WO2024103614A1 - Method for reducing content of magnetic substances in lithium battery positive electrode material - Google Patents

Method for reducing content of magnetic substances in lithium battery positive electrode material Download PDF

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Publication number
WO2024103614A1
WO2024103614A1 PCT/CN2023/086978 CN2023086978W WO2024103614A1 WO 2024103614 A1 WO2024103614 A1 WO 2024103614A1 CN 2023086978 W CN2023086978 W CN 2023086978W WO 2024103614 A1 WO2024103614 A1 WO 2024103614A1
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positive electrode
lithium
electrode material
lithium battery
battery positive
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PCT/CN2023/086978
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French (fr)
Chinese (zh)
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邱新民
许开华
张翔
陈玉君
施杨
金健
任正田
黄芬
许玉松
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格林美（无锡）能源材料有限公司
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Publication of WO2024103614A1 publication Critical patent/WO2024103614A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application belongs to the technical field of lithium-ion batteries and relates to a positive electrode material for a lithium battery, for example, a method for reducing the content of magnetic substances in a positive electrode material for a lithium battery.
  • lithium-ion batteries have been widely used in various fields such as mobile phones, digital cameras, laptops, electronic cigarettes, drones and new energy vehicles due to their high energy density and rate performance, as well as long service life.
  • the conventional method to reduce the content of magnetic foreign matter is mainly to remove iron through screening, that is, to pass the material through a high-strength Gaussian flux magnetic core to adsorb the magnetic material.
  • This method needs to be repeated many times, and the demagnetization effect is not ideal, especially for the weak magnetic materials in the material.
  • the adsorption capacity is poor, and it has no effect on products tested using the weak magnetic method.
  • the present application provides a method for reducing the content of magnetic substances in lithium battery positive electrode materials.
  • the method is particularly targeted at weakly magnetic substances, avoiding their adverse effects on battery performance, improving the demagnetization effect while increasing the demagnetization efficiency, and reducing safety risks and process costs.
  • step (2) sintering the positive electrode mixture obtained in step (1) to obtain a second lithium battery positive electrode material
  • the magnetic content in the second lithium battery positive electrode material is ⁇ 100ppb, for example, it can be 10ppb, 20ppb, 30ppb, 40ppb, 50ppb, 60ppb, 70ppb, 80ppb, 90ppb or 100ppb, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the present application achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by uniformly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and utilizing the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe, Fe2O3, etc., to generate non-magnetic substances such as LizFexCoyO2 , thereby achieving the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery, and the content of magnetic substances is reduced by more than 50% or the content of magnetic substances is reduced to less than 100ppb, without adversely affecting the performance and safety performance of the battery, and the process flow is simple, the cost is low, and it is convenient for large-scale promotion and application.
  • the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content ⁇ 100 ppb, for example, 100 ppb, 200 ppb, 300 ppb, 400 ppb, 500 ppb, 600 ppb, 700 ppb, 800 ppb or 900 ppb, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the first lithium battery positive electrode material comprises any one of nickel cobalt manganese oxide, nickel cobalt aluminum oxide, nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof.
  • Typical but non-limiting combinations include a combination of nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide, a combination of nickel cobalt aluminum oxide and lithium nickel manganese oxide, a combination of nickel manganese oxide and lithium cobalt oxide, a combination of lithium cobalt oxide and lithium manganese oxide, a combination of nickel cobalt manganese oxide, lithium cobalt aluminum oxide and lithium manganese oxide, a combination of nickel cobalt aluminum oxide, lithium manganese oxide and lithium cobalt oxide, or a combination of nickel manganese oxide, lithium cobalt oxide and lithium manganese oxide.
  • the lithium salt in step (1) comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two of them.
  • Typical but non-limiting combinations include a combination of lithium carbonate and lithium hydroxide, a combination of lithium hydroxide and lithium oxide, a combination of lithium carbonate and lithium oxide, or a combination of lithium carbonate, lithium hydroxide and lithium oxide.
  • the mixed mass of the lithium salt in step (1) accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0, for example, it can be 0.01%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the mixing in step (1) is accompanied by stirring, and the stirring rate is 100-500 rpm, for example, it can be 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the sintering process in step (2) is carried out in a sagger, and the sagger is placed in a kiln.
  • the heating rate of the sintering treatment in step (2) is 0.1-5°C/min, for example, it can be 0.1°C/min, 0.5°C/min, 1.5°C/m, 1.5°C/min, 2.5°C/m, 2.5°C/min, 3.5°C/m, 3.5°C/min, 4.5°C/m, 4.5°C/min or 5°C/min, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the target temperature of the sintering treatment in step (2) is 300-950°C, for example, it can be 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C or 950°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the target temperature of the sintering treatment needs to be controlled within a reasonable range.
  • the target temperature is lower than 300°C, the reaction between the lithium salt and the weakly magnetic substance in the positive electrode material is not complete, thereby reducing the demagnetization efficiency and the demagnetization effect is not ideal; when the target temperature is higher than 950°C, it will cause an unnecessary increase in the processing cost.
  • the holding time of the sintering treatment in step (2) is 12-30h, for example, it can be 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h or 30h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
  • the method comprises the following steps:
  • the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content of ⁇ 100 ppb
  • the first lithium battery positive electrode material comprises any one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof
  • the lithium salt comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two thereof, and the mixed mass of the lithium salt accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0;
  • step (2) (2) transferring the positive electrode mixture obtained in step (1) into a sagger, and placing the sagger in a kiln for sintering, wherein the heating rate of the sintering treatment is 0.1-5°C/min, the target temperature is 300-950°C, and the insulation time is 12-30h, and finally obtaining a second lithium battery positive electrode material; wherein the magnetic content in the second lithium battery positive electrode material is reduced by ⁇ 50% compared with the first lithium battery positive electrode material; or, the magnetic content in the second lithium battery positive electrode material is ⁇ 100ppb.
  • the present invention achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by uniformly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and using the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe , Fe2O3 , etc., to generate non-magnetic substances such as LizFexCoyO2 , and the like, and the reduction in the content of magnetic substances is more than 50% or the reduction in the content of magnetic substances is less than 1%. To below 100ppb, it has no adverse effect on battery performance and safety performance. The process is simple, the cost is low, and it is easy to promote and apply on a large scale.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 1°C/min, the target temperature is 600°C, and the insulation time is 18h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 30ppb is obtained.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 1°C/min, the target temperature is 300°C, and the insulation time is 24h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 11 ppb is obtained, and the magnetic content is reduced by 97.8%.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 2°C/min, the target temperature is 900°C, and the insulation time is 12h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 50ppb is obtained.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 5°C/min, the target temperature is 900°C, and the insulation time is 12h, and finally a nickel cobalt manganese oxide lithium positive electrode material with a magnetic content of 15ppb is obtained, and the magnetic content is reduced by 97.5%.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 3°C/min, the target temperature is 600°C, and the insulation time is 20h, and finally a nickel cobalt aluminum oxide lithium positive electrode material with a magnetic content of 40ppb is obtained.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
  • step (2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 3°C/min, the target temperature is 600°C, and the insulation time is 20h, and finally a nickel manganese oxide lithium positive electrode material with a magnetic content of 80 ppb is obtained, and the magnetic content is reduced by 87.7%.
  • This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the lithium carbonate in step (1) is replaced by an equal mass mixture of lithium carbonate and lithium hydroxide, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium positive electrode material for the lithium battery obtained in this example is 28 ppb.
  • This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the lithium carbonate in step (1) is replaced by an equal mass mixture of lithium hydroxide and lithium oxide, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium battery positive electrode material obtained in this example is 26 ppb.
  • This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the ratio of the mixed mass of lithium carbonate to the mass of lithium cobalt oxide in step (1) is changed to 0.005%, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium cobalt oxide positive electrode material obtained in this example is 50 ppb.
  • This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the ratio of the mixed mass of lithium carbonate to the mass of lithium cobalt oxide in step (1) is changed to 5.5%, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium battery positive electrode material obtained in this example is 22 ppb.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery. Except for changing the target temperature of the sintering treatment in step (2) to 250° C., the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium battery positive electrode material obtained in this example is 48 ppb.
  • This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery. Except for changing the target temperature of the sintering treatment in step (2) to 1000° C., the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
  • the magnetic content of the lithium battery positive electrode material obtained in this example is 26 ppb.
  • This comparative example provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery.
  • the method is to add a magnetic removal rod and an iron removal machine to the production line to remove trace amounts of magnetic substances in the positive electrode material.
  • Example 1 Compared with Example 1, although this comparative example can remove magnetic materials, it cannot completely remove weakly magnetic materials, and needs to undergo repeated demagnetization, the process is relatively complicated, and the equipment cost is high.
  • the present application achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by evenly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and utilizing the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe , Fe2O3, etc., to generate non-magnetic substances such as LizFexCoyO2 , thereby achieving the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery, and the content of magnetic substances is reduced by more than 50% or the content of magnetic substances is reduced to less than 100ppb, without adversely affecting the performance and safety performance of the battery, and the process flow is simple, the cost is low, and it is convenient for large-scale promotion and application.

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  • Inorganic Chemistry (AREA)
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Abstract

A method for reducing the content of magnetic substances in a lithium battery positive electrode material. The method comprises the following steps: (1) uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixture; and (2) sintering the positive electrode mixture obtained in the step (1) to obtain a second lithium battery positive electrode material, wherein compared with the first lithium battery positive electrode material, the content of magnetic substances in the second lithium battery positive electrode material is reduced by more than or equal to 50%; or the content of magnetic substances in the second lithium battery positive electrode material is less than or equal to 100 ppb. The method is particularly aimed at weak magnetic substances, avoids the adverse effect thereof on battery performance, increases the demagnetizing efficiency while improving the demagnetizing effect, and reduces the safety risk and the process cost.

Description

一种降低锂电池正极材料中磁性物含量的方法A method for reducing the content of magnetic substances in positive electrode materials of lithium batteries 技术领域Technical Field
本申请属于锂离子电池技术领域，涉及一种锂电池正极材料，例如一种降低锂电池正极材料中磁性物含量的方法。The present application belongs to the technical field of lithium-ion batteries and relates to a positive electrode material for a lithium battery, for example, a method for reducing the content of magnetic substances in a positive electrode material for a lithium battery.
背景技术Background technique
随着锂离子电池行业的快速发展，锂离子电池凭借其较高的能量密度和倍率性能，以及较长的使用寿命，已被广泛应用于移动电话、数码相机、笔记本电脑、电子烟、无人机和新能源汽车等各个领域。With the rapid development of the lithium-ion battery industry, lithium-ion batteries have been widely used in various fields such as mobile phones, digital cameras, laptops, electronic cigarettes, drones and new energy vehicles due to their high energy density and rate performance, as well as long service life.
众所周知，正极材料是锂离子电池的关键组成部分，其性能直接影响了锂离子电池的多项重要指标。当正极材料中存在铁、铬、镍、锌等磁性物质时，电池在化成阶段的电压达到上述磁性异物金属元素的氧化还原电位之后，这些磁性异物金属元素首先会在正极氧化并溶解，然后迁移到负极被还原成金属单质。当负极处的金属单质积累到一定程度后会形成金属枝晶刺破隔膜，从而造成电池自放电失效，严重情况下甚至还会导致锂离子电池燃烧爆炸。因此，在正极材料生产过程中，尽可能地去除材料中的磁性物质便显得尤为重要。As we all know, positive electrode materials are key components of lithium-ion batteries, and their performance directly affects many important indicators of lithium-ion batteries. When magnetic substances such as iron, chromium, nickel, and zinc exist in the positive electrode materials, after the voltage of the battery in the formation stage reaches the redox potential of the above-mentioned magnetic foreign metal elements, these magnetic foreign metal elements will first be oxidized and dissolved at the positive electrode, and then migrate to the negative electrode to be reduced to metal elements. When the metal elements at the negative electrode accumulate to a certain extent, metal dendrites will form and pierce the diaphragm, causing the battery to self-discharge and fail, and in severe cases, it may even cause the lithium-ion battery to burn and explode. Therefore, in the production process of positive electrode materials, it is particularly important to remove magnetic substances in the material as much as possible.
针对锂电池正极材料，本领域技术人员在降低其中磁性物含量时普遍采用物理方法，即在锂电池正极材料生产过程中，通过产线设计除磁棒和除铁机等设备来除去产品中微量的磁性物。这种方法虽然能够除去磁性物，但是存在除磁效果不佳的问题，尤其是弱磁性物质无法被磁铁完全去除，从而无法有效避免磁性物对电池性能的不利影响。For lithium battery positive electrode materials, technicians in this field generally use physical methods to reduce the content of magnetic substances in them, that is, in the production process of lithium battery positive electrode materials, the production line is designed with demagnetizing rods and iron removers to remove trace magnetic substances in the product. Although this method can remove magnetic substances, it has the problem of poor demagnetization effect, especially weak magnetic substances cannot be completely removed by magnets, so it is impossible to effectively avoid the adverse effects of magnetic substances on battery performance.
而且，由于三元材料本身具有弱磁性，较强的磁场强度很容易堵塞管道，因此一般需要将除铁机调至较低的磁场强度进行除磁，如此便显著降低了三元正极材料的除磁效果。三元正极材料一旦被污染，材料中的磁性物就很难去除，进而导致磁性物含量偏高，容易引起安全风险，尤其是弱磁性物质更难以去除。Moreover, since the ternary material itself has weak magnetism, a strong magnetic field strength can easily clog the pipeline, so it is generally necessary to adjust the iron remover to a lower magnetic field strength for demagnetization, which significantly reduces the demagnetization effect of the ternary positive electrode material. Once the ternary positive electrode material is contaminated, the magnetic material in the material is difficult to remove, which leads to a high content of magnetic material, which can easily cause safety risks, especially weak magnetic materials are more difficult to remove.
此外，在锂电池的生产过程中，往往会产生一些高磁性物，常规降低磁性异物含量的方法主要是过筛除铁，也就是将物料通过高强度的高斯通量磁芯以吸附磁性物。然而，由于存在弱磁性物质的干扰，这种方法需要重复多次，且除磁效果并不理想，尤其是对于物料中的弱磁性物质吸附能力不佳，对使用弱磁法检测的产品毫无效果。In addition, during the production process of lithium batteries, some highly magnetic materials are often produced. The conventional method to reduce the content of magnetic foreign matter is mainly to remove iron through screening, that is, to pass the material through a high-strength Gaussian flux magnetic core to adsorb the magnetic material. However, due to the interference of weak magnetic materials, this method needs to be repeated many times, and the demagnetization effect is not ideal, especially for the weak magnetic materials in the material. The adsorption capacity is poor, and it has no effect on products tested using the weak magnetic method.
CN 112125347A公开了一种低能耗快速的钴酸锂制备方法及系统，所述方法包括以下步骤：(1)制作3D打印混合料：将原料进行混合均匀得到3D打印混合料；(2)采用3D打印技术将3D打印混合料制作成匀实型混合料；(3)对匀实型混合料进行烧结处理得到块状固体料；(4)破碎处理：对块状固体料进行破碎处理，得到初级钴酸锂料；(5)通过筛分处理筛除初级钴酸锂产品中的大颗粒物，通过磁选处理除去或降低初级钴酸锂产品中铁、铬、镍、锌等磁性异物，得到钴酸锂产品。然而，所述发明采用的磁选处理并不能完全去除钴酸锂产品中的弱磁性物质，且需要重复多次，磁选效率较低且磁选效果有待进一步改善。 CN 112125347A discloses a low-energy consumption and fast lithium cobalt oxide preparation method and system, the method comprising the following steps: (1) preparing a 3D printing mixture: mixing the raw materials uniformly to obtain a 3D printing mixture; (2) using 3D printing technology to prepare the 3D printing mixture into a uniform mixture; (3) sintering the uniform mixture to obtain a block solid material; (4) crushing treatment: crushing the block solid material to obtain a primary lithium cobalt oxide material; (5) screening out large particles in the primary lithium cobalt oxide product by screening treatment, and removing or reducing magnetic foreign matter such as iron, chromium, nickel, zinc, etc. in the primary lithium cobalt oxide product by magnetic separation treatment to obtain a lithium cobalt oxide product. However, the magnetic separation treatment used in the invention cannot completely remove weakly magnetic substances in the lithium cobalt oxide product, and needs to be repeated many times, the magnetic separation efficiency is low, and the magnetic separation effect needs to be further improved.
由此可见，如何提供一种降低锂电池正极材料中磁性物含量的方法，特别是针对弱磁性物质，避免其对电池性能的不利影响，改善除磁效果的同时提升除磁效率，降低安全风险和工艺成本，成为了目前本领域技术人员迫切需要解决的问题。It can be seen that how to provide a method to reduce the content of magnetic substances in lithium battery positive electrode materials, especially for weakly magnetic substances, to avoid their adverse effects on battery performance, improve the demagnetization effect while increasing the demagnetization efficiency, and reduce safety risks and process costs has become a problem that technical personnel in this field urgently need to solve.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
本申请提供了一种降低锂电池正极材料中磁性物含量的方法，所述方法特别针对于弱磁性物质，避免了其对电池性能的不利影响，改善了除磁效果的同时提升了除磁效率，降低了安全风险和工艺成本。The present application provides a method for reducing the content of magnetic substances in lithium battery positive electrode materials. The method is particularly targeted at weakly magnetic substances, avoiding their adverse effects on battery performance, improving the demagnetization effect while increasing the demagnetization efficiency, and reducing safety risks and process costs.
本申请提供了一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：The present application provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将第一锂电池正极材料和锂盐混合均匀，得到正极混料；和(1) uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料进行烧结处理，得到第二锂电池正极材料；(2) sintering the positive electrode mixture obtained in step (1) to obtain a second lithium battery positive electrode material;
其中，所述第二锂电池正极材料中的磁性物含量与第一锂电池正极材料相比，降低幅度≥50％，例如可以是50％、55％、60％、65％、70％、75％、80％、85％或90％，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用；The magnetic substance content in the second lithium battery positive electrode material is reduced by ≥50% compared with the first lithium battery positive electrode material, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, but it is not limited to the listed values, and other values not listed within the numerical range are also applicable;
或者，所述第二锂电池正极材料中的磁性物含量≤100ppb，例如可以是10ppb、20ppb、30ppb、40ppb、50ppb、60ppb、70ppb、80ppb、90ppb或100ppb，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Alternatively, the magnetic content in the second lithium battery positive electrode material is ≤100ppb, for example, it can be 10ppb, 20ppb, 30ppb, 40ppb, 50ppb, 60ppb, 70ppb, 80ppb, 90ppb or 100ppb, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
本申请通过锂电池正极材料与锂盐混合均匀并进行烧结处理，利用锂盐与正极材料中的弱磁性物质，如Fe、Fe2O3等发生反应，生成无磁性的LizFexCoyO2等物质，从而实现了降低锂电池正极材料中磁性物含量的目的，且磁性物含量降低幅度达50％以上或者磁性物含量降至100ppb以下，对电池性能和安全性能并无不利影响，工艺流程简单，成本低廉，便于大规模推广应用。The present application achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by uniformly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and utilizing the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe, Fe2O3, etc., to generate non-magnetic substances such as LizFexCoyO2 , thereby achieving the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery, and the content of magnetic substances is reduced by more than 50% or the content of magnetic substances is reduced to less than 100ppb, without adversely affecting the performance and safety performance of the battery, and the process flow is simple, the cost is low, and it is convenient for large-scale promotion and application.
优选地，步骤(1)所述第一锂电池正极材料包括磁性物含量≥100ppb的锂电池正极材料，例如可以是100ppb、200ppb、300ppb、400ppb、500ppb、600ppb、700ppb、800ppb或900ppb，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, in step (1), the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content ≥ 100 ppb, for example, 100 ppb, 200 ppb, 300 ppb, 400 ppb, 500 ppb, 600 ppb, 700 ppb, 800 ppb or 900 ppb, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
优选地，步骤(1)所述第一锂电池正极材料包括镍钴锰酸锂、镍钴铝酸锂、镍锰酸锂、钴酸锂或锰酸锂中的任意一种或至少两种的组合，典型但非限制性的组合包括镍钴锰酸锂与镍钴铝酸锂的组合，镍钴铝酸锂与镍锰酸锂的组合，镍锰酸锂与钴酸锂的组合，钴酸锂与锰酸锂的组合，镍钴锰酸锂、镍钴铝酸锂与镍锰酸锂的组合，镍钴铝酸锂、镍锰酸锂与钴酸锂的组合，或镍锰酸锂、钴酸锂与锰酸锂的组合。Preferably, in step (1), the first lithium battery positive electrode material comprises any one of nickel cobalt manganese oxide, nickel cobalt aluminum oxide, nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide, a combination of nickel cobalt aluminum oxide and lithium nickel manganese oxide, a combination of nickel manganese oxide and lithium cobalt oxide, a combination of lithium cobalt oxide and lithium manganese oxide, a combination of nickel cobalt manganese oxide, lithium cobalt aluminum oxide and lithium manganese oxide, a combination of nickel cobalt aluminum oxide, lithium manganese oxide and lithium cobalt oxide, or a combination of nickel manganese oxide, lithium cobalt oxide and lithium manganese oxide.
优选地，步骤(1)所述锂盐包括碳酸锂、氢氧化锂或氧化锂中的任意一种或至少两种的组合，典型但非限制性的组合包括碳酸锂与氢氧化锂的组合，氢氧化锂与氧化锂的组合，碳酸锂与氧化锂的组合，或碳酸锂、氢氧化锂与氧化锂的组合。Preferably, the lithium salt in step (1) comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two of them. Typical but non-limiting combinations include a combination of lithium carbonate and lithium hydroxide, a combination of lithium hydroxide and lithium oxide, a combination of lithium carbonate and lithium oxide, or a combination of lithium carbonate, lithium hydroxide and lithium oxide.
优选地，步骤(1)所述锂盐的混合质量占第一锂电池正极材料质量的0-5％，但不包括 0，例如可以是0.01％、0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％或5％，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the mixed mass of the lithium salt in step (1) accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0, for example, it can be 0.01%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
优选地，步骤(1)所述混合还伴随着搅拌，且搅拌的速率为100-500rpm，例如可以是100rpm、150rpm、200rpm、250rpm、300rpm、350rpm、400rpm、450rpm或500rpm，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the mixing in step (1) is accompanied by stirring, and the stirring rate is 100-500 rpm, for example, it can be 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
优选地，步骤(2)所述烧结处理在匣钵中进行，并将所述匣钵置于窑炉内。Preferably, the sintering process in step (2) is carried out in a sagger, and the sagger is placed in a kiln.
优选地，步骤(2)所述烧结处理的升温速率为0.1-5℃/min，例如可以是0.1℃/min、0.5℃/min、1.5℃/m、1.5℃/min、2.5℃/m、2.5℃/min、3.5℃/m、3.5℃/min、4.5℃/m、4.5℃/min或5℃/min，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the heating rate of the sintering treatment in step (2) is 0.1-5°C/min, for example, it can be 0.1°C/min, 0.5°C/min, 1.5°C/m, 1.5°C/min, 2.5°C/m, 2.5°C/min, 3.5°C/m, 3.5°C/min, 4.5°C/m, 4.5°C/min or 5°C/min, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
优选地，步骤(2)所述烧结处理的目标温度为300-950℃，例如可以是300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃、900℃或950℃，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the target temperature of the sintering treatment in step (2) is 300-950°C, for example, it can be 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, 850°C, 900°C or 950°C, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
本申请中，所述烧结处理的目标温度需控制在合理范围内。当目标温度低于300℃时，锂盐与正极材料中的弱磁性物质反应并不彻底，从而降低了除磁效率，且除磁效果并不理想；当目标温度高于950℃时，又会造成处理成本的不必要升高。In this application, the target temperature of the sintering treatment needs to be controlled within a reasonable range. When the target temperature is lower than 300°C, the reaction between the lithium salt and the weakly magnetic substance in the positive electrode material is not complete, thereby reducing the demagnetization efficiency and the demagnetization effect is not ideal; when the target temperature is higher than 950°C, it will cause an unnecessary increase in the processing cost.
优选地，步骤(2)所述烧结处理的保温时间为12-30h，例如可以是12h、14h、16h、18h、20h、22h、24h、26h、28h或30h，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。Preferably, the holding time of the sintering treatment in step (2) is 12-30h, for example, it can be 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h or 30h, but is not limited to the listed values, and other unlisted values within the numerical range are also applicable.
在本申请一优选实施方式中，所述方法包括以下步骤：In a preferred embodiment of the present application, the method comprises the following steps:
(1)将第一锂电池正极材料和锂盐混合均匀，并伴随着速率为100-500rpm的搅拌，得到正极混料；所述第一锂电池正极材料包括磁性物含量≥100ppb的锂电池正极材料，且所述第一锂电池正极材料包括镍钴锰酸锂、镍钴铝酸锂、镍锰酸锂、钴酸锂或锰酸锂中的任意一种或至少两种的组合；所述锂盐包括碳酸锂、氢氧化锂或氧化锂中的任意一种或至少两种的组合，且所述锂盐的混合质量占第一锂电池正极材料质量的0-5％，但不包括0；和(1) uniformly mixing a first lithium battery positive electrode material and a lithium salt, accompanied by stirring at a rate of 100-500 rpm, to obtain a positive electrode mixture; the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content of ≥100 ppb, and the first lithium battery positive electrode material comprises any one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof; the lithium salt comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two thereof, and the mixed mass of the lithium salt accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为0.1-5℃/min，目标温度为300-950℃，保温时间为12-30h，最终得到第二锂电池正极材料；其中，所述第二锂电池正极材料中的磁性物含量与第一锂电池正极材料相比，降低幅度≥50％；或者，所述第二锂电池正极材料中的磁性物含量≤100ppb。(2) transferring the positive electrode mixture obtained in step (1) into a sagger, and placing the sagger in a kiln for sintering, wherein the heating rate of the sintering treatment is 0.1-5°C/min, the target temperature is 300-950°C, and the insulation time is 12-30h, and finally obtaining a second lithium battery positive electrode material; wherein the magnetic content in the second lithium battery positive electrode material is reduced by ≥50% compared with the first lithium battery positive electrode material; or, the magnetic content in the second lithium battery positive electrode material is ≤100ppb.
本申请所述的数值范围不仅包括上述列举的点值，还包括没有列举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。The numerical range described in this application includes not only the point values listed above, but also any point values between the above numerical ranges that are not listed. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
与现有技术相比，本申请的有益效果为：Compared with the prior art, the beneficial effects of this application are:
本申请通过锂电池正极材料与锂盐混合均匀并进行烧结处理，利用锂盐与正极材料中的弱磁性物质，如Fe、Fe2O3等发生反应，生成无磁性的LizFexCoyO2等物质，从而实现了降低锂电池正极材料中磁性物含量的目的，且磁性物含量降低幅度达50％以上或者磁性物含量降 至100ppb以下，对电池性能和安全性能并无不利影响，工艺流程简单，成本低廉，便于大规模推广应用。The present invention achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by uniformly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and using the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe , Fe2O3 , etc., to generate non-magnetic substances such as LizFexCoyO2 , and the like, and the reduction in the content of magnetic substances is more than 50% or the reduction in the content of magnetic substances is less than 1%. To below 100ppb, it has no adverse effect on battery performance and safety performance. The process is simple, the cost is low, and it is easy to promote and apply on a large scale.
具体实施方式Detailed ways
下面通过具体实施方式来进一步说明本申请的技术方案。The technical solution of the present application is further illustrated below through specific implementation methods.
实施例1Example 1
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将钴酸锂和碳酸锂混合均匀，且所述碳酸锂的混合质量占钴酸锂质量的0.1％，并伴随着速率为200rpm的搅拌，得到正极混料；和(1) mixing lithium cobalt oxide and lithium carbonate uniformly, wherein the mixed mass of the lithium carbonate accounts for 0.1% of the mass of the lithium cobalt oxide, and stirring at a rate of 200 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为1℃/min，目标温度为600℃，保温时间为18h，最终得到磁性物含量为30ppb的钴酸锂正极材料。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 1°C/min, the target temperature is 600°C, and the insulation time is 18h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 30ppb is obtained.
实施例2Example 2
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将磁性物含量为500ppb的钴酸锂和碳酸锂混合均匀，且所述碳酸锂的混合质量占钴酸锂质量的0.2％，并伴随着速率为100rpm的搅拌，得到正极混料；和(1) mixing lithium cobalt oxide and lithium carbonate having a magnetic material content of 500 ppb, wherein the mixed mass of the lithium carbonate accounts for 0.2% of the mass of the lithium cobalt oxide, and stirring at a rate of 100 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为1℃/min，目标温度为300℃，保温时间为24h，最终得到磁性物含量为11ppb的钴酸锂正极材料，磁性物含量降低幅度达97.8％。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 1°C/min, the target temperature is 300°C, and the insulation time is 24h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 11 ppb is obtained, and the magnetic content is reduced by 97.8%.
实施例3Example 3
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将钴酸锂和氢氧化锂混合均匀，且所述氢氧化锂的混合质量占钴酸锂质量的0.01％，并伴随着速率为300rpm的搅拌，得到正极混料；和(1) mixing lithium cobalt oxide and lithium hydroxide uniformly, wherein the mixed mass of the lithium hydroxide accounts for 0.01% of the mass of the lithium cobalt oxide, and stirring at a rate of 300 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为2℃/min，目标温度为900℃，保温时间为12h，最终得到磁性物含量为50ppb的钴酸锂正极材料。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 2°C/min, the target temperature is 900°C, and the insulation time is 12h, and finally a lithium cobalt oxide positive electrode material with a magnetic content of 50ppb is obtained.
实施例4Example 4
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将磁性物含量为600ppb的镍钴锰酸锂和氢氧化锂混合均匀，且所述氢氧化锂的混合质量占镍钴锰酸锂质量的2.5％，并伴随着速率为250rpm的搅拌，得到正极混料；和(1) mixing lithium nickel cobalt manganese oxide with a magnetic material content of 600 ppb and lithium hydroxide, wherein the mixed mass of the lithium hydroxide accounts for 2.5% of the mass of the lithium nickel cobalt manganese oxide, and stirring at a rate of 250 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为5℃/min，目标温度为900℃，保温时间为12h，最终得到磁性物含量为15ppb的镍钴锰酸锂正极材料，磁性物含量降低幅度达97.5％。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 5°C/min, the target temperature is 900°C, and the insulation time is 12h, and finally a nickel cobalt manganese oxide lithium positive electrode material with a magnetic content of 15ppb is obtained, and the magnetic content is reduced by 97.5%.
实施例5Example 5
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤： This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将镍钴铝酸锂和氧化锂混合均匀，且所述氧化锂的混合质量占镍钴铝酸锂质量的4％，并伴随着速率为200rpm的搅拌，得到正极混料；和(1) mixing lithium nickel cobalt aluminum oxide and lithium oxide uniformly, wherein the mixed mass of the lithium oxide accounts for 4% of the mass of the lithium nickel cobalt aluminum oxide, and stirring at a rate of 200 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为3℃/min，目标温度为600℃，保温时间为20h，最终得到磁性物含量为40ppb的镍钴铝酸锂正极材料。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 3°C/min, the target temperature is 600°C, and the insulation time is 20h, and finally a nickel cobalt aluminum oxide lithium positive electrode material with a magnetic content of 40ppb is obtained.
实施例6Example 6
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法包括以下步骤：This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, the method comprising the following steps:
(1)将磁性物含量为650ppb的镍锰酸锂和氧化锂混合均匀，且所述氧化锂的混合质量占镍锰酸锂质量的5％，并伴随着速率为200rpm的搅拌，得到正极混料；和(1) mixing lithium nickel manganese oxide having a magnetic material content of 650 ppb and lithium oxide uniformly, wherein the mixed mass of the lithium oxide accounts for 5% of the mass of the lithium nickel manganese oxide, and stirring at a rate of 200 rpm to obtain a positive electrode mixture; and
(2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为3℃/min，目标温度为600℃，保温时间为20h，最终得到磁性物含量为80ppb的镍锰酸锂正极材料，磁性物含量降低幅度达87.7％。(2) The positive electrode mixture obtained in step (1) is transferred to a sagger, and the sagger is placed in a kiln for sintering, and the heating rate of the sintering treatment is 3°C/min, the target temperature is 600°C, and the insulation time is 20h, and finally a nickel manganese oxide lithium positive electrode material with a magnetic content of 80 ppb is obtained, and the magnetic content is reduced by 87.7%.
实施例7Example 7
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(1)中的碳酸锂改为碳酸锂和氢氧化锂的等质量混合物，其余步骤及条件均与实施例1相同，故在此不做赘述。This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the lithium carbonate in step (1) is replaced by an equal mass mixture of lithium carbonate and lithium hydroxide, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得锂电池锂正极材料的磁性物含量为28ppb。The magnetic content of the lithium positive electrode material for the lithium battery obtained in this example is 28 ppb.
实施例8Example 8
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(1)中的碳酸锂改为氢氧化锂和氧化锂的等质量混合物，其余步骤及条件均与实施例1相同，故在此不做赘述。This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the lithium carbonate in step (1) is replaced by an equal mass mixture of lithium hydroxide and lithium oxide, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得锂电池正极材料的磁性物含量为26ppb。The magnetic content of the lithium battery positive electrode material obtained in this example is 26 ppb.
实施例9Example 9
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(1)中碳酸锂的混合质量占钴酸锂质量的比例改为0.005％，其余步骤及条件均与实施例1相同，故在此不做赘述。This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the ratio of the mixed mass of lithium carbonate to the mass of lithium cobalt oxide in step (1) is changed to 0.005%, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得钴酸锂正极材料的磁性物含量为50ppb。The magnetic content of the lithium cobalt oxide positive electrode material obtained in this example is 50 ppb.
实施例10Example 10
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(1)中碳酸锂的混合质量占钴酸锂质量的比例改为5.5％，其余步骤及条件均与实施例1相同，故在此不做赘述。This embodiment provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. Except that the ratio of the mixed mass of lithium carbonate to the mass of lithium cobalt oxide in step (1) is changed to 5.5%, the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得锂电池正极材料的磁性物含量为22ppb。The magnetic content of the lithium battery positive electrode material obtained in this example is 22 ppb.
实施例11Embodiment 11
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(2)中烧结处理的目标温度改为250℃，其余步骤及条件均与实施例1相同，故在此不做赘述。 This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery. Except for changing the target temperature of the sintering treatment in step (2) to 250° C., the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得锂电池正极材料的磁性物含量为48ppb。The magnetic content of the lithium battery positive electrode material obtained in this example is 48 ppb.
实施例12Example 12
本实施例提供一种降低锂电池正极材料中磁性物含量的方法，除了将步骤(2)中烧结处理的目标温度改为1000℃，其余步骤及条件均与实施例1相同，故在此不做赘述。This embodiment provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery. Except for changing the target temperature of the sintering treatment in step (2) to 1000° C., the remaining steps and conditions are the same as those in Example 1 and are not described in detail here.
本实施例所得锂电池正极材料的磁性物含量为26ppb。The magnetic content of the lithium battery positive electrode material obtained in this example is 26 ppb.
对比例1Comparative Example 1
本对比例提供一种降低锂电池正极材料中磁性物含量的方法，所述方法为在产线上增设除磁棒和除铁机，以便去除正极材料中微量的磁性物。This comparative example provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery. The method is to add a magnetic removal rod and an iron removal machine to the production line to remove trace amounts of magnetic substances in the positive electrode material.
相较于实施例1，本对比例虽然能够去除磁性物，但是无法完全去除弱磁性物，且需要经过多次重复除磁，工序较为复杂，且设备成本高昂。Compared with Example 1, although this comparative example can remove magnetic materials, it cannot completely remove weakly magnetic materials, and needs to undergo repeated demagnetization, the process is relatively complicated, and the equipment cost is high.
由此可见，本申请通过锂电池正极材料与锂盐混合均匀并进行烧结处理，利用锂盐与正极材料中的弱磁性物质，如Fe、Fe2O3等发生反应，生成无磁性的LizFexCoyO2等物质，从而实现了降低锂电池正极材料中磁性物含量的目的，且磁性物含量降低幅度达50％以上或者磁性物含量降至100ppb以下，对电池性能和安全性能并无不利影响，工艺流程简单，成本低廉，便于大规模推广应用。It can be seen that the present application achieves the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery by evenly mixing the positive electrode material of the lithium battery with the lithium salt and performing a sintering treatment, and utilizing the lithium salt to react with weakly magnetic substances in the positive electrode material, such as Fe , Fe2O3, etc., to generate non-magnetic substances such as LizFexCoyO2 , thereby achieving the purpose of reducing the content of magnetic substances in the positive electrode material of the lithium battery, and the content of magnetic substances is reduced by more than 50% or the content of magnetic substances is reduced to less than 100ppb, without adversely affecting the performance and safety performance of the battery, and the process flow is simple, the cost is low, and it is convenient for large-scale promotion and application.
以上所述的具体实施例，对本申请的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本申请的具体实施例而已，并不用于限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。 The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims (10)

  1. 一种降低锂电池正极材料中磁性物含量的方法，其包括以下步骤：A method for reducing the content of magnetic substances in a lithium battery positive electrode material comprises the following steps:
    (1)将第一锂电池正极材料和锂盐混合均匀，得到正极混料；以及(1) uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixture; and
    (2)将步骤(1)所得正极混料进行烧结处理，得到第二锂电池正极材料；(2) sintering the positive electrode mixture obtained in step (1) to obtain a second lithium battery positive electrode material;
    其中，所述第二锂电池正极材料中的磁性物含量与第一锂电池正极材料相比，降低幅度≥50％；Wherein, the magnetic substance content in the second lithium battery positive electrode material is reduced by ≥50% compared with the first lithium battery positive electrode material;
    或者，所述第二锂电池正极材料中的磁性物含量≤100ppb。Alternatively, the magnetic content in the second lithium battery positive electrode material is ≤100 ppb.
  2. 根据权利要求1所述的方法，其中，步骤(1)所述第一锂电池正极材料包括磁性物含量≥100ppb的锂电池正极材料；The method according to claim 1, wherein in step (1), the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content of ≥ 100 ppb;
    优选地，步骤(1)所述第一锂电池正极材料包括镍钴锰酸锂、镍钴铝酸锂、镍锰酸锂、钴酸锂或锰酸锂中的任意一种或至少两种的组合。Preferably, in step (1), the first lithium battery positive electrode material includes any one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof.
  3. 根据权利要求1或2所述的方法，其中，步骤(1)所述锂盐包括碳酸锂、氢氧化锂或氧化锂中的任意一种或至少两种的组合。The method according to claim 1 or 2, wherein the lithium salt in step (1) comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two thereof.
  4. 根据权利要求1-3任一项所述的方法，其中，步骤(1)所述锂盐的混合质量占第一锂电池正极材料质量的0-5％，但不包括0。The method according to any one of claims 1 to 3, wherein the mixed mass of the lithium salt in step (1) accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0.
  5. 根据权利要求1-4任一项所述的方法，其中，步骤(1)所述混合还伴随着搅拌，且搅拌的速率为100-500rpm。The method according to any one of claims 1 to 4, wherein the mixing in step (1) is also accompanied by stirring, and the stirring rate is 100-500 rpm.
  6. 根据权利要求1-5任一项所述的方法，其中，步骤(2)所述烧结处理在匣钵中进行，并将所述匣钵置于窑炉内。The method according to any one of claims 1 to 5, wherein the sintering treatment in step (2) is carried out in a sagger, and the sagger is placed in a kiln.
  7. 根据权利要求1-6任一项所述的方法，其中，步骤(2)所述烧结处理的升温速率为0.1-5℃/min。The method according to any one of claims 1 to 6, wherein the heating rate of the sintering treatment in step (2) is 0.1-5°C/min.
  8. 根据权利要求1-7任一项所述的方法，其中，步骤(2)所述烧结处理的目标温度为300-950℃。The method according to any one of claims 1 to 7, wherein the target temperature of the sintering treatment in step (2) is 300-950°C.
  9. 根据权利要求1-8任一项所述的方法，其中，步骤(2)所述烧结处理的保温时间为12-30h。The method according to any one of claims 1 to 8, wherein the holding time of the sintering treatment in step (2) is 12 to 30 hours.
  10. 根据权利要求1-9任一项所述的方法，其包括以下步骤：The method according to any one of claims 1 to 9, comprising the following steps:
    (1)将第一锂电池正极材料和锂盐混合均匀，并伴随着速率为100-500rpm的搅拌，得到正极混料；所述第一锂电池正极材料包括磁性物含量≥100ppb的锂电池正极材料，且所述第一锂电池正极材料包括镍钴锰酸锂、镍钴铝酸锂、镍锰酸锂、钴酸锂或锰酸锂中的任意一种或至少两种的组合；所述锂盐包括碳酸锂、氢氧化锂或氧化锂中的任意一种或至少两种的 组合，且所述锂盐的混合质量占第一锂电池正极材料质量的0-5％，但不包括0；以及(1) uniformly mixing a first lithium battery positive electrode material and a lithium salt, accompanied by stirring at a rate of 100-500 rpm, to obtain a positive electrode mixture; the first lithium battery positive electrode material comprises a lithium battery positive electrode material having a magnetic content of ≥100 ppb, and the first lithium battery positive electrode material comprises any one of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel manganese oxide, lithium cobalt oxide or lithium manganese oxide, or a combination of at least two thereof; the lithium salt comprises any one of lithium carbonate, lithium hydroxide or lithium oxide, or a combination of at least two thereof; The mixed mass of the lithium salt accounts for 0-5% of the mass of the first lithium battery positive electrode material, but does not include 0; and
    (2)将步骤(1)所得正极混料转移至匣钵中，并将所述匣钵置于窑炉内进行烧结处理，且所述烧结处理的升温速率为0.1-5℃/min，目标温度为300-950n，保温时间为12-30h，最终得到第二锂电池正极材料；其中，所述第二锂电池正极材料中的磁性物含量与第一锂电池正极材料相比，降低幅度≥50％；或者，所述第二锂电池正极材料中的磁性物含量≤100ppb。 (2) transferring the positive electrode mixture obtained in step (1) into a sagger, and placing the sagger in a kiln for sintering, wherein the heating rate of the sintering treatment is 0.1-5°C/min, the target temperature is 300-950n, and the insulation time is 12-30h, and finally obtaining a second lithium battery positive electrode material; wherein the magnetic content in the second lithium battery positive electrode material is reduced by ≥50% compared with the first lithium battery positive electrode material; or, the magnetic content in the second lithium battery positive electrode material is ≤100ppb.
PCT/CN2023/086978 2022-11-18 2023-04-07 Method for reducing content of magnetic substances in lithium battery positive electrode material WO2024103614A1 (en)

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