaltate cathode
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王梦
徐磊敏
梁成都
王亮
王巍
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Ningde Amperex Technology Ltd
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Abstract

The invention provides a positive electrode material, a preparation method thereof and a positive electrodeThe anode material comprises a modified lithium cobaltate anode material A 'and a modified lithium cobaltate anode material B', the mass ratio of the modified lithium cobaltate anode material A 'to the modified lithium cobaltate anode material B' is D:1, the D50 of the modified lithium cobaltate anode material A 'to the modified lithium cobaltate anode material B' is 10-25 mu m, the D99 of the modified lithium cobaltate anode material D50 is 30-60 mu m, the shape of the modified lithium cobaltate anode material D is spherical or flaky like single particles, the D50 of the modified lithium cobaltate anode material D50 is 1-10 mu m, the D99 of the modified lithium cobaltate anode material D99 is 8-30 mu m, the shape of the modified lithium cobaltate anode1+ aCo1‑bMbO2+cXmThe positive electrode material can improve the compaction density of a compacted positive electrode piece, and further remarkably improve the energy density, the safety performance, the storage performance and the cycle stability of the lithium ion battery at high temperature and high voltage.

Description

正极材料及其制备方法、正极极片及锂离子电池Positive electrode material and preparation method thereof, positive electrode sheet and lithium ion battery

技术领域technical field

本发明涉及锂离子电池技术领域，具体涉及一种正极材料及其制备方法、正极极片及锂离子电池。The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material, a preparation method thereof, a positive electrode sheet and a lithium ion battery.

背景技术Background technique

随着手机、数码相机、笔记本电脑和便携式DVD等移动设备的日益小型化和轻薄化，市场对锂离子电池的能量密度、安全性能和循环寿命的要求也不断提高。With the increasing miniaturization and thinning of mobile devices such as mobile phones, digital cameras, notebook computers and portable DVDs, the market's requirements for energy density, safety performance and cycle life of lithium-ion batteries are also increasing.

锂离子电池一般包括：正极极片、负极极片、间隔于正负极极片之间的隔离膜以及电解液。其中，正极极片包括正极集流体和分布在正极集流体上的正极材料，负极极片包括负极集流体和分布在负极集流体上的负极材料。目前，消费类电子产品使用的锂离子电池正极材料主要是钴酸锂(LiCoO2)。Lithium-ion batteries generally include: a positive pole piece, a negative pole piece, a separator spaced between the positive and negative pole pieces, and an electrolyte. Wherein, the positive electrode sheet includes a positive electrode collector and a positive electrode material distributed on the positive electrode collector, and the negative electrode sheet includes a negative electrode collector and a negative electrode material distributed on the negative electrode collector. At present, lithium cobalt oxide (LiCoO 2 ) is mainly used as the anode material of lithium-ion batteries in consumer electronic products.

现在消费类电子产品特别是手机对锂离子电池的续航能力要求越来越高，为了满足市场需求，提高锂离子电池的能量密度是当务之急。提高充电截止电压是目前提高锂离子电池的能量密度最有效的途径。但是，LiCoO2在高电压下的结构很不稳定，会产生不可逆的相变，在循环过程中结构极易发生坍塌，而对LiCoO2进行表面包覆只能稳定表面结构防止LiCoO2与电解液发生反应，无法抑制其体相结构的坍塌。Nowadays, consumer electronics products, especially mobile phones, have higher and higher requirements on the battery life of lithium-ion batteries. In order to meet market demand, it is imperative to increase the energy density of lithium-ion batteries. Improving the charge cut-off voltage is currently the most effective way to increase the energy density of lithium-ion batteries. However, the structure of LiCoO 2 is very unstable under high voltage, and irreversible phase transition will occur, and the structure is prone to collapse during cycling, and the surface coating of LiCoO 2 can only stabilize the surface structure and prevent LiCoO 2 from interacting with the electrolyte. The reaction occurs, and the collapse of its bulk phase structure cannot be suppressed.

现有技术中已经揭示了多种正极材料的改性处理方法，如于2010年02月16日公告的中国专利CN101734728A就揭示了通过液相法在Co3O4表面包覆Al，然后将干燥后的前躯体锂化形成LiCoO2，以对正极材料进行体相掺杂处理。但是，根据上述方法制备体相掺杂正极材料时，掺杂元素Al仅分布在Co3O4表面，锂化后不能保证掺杂元素Al均匀分许在LiCoO2的体相，在高电压循环过程中可能会导致LiCoO2局部结构坍塌，影响锂离子电池的能量密度、安全性能和充放电循环稳定性。A variety of modification methods for positive electrode materials have been disclosed in the prior art. For example, the Chinese patent CN101734728A published on February 16, 2010 discloses that Al is coated on the surface of Co 3 O 4 by a liquid phase method, and then dried The final precursor is lithiated to form LiCoO 2 , so as to perform bulk phase doping treatment on the positive electrode material. However, when the bulk phase doped cathode material is prepared according to the above method, the doping element Al is only distributed on the surface of Co 3 O 4 , and it cannot be ensured that the doping element Al is uniformly distributed in the bulk phase of LiCoO 2 after lithiation. The process may cause the local structure of LiCoO2 to collapse, affecting the energy density, safety performance and charge-discharge cycle stability of lithium-ion batteries.

发明内容Contents of the invention

鉴于背景技术中存在的问题，本发明的目的在于提供一种正极材料及其制备方法、正极极片及锂离子电池，所述正极材料可显著提高锂离子电池高温高电压下的能量密度、安全性能、存储性能以及循环稳定性。In view of the problems existing in the background technology, the object of the present invention is to provide a positive electrode material and a preparation method thereof, a positive electrode sheet and a lithium-ion battery, and the positive electrode material can significantly improve the energy density and safety of the lithium-ion battery under high temperature and high voltage. performance, memory performance, and cycle stability.

为了达到上述目的，在本发明的第一方面，本发明提供了一种正极材料，所述正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1；所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99；其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置，X包覆于钴酸锂的表面。In order to achieve the above object, in the first aspect of the present invention, the present invention provides a positive electrode material, the positive electrode material includes a modified lithium cobaltate positive electrode material A' and a modified lithium cobaltate positive electrode material B', so The mass ratio of the modified lithium cobaltate cathode material A' to the modified lithium cobaltate cathode material B' is d:1; the D50 of the particles of the modified lithium cobaltate cathode material A' is 10 μm ～25μm, D99 is 30μm～60μm, the morphology of the modified lithium cobaltate positive electrode material A' is a single-particle spherical or flake shape; the D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and D99 is 8 μm to 30 μm, the appearance of the modified lithium cobaltate positive electrode material B' is a spherical shape of a single particle or a spherical shape of a secondary particle; the modified lithium cobaltate positive electrode material The D50 of the particles of A' is greater than the D50 of the particles of the modified lithium cobaltate cathode material B'; the D99 of the particles of the modified lithium cobaltate cathode material A' is greater than the modified lithium cobaltate cathode material D99 of the particles of material B'; wherein, the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' have the same general chemical formula and are Li 1+a Co 1- b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from Mg, Al, Zr, Ti, Ni, Mn, Y, Nb One or more of them, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located at the bulk phase doping position of lithium cobaltate, X is coated on the surface of lithium cobaltate.

在本发明的第二方面，本发明提供了一种正极材料的制备方法，用于制备本发明第一方面所述的正极材料，包括步骤：(1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(2)将沉淀物A、锂盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(3)将沉淀物B、锂盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。In the second aspect of the present invention, the present invention provides a method for preparing a positive electrode material, which is used to prepare the positive electrode material described in the first aspect of the present invention, comprising the steps of: (1) precipitating agent solution, Co salt solution, metal The solution of M salt is added into the reaction kettle and mixed for co-precipitation reaction. After drying, precipitate A and precipitate B with different particle sizes are obtained respectively. The D50 of the primary particle of the precipitate A is 1 μm to 5 μm, and the D50 of the secondary particle is 5 μm. ~20μm, the D50 of the primary particles of the precipitate B is 0.05μm～1μm, and the D50 of the secondary particles is 1μm～10μm; Mixing and performing secondary sintering to obtain a modified lithium cobaltate positive electrode material A', the D50 of the particles of the modified lithium cobaltate positive electrode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm. The modified The morphology of the lithium cobaltate cathode material A' is a single-particle spherical or flake-like shape; (3) the precipitate B and the lithium salt are mixed and sintered for the first time, and then mixed with the compound of the metal X for the second sintering to obtain Modified lithium cobaltate cathode material B', the D50 of the particles of the modified lithium cobaltate cathode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm, and the modified lithium cobaltate cathode material B' The morphology of the single particle is spherical or the spherical shape of the secondary particle; (4) the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' according to the mass ratio d : 1 mixing, that is to complete the preparation of the positive electrode material, wherein, the D50 of the particles of the modified lithium cobaltate positive electrode material A' is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B', the modified The D99 of the particles of the positive lithium cobaltate positive electrode material A' is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B', and the modified lithium cobaltate positive electrode material A' and the modified cobalt Lithium acid cathode material B' has the same general chemical formula and is Li 1+a Co 1-b M b O 2+c X m , and M is selected from one of Al, Mg, Y, Ni, Mn, La or Several, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m ≤0.1, 0<d≤10.

在本发明的第三方面，本发明提供了另一种正极材料，所述正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1；所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99；其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+ cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置和固溶体过渡层掺杂位置，X包覆于钴酸锂的表面。In a third aspect of the present invention, the present invention provides another positive electrode material, which includes a modified lithium cobaltate positive electrode material A' and a modified lithium cobaltate positive electrode material B', the modified The mass ratio of the lithium cobaltate cathode material A' to the modified lithium cobaltate cathode material B' is d:1; the D50 of the particles of the modified lithium cobaltate cathode material A' is 10 μm to 25 μm, D99 is 30 μm to 60 μm, and the morphology of the modified lithium cobaltate positive electrode material A’ is a single-particle spherical or flake shape; the D50 of the particles of the modified lithium cobaltate positive electrode material B’ is 1 μm to 10 μm , D99 is 8 μm to 30 μm, the morphology of the modified lithium cobaltate positive electrode material B’ is a spherical shape of a single particle or a spherical shape of a secondary particle; the particles of the modified lithium cobaltate positive electrode material A’ The D50 is greater than the D50 of the particles of the modified lithium cobaltate cathode material B'; the D99 of the particles of the modified lithium cobaltate cathode material A' is greater than that of the modified lithium cobaltate cathode material B' Particle D99; wherein, the modified lithium cobaltate cathode material A' and the modified lithium cobaltate cathode material B' have the same general chemical formula and are Li 1+a Co 1-b M b O 2+ c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from one of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb or several, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located in the bulk phase doping position of lithium cobaltate and the solid solution transition layer doping The hetero position, X covers the surface of lithium cobalt oxide.

在本发明的第四方面，本发明提供了另一种正极材料的制备方法，用于制备本发明第三方面所述的正极材料，包括步骤：(1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(2)将沉淀物A、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(3)将沉淀物B、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。In the fourth aspect of the present invention, the present invention provides another method for preparing a positive electrode material, which is used to prepare the positive electrode material described in the third aspect of the present invention, comprising steps: (1) Precipitating agent solution, Co salt solution, Add the solution of metal M salt into the reaction kettle and mix it for co-precipitation reaction. After drying, precipitate A and precipitate B with different particle sizes are obtained respectively. The D50 of the primary particle of precipitate A is 1 μm to 5 μm, and the D50 of the secondary particle is 5 μm to 20 μm, the D50 of the primary particle of the precipitate B is 0.05 μm to 1 μm, and the D50 of the secondary particle is 1 μm to 10 μm; (2) After the precipitate A, lithium salt and metal M salt are mixed and sintered for the first time, then Mixing with a compound of metal X for secondary sintering to obtain a modified lithium cobaltate positive electrode material A', the D50 of the particles of the modified lithium cobaltate positive electrode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm, The morphology of the modified lithium cobaltate positive electrode material A' is a single-particle spherical or flake shape; (3) after mixing the precipitate B, lithium salt and metal M salt and sintering for the first time, and then mixing with metal X The compounds are mixed for secondary sintering to obtain a modified lithium cobaltate positive electrode material B', the D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm. The morphology of the active lithium cobaltate positive electrode material B' is a spherical shape of a single particle or a spherical shape of a secondary particle; (4) the modified lithium cobaltate positive electrode material A' and the modified cobaltic acid Lithium cathode material B' is mixed at a mass ratio of d:1 to complete the preparation of the cathode material, wherein the D50 of the particles of the modified lithium cobaltate cathode material A' is greater than that of the modified lithium cobaltate cathode material B The D50 of the particles of ', the D99 of the particles of the modified lithium cobaltate positive electrode material A' is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B', the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate cathode material B' have the same general chemical formula and are both Li 1+a Co 1-b M b O 2+c X m , and M is selected from Al, Mg, Y, Ni , one or more of Mn, La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10.

在本发明的第五方面，本发明提供了一种正极极片，其包括正极集流体以及正极膜片。正极膜片设置于正极集流体上且正极膜片包括正极材料、导电剂以及粘结剂。其中，所述正极材料为根据本发明第一方面所述的正极材料或所述正极材料为根据本发明第三方面所述的正极材料。In a fifth aspect of the present invention, the present invention provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode membrane. The positive electrode film is arranged on the positive electrode current collector, and the positive electrode film includes positive electrode material, conductive agent and binder. Wherein, the positive electrode material is the positive electrode material according to the first aspect of the present invention or the positive electrode material is the positive electrode material according to the third aspect of the present invention.

在本发明的第六方面，本发明提供了一种锂离子电池，其包括根据本发明第五方面所述的正极极片。In a sixth aspect of the present invention, the present invention provides a lithium ion battery, which includes the positive electrode sheet according to the fifth aspect of the present invention.

相对于现有技术，本发明的有益效果为：Compared with the prior art, the beneficial effects of the present invention are:

根据本发明的正极材料可显著提高锂离子电池高温高电压下的能量密度、安全性能、存储性能以及循环稳定性。The positive electrode material according to the invention can significantly improve the energy density, safety performance, storage performance and cycle stability of the lithium ion battery under high temperature and high voltage.

附图说明Description of drawings

图1示出实施例4的步骤(2)的沉淀物B(Co0.97Al0.03)(OH)0.03CO3的SEM图。Fig. 1 shows the SEM image of the precipitate B(Co 0.97 Al 0.03 )(OH) 0.03 CO 3 in step (2) of Example 4.

图2示出实施例4的步骤(1)的沉淀物A(Co0.97Al0.03)(OH)0.03CO3的SEM图。Fig. 2 shows the SEM image of the precipitate A (Co 0.97 Al 0.03 )(OH) 0.03 CO 3 in step (1) of Example 4.

图3示出实施例4的步骤(1)的单颗粒的类球形形貌的正极材料Li1.02Co0.97Al0.03O2.08Zr0.02Al0.03的SEM图。Fig. 3 shows the SEM image of the positive electrode material Li 1.02 Co 0.97 Al 0.03 O 2.08 Zr 0.02 Al 0.03 in the step (1) of Example 4 with a single particle spherical shape.

图4示出实施例4的步骤(2)的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Al0.03O2.08Zr0.02Al0.03的SEM图。Fig. 4 shows the SEM image of the positive electrode material Li 1.02 Co 0.97 Al 0.03 O 2.08 Zr 0.02 Al 0.03 in step (2) of Example 4 with a spherical shape of secondary particles.

图5示出实施例4的冷压后的正极极片的SEM图。FIG. 5 shows the SEM image of the cold-pressed positive electrode sheet of Example 4. FIG.

具体实施方式detailed description

下面详细说明根据本发明的正极材料及其制备方法、正极极片及锂离子电池。The positive electrode material, the preparation method thereof, the positive electrode sheet and the lithium ion battery according to the present invention will be described in detail below.

首先说明根据本发明第一方面的正极材料。First, the positive electrode material according to the first aspect of the present invention will be described.

根据本发明第一方面所述的正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1。所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状。所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形。所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99。其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置，X包覆于钴酸锂的表面。The positive electrode material according to the first aspect of the present invention includes a modified lithium cobaltate positive electrode material A' and a modified lithium cobaltate positive electrode material B', the modified lithium cobaltate positive electrode material A' and the modified The mass ratio of the positive lithium cobaltate cathode material B' is d:1. The D50 of the particles of the modified lithium cobaltate cathode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm, and the morphology of the modified lithium cobaltate cathode material A' is a single-particle spherical or flake shape. The D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm. Spherical shape of sub-particles. The D50 of the particles of the modified lithium cobaltate cathode material A' is greater than the D50 of the particles of the modified lithium cobaltate cathode material B'; the D99 of the particles of the modified lithium cobaltate cathode material A' greater than the D99 of the particles of the modified lithium cobaltate cathode material B'. Wherein, the modified lithium cobaltate cathode material A' and the modified lithium cobaltate cathode material B' have the same general chemical formula and are both Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located at the bulk phase doping position of lithium cobalt oxide, X is coated on the lithium cobalt oxide surface.

在根据本发明第一方面所述的正极材料中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’是对常规的钴酸锂材料(尤其是层状钴酸锂)进行改性，其中对常规的钴酸锂材料的改性包括元素掺杂改性以及元素表面包覆改性。其中，在本发明第一方面所述的正极材料中，元素M位于钴酸锂的体相掺杂位置，起到对钴酸锂进行掺杂改性的目的。X包覆于钴酸锂的表面是指X作为包覆层形成于钴酸锂的表面，起到对钴酸锂进行表面包覆改性的目的。In the positive electrode material according to the first aspect of the present invention, the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' are conventional lithium cobaltate materials (especially layered lithium cobaltate) for modification, wherein the modification of conventional lithium cobaltate materials includes element doping modification and element surface coating modification. Wherein, in the positive electrode material described in the first aspect of the present invention, the element M is located at the bulk phase doping position of lithium cobaltate, so as to achieve the purpose of doping and modifying lithium cobaltate. The coating of X on the surface of lithium cobaltate means that X is formed on the surface of lithium cobaltate as a coating layer, and serves the purpose of coating and modifying the surface of lithium cobaltate.

在根据本发明第一方面所述的正极材料中，所述正极材料既包括粒径较大的改性的钴酸锂正极材料A’又包括粒径较小的改性的钴酸锂正极材料B’，这样有利于提高压实后的正极极片的压实密度，从而提高正极材料的体积能量密度，显著提高锂离子电池高温高电压下的能量密度、安全性能、存储性能以及循环稳定性。In the positive electrode material according to the first aspect of the present invention, the positive electrode material includes both a modified lithium cobaltate positive electrode material A' with a larger particle size and a modified lithium cobaltate positive electrode material with a smaller particle size B', which is beneficial to increase the compaction density of the positive electrode sheet after compaction, thereby increasing the volume energy density of the positive electrode material, and significantly improving the energy density, safety performance, storage performance and cycle stability of lithium-ion batteries under high temperature and high voltage .

在根据本发明第一方面所述的正极材料中，X以氧化物的形态包覆于钴酸锂的表面。In the positive electrode material according to the first aspect of the present invention, X is coated on the surface of lithium cobalt oxide in the form of oxide.

其次说明根据本发明第二方面的正极材料的制备方法，其用于制备本发明第一方面所述的正极材料。Next, the preparation method of the positive electrode material according to the second aspect of the present invention is described, which is used to prepare the positive electrode material described in the first aspect of the present invention.

根据本发明第二方面的正极材料的制备方法包括步骤：(1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(2)将沉淀物A、锂盐混合并进行首次烧结(对应形成钴酸锂的过程，下同)后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(3)将沉淀物B、锂盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La、Ti中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。The preparation method of the positive electrode material according to the second aspect of the present invention includes the steps: (1) adding the solution of the precipitating agent solution, the Co salt solution, and the metal M salt into the reaction kettle and mixing them for coprecipitation reaction, and obtaining particles of different particle sizes after drying. Precipitate A and Precipitate B, the D50 of the primary particle of the precipitate A is 1 μm to 5 μm, the D50 of the secondary particle is 5 μm to 20 μm, the D50 of the primary particle of the precipitate B is 0.05 μm to 1 μm, and the D50 of the secondary particle 1 μm to 10 μm; (2) Mix the precipitate A and the lithium salt for the first sintering (corresponding to the process of forming lithium cobaltate, the same below), and then mix it with the compound of metal X for the second sintering to obtain the modified Lithium cobaltate positive electrode material A', the D50 of the particles of the modified lithium cobaltate positive electrode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm, and the morphology of the modified lithium cobaltate positive electrode material A' is It is single-particle spherical or flake-like; (3) After the precipitate B and lithium salt are mixed and sintered for the first time, they are mixed with the compound of metal X for secondary sintering to obtain the modified lithium cobaltate cathode material B' , the D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm, and the morphology of the modified lithium cobaltate positive electrode material B' is a single-particle spherical or The spherical shape of the secondary particles; (4) the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' are mixed according to the mass ratio d: 1 to complete the preparation of the positive electrode material , wherein, the D50 of the particles of the modified lithium cobaltate cathode material A' is greater than the D50 of the particles of the modified lithium cobaltate cathode material B', and the modified lithium cobaltate cathode material A' is The D99 of the particles is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B', the chemical general formula of the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' The same and all are Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, Ti, and X is selected from Mg, One or more of Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10 .

在根据本发明第二方面所述的正极材料的制备方法中，首先对LiCoO2进行掺杂改性，以提高其在高电压下的结构稳定性，之后对LiCoO2进行表面包覆改性，进一步改善其在高电压下的结构稳定性。其中，在步骤(1)中加入的金属M盐在步骤(2)和步骤(3)的首次烧结过程中，元素M进入钴酸锂的体相掺杂位置，起到对钴酸锂进行掺杂改性的目的。在步骤(2)和步骤(3)的二次烧结过程中，元素X(可为氧化物的形态)包覆在钴酸锂的表面，起到对钴酸锂进行表面包覆改性的目的。In the preparation method of the positive electrode material according to the second aspect of the present invention, LiCoO2 is firstly modified by doping to improve its structural stability under high voltage, and then the LiCoO2 is surface - coated and modified, Further improve its structural stability under high voltage. Wherein, the metal M salt added in step (1) is in the first sintering process of step (2) and step (3), the element M enters the bulk phase doping position of lithium cobaltate, plays a role in doping lithium cobaltate The purpose of hybridization. In the secondary sintering process of step (2) and step (3), element X (which can be in the form of oxide) is coated on the surface of lithium cobalt oxide, so as to achieve the purpose of coating and modifying the surface of lithium cobalt oxide .

在这里补充说明的是，步骤(2)和步骤(3)的执行可以同时执行，或者步骤(2)先执行而步骤(3)后执行，或者步骤(3)先执行而步骤(2)后执行，不以书写顺序为限。What is supplemented here is that step (2) and step (3) can be executed at the same time, or step (2) is executed first and step (3) is executed later, or step (3) is executed first and step (2) is followed Execution is not limited to the order of writing.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，沉淀剂选自NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3、LiOH、NaOH中的一种或几种。沉淀剂溶液的浓度为40g/L～250g/L。沉淀剂溶液的进料速度为0.01m3/h～3m3/h。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (1), the precipitating agent is selected from NH 4 HCO 3 , (NH 4 ) 2 CO 3 , Na 2 CO 3 , NaHCO 3 , LiOH , NaOH in one or more. The concentration of the precipitant solution is 40g/L-250g/L. The feed rate of the precipitant solution is 0.01m 3 /h～3m 3 /h.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，Co盐选自硝酸钴、氯化钴、醋酸钴、硫酸钴中的一种或几种。Co盐溶液的浓度为50g/L～300g/L。Co盐溶液的进料速度为0.1m3/h～1m3/h。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (1), the Co salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt sulfate. The concentration of the Co salt solution is 50g/L-300g/L. The feeding rate of the Co salt solution is 0.1 m 3 /h˜1 m 3 /h.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。金属M盐的溶液的浓度为1g/L～100g/L。金属M盐的溶液的进料速度为0.1m3/h～0.8m3/h。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (1), the metal M salt is selected from one of metal M nitrates, hydrochlorides, acetates, sulfates or Several kinds. The concentration of the metal M salt solution is 1 g/L˜100 g/L. The feeding rate of the solution of the metal M salt is 0.1 m 3 /h to 0.8 m 3 /h.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，采用并流加料法进行混合。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (1), the mixing is carried out by adopting a co-current feeding method.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，控制反应体系的pH为6～9。In the preparation method of the cathode material according to the second aspect of the present invention, in step (1), the pH of the reaction system is controlled to be 6-9.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(1)中，反应温度为30℃～60℃，反应时间为4h～200h。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (1), the reaction temperature is 30°C-60°C, and the reaction time is 4h-200h.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(2)中，锂盐选自碳酸锂、氢氧化锂中的一种或几种。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (2), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(3)中，锂盐选自碳酸锂、氢氧化锂中的一种或几种。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (3), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(2)中，金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (2), the compound of metal X is selected from carbonates of metal X, nitrates of metal X, hydroxides of metal X, One or more of metal X oxides and metal X basic carbonates.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(3)中，金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (3), the compound of metal X is selected from carbonates of metal X, nitrates of metal X, hydroxides of metal X, One or more of metal X oxides and metal X basic carbonates.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(2)中，首次烧结的温度为600℃～1300℃，二次烧结的温度为600℃～1100℃。优选地，二次烧结的温度不大于首次烧结的温度。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (2), the temperature of the first sintering is 600°C-1300°C, and the temperature of the second sintering is 600°C-1100°C. Preferably, the temperature of the second sintering is not higher than the temperature of the first sintering.

在根据本发明第二方面所述的正极材料的制备方法中，在步骤(3)中，首次烧结的温度为500℃～1200℃，二次烧结的温度为600℃～1100℃。优选地，二次烧结的温度不大于首次烧结的温度。In the preparation method of the positive electrode material according to the second aspect of the present invention, in step (3), the temperature of the first sintering is 500°C-1200°C, and the temperature of the second sintering is 600°C-1100°C. Preferably, the temperature of the second sintering is not higher than the temperature of the first sintering.

再次说明根据本发明第三方面的正极材料。The positive electrode material according to the third aspect of the present invention will be described again.

根据本发明第三方面所述的正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1。所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状。所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形。所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99。其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置和固溶体过渡层掺杂位置，X包覆于钴酸锂的表面。The positive electrode material according to the third aspect of the present invention includes a modified lithium cobaltate positive electrode material A' and a modified lithium cobaltate positive electrode material B', the modified lithium cobaltate positive electrode material A' and the modified The mass ratio of the positive lithium cobaltate cathode material B' is d:1. The D50 of the particles of the modified lithium cobaltate cathode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm, and the morphology of the modified lithium cobaltate cathode material A' is a single-particle spherical or flake shape. The D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm. Spherical shape of sub-particles. The D50 of the particles of the modified lithium cobaltate cathode material A' is greater than the D50 of the particles of the modified lithium cobaltate cathode material B'; the D99 of the particles of the modified lithium cobaltate cathode material A' greater than the D99 of the particles of the modified lithium cobaltate cathode material B'. Wherein, the modified lithium cobaltate cathode material A' and the modified lithium cobaltate cathode material B' have the same general chemical formula and are both Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located at the bulk phase doping position and solid solution transition layer doping position of lithium cobaltate, X Coated on the surface of lithium cobalt oxide.

在根据本发明第三方面所述的正极材料中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’是对常规的钴酸锂材料(尤其是层状钴酸锂)进行改性，其中对常规的钴酸锂材料的改性包括元素掺杂改性以及元素表面包覆改性。其中，在本发明第三方面所述的正极材料中，元素M位于钴酸锂的体相掺杂位置和固溶体过渡层掺杂位置(介于体相掺杂位置与表面包覆位置之间)，起到对钴酸锂进行掺杂改性的目的。X包覆于钴酸锂的表面是指X作为包覆层形成于钴酸锂的表面，起到对钴酸锂进行表面包覆改性的目的。In the positive electrode material according to the third aspect of the present invention, the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' are conventional lithium cobaltate materials (especially layered lithium cobaltate) for modification, wherein the modification of conventional lithium cobaltate materials includes element doping modification and element surface coating modification. Wherein, in the positive electrode material described in the third aspect of the present invention, the element M is located at the bulk phase doping position and the solid solution transition layer doping position of lithium cobaltate (between the bulk phase doping position and the surface coating position) , to achieve the purpose of doping and modifying lithium cobaltate. The coating of X on the surface of lithium cobaltate means that X is formed on the surface of lithium cobaltate as a coating layer, and serves the purpose of coating and modifying the surface of lithium cobaltate.

在根据本发明第三方面所述的正极材料中，所述正极材料既包括粒径较大的改性的钴酸锂正极材料A’又包括粒径较小的改性的钴酸锂正极材料B’，这样有利于提高压实后的正极极片的压实密度，从而提高正极材料的体积能量密度，显著提高锂离子电池高温高电压下的能量密度、安全性能、存储性能以及循环稳定性。In the positive electrode material according to the third aspect of the present invention, the positive electrode material includes both a modified lithium cobaltate positive electrode material A' with a larger particle size and a modified lithium cobaltate positive electrode material with a smaller particle size B', which is beneficial to increase the compaction density of the positive electrode sheet after compaction, thereby increasing the volume energy density of the positive electrode material, and significantly improving the energy density, safety performance, storage performance and cycle stability of lithium-ion batteries under high temperature and high voltage .

在根据本发明第三方面所述的正极材料中，X以氧化物的形态包覆于钴酸锂的表面。In the positive electrode material according to the third aspect of the present invention, X is coated on the surface of lithium cobalt oxide in the form of oxide.

下面说明根据本发明第四方面的正极材料的制备方法，其用于制备本发明第三方面所述的正极材料。The following describes the preparation method of the positive electrode material according to the fourth aspect of the present invention, which is used to prepare the positive electrode material described in the third aspect of the present invention.

根据本发明第四方面所述的正极材料的制备方法包括步骤：(1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(2)将沉淀物A、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(3)将沉淀物B、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。The preparation method of the positive electrode material according to the fourth aspect of the present invention includes the steps: (1) adding the solution of the precipitant solution, the Co salt solution, and the metal M salt into the reaction kettle and mixing them for coprecipitation reaction, and obtaining different particles after drying. The diameter of the precipitate A and precipitate B, the D50 of the primary particle of the precipitate A is 1 μm ~ 5 μm, the D50 of the secondary particle is 5 μm ~ 20 μm, the D50 of the primary particle of the precipitate B is 0.05 μm ~ 1 μm, the secondary particle The D50 is 1 μm to 10 μm; (2) The precipitate A, lithium salt and metal M salt are mixed and sintered for the first time, and then mixed with the compound of metal X for secondary sintering to obtain the modified lithium cobaltate cathode material A ', the D50 of the particles of the modified lithium cobaltate cathode material A' is 10 μm to 25 μm, and the D99 is 30 μm to 60 μm, and the morphology of the modified lithium cobaltate cathode material A' is a single-particle spherical shape or flake; (3) Precipitate B, lithium salt and metal M salt are mixed and sintered for the first time, and then mixed with a compound of metal X for secondary sintering to obtain a modified lithium cobaltate positive electrode material B'. The D50 of the particles of the modified lithium cobaltate positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm, and the morphology of the modified lithium cobaltate positive electrode material B' is a single particle spherical or secondary The spherical shape of the particles; (4) the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' are mixed in a mass ratio of d: 1 to complete the preparation of the positive electrode material, wherein , the D50 of the particles of the modified lithium cobaltate positive electrode material A' is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B', and the D50 of the particles of the modified lithium cobaltate positive electrode material A' D99 is greater than the D99 of the particles of the modified lithium cobaltate cathode material B', the modified lithium cobaltate cathode material A' and the modified lithium cobaltate cathode material B' have the same general chemical formula and All are Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, and X is selected from Mg, Al, Zr, One or more of Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10.

在根据本发明第四方面所述的正极材料的制备方法中，首先对LiCoO2进行掺杂改性，以提高其在高电压下的结构稳定性，之后对LiCoO2进行表面包覆改性，进一步改善其在高电压下的结构稳定性。其中，在步骤(1)中加入的金属M盐在步骤(2)和步骤(3)的首次烧结过程中，元素M进入钴酸锂的体相掺杂位置，在步骤(2)和步骤(3)中加入的金属M盐在步骤(2)和步骤(3)的首次烧结过程中元素M进入钴酸锂的固溶体过渡层掺杂位置，一起起到对钴酸锂进行掺杂改性的目的。在步骤(2)和步骤(3)的二次烧结过程中，元素X(可为氧化物的形态)包覆在钴酸锂的表面，起到对钴酸锂进行表面包覆改性的目的。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, LiCoO2 is firstly modified by doping to improve its structural stability under high voltage, and then the LiCoO2 is surface - coated and modified, Further improve its structural stability under high voltage. Wherein, the metal M salt added in step (1) is in the first sintering process of step (2) and step (3), element M enters the bulk phase doping position of lithium cobaltate, in step (2) and step ( 3) The metal M salt added in the first sintering process of step (2) and step (3) enters the doping position of the solid solution transition layer of lithium cobaltate, and plays the role of doping and modifying lithium cobaltate together Purpose. In the secondary sintering process of step (2) and step (3), element X (which can be in the form of oxide) is coated on the surface of lithium cobalt oxide, so as to achieve the purpose of coating and modifying the surface of lithium cobalt oxide .

在这里补充说明的是，步骤(2)和步骤(3)的执行可以同时执行，或者步骤(2)先执行而步骤(3)后执行，或者步骤(3)先执行而步骤(2)后执行，不以书写顺序为限。It is supplemented here that the execution of step (2) and step (3) can be executed at the same time, or step (2) is executed first and step (3) is executed later, or step (3) is executed first and step (2) is executed after Execution is not limited to the order of writing.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，沉淀剂选自NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3、LiOH、NaOH中的一种或几种。沉淀剂溶液的浓度为40g/L～250g/L。沉淀剂溶液的进料速度为0.01m3/h～3m3/h。In the preparation method of the cathode material according to the fourth aspect of the present invention, in step (1), the precipitation agent is selected from NH 4 HCO 3 , (NH 4 ) 2 CO 3 , Na 2 CO 3 , NaHCO 3 , LiOH , NaOH in one or more. The concentration of the precipitant solution is 40g/L-250g/L. The feed rate of the precipitant solution is 0.01m 3 /h～3m 3 /h.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，Co盐选自硝酸钴、氯化钴、醋酸钴、硫酸钴中的一种或几种。Co盐溶液的浓度为50g/L～300g/L。Co盐溶液的进料速度为0.1m3/h～1m3/h。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (1), the Co salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt sulfate. The concentration of the Co salt solution is 50g/L-300g/L. The feeding rate of the Co salt solution is 0.1 m 3 /h˜1 m 3 /h.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。金属M盐的溶液的浓度为1g/L～100g/L。金属M盐的溶液的进料速度为0.1m3/h～0.8m3/h。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (1), the metal M salt is selected from one of metal M nitrates, hydrochlorides, acetates, sulfates or Several kinds. The concentration of the metal M salt solution is 1 g/L˜100 g/L. The feeding rate of the solution of the metal M salt is 0.1 m 3 /h to 0.8 m 3 /h.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，采用并流加料法进行混合。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (1), a parallel feeding method is used for mixing.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，控制反应体系的pH为6～9。In the preparation method of the cathode material according to the fourth aspect of the present invention, in step (1), the pH of the reaction system is controlled to be 6-9.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(1)中，反应温度为30℃～60℃，反应时间为4h～200h。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (1), the reaction temperature is 30°C-60°C, and the reaction time is 4h-200h.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(2)中，首次烧结的温度为600℃～1300℃，二次烧结的温度为600℃～1100℃。优选地，二次烧结的温度不大于首次烧结的温度。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (2), the temperature of the first sintering is 600°C-1300°C, and the temperature of the second sintering is 600°C-1100°C. Preferably, the temperature of the second sintering is not higher than the temperature of the first sintering.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(3)中，首次烧结的温度为500℃～1200℃，二次烧结的温度为600℃～1100℃。优选地，二次烧结的温度不大于首次烧结的温度。在根据本发明第四方面所述的正极材料的制备方法中，在步骤(2)中，锂盐选自碳酸锂、氢氧化锂中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (3), the temperature of the first sintering is 500°C-1200°C, and the temperature of the second sintering is 600°C-1100°C. Preferably, the temperature of the second sintering is not higher than the temperature of the first sintering. In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (2), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(3)中，锂盐选自碳酸锂、氢氧化锂中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (3), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(2)中，金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (2), the compound of metal X is selected from carbonates of metal X, nitrates of metal X, hydroxides of metal X, One or more of metal X oxides and metal X basic carbonates.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(3)中，金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (3), the compound of metal X is selected from carbonates of metal X, nitrates of metal X, hydroxides of metal X, One or more of metal X oxides and metal X basic carbonates.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(2)中，金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (2), the metal M salt is selected from one of metal M nitrates, hydrochlorides, acetates, sulfates or Several kinds.

在根据本发明第四方面所述的正极材料的制备方法中，在步骤(3)中，金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, in step (3), the metal M salt is selected from one of metal M nitrates, hydrochlorides, acetates, sulfates or Several kinds.

在根据本发明第四方面所述的正极材料的制备方法中，步骤(1)中加入的金属M盐与步骤(2)和步骤(3)中加入的金属M盐可以相同，也可以不同。In the preparation method of the positive electrode material according to the fourth aspect of the present invention, the metal M salt added in step (1) can be the same as or different from the metal M salt added in step (2) and step (3).

接下来说明根据本发明第五方面的正极极片。Next, the positive electrode sheet according to the fifth aspect of the present invention will be described.

根据本发明第五方面的正极极片包括正极集流体以及正极膜片。正极膜片设置于正极集流体上且正极膜片包括正极材料、导电剂以及粘结剂。其中，所述正极材料为根据本发明第一方面所述的正极材料或所述正极材料为根据本发明第三方面所述的正极材料。The positive electrode sheet according to the fifth aspect of the present invention includes a positive electrode current collector and a positive electrode membrane. The positive electrode film is arranged on the positive electrode current collector, and the positive electrode film includes positive electrode material, conductive agent and binder. Wherein, the positive electrode material is the positive electrode material according to the first aspect of the present invention or the positive electrode material is the positive electrode material according to the third aspect of the present invention.

在根据本发明第五方面所述的正极极片中，所述正极极片在压实后达到的压实密度≥4.0g/cm3。In the positive electrode sheet according to the fifth aspect of the present invention, the compacted density of the positive electrode sheet after compaction is ≥4.0 g/cm 3 .

接下来说明根据本发明第六方面的锂离子电池，其包括正极极片、负极极片、间隔于正负极极片之间的隔离膜以及电解液，其中，所述正极极片为根据本发明第五方面所述的正极极片。Next, the lithium ion battery according to the sixth aspect of the present invention is described, which includes a positive pole piece, a negative pole piece, a separator and an electrolyte spaced between the positive and negative pole pieces, wherein the positive pole piece is according to the present invention. The positive electrode sheet described in the fifth aspect of the invention.

下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。Below in conjunction with embodiment, further elaborate the present application. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application.

实施例1Example 1

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为2μm、二次颗粒的D50为13μm。(1) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 2 μm, and the secondary The D50 of the particles was 13 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结10h，得到D50为17μm、D99为40μm的单颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was ball milled with 1.48g Al 2 O 3 and 2.46g ZrO 2 and mixed in After sintering at 980°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 with D50 of 17 μm and D99 of 40 μm with a single particle spherical shape was obtained (corresponding to the modified lithium cobaltate positive electrode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm，D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。 119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate. After sintering at 900°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified lithium cobaltate positive electrode material B' ).

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 7:3 to obtain the final positive electrode material.

实施例2Example 2

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.05m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料50h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1μm、二次颗粒的D50为8μm。(1) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 50h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1 μm, and the secondary The D50 of the particles is 8 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在850℃烧结12h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在850℃烧结11h，得到D50为17μm、D99为40μm的单颗粒的片状形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 850°C for 12h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 by ball milling and mixed in After sintering at 850°C for 11 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 with D50 of 17 μm and D99 of 40 μm in flake shape was obtained (corresponding to the modified lithium cobaltate positive electrode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.1m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。 119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate. After sintering at 900°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified lithium cobaltate positive electrode material B' ).

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 7:3 to obtain the final positive electrode material.

实施例3Example 3

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料50h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1μm、二次颗粒的D50为8μm。(1) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 50h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1 μm, and the secondary The D50 of the particles is 8 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在850℃烧结12h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在930℃烧结11h，得到D50为17μm、D99为40μm的单颗粒的片状形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 850°C for 12h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 by ball milling and mixed in After sintering at 930°C for 11 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 with D50 of 17 μm and D99 of 40 μm in flake shape was obtained (corresponding to the modified lithium cobaltate positive electrode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、286.7g/L硝酸钴溶液、4.05g/L醋酸镁溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、醋酸镁溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Add 80g/L NH 4 HCO 3 solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the magnesium acetate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。 119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate. After sintering at 900°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified lithium cobaltate positive electrode material B' ).

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为8:2的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 8:2 to obtain the final positive electrode material.

实施例4Example 4

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、282.3g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为2μm、二次颗粒的D50为13μm。(1) Add 80g/L NH 4 HCO 3 solution, 282.3g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution through a peristaltic pump by feeding in parallel Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 2 μm, and the secondary The D50 of the particles was 13 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结10h，得到D50为17μm、D99为40μm的单颗粒的类球形形貌的正极材料Li1.02Co0.97Al0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was ball milled with 1.48g Al 2 O 3 and 2.46g ZrO 2 and mixed in After sintering at 980°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Al 0.03 O 2.08 Zr 0.02 Al 0.03 with D50 of 17 μm and D99 of 40 μm and single particle spherical shape was obtained (corresponding to the modified lithium cobaltate positive electrode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、282.3g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Add the NH 4 HCO 3 solution with a concentration of 80g/L, 282.3g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution through a peristaltic pump by means of co-current feeding Co-precipitation reaction was carried out in a reaction kettle previously added with 5L deionized water. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Al0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。 119g of the precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate. After sintering at 900°C for 10 hours, the positive electrode material Li 1.02 Co 0.97 Al 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified lithium cobaltate positive electrode material B' ).

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 7:3 to obtain the final positive electrode material.

实施例5Example 5

(1)并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为2μm、二次颗粒的D50为13μm。(1) The way of co-current feeding is that the NH 4 HCO 3 solution with a concentration of 80g/L, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added to the pre- Add 5L of deionized water to the reaction kettle for co-precipitation reaction. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 2 μm, and the secondary The D50 of the particles was 13 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结10h，得到D50为17μm、D99为40μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 980°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 900°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to the modified Lithium cobaltate cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的改性的钴酸锂正极材料。(3) Mechanically mixing the positive electrode material of step (1) with the positive electrode material of step (2) according to the mass ratio of 7:3 to obtain the final modified lithium cobaltate positive electrode material.

实施例6Example 6

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1μm、二次颗粒的D50为8μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1 μm, and the secondary The D50 of the particles is 8 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在850℃烧结12h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在850℃烧结11h，得到D50为17μm、D99为40μm的单颗粒的片状形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 850°C for 12h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 850°C for 11 hours to obtain the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为5μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles was 5 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在930℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 930°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified Lithium cobaltate cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 7:3 to obtain the final positive electrode material.

实施例7Example 7

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1μm、二次颗粒的D50为8μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1 μm, and the secondary The D50 of the particles is 8 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在850℃烧结12h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在850℃烧结11h，得到D50为17μm、D99为40μm的单颗粒的片状形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 850°C for 12h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 850°C for 11 hours to obtain the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.1μm、二次颗粒的D50为2μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.1 μm, two The D50 of the secondary particles is 2 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在880℃烧结8h，得到D50为3.2μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 880°C for 8h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified Lithium cobaltate cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为8:2的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 8:2 to obtain the final positive electrode material.

实施例8Example 8

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1μm、二次颗粒的D50为8μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1 μm, and the secondary The D50 of the particles is 8 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在850℃烧结12h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结10h，得到D50为17μm、D99为40μm的单颗粒的片状形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 850°C for 12h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 980°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.10m3/h、NH4HCO3溶液的进料速度为0.20m3/h、氢氧化锂溶液的进料速度为0.5m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料20h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒的D50为0.05μm、二次颗粒的D50为1μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.10m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.20m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.5m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 20h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the D50 of the primary particle is 0.05 μm, two The D50 of the secondary particles is 1 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在850℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在800℃烧结10h，得到D50为2μm、D99为15μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 850°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 800°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为8:2的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 8:2 to obtain the final positive electrode material.

实施例9Example 9

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料55h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为1.5μm、二次颗粒的D50为10μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 55h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 1.5 μm, two The D50 of the secondary particles is 10 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在980℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在950℃烧结10h，得到D50为14.1μm、D99为35μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 980°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 950°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒D50为0.1μm，二次颗粒D50为5μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the primary particle D50 is 0.1 μm, and the secondary The particle D50 is 5 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 900°C for 10 h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to the modified Lithium cobaltate cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为5:5的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 5:5 to obtain the final positive electrode material.

实施例10Example 10

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料50h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒D50为1.2μm，二次颗粒D50为9.5μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 50h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the primary particle D50 is 1.2 μm, and the secondary The particle D50 is 9.5 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在950℃烧结12h，得到D50为12.3μm、D99为55μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 950°C for 12 hours to obtain a positive electrode material with a spherical shape of a single particle with a D50 of 12.3 μm and a D99 of 55 μm Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料35h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒D50为0.8μm，二次颗粒D50为6μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 35h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the primary particle D50 is 0.8 μm, and the secondary The particle D50 is 6 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结11h，得到D50为8μm、D99为32μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 900°C for 11 hours, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为9:1的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 9:1 to obtain the final positive electrode material.

实施例11Example 11

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料80h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒D50为2μm，二次颗粒D50为20μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 80h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the primary particle D50 is 2 μm, and the secondary particle D50 is 20 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结12h，得到D50为23.5μm、D99为55μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 980°C for 12h, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料35h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒D50为0.8μm，二次颗粒D50为6μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.15m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 35h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), the primary particle D50 is 0.8 μm, and the secondary The particle D50 is 6 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在950℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在950℃烧结9h，得到D50为8μm、D99为32μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 950°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 950°C for 9 hours to obtain the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为3:7的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 3:7 to obtain the final positive electrode material.

对比例1Comparative example 1

(1)采用并流加料的方式将浓度为200g/L的NH4HCO3溶液和286.7g/L硝酸钴溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为40℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h，连续进料60h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物，其一次颗粒的D50为1.1μm，二次颗粒的D50为14μm。(1) The NH 4 HCO 3 solution with a concentration of 200g/L and the cobalt nitrate solution with a concentration of 286.7g/L were fed into the reactor pre-filled with 5L deionized water through a peristaltic pump to carry out co-precipitation reaction. Control the temperature of the reactor to 40°C, adjust the pH to 8, adjust the feeding rate of the cobalt nitrate solution to 0.3m 3 /h, and the feeding rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and continuously feed for 60h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate, the D50 of the primary particle is 1.1 μm, and the D50 of the secondary particle is 14 μm .

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在1000℃烧结10h形成钴酸锂(未改性的钴酸锂)，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结12h，得到D50为17.5μm、D99为45μm的单颗粒的类球形形貌的正极材料LiCoO2.08Zr0.02Al0.03。119g of precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate (unmodified lithium cobaltate). g ZrO 2 was mixed by ball milling and sintered at 980°C for 12 hours to obtain the positive electrode material LiCoO 2.08 Zr 0.02 Al 0.03 with D50 of 17.5 μm and D99 of 45 μm with a single particle spherical shape.

(2)采用并流加料的方式将浓度为200g/L的NH4HCO3溶液和286.7g/L硝酸钴溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为35℃，调节pH至8，调节硝酸钴溶液的进料速度为0.15m3/h、NH4HCO3溶液的进料速度为0.28m3/h，连续进料24h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物，其一次颗粒的D50为0.5μm，二次颗粒的D50为5μm。(2) The NH 4 HCO 3 solution with a concentration of 200g/L and the cobalt nitrate solution with a concentration of 286.7g/L were fed into the reaction kettle pre-filled with 5L deionized water through a peristaltic pump to carry out co-precipitation reaction. Control the temperature of the reactor to 35°C, adjust the pH to 8, adjust the feeding rate of the cobalt nitrate solution to 0.15m 3 /h, and the feeding rate of the NH 4 HCO 3 solution to 0.28m 3 /h, and continuously feed for 24h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate, the D50 of the primary particle is 0.5 μm, and the D50 of the secondary particle is 5 μm .

将119g前驱体沉淀物、100g碳酸锂进行球磨混匀并在900℃烧结10h形成钴酸锂(未改性的钴酸锂)，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在900℃烧结10h，得到D50为6.5μm、D99为28μm的二次颗粒的类球形形貌的正极材料LiCoO2.08Zr0.02Al0.03。119g of precursor precipitate and 100g of lithium carbonate were mixed by ball milling and sintered at 900°C for 10h to form lithium cobaltate (unmodified lithium cobaltate). g ZrO 2 was ball milled and sintered at 900°C for 10 h to obtain a positive electrode material LiCoO 2.08 Zr 0.02 Al 0.03 with a spherical shape of secondary particles with a D50 of 6.5 μm and a D99 of 28 μm.

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的正极材料。(3) Mechanically mixing the positive electrode material in step (1) with the positive electrode material in step (2) according to a mass ratio of 7:3 to obtain the final positive electrode material.

对比例2Comparative example 2

仅使用实施例6中步骤(2)中的D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。Only use the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding modified Lithium cobalt oxide cathode material B').

对比例3Comparative example 3

仅使用实施例11中步骤(1)中的D50为23.5μm、D99为55μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。Only use the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified Lithium cobalt oxide cathode material A').

对比例4Comparative example 4

(1)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.05m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料90h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物A)，其一次颗粒的D50为3μm，二次颗粒的D50为25μm。(1) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.05m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 90h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate A), the D50 of the primary particle is 3 μm, and the secondary The D50 of the particles is 25 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在980℃烧结12h，得到D50为28μm、D99为62μm的单颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 980°C for 12 hours, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt acid Lithium cathode material A').

(2)采用并流加料的方式将浓度为80g/L的NH4HCO3溶液、280g/L硝酸钴溶液、11.25g/L硝酸铝溶液和40g/L的氢氧化锂溶液通过蠕动泵加入到预先加入5L去离子水的反应釜中进行共沉淀反应。控制反应釜的温度为50℃，调节pH至8，调节硝酸钴溶液的进料速度为0.3m3/h、NH4HCO3溶液的进料速度为0.7m3/h、氢氧化锂溶液的进料速度为0.1m3/h、硝酸铝溶液的进料速度为0.12m3/h，连续进料50h。然后停止搅拌并抽滤，用去离子水洗涤沉淀物至滤液的pH小于7，在90℃下干燥得到球形的前驱体沉淀物(对应沉淀物B)，其一次颗粒D50为1.1μm、二次颗粒D50为10.5μm。(2) Adopting the mode of co-current feeding, the lithium hydroxide solution that concentration is 80g/L NH 4 HCO 3 solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L is added into by peristaltic pump The co-precipitation reaction was carried out in a reaction kettle with 5L of deionized water added in advance. Control the temperature of the reactor to 50°C, adjust the pH to 8, adjust the feed rate of the cobalt nitrate solution to 0.3m 3 /h, the feed rate of the NH 4 HCO 3 solution to 0.7m 3 /h, and the feed rate of the lithium hydroxide solution The feeding rate is 0.1m 3 /h, the feeding rate of the aluminum nitrate solution is 0.12m 3 /h, and the continuous feeding is 50h. Then stop stirring and filter with suction, wash the precipitate with deionized water until the pH of the filtrate is less than 7, and dry at 90°C to obtain a spherical precursor precipitate (corresponding to precipitate B), whose primary particle D50 is 1.1 μm, secondary The particle D50 is 10.5 μm.

将119g前驱体沉淀物、100g碳酸锂和0.84g碳酸镁进行球磨混匀并在1000℃烧结10h形成钴酸锂，之后将得到的钴酸锂与1.48g Al2O3和2.46g ZrO2进行球磨混匀并在950℃烧结10h，得到D50为12μm、D99为40μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate were mixed by ball milling and sintered at 1000°C for 10h to form lithium cobaltate, and then the obtained lithium cobaltate was mixed with 1.48g Al 2 O 3 and 2.46g ZrO 2 Mixed by ball milling and sintered at 950°C for 10 hours, the positive electrode material Li 1.02 Co 0.96 Al 0.03 Mg 0.01 O 2.07 Zr 0.02 Al 0.03 (corresponding to modified cobalt lithium acid cathode material B').

(3)将步骤(1)的正极材料与步骤(2)的正极材料按照质量比为7:3的比例进行机械混合，得到最终的改性的钴酸锂正极材料。(3) Mechanically mixing the positive electrode material of step (1) with the positive electrode material of step (2) according to the mass ratio of 7:3 to obtain the final modified lithium cobaltate positive electrode material.

对比例5Comparative example 5

仅使用实施例1中步骤(1)中的D50为17μm、D99为40μm的单颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料A’)。Only use the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified lithium cobaltate Cathode material A').

对比例6Comparative example 6

仅使用实施例1中步骤(2)中的D50为6.3μm、D99为25μm的二次颗粒的类球形形貌的正极材料Li1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(对应改性的钴酸锂正极材料B’)。Only use the positive electrode material Li 1.02 Co 0.97 Mg 0.03 O 2.08 Zr 0.02 Al 0.03 (corresponding to the modified cobalt lithium acid cathode material B').

对比例7Comparative example 7

正极材料的制备于实施例2相同，区别在于步骤(1)的正极材料与步骤(2)的正极材料的质量比为11:1。The preparation of the positive electrode material was the same as in Example 2, except that the mass ratio of the positive electrode material in step (1) to the positive electrode material in step (2) was 11:1.

下面说明锂离子电池的制备。The preparation of the lithium ion battery will be described below.

正极极片的制备：以实施例1-11和对比例1-7中制得的正极材料作为锂离子电池的正极材料、以Super-P作为导电剂、以PVDF作为粘结剂，将正极材料、导电剂、粘结剂按质量比为97:1:2加入NMP中，搅拌均匀，涂覆在正极集流体铝箔(厚度为12μm)的两面上，经过干燥、冷压、分切后得到正极极片。Preparation of the positive electrode sheet: the positive electrode material obtained in Examples 1-11 and Comparative Examples 1-7 is used as the positive electrode material of the lithium ion battery, with Super-P as the conductive agent, with PVDF as the binding agent, the positive electrode material , conductive agent, and binder are added to NMP at a mass ratio of 97:1:2, stirred evenly, coated on both sides of the positive electrode current collector aluminum foil (thickness 12 μm), dried, cold pressed, and cut to obtain the positive electrode pole piece.

负极极片的制备：将负极材料人造石墨、增稠剂CMC、粘结剂SBR按照重量比98:1:1进行混合，加入去离子水搅拌均匀，涂覆到负极集流体铜箔(厚度为8μm)的两面上，经过干燥、冷压、分切后得到负极极片。Preparation of the negative electrode sheet: mix the negative electrode material artificial graphite, the thickener CMC, and the binder SBR according to the weight ratio of 98:1:1, add deionized water and stir evenly, and coat the negative electrode current collector copper foil (thickness: 8 μm) on both sides, after drying, cold pressing, and cutting, the negative electrode sheet is obtained.

电解液的制备：电解液包括有机溶剂和锂盐，有机溶剂为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸乙烯酯(EC)的混合物，三种有机溶剂的体积比为1:1:1，锂盐为LiPF6，浓度为1mol/L。The preparation of electrolytic solution: electrolytic solution comprises organic solvent and lithium salt, and organic solvent is the mixture of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylene carbonate (EC), and the volume ratio of three kinds of organic solvents is 1:1:1, the lithium salt is LiPF 6 , the concentration is 1mol/L.

锂离子电池的制备：将正极极片、负极极片和隔离膜(PE膜)以常规工艺卷绕，然后经过端子焊接、包装铝箔封装、注液、封装化成、抽气成型制得软包装锂离子电池。Lithium-ion battery preparation: wind the positive pole piece, negative pole piece and separator (PE film) in a conventional process, and then undergo terminal welding, packaging aluminum foil packaging, liquid injection, packaging formation, and suction molding to obtain a flexible packaging lithium-ion battery. Battery.

接下来说明锂离子电池的性能测试。Next, the performance test of the lithium-ion battery will be described.

1、正极极片的压实密度测试1. The compaction density test of the positive pole piece

取冷压后的正极极片，裁切得到面积为1540.25mm2的小圆片，测得冷压后的极片厚度为h1(mm)，正极集流体铝箔的厚度为h2(mm)，小圆片的重量为m(g)，则正极极片的压实密度PD＝1000m/1540.25(h1-h2)(单位：g/cm3)。Take the cold-pressed positive pole piece, cut it into a small disc with an area of 1540.25mm 2 , measure the thickness of the cold-pressed pole piece as h 1 (mm), and the thickness of the positive electrode current collector aluminum foil as h 2 (mm) , the weight of the small disc is m (g), then the compacted density of the positive pole piece PD = 1000m/1540.25(h 1 -h 2 ) (unit: g/cm 3 ).

2、锂离子电池的循环性能测试2. Cycle performance test of lithium ion battery

在25℃下，以0.5C(1225mA)恒流充电至4.45V，4.45V恒压至0.05C(123mA)，然后0.5C(1225mA)放电至3.0V，反复进行上述充放电循环，记录锂离子电池的容量保持率衰减到80％时的循环圈数。At 25°C, charge at 0.5C (1225mA) constant current to 4.45V, 4.45V constant voltage to 0.05C (123mA), and then discharge at 0.5C (1225mA) to 3.0V, repeat the above charge and discharge cycle, and record lithium ion The number of cycles when the capacity retention rate of the battery decays to 80%.

3、锂离子电池的高温存储性能测试3. High temperature storage performance test of lithium ion battery

在25℃下，以0.5C(1225mA)恒流充电至4.45V，4.45V恒压至0.05C(123mA)，然后0.5C(1225mA)放电至3.0V，记录其第一次放电容量；随后，在25℃下，以0.5C(1225mA)恒流充电至4.45V，4.45V恒压至0.05C(123mA)，测定存储前的锂离子电池的厚度。接着，将上述满充的锂离子电池在85℃烘箱中存储6h后，趁热测试存储后的锂离子电池的厚度。锂离子电池存储后的厚度膨胀率＝(存储后锂离子电池的厚度-存储前锂离子电池的厚度)/(存储前锂离子电池的厚度)×100％。At 25°C, charge to 4.45V at 0.5C (1225mA) constant current, 4.45V constant voltage to 0.05C (123mA), and then discharge to 3.0V at 0.5C (1225mA), record its first discharge capacity; then, At 25°C, charge at a constant current of 0.5C (1225mA) to 4.45V, and a constant voltage of 4.45V to 0.05C (123mA), and measure the thickness of the lithium-ion battery before storage. Next, after the above-mentioned fully charged lithium-ion battery was stored in an oven at 85°C for 6 hours, the thickness of the stored lithium-ion battery was tested while it was still hot. Thickness expansion rate of the lithium-ion battery after storage=(thickness of the lithium-ion battery after storage-thickness of the lithium-ion battery before storage)/(thickness of the lithium-ion battery before storage)×100%.

4、锂离子电池的安全性能测试4. Safety performance test of lithium ion battery

在25℃下，以0.5C(1225mA)恒流充电至4.50V，4.50V恒压至0.05C(123mA)，在氩气保护的手套箱内将锂离子电池拆开，取出正极极片后在DMC溶液中清洗，待DMC完全挥发后，从正极极片表面刮下正极材料，称取10mg的正极材料放入特制的铝坩埚中，并加入0.1μL的电解液(与锂离子电池的制备过程相同)后密封进行DSC测试。DSC测试的扫描温度范围为50℃～500℃，升温速率为10℃/min，测试主峰所对应的温度即为释氧温度。At 25°C, charge at 0.5C (1225mA) constant current to 4.50V, 4.50V constant voltage to 0.05C (123mA), disassemble the lithium-ion battery in an argon-protected glove box, take out the positive pole piece Wash in DMC solution, after DMC volatilizes completely, scrape off the positive electrode material from the surface of the positive electrode sheet, weigh 10 mg of the positive electrode material and put it into a special aluminum crucible, and add 0.1 μ L of electrolyte (with the preparation process of lithium-ion battery Same) after sealing for DSC test. The scanning temperature range of the DSC test is 50°C to 500°C, and the heating rate is 10°C/min. The temperature corresponding to the main peak of the test is the oxygen release temperature.

表1实施例1-11和对比例1-7的性能测试结果The performance test result of table 1 embodiment 1-11 and comparative example 1-7

从表1中可以看出，由本发明的正极材料制备的正极极片具有更高的压实密度，锂离子电池的循环圈数增加、且高温存储后的厚度膨胀率降低且正极材料的释氧温度提高，能得到循环性能、存储性能以及安全性能均更优的锂离子电池。As can be seen from Table 1, the positive electrode sheet prepared by the positive electrode material of the present invention has a higher compaction density, the number of cycles of the lithium-ion battery increases, and the thickness expansion rate after high-temperature storage decreases and the oxygen release rate of the positive electrode material When the temperature is increased, a lithium-ion battery with better cycle performance, storage performance and safety performance can be obtained.

参照图1和图2，分别为实施例4中的沉淀物B和沉淀物A的SEM。参照图3和图4分别为实施例4的大粒径的改性的钴酸锂正极材料A’以及小粒径的改性的钴酸锂正极材料B’的SEM图。图5为实施例4的冷压后的正极极片的SEM图。从图5中可以看出，正极材料颗粒呈现紧密堆积的状态，因此正极极片的压实密度较高。Referring to Fig. 1 and Fig. 2, it is the SEM of precipitate B and precipitate A in embodiment 4 respectively. 3 and 4 are the SEM images of the modified lithium cobaltate positive electrode material A' of the large particle size and the modified lithium cobaltate positive electrode material B' of the small particle size of Example 4, respectively. FIG. 5 is an SEM image of the cold-pressed positive electrode sheet of Example 4. FIG. It can be seen from Figure 5 that the positive electrode material particles are in a tightly packed state, so the compaction density of the positive electrode sheet is relatively high.

对比例1中没有对钴酸锂进行体相掺杂，导致锂离子电池的循环性能、存储性能以及安全性能均较差。对比例2、对比例6中仅使用单一的小粒径的改性的钴酸锂正极材料B’，导致正极极片的压实密度较低，锂离子电池的循环性能变差，正极材料的释氧温度降低，锂离子电池的安全性能变差，且由于小粒径的改性的钴酸锂正极材料B’与电解液接触的比表面积更大，导致锂离子电池高温存储后的厚度膨胀率明显增加，存储性能严重恶化。对比例3、对比例5中仅使用单一的大粒径的改性的钴酸锂正极材料A’，导致正极极片的压实密度也较低，大粒径的改性的钴酸锂正极材料A’的极化较大，且冷压后的正极极片中的正极材料颗粒容易破碎，使得破碎处的正极材料与电解液反应，导致锂离子电池的循环性能较差。对比例4中，改性的钴酸锂正极材料A’和改性的钴酸锂正极材料B’的粒径均过高，反而导致正极极片的压实密度降低，锂离子电池的性能恶化。在对比例7中，改性的钴酸锂正极材料A’与改性的钴酸锂正极材料B’的质量比过大，在得到的正极材料中大粒径的改性的钴酸锂正极材料A’占比过大，容易导致冷压后的正极极片中的正极材料颗粒破碎，使得破碎处的正极材料与电解液反应，反而导致锂离子电池的性能变差。In Comparative Example 1, lithium cobaltate was not doped in bulk, resulting in poor cycle performance, storage performance and safety performance of the lithium-ion battery. In Comparative Example 2 and Comparative Example 6, only the modified lithium cobaltate positive electrode material B' with a single small particle size is used, resulting in low compaction density of the positive electrode sheet, poor cycle performance of the lithium-ion battery, and poor performance of the positive electrode material. As the oxygen release temperature decreases, the safety performance of the lithium-ion battery deteriorates, and because the small particle size modified lithium cobaltate cathode material B' has a larger specific surface area in contact with the electrolyte, resulting in thickness expansion of the lithium-ion battery after high-temperature storage The rate increases significantly, and the storage performance deteriorates severely. In Comparative Example 3 and Comparative Example 5, only a single modified lithium cobaltate positive electrode material A' with a large particle size was used, resulting in a low compaction density of the positive electrode sheet, and the modified lithium cobaltate positive electrode with a large particle size The polarization of material A' is relatively large, and the positive electrode material particles in the cold-pressed positive electrode sheet are easily broken, so that the positive electrode material at the broken place reacts with the electrolyte, resulting in poor cycle performance of the lithium-ion battery. In Comparative Example 4, the particle sizes of the modified lithium cobaltate positive electrode material A' and the modified lithium cobaltate positive electrode material B' are too high, which instead leads to a decrease in the compaction density of the positive electrode sheet and deterioration of the performance of the lithium-ion battery. . In Comparative Example 7, the mass ratio of the modified lithium cobaltate positive electrode material A' to the modified lithium cobaltate positive electrode material B' is too large, and the modified lithium cobaltate positive electrode with a large particle size in the obtained positive electrode material If the proportion of material A' is too large, it is easy to cause the cathode material particles in the cold-pressed cathode sheet to be broken, so that the cathode material at the broken place reacts with the electrolyte, which in turn leads to the deterioration of the performance of the lithium-ion battery.

Claims (13)

1. a kind of positive electrode, it is characterised in that the positive electrode includes modified lithium cobaltate cathode material A ' and is modified Lithium cobaltate cathode material B ', the lithium cobaltate cathode material A ' of the modification and the lithium cobaltate cathode material B ' of the modification Mass ratio is d:1；
The D50 of the lithium cobaltate cathode material A ' of modification particle is 10 μm~25 μm, D99 is 30 μm~60 μm, described to change Property lithium cobaltate cathode material A ' pattern be individual particle spherical or sheet；
The D50 of the lithium cobaltate cathode material B ' of modification particle is 1 μm~10 μm, D99 is 8 μm~30 μm, the modification Lithium cobaltate cathode material B ' pattern it is spherical or second particle spherical for individual particle；
The D50 of the lithium cobaltate cathode material A ' of modification particle is more than the lithium cobaltate cathode material B ' of modification particle D50；
The D99 of the lithium cobaltate cathode material A ' of modification particle is more than the lithium cobaltate cathode material B ' of modification particle D99；
Wherein, the lithium cobaltate cathode material A ' of the modification is identical with the lithium cobaltate cathode material B ' of modification chemical general formula And it is Li1+aCo1-bMbO2+cXm, one or more of the M in Al, Mg, Y, Ni, Mn, La, X be selected from Mg, Al, Zr, Ti, Ni, One or more in Mn, Y, Nb, 0≤a≤0.1, the 0 ＜ ＜ of b≤0.1,0≤c≤1,0 m≤0.1,0 ＜ d≤10, M are located at cobalt The bulk phase-doped position of sour lithium, X are coated on the surface of cobalt acid lithium.
2. positive electrode according to claim 1, it is characterised in that X is coated on the table of cobalt acid lithium in the form of oxide Face.
A kind of 3. preparation method of positive electrode, for preparing the positive electrode any one of claim 1-2, including step Suddenly：
(1) solution of precipitant solution, Co salting liquids, metal M salt is added into mixing in reactor and carries out coprecipitation reaction, dried The sediment A and sediment B of different-grain diameter are respectively obtained afterwards, and the D50 of sediment A primary particle is 1 μm~5 μm, secondary The D50 of grain is 5 μm~20 μm, and the D50 of the primary particle of sediment B is 0.05 μm~1 μm, the D50 of second particle is 1 μm~10 μm；
(2) after mixing sediment A, lithium salts and being sintered first, then mixed with metal X compound and carry out double sintering, Obtain modified lithium cobaltate cathode material A ', the D50 of the lithium cobaltate cathode material A ' of modification particle is 10 μm~25 μm, D99 is 30 μm~60 μm, and the lithium cobaltate cathode material A ' of modification pattern is the spherical or sheet of individual particle；
(3) after mixing sediment B, lithium salts and being sintered first, then mixed with metal X compound and carry out double sintering, Obtain modified lithium cobaltate cathode material B ', the D50 of the lithium cobaltate cathode material B ' of modification particle is 1 μm~10 μm, D99 is 8 μm~30 μm, and the lithium cobaltate cathode material B ' of modification pattern is spherical or second particle the class of individual particle It is spherical；
(4) by the lithium cobaltate cathode material A ' of the modification and the lithium cobaltate cathode material B ' d in mass ratio of the modification:1 is mixed Close, that is, complete the preparation of positive electrode, wherein, the D50 of the lithium cobaltate cathode material A ' of modification particle is more than described change Property lithium cobaltate cathode material B ' particle D50, the D99 of the lithium cobaltate cathode material A ' of modification particle is more than described The D99 of modified lithium cobaltate cathode material B ' particle, the lithium cobaltate cathode material A ' of the modification and the cobalt acid of the modification Lithium anode material B ' chemical general formula is identical and is Li1+aCo1-bMbO2+cXm, the one kind of M in Al, Mg, Y, Ni, Mn, La Or several, one or more of the X in Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1,0 ＜ b≤0.1,0≤c≤1, 0 ＜ m≤0.1,0 ＜ d≤10.
4. the preparation method of positive electrode according to claim 3, it is characterised in that in step (1),
Precipitating reagent is selected from NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3, one or more in LiOH, NaOH；
One or more of the Co salt in cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate；
One or more in nitrate of the metal M salt selected from metal M, hydrochloride, acetate, sulfate.
5. the preparation method of positive electrode according to claim 3, it is characterised in that in step (2) and step (3),
One or more of the lithium salts in lithium carbonate, lithium hydroxide；
Metal X compound be selected from metal X carbonate, metal X nitrate, metal X hydroxide, metal X oxidation Thing, metal X subcarbonate in one or more.
6. a kind of positive electrode, it is characterised in that the positive electrode includes modified lithium cobaltate cathode material A ' and is modified Lithium cobaltate cathode material B ', the lithium cobaltate cathode material A ' of the modification and the lithium cobaltate cathode material B ' of the modification Mass ratio is d:1；
The D50 of the lithium cobaltate cathode material A ' of modification particle is 10 μm~25 μm, D99 is 30 μm~60 μm, described to change Property lithium cobaltate cathode material A ' pattern be individual particle spherical or sheet；
The D50 of the lithium cobaltate cathode material B ' of modification particle is 1 μm~10 μm, D99 is 8 μm~30 μm, the modification Lithium cobaltate cathode material B ' pattern it is spherical or second particle spherical for individual particle；
The D50 of the lithium cobaltate cathode material A ' of modification particle is more than the lithium cobaltate cathode material B ' of modification particle D50；
The D99 of the lithium cobaltate cathode material A ' of modification particle is more than the lithium cobaltate cathode material B ' of modification particle D99；
Wherein, the lithium cobaltate cathode material A ' of the modification is identical with the lithium cobaltate cathode material B ' of modification chemical general formula And it is Li1+aCo1-bMbO2+cXm, one or more of the M in Al, Mg, Y, Ni, Mn, La, X be selected from Mg, Al, Zr, Ti, Ni, One or more in Mn, Y, Nb, 0≤a≤0.1, the 0 ＜ ＜ of b≤0.1,0≤c≤1,0 m≤0.1,0 ＜ d≤10, M are located at cobalt The bulk phase-doped position of sour lithium and solid solution transition zone doping position, X are coated on the surface of cobalt acid lithium.
7. positive electrode according to claim 6, it is characterised in that X is coated on the table of cobalt acid lithium in the form of oxide Face.
A kind of 8. preparation method of positive electrode, for preparing the positive electrode any one of claim 6-7, including step Suddenly：
(1) solution of precipitant solution, Co salting liquids, metal M salt is added into mixing in reactor and carries out coprecipitation reaction, dried The sediment A and sediment B of different-grain diameter are respectively obtained afterwards, and the D50 of sediment A primary particle is 1 μm~5 μm, secondary The D50 of grain is 5 μm~20 μm, and the D50 of the primary particle of sediment B is 0.05 μm~1 μm, the D50 of second particle is 1 μm~10 μm；
(2) after sediment A, lithium salts and metal M salt being mixed and sintered first, then it is mixed into metal X compound Row double sintering, obtains modified lithium cobaltate cathode material A ', and the D50 of the lithium cobaltate cathode material A ' of modification particle is 10 μm~25 μm, D99 be 30 μm~60 μm, the lithium cobaltate cathode material A ' of modification pattern for the spherical of individual particle or Sheet；
(3) after sediment B, lithium salts and metal M salt being mixed and sintered first, then it is mixed into metal X compound Row double sintering, obtains modified lithium cobaltate cathode material B ', and the D50 of the lithium cobaltate cathode material B ' of modification particle is 1 μm~10 μm, D99 be 8 μm~30 μm, the lithium cobaltate cathode material B ' of modification pattern is individual particle spherical or two Secondary particle it is spherical；
(4) by the lithium cobaltate cathode material A ' of the modification and the lithium cobaltate cathode material B ' d in mass ratio of the modification:1 is mixed Close, that is, complete the preparation of positive electrode, wherein, the D50 of the lithium cobaltate cathode material A ' of modification particle is more than described change Property lithium cobaltate cathode material B ' particle D50, the D99 of the lithium cobaltate cathode material A ' of modification particle is more than described The D99 of modified lithium cobaltate cathode material B ' particle, the lithium cobaltate cathode material A ' of the modification and the cobalt acid of the modification Lithium anode material B ' chemical general formula is identical and is Li1+aCo1-bMbO2+cXm, the one kind of M in Al, Mg, Y, Ni, Mn, La Or several, one or more of the X in Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1,0 ＜ b≤0.1,0≤c≤1, 0 ＜ m≤0.1,0 ＜ d≤10.
9. the preparation method of positive electrode according to claim 8, it is characterised in that in step (1),
Precipitating reagent is selected from NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3, one or more in LiOH, NaOH；
One or more of the Co salt in cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate；
One or more in nitrate of the metal M salt selected from metal M, hydrochloride, acetate, sulfate.
10. the preparation method of positive electrode according to claim 8, it is characterised in that in step (2) and step (3),
One or more in nitrate of the metal M salt selected from metal M, hydrochloride, acetate, sulfate；
One or more of the lithium salts in lithium carbonate, lithium hydroxide；
Metal X compound be selected from metal X carbonate, metal X nitrate, metal X hydroxide, metal X oxidation Thing, metal X subcarbonate in one or more.
11. a kind of anode pole piece, including：
Plus plate current-collecting body；And
Positive pole diaphragm, it is arranged on plus plate current-collecting body and including positive electrode, conductive agent and binding agent；
Characterized in that,
The positive electrode is the positive electrode according to any one of claim 1-2,6-7.
12. anode pole piece according to claim 11, it is characterised in that the compacting that the anode pole piece reaches after compaction Density >=4.0g/cm3。
13. a kind of lithium ion battery, it is characterised in that including the anode pole piece according to claim 11 or 12.
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