WO2021212729A1 - Nickel-manganese-based positive electrode material precursor and synthesis method for positive electrode material thereof - Google Patents

Nickel-manganese-based positive electrode material precursor and synthesis method for positive electrode material thereof Download PDF

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WO2021212729A1
WO2021212729A1 PCT/CN2020/115848 CN2020115848W WO2021212729A1 WO 2021212729 A1 WO2021212729 A1 WO 2021212729A1 CN 2020115848 W CN2020115848 W CN 2020115848W WO 2021212729 A1 WO2021212729 A1 WO 2021212729A1
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nickel
manganese
precursor
positive electrode
cathode material
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周君
钟辉
付烨
向肪吾
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四川万邦胜辉新能源科技有限公司
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of lithium ion battery material preparation, and specifically relates to a method for synthesizing a binary, ternary, or quaternary or above multi-element cathode material NMT cathode material and its precursor with nickel and manganese as main components. It is a nickel-manganese-based cathode material precursor and a method for synthesizing the anode material.
  • the ternary cathode material As the key intermediate of the ternary cathode material-the precursor of NCA and NCM, Ni 1-xy Mn x T y (OH) 2 , it has great influence on the electrochemical performance and cycle stability of the ternary cathode material (referred to as the target cathode material) Very important influence, therefore, the synthesis technology of the precursor of the ternary cathode material has become a bottleneck technology restricting the development of the ternary cathode material.
  • the current synthesis technology of ternary cathode material precursors is: generally adopt the co-precipitation-ammonium method, that is, add alkaline solution to the mixed aqueous solution of soluble nickel salt, cobalt salt, manganese salt, aluminum salt and doped salt to cause co-precipitation.
  • the reaction produces a co-precipitation product—Ni 1-xy Mn x T y (OH) 2.
  • ammonium or ammonia such as ammonium salt or ammonium hydroxide, or ammonia, is also added at a higher temperature (80 °C above), stir under a longer reaction time (10-30 hours), then filter and dry to synthesize the precursor.
  • the more mature forming process of the ternary cathode material is: mix the ternary precursor and lithium hydroxide uniformly, charge it, and use a roller kiln or pusher kiln for two calcinations.
  • the first calcination temperature is 300- 550°C
  • the second calcination temperature is 600-950°C
  • the calcination time is 10-40 hours, and oxygen is continuously supplied throughout the entire process.
  • the electrochemical performance is unstable, and the capacity retention rate is less than or equal to 80% under 100 times of 1C charge and discharge rate;
  • the precursor is generally prepared by the co-precipitation method.
  • the formed precursor hydrooxide colloid
  • ammonium salt or ammonium hydroxide etc.
  • Complexing agents such as ammonium or ammonia can complex heavy metal ions such as nickel and manganese to form a spherical particle precursor that is easy to filter.
  • the present invention provides a nickel-manganese-based cathode material precursor and a method for synthesizing the anode material.
  • This method can solve the following technical problems: (1) Improve the electrochemical stability and low charge-discharge capacity of binary, ternary, or quaternary and above multi-element cathode materials with nickel and manganese as the main components; (2) ) The problem of difficult filtration of the precursors of the ternary cathode material in the co-precipitation process; (2) The problems of long co-precipitation reaction time and low yield; (3) Completely eliminate the recovery and pollution of heavy metal ions in the production process of the ternary cathode material problem.
  • a method for synthesizing a precursor of a nickel-manganese-based cathode material which comprises the following steps:
  • step 3 In the precipitation reactor, first add pure water, metal powder or metal oxide, and control the temperature at 40-100°C, and then combine the metal salt solution in step 2) and the precipitant solution prepared in step 3) respectively. After heating, co-currently added to the precipitation reactor for co-precipitation reaction, the precipitation reaction time is 50-80min; filter while hot; finally, the filtered precipitate is washed with deionized water and vacuum dried to obtain nickel manganese Base cathode material precursor.
  • the T is any one or more of Al, Mg, Co, Zr, Ti, Fe, Zn, Ce, Mo, Cr, La, W and Sn.
  • the soluble T salt is aluminum sulfate octahydrate.
  • the soluble nickel salt is nickel sulfate hexahydrate.
  • the soluble manganese salt is manganese sulfate monohydrate.
  • the metal powder is nano-metal nickel powder and metal manganese powder (particle size is 10-50 nanometers, purity ⁇ 99.9%); the metal oxide is nano-NiO powder and nano-MnO powder (particle size is 10-50 nanometers). Nanometer, purity ⁇ 99.9%).
  • the amount of metal powder or metal oxide added is 0.01 to 5% of the number of moles of nickel and manganese determined by the stoichiometric formula of the precursor Ni 1-xy Mn x T y (OH) 2.
  • the addition amount of the soluble nickel salt and the soluble manganese salt is 95-99.99% of the number of moles of nickel and manganese determined in the Ni 1-xy Mn x T y (OH) 2 stoichiometric formula.
  • the amount of pure water added is 10-30% of the total volume of the reaction.
  • the conditions of the co-precipitation reaction are: holding temperature 40-100° C., stirring for 0.5-3.0 h, and aging for 0.5-2.0 h.
  • the method for further synthesizing the nickel-manganese-based positive electrode material using the nickel-manganese-based positive electrode material precursor prepared by the synthesis method includes the following steps:
  • the precursor and the lithium source are fully mixed, pre-baked in a tube furnace under oxygen flow for 5-15h, then heated to 750-900°C, sintered in an oxygen atmosphere for 10-30h, taken out, and ground, and it is nickel Manganese-based cathode material.
  • the pre-baking temperature is 500-650°C.
  • the lithium source is lithium hydroxide or lithium carbonate.
  • the ratio between the precursor and the lithium source is 0.8-1.2.
  • the co-precipitation product grows on the aforementioned seed crystals and grows rapidly. It is spherical or quasi-spherical, and the precipitation reaction time is only 50-80 minutes.
  • the co-precipitation product is easy to filter, which overcomes the problems of too long reaction time and difficult filtration in the prior art. Settling time and previous aging time
  • the binary, ternary and above cathode materials produced by the high-temperature solid-phase reaction have a perfect layered structure, good crystallinity, stable electrochemical performance, and their charge and discharge capacity can reach 200mAh/ g above.
  • Figure 1 is an electron microscope image (SEM image) of the precursor synthesized in Example 5.
  • FIG. 2 is an electron microscope image (SEM image) of the precursor synthesized in Example 4.
  • FIG. 2 is an electron microscope image (SEM image) of the precursor synthesized in Example 4.
  • Fig. 3 is an electron microscope picture (SEM picture) of the ternary cathode material synthesized in Example 4.
  • Example 4 is an XRD pattern of the ternary cathode material synthesized in Example 5.
  • FIG. 5 is a charge-discharge curve diagram of the ternary high nickel cathode material synthesized in Example 5.
  • the particle size of the metal nickel powder and the metal manganese powder used in the following embodiments are both 10-50 nanometers, and the purity is ⁇ 99.9%; the particle size of the nano-NiO powder and the nano-MnO powder are also 10-50 nanometers, and the purity is ⁇ 99.9%.
  • The% used in this application means its mass percentage content, that is, wt%.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor.
  • reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, aging time 1h, reaction temperature 80°C.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor.
  • take 50g of the precursor add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-calcin in a tubular oxygen atmosphere furnace.
  • the pre-calcining temperature is 600°C and the pre-calcination time is 15h. After the pre-calcination is completed, take it out and grind.
  • sintering temperature is 800 °C
  • sintering time is 20h
  • sintering is completed, take out, grind, sieving, that is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct electrical performance measurement .
  • the experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a pre-baking temperature of 500°C and a pre-baking time of 5h. After the pre-baking is completed, take it out and grind Sintered in an oxygen atmosphere furnace at a sintering temperature of 750°C and a sintering time of 20h. After sintering, it is taken out, ground, and sieved, which is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then the electrical properties are measured. . The experimental results are shown in Table 1.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C, and a pre-baked time of 20h. After the pre-baked is completed, take it out and grind.
  • the reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, The aging time is 1h, and the reaction temperature is 80°C.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor.
  • the precursor Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h. After the pre-baked is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, the sintering temperature is 800 °C, the sintering time is 20h, after the sintering is completed, take it out, grind, and sieving to obtain the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 .
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h.
  • the sintering temperature is 800 °C
  • the sintering time is 20h
  • the cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 .
  • Comparative Example 3 (same as Example 1, except that the particle size of the added metal powder is 200-1000 nm)
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor.
  • the pre-calcin temperature is 550°C
  • the pre-calcin time is 5h
  • the sintering time is 20h
  • the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
  • Vacuum filter while hot remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time.
  • the filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor.
  • the pre-calcin temperature is 550°C
  • the pre-calcin time is 5h
  • the sintering time is 20h
  • the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
  • the first charge-discharge specific capacity and the first charge-discharge efficiency are measured using GB/T 37201-2018.

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Abstract

A nickel-manganese-based positive electrode material precursor and a synthesis method for a positive electrode material thereof. The synthesis method comprises the steps of: 1) adding a soluble T salt, a soluble nickel salt and a soluble manganese salt into deionized water, and preparing a metal salt solution in proportion; 2) preparing a precipitant solution from sodium hydroxide, potassium hydroxide or lithium hydroxide; and 3) adding pure water, metal powder or metal oxide into a precipitation reactor, then respectively heating the metal salt solution and the precipitant solution, and then adding into the precipitation reactor for coprecipitation reaction, and filtering the reaction product while hot; and finally, stirring and washing the filtered precipitate with deionized water, and carrying out vacuum drying treatment to obtain the nickel-manganese-based positive electrode material precursor. The precursor and a lithium source are mixed, pre-roasted and calcined at high temperature, the prepared positive electrode material is perfect in layered structure, good in crystallization degree and stable in electrochemical performance, and the charge-discharge capacity of the positive electrode material reaches 200 mAh/g or above.

Description

一种镍锰基正极材料前驱体及其正极材料的合成方法A nickel-manganese-based positive electrode material precursor and a method for synthesizing the positive electrode material 技术领域Technical field
本发明属于锂离子电池材料制备领域，具体涉及合成一种以镍和锰作为主要成分的二元、三元、或者四元及以上的多元正极材料NMT正极材料及其前驱体的合成方法，具体为一种镍锰基正极材料前驱体及其正极材料的合成方法。The invention belongs to the field of lithium ion battery material preparation, and specifically relates to a method for synthesizing a binary, ternary, or quaternary or above multi-element cathode material NMT cathode material and its precursor with nickel and manganese as main components. It is a nickel-manganese-based cathode material precursor and a method for synthesizing the anode material.
背景技术Background technique
随着新能源的高速发展，高容量锂离子动力电池成为全球新能源产和科技的发展热点。作为影响锂电池容量关键部分的正极材料，更是目前技术攻关的重点，三元正极材料NCA、NCM，尤其是高镍NCA、NCM，具有容量大、电压平台高等优点，是目前锂电池研发的新热点。作为三元正极材料的关键中间体——NCA、NCM的前驱体Ni 1-x-yMn xT y(OH) 2，对三元正极材料(简称目标正极材料)的电化学性能和循环稳定性有十分重要的影响，因而三元正极材料前驱体的合成技术，又成为制约三元正极材料发展的瓶颈技术。 With the rapid development of new energy, high-capacity lithium-ion power batteries have become a hot spot for global new energy production and technology development. As a key part of the cathode material that affects the capacity of lithium batteries, it is the focus of current technological research. Ternary cathode materials NCA and NCM, especially high nickel NCA and NCM, have the advantages of large capacity and high voltage platform. They are currently developed by lithium batteries. New hot spot. As the key intermediate of the ternary cathode material-the precursor of NCA and NCM, Ni 1-xy Mn x T y (OH) 2 , it has great influence on the electrochemical performance and cycle stability of the ternary cathode material (referred to as the target cathode material) Very important influence, therefore, the synthesis technology of the precursor of the ternary cathode material has become a bottleneck technology restricting the development of the ternary cathode material.
目前三元正极材料前驱体合成技术是：一般采用共沉淀——铵法，即在可溶性镍盐、钴盐、锰盐、铝盐及掺杂盐的混合水溶液中，加入碱溶液，发生共沉淀反应，生成共沉淀产物——Ni 1-x-yMn xT y(OH) 2，在共沉淀反应过程中，还加入铵盐或氢氧化铵等铵、或氨类物质，在较高温度(80℃以上)，较长反应时间(10-30小时)下搅拌，然后过滤、干燥，合成出前驱体。 The current synthesis technology of ternary cathode material precursors is: generally adopt the co-precipitation-ammonium method, that is, add alkaline solution to the mixed aqueous solution of soluble nickel salt, cobalt salt, manganese salt, aluminum salt and doped salt to cause co-precipitation. The reaction produces a co-precipitation product—Ni 1-xy Mn x T y (OH) 2. During the co-precipitation reaction, ammonium or ammonia such as ammonium salt or ammonium hydroxide, or ammonia, is also added at a higher temperature (80 ℃ above), stir under a longer reaction time (10-30 hours), then filter and dry to synthesize the precursor.
三元正极材料比较成熟的成工艺是：将三元前驱体和氢氧化锂混合均匀，装料，采用辊道窑或推板窑分两次进行二次煅烧，第一次煅烧温度在300-550℃，第二次煅烧温度在600-950℃；煅烧时间在10-40小时，全程连续通入氧气。The more mature forming process of the ternary cathode material is: mix the ternary precursor and lithium hydroxide uniformly, charge it, and use a roller kiln or pusher kiln for two calcinations. The first calcination temperature is 300- 550°C, the second calcination temperature is 600-950°C; the calcination time is 10-40 hours, and oxygen is continuously supplied throughout the entire process.
目前一种以镍和锰作为主要成分的二元、三元、或者四元及以上的多元正极材料存在的主要问题是：At present, the main problems of a binary, ternary, or quaternary and above multi-element cathode material with nickel and manganese as the main components are:
(1)电化学性能不稳定，在100次1C充放电倍率下，容量保持率≤80％；(1) The electrochemical performance is unstable, and the capacity retention rate is less than or equal to 80% under 100 times of 1C charge and discharge rate;
(2)充放电容量不够高，首次充放电容量为170-190mAh/h；(2) The charge and discharge capacity is not high enough, the first charge and discharge capacity is 170-190mAh/h;
(3)前驱体一般采用共沉淀法制备，为使其形成的前驱体(氢氧化物胶体)易于过滤，以得到纯度高、化学计量准确的前驱体，一般需加入铵盐或氢氧化铵等铵、或氨类等络合剂，使镍、锰等重金属离子被络合，从而形成易于过滤的球形颗粒前驱体，但也导致了镍、锰等重金属离子由于形成络离子而沉淀不完全(沉淀率≤95％)，致使过滤母液中镍、锰等重金属离子含量高，其回收难度大，成本高，生产的环境负荷大；且共沉淀反应时间较长(20-30小时)使产率低。(3) The precursor is generally prepared by the co-precipitation method. In order to make the formed precursor (hydroxide colloid) easy to filter to obtain a precursor with high purity and accurate stoichiometry, it is generally necessary to add ammonium salt or ammonium hydroxide, etc. Complexing agents such as ammonium or ammonia can complex heavy metal ions such as nickel and manganese to form a spherical particle precursor that is easy to filter. However, it also leads to incomplete precipitation of heavy metal ions such as nickel and manganese due to the formation of complex ions ( Precipitation rate ≤ 95%), resulting in high content of heavy metal ions such as nickel and manganese in the filtered mother liquor, which is difficult to recover, high cost, and environmental load for production; and the co-precipitation reaction time is long (20-30 hours) to increase the yield Low.
发明内容Summary of the invention
本发明根据现有技术中存在的不足，提供一种镍锰基正极材料前驱体及其正极材料的合成方法。该方法可解决了以下技术问题：(1)提高镍和锰作为主要成分的二元、三元、或者四元及以上的多元正极材料的电化学稳定性和充放电容量低的问题；(2)三元正极材料前驱体在共沉淀过程中的过滤难问题；(2)共沉淀反应时间长、产率低的问题；(3)彻底消除三元正极材料生产过程中的重金属离子回收与污染问题。According to the deficiencies in the prior art, the present invention provides a nickel-manganese-based cathode material precursor and a method for synthesizing the anode material. This method can solve the following technical problems: (1) Improve the electrochemical stability and low charge-discharge capacity of binary, ternary, or quaternary and above multi-element cathode materials with nickel and manganese as the main components; (2) ) The problem of difficult filtration of the precursors of the ternary cathode material in the co-precipitation process; (2) The problems of long co-precipitation reaction time and low yield; (3) Completely eliminate the recovery and pollution of heavy metal ions in the production process of the ternary cathode material problem.
为了实现以上发明目的，本发明的具体技术方案如下：In order to achieve the above objectives of the invention, the specific technical solutions of the present invention are as follows:
一种镍锰基正极材料前驱体的合成方法，其包括以下步骤：A method for synthesizing a precursor of a nickel-manganese-based cathode material, which comprises the following steps:
1)将可溶性T盐、可溶性镍盐和可溶性锰盐加入去离子水中，按照Ni 1-x-yMn xT y(OH) 2进行配置，制得浓度为1-6mol/l的金属盐溶液。 1) Add soluble T salt, soluble nickel salt and soluble manganese salt to deionized water and configure according to Ni 1-xy Mn x T y (OH) 2 to prepare a metal salt solution with a concentration of 1-6 mol/l.
2)取氢氧化钠、氢氧化钾或氢氧化锂配制成浓度为1-15mol/l的溶液作为沉淀剂溶液；2) Take sodium hydroxide, potassium hydroxide or lithium hydroxide to prepare a solution with a concentration of 1-15 mol/l as the precipitant solution;
3)在沉淀反应器中先加入纯水，金属粉末或金属氧化物，并将温度控制在40-100℃，然后将步骤2)中的金属盐溶液、步骤3)配成的沉淀剂溶液各自加热后，再并流加入到沉淀反应器中进行共沉淀反应，沉淀反应时间为50-80min；趁热过滤；最后对过滤出的沉淀物用去离子水搅拌洗涤、真空干燥处理，得到镍锰基正极材料前驱体。3) In the precipitation reactor, first add pure water, metal powder or metal oxide, and control the temperature at 40-100°C, and then combine the metal salt solution in step 2) and the precipitant solution prepared in step 3) respectively. After heating, co-currently added to the precipitation reactor for co-precipitation reaction, the precipitation reaction time is 50-80min; filter while hot; finally, the filtered precipitate is washed with deionized water and vacuum dried to obtain nickel manganese Base cathode material precursor.
所述的T为Al、Mg、Co、Zr、Ti、Fe、Zn、Ce、Mo、Cr、La、W和Sn中的任意一种或者几种。The T is any one or more of Al, Mg, Co, Zr, Ti, Fe, Zn, Ce, Mo, Cr, La, W and Sn.
作为优选，0.01＜Y＜0.5，0.01＜X＜0.5。Preferably, 0.01<Y<0.5, 0.01<X<0.5.
作为优选，所述的可溶性T盐为十八水硫酸铝。Preferably, the soluble T salt is aluminum sulfate octahydrate.
作为优选，所述的可溶性镍盐为六水硫酸镍。Preferably, the soluble nickel salt is nickel sulfate hexahydrate.
作为优选，所述的可溶性锰盐为单水硫酸锰。Preferably, the soluble manganese salt is manganese sulfate monohydrate.
所述的金属粉末为纳米金属镍粉和金属锰粉(粒径为10-50纳米，纯度≥99.9％)；所述的金属氧化物为纳米NiO粉末和纳米MnO粉末(粒径为10-50纳米，纯度≥99.9％)。金属粉末或金属氧化物的加入量为前驱体Ni 1-x-yMn xT y(OH) 2化学计量式确定的镍、锰摩尔数的0.01-5％。 The metal powder is nano-metal nickel powder and metal manganese powder (particle size is 10-50 nanometers, purity ≥99.9%); the metal oxide is nano-NiO powder and nano-MnO powder (particle size is 10-50 nanometers). Nanometer, purity ≥99.9%). The amount of metal powder or metal oxide added is 0.01 to 5% of the number of moles of nickel and manganese determined by the stoichiometric formula of the precursor Ni 1-xy Mn x T y (OH) 2.
作为优选，可溶性镍盐和可溶性锰盐的添加量为Ni 1-x-yMn xT y(OH) 2化学计量式中确定的镍、锰摩尔数的的95-99.99％。纯水的添加量为反应总体积量的10-30％。 Preferably, the addition amount of the soluble nickel salt and the soluble manganese salt is 95-99.99% of the number of moles of nickel and manganese determined in the Ni 1-xy Mn x T y (OH) 2 stoichiometric formula. The amount of pure water added is 10-30% of the total volume of the reaction.
所述共沉淀反应的条件为：保温温度40-100℃、搅拌0.5-3.0h，陈化0.5-2.0h。The conditions of the co-precipitation reaction are: holding temperature 40-100° C., stirring for 0.5-3.0 h, and aging for 0.5-2.0 h.
利用所述合成方法制备得到的镍锰基正极材料前驱体进一步合成镍锰基正极材料的方法，包括以下步骤：The method for further synthesizing the nickel-manganese-based positive electrode material using the nickel-manganese-based positive electrode material precursor prepared by the synthesis method includes the following steps:
将前驱体与锂源充分混合，在通氧条件下的管式炉中进行预焙烧5-15h，然后升温至750-900℃在氧气气氛中进行烧结10-30h，取出，研磨，即为镍锰基正极材料。预焙烧的温度为500-650℃。The precursor and the lithium source are fully mixed, pre-baked in a tube furnace under oxygen flow for 5-15h, then heated to 750-900℃, sintered in an oxygen atmosphere for 10-30h, taken out, and ground, and it is nickel Manganese-based cathode material. The pre-baking temperature is 500-650°C.
所述的锂源为氢氧化锂或碳酸锂。前驱体与锂源的比例关系为：0.8-1.2。The lithium source is lithium hydroxide or lithium carbonate. The ratio between the precursor and the lithium source is 0.8-1.2.
本发明的积极效果体现在：The positive effects of the present invention are embodied in:
(一)、在前驱体合成的共沉淀反应中，由于加入晶种(纳米镍粉、钴粉、锰粉或它们的氧化物)，使共沉淀产物在上述晶种上生长并迅速长大，呈球形或类球形，且沉淀反应时间仅50-80min，该共沉淀产物易于过滤，克服了现有技术中反应时间过长、过滤难的问题。沉淀时间与前面陈化时间(1) In the co-precipitation reaction of precursor synthesis, due to the addition of seed crystals (nano nickel powder, cobalt powder, manganese powder or their oxides), the co-precipitation product grows on the aforementioned seed crystals and grows rapidly. It is spherical or quasi-spherical, and the precipitation reaction time is only 50-80 minutes. The co-precipitation product is easy to filter, which overcomes the problems of too long reaction time and difficult filtration in the prior art. Settling time and previous aging time
(二)、由于不加入络合剂NH 4 +(如铵盐或氢氧化铵等铵、或氨类物质)，使Ni 2+、Co 2+、Mn 2+、Al 3+等金属离子沉淀十分完全，沉淀率可达99.9％以上，过滤母液中几乎不含重金属离子，彻底消除现有技术中二元、三元及以上正极材料前驱体生产过程中的重金属离子回收与污染问题，具有显著的环境效益。 (2) Since no complexing agent NH 4 + (such as ammonium salt or ammonium hydroxide, or ammonia substances) is added, metal ions such as Ni 2+ , Co 2+ , Mn 2+ , Al 3+ are precipitated It is very complete, the precipitation rate can reach more than 99.9%, and the filtered mother liquor contains almost no heavy metal ions, which completely eliminates the heavy metal ion recovery and pollution problems in the production process of the binary, ternary and above cathode material precursors in the prior art, and has significant Environmental benefits.
(三)、由于以纳米镍粉、锰粉或其氧化物为晶核，使形成的前驱体密度较高，振实密度达到1.2-1.5g/cm 3。 (3) Due to the use of nano-nickel powder, manganese powder or their oxides as crystal nuclei, the density of the precursor formed is higher, and the tap density reaches 1.2-1.5g/cm 3 .
(四)、由于前驱体各成分分布均匀，其高温固相反应生成的二元、三元及以上正极材料层状结构完善、晶化度好，电化学性能稳定，其充放电容量达200mAh/g以上。(4) Due to the uniform distribution of the components of the precursor, the binary, ternary and above cathode materials produced by the high-temperature solid-phase reaction have a perfect layered structure, good crystallinity, stable electrochemical performance, and their charge and discharge capacity can reach 200mAh/ g above.
附图说明：Description of the drawings:
图1为实施例5中合成得到的前驱体的电子显微镜图片(SEM图)。Figure 1 is an electron microscope image (SEM image) of the precursor synthesized in Example 5.
图2是实施例4中合成得到的前驱体的电子显微镜图片(SEM图)。FIG. 2 is an electron microscope image (SEM image) of the precursor synthesized in Example 4. FIG.
图3为实施例4中合成得到的三元正极材料的电子显微镜图片(SEM图)。Fig. 3 is an electron microscope picture (SEM picture) of the ternary cathode material synthesized in Example 4.
图4为实施例5合成出的三元正极材料的XRD图。4 is an XRD pattern of the ternary cathode material synthesized in Example 5.
图5是实施例5合成的三元高镍正极材料的充放电曲线图。FIG. 5 is a charge-discharge curve diagram of the ternary high nickel cathode material synthesized in Example 5. FIG.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合具体实施方式对本发明作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于下述实施例。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments, but it should not be understood that the scope of the above-mentioned subject of the present invention is limited to the following embodiments.
以下实施例中所采用的金属镍粉和金属锰粉的粒径均为10-50纳米，纯度均≥99.9％；纳米NiO粉末和纳米MnO粉末的粒径也均为10-50纳米，纯度≥99.9％。本申请中所采用的％，如无特殊说明，均表示其质量百分含量，即wt％。The particle size of the metal nickel powder and the metal manganese powder used in the following embodiments are both 10-50 nanometers, and the purity is ≥99.9%; the particle size of the nano-NiO powder and the nano-MnO powder are also 10-50 nanometers, and the purity is ≥ 99.9%. The% used in this application, unless otherwise specified, means its mass percentage content, that is, wt%.
实施例1：Example 1:
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先将纳米金属镍粉2.11g、纳米金属锰粉1.98g置于反应器中，再将A溶液和B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间1.0h，陈化时间0.5h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预 焙烧温度550℃，预焙烧时间5h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为750℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即为本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first put 2.11g of nano metal nickel powder and 1.98g of nano metal manganese powder into the reactor, and then pump the A solution and B solution into the 3L reactor at the same time. The co-precipitation reaction was carried out, and the reaction conditions were: stirring intensity: medium, feeding time 30 min, reaction time 1.0 h, aging time 0.5 h, and reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-calcin in a tubular oxygen atmosphere furnace, the pre-calcin temperature is 550℃, the pre-calcin time is 5h, after the pre-calcin is completed, take it out and grind Sintered in an oxygen atmosphere furnace at a sintering temperature of 750°C and a sintering time of 20h. After sintering, it is taken out, ground, and sieved, which is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then the electrical properties are measured. . The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
实施例2Example 2
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先加入氧化镍粉2.68g、氧化锰粉2.55g于反应器中，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度600℃，预焙烧时间15h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为800℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即为本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first add 2.68g of nickel oxide powder and 2.55g of manganese oxide powder to the reactor, and then simultaneously pump the A and B solutions into the 3L reactor for co-precipitation reaction The reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, aging time 1h, reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-calcin in a tubular oxygen atmosphere furnace. The pre-calcining temperature is 600°C and the pre-calcination time is 15h. After the pre-calcination is completed, take it out and grind. , And then sintered in an oxygen atmosphere furnace, sintering temperature is 800 ℃, sintering time is 20h, after sintering is completed, take out, grind, sieving, that is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct electrical performance measurement . The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
实施例3Example 3
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫 酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先加入金属Ni粉末5.28g、Mn粉末4.944g于反应器中，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度500℃，预焙烧时间5h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为750℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即为本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。实验结果见表1. Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first add 5.28g of metal Ni powder and 4.944g of Mn powder to the reactor, and then simultaneously pump the A and B solutions into the 3L reactor for co-precipitation reaction. The reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, aging time 1h, reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a pre-baking temperature of 500°C and a pre-baking time of 5h. After the pre-baking is completed, take it out and grind Sintered in an oxygen atmosphere furnace at a sintering temperature of 750°C and a sintering time of 20h. After sintering, it is taken out, ground, and sieved, which is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then the electrical properties are measured. . The experimental results are shown in Table 1.
实施例4Example 4
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先加入粒径为10-50纳米、纯度≥99.9％NiO粉末6.72g、MnO粉末6.38g于反应器中，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入 1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度650℃，预焙烧时间15h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为800℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即为本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first add 6.72g of NiO powder with a particle size of 10-50 nanometers and a purity of ≥99.9% and 6.38g of MnO powder in the reactor, and then combine the A and B solutions at the same time. The flow is pumped into a 3L reactor for co-precipitation reaction. The reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, aging time 1h, reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h. After the pre-baked is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, sintering temperature is 800 ℃, sintering time is 20h, after sintering is completed, take out, grind, sieving, that is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct electrical performance measurement . The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
实施例5Example 5
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先加入粒径为10-50纳米、纯度≥99.9％的氧化镍粉0.04g、氧化锰粉0.039g于反应器中，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度650℃，预焙烧时间20h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为780℃，烧结时间为30h，烧结完成后 取出，研磨，筛分，即为本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first add 0.04g of nickel oxide powder with a particle size of 10-50 nanometers and a purity of ≥99.9% and 0.039g of manganese oxide powder in the reactor, and then add A, B The solution was simultaneously pumped into a 3L reactor for co-precipitation reaction. The reaction conditions were: stirring intensity: medium, feeding time 30 min, reaction time 2 h, aging time 1 h, and reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C, and a pre-baked time of 20h. After the pre-baked is completed, take it out and grind. Sintered in an oxygen atmosphere furnace at a sintering temperature of 780℃ and a sintering time of 30h. After sintering, take it out, grind and sieving, which is the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct electrical performance measurement . The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
对比例1(与实施例4相同，只是不加纳米金属粉末)Comparative Example 1 (same as Example 4, except that nano metal powder is not added)
取电池级六水硫酸镍416.3+30.08g，电池级单水硫酸锰27.38+19.62g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度650℃，预焙烧时间15h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为800℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即得本目标正极材料LiNi 0.88Mn 0.09Al 0.030 2。 Take battery grade nickel sulfate hexahydrate 416.3+30.08g, battery grade manganese sulfate monohydrate 27.38+19.62g, battery grade aluminum sulfate octahydrate 36.3g, add deionized water, make 1L solution, converted into nickel sulfate, sulfuric acid The total metal ion concentration in the mixed aqueous solution of manganese and aluminum sulfate is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide and add deionized water to prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol /l, this is solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), and then simultaneously pump A and B solutions into the 3L reactor for co-precipitation reaction. The reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, The aging time is 1h, and the reaction temperature is 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h. After the pre-baked is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, the sintering temperature is 800 ℃, the sintering time is 20h, after the sintering is completed, take it out, grind, and sieving to obtain the target cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 .
对比例2(与实施例4相同，只是加入一种纳米金属镍粉末)Comparative Example 2 (same as Example 4, except that a nano-metal nickel powder was added)
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38+19.62g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先加入粒径为10-50纳 米、纯度≥99.9％NiO粉末6.72g于反应器中，再将A、B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间2h，陈化时间1h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度650℃，预焙烧时间15h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为800℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即得正极材料LiNi 0.88Mn 0.09Al 0.030 2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38+19.62g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade aluminum sulfate octahydrate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, The total metal ion concentration in the mixed aqueous solution of aluminum sulfate is 1.8mol/l, which is solution A; take 144g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, converted to a sodium hydroxide concentration of 3.6mol/l , This is solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first add 6.72g of NiO powder with a particle size of 10-50 nanometers and a purity of ≥99.9% into the reactor, and then pump the A and B solutions into the 3L reaction at the same time. The reactor performs co-precipitation reaction, and the reaction conditions are: stirring intensity: medium, feeding time 30min, reaction time 2h, aging time 1h, reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-baked in a tubular oxygen atmosphere furnace at a temperature of 650°C and a pre-baked time of 15h. After the pre-baked is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, the sintering temperature is 800 ℃, the sintering time is 20h, after sintering is completed, take it out, grind, and sieving to obtain the cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 .
对比例3(与实施例1相同，只是加入金属粉末的粒径为200-1000纳米)Comparative Example 3 (same as Example 1, except that the particle size of the added metal powder is 200-1000 nm)
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先将纳米金属镍粉2.11g、纳米金属锰粉1.98g置于反应器中，再将A溶液和B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间1.0h，陈化时间0.5h，反应温度80℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预 焙烧温度550℃，预焙烧时间5h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为750℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即得正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first put 2.11g of nano metal nickel powder and 1.98g of nano metal manganese powder into the reactor, and then pump the A solution and B solution into the 3L reactor at the same time. The co-precipitation reaction was carried out, and the reaction conditions were: stirring intensity: medium, feeding time 30 min, reaction time 1.0 h, aging time 0.5 h, and reaction temperature 80°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-calcin in a tubular oxygen atmosphere furnace, the pre-calcin temperature is 550℃, the pre-calcin time is 5h, after the pre-calcin is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, the sintering temperature is 750℃, the sintering time is 20h, after the sintering is completed, take it out, grind, and sieving to obtain the cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct the electrical performance measurement. The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
对比例4(与实施例1相同，只是共沉淀温度下降为40℃)Comparative Example 4 (same as Example 1, except that the co-precipitation temperature dropped to 40°C)
取电池级六水硫酸镍416.3g，电池级单水硫酸锰27.38g，电池级十八水硫酸铝36.3g，加入去离子水，配制成1L的溶液，换算为硫酸镍、硫酸锰、硫酸铝混合水溶液中总金属离子浓度为1.8mol/l，此为溶液A；取分析纯氢氧化钠144g，加入去离子水，配制成1L的溶液，换算为氢氧化钠浓度为3.6mol/l，此为溶液B。用3L反应器加入底水(去离子水)450ml，先将纳米金属镍粉2.11g、纳米金属锰粉1.98g置于反应器中，再将A溶液和B溶液同时并流泵入3L反应器进行共沉淀反应，反应条件是：搅拌强度：中，加料时间30min，反应时间1.0h，陈化时间0.5h，反应温度40℃。趁热真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤饼取出，加入1L去离子水，于60℃搅拌洗涤30min，真空过滤，滤液保存，并用于下次配制硫酸镍溶液。滤饼于80℃烘干3h，取出研磨，即为目标正极材料前驱体。将该前驱体取50g，加入电池级一水氢氧化锂25g，研磨混合，再于管式氧气气氛炉中进行预焙烧，预焙烧温度550℃，预焙烧时间5h，预焙烧完成后取出，研磨，再于氧气气氛炉中烧结，烧结温度为750℃，烧结时间为20h，烧结完成后取出，研磨，筛分，即得正极材料LiNi 0.88Mn 0.09Al 0.030 2，然后进行电性能测定。合成的前驱体实验结果见表1，合成得正极材料电性能测试结果见表2。 Take 416.3g of battery-grade nickel sulfate hexahydrate, 27.38g of battery-grade manganese sulfate monohydrate, and 36.3g of battery-grade octadecahydrate aluminum sulfate. Add deionized water to prepare a 1L solution, which is converted into nickel sulfate, manganese sulfate, and aluminum sulfate. The total metal ion concentration in the mixed aqueous solution is 1.8 mol/l, which is solution A; take 144 g of analytically pure sodium hydroxide, add deionized water, and prepare a 1L solution, which is converted into a sodium hydroxide concentration of 3.6 mol/l. For solution B. Use a 3L reactor to add 450ml of bottom water (deionized water), first put 2.11g of nano metal nickel powder and 1.98g of nano metal manganese powder into the reactor, and then pump the A solution and B solution into the 3L reactor at the same time. The co-precipitation reaction was carried out, and the reaction conditions were: stirring intensity: medium, feeding time 30 min, reaction time 1.0 h, aging time 0.5 h, and reaction temperature 40°C. Vacuum filter while hot, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, remove the filter cake, add 1L deionized water, stir and wash at 60°C for 30min, vacuum filter, save the filtrate, and use Prepare nickel sulfate solution next time. The filter cake was dried at 80°C for 3 hours, and then taken out and ground to become the target cathode material precursor. Take 50g of the precursor, add 25g of battery-grade lithium hydroxide monohydrate, grind and mix, and then pre-calcin in a tubular oxygen atmosphere furnace, the pre-calcin temperature is 550℃, the pre-calcin time is 5h, after the pre-calcin is completed, take it out and grind , And then sintered in an oxygen atmosphere furnace, the sintering temperature is 750℃, the sintering time is 20h, after the sintering is completed, take it out, grind, and sieving to obtain the cathode material LiNi 0.88 Mn 0.09 Al 0.03 0 2 , and then conduct the electrical performance measurement. The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
将实施例1至实施例5，以及对比例1至对比例4中合成得到的前驱体和正极材料进行电性能测定。)合成的前驱体实验结果见表1，合成得正极材料电性 能测试结果见表2。The electrical properties of the precursors and cathode materials synthesized in Example 1 to Example 5 and Comparative Example 1 to Comparative Example 4 were measured. ) The experimental results of the synthesized precursor are shown in Table 1, and the electrical performance test results of the synthesized positive electrode material are shown in Table 2.
表1 实施例和对比例前驱体实验结果Table 1 Experimental results of precursors of Examples and Comparative Examples
Figure PCTCN2020115848-appb-000001
Figure PCTCN2020115848-appb-000001
注：振实密度采用GB/T 5162金属粉末标准进行检测。Note: The tap density is tested according to the GB/T 5162 metal powder standard.
表2 实施例和对比例目标正极材料电化学性能Table 2 The electrochemical performance of the target cathode material of the embodiment and the comparative example
Figure PCTCN2020115848-appb-000002
Figure PCTCN2020115848-appb-000002
注：首次充放电比容量及首次充放电效率采用GB/T 37201--2018进行测定。Note: The first charge-discharge specific capacity and the first charge-discharge efficiency are measured using GB/T 37201-2018.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (10)

  1. 一种镍锰基正极材料前驱体的合成方法，其特征在于包括以下步骤：A method for synthesizing a precursor of a nickel-manganese-based cathode material, which is characterized in that it comprises the following steps:
    1)将可溶性T盐、可溶性镍盐和可溶性锰盐加入去离子水中，按照Ni 1-x-yMn xT y(OH) 2进行配置，制得浓度为1-6mol/l的金属盐溶液； 1) Add soluble T salt, soluble nickel salt and soluble manganese salt to deionized water, and configure according to Ni 1-xy Mn x T y (OH) 2 to prepare a metal salt solution with a concentration of 1-6 mol/l;
    2)取氢氧化钠、氢氧化钾或氢氧化锂配制成浓度为1-15mol/l的沉淀剂溶液；2) Take sodium hydroxide, potassium hydroxide or lithium hydroxide to prepare a precipitation agent solution with a concentration of 1-15 mol/l;
    3)在沉淀反应器中加入纯水，金属粉末或金属氧化物，并将温度控制在40-100℃，然后将步骤1)中的金属盐溶液、步骤2)配成的沉淀剂溶液各自加热后，再并流加入到沉淀反应器中进行共沉淀反应；趁热过滤；最后对过滤出的沉淀物用去离子水搅拌洗涤、真空干燥处理，得到镍锰基正极材料前驱体。3) Add pure water, metal powder or metal oxide to the precipitation reactor, and control the temperature at 40-100°C, and then heat the metal salt solution in step 1) and the precipitant solution prepared in step 2) respectively Then, co-currently added to the precipitation reactor for co-precipitation reaction; filtered while hot; finally, the filtered precipitate was washed with deionized water and vacuum dried to obtain a nickel-manganese-based positive electrode material precursor.
  2. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于：所述的T为Al、Mg、Co、Zr、Ti、Fe、Zn、Ce、Mo、Cr、La、W和Sn中的任意一种或者几种。The method for synthesizing a precursor of a nickel-manganese-based cathode material according to claim 1, wherein the T is Al, Mg, Co, Zr, Ti, Fe, Zn, Ce, Mo, Cr, La, W and Any one or several of Sn.
  3. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于：0.01＜Y＜0.5，0.01＜X＜0.5。The method for synthesizing a precursor of a nickel-manganese-based cathode material according to claim 1, wherein 0.01<Y<0.5, 0.01<X<0.5.
  4. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于：可溶性镍盐和可溶性锰盐的添加量为Ni 1-x-yMn xT y(OH) 2化学计量式确定的镍、锰摩尔数的95-99.99％。 The method for synthesizing the precursor of the nickel-manganese-based cathode material according to claim 1, wherein the addition amount of the soluble nickel salt and the soluble manganese salt is Ni 1-xy Mn x T y (OH) 2 nickel determined by the stoichiometric formula , 95-99.99% of the moles of manganese.
  5. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于所述的金属粉末为纳米金属镍粉和纳米金属锰粉；所述的金属氧化物为纳米NiO和纳米MnO粉末；金属粉末或金属氧化物的粒径为10-50纳米，纯度均≥99.9％。The method for synthesizing a precursor of a nickel-manganese-based cathode material according to claim 1, wherein the metal powder is nano-metal nickel powder and nano-metal manganese powder; and the metal oxide is nano-NiO and nano-MnO powder; The particle size of the metal powder or metal oxide is 10-50 nanometers, and the purity is ≥99.9%.
  6. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于：金属粉末或金属氧化物加入量为前驱体Ni 1-x-yMn xT y(OH) 2化学计量式确定的镍、锰摩尔数的0.01-5％；纯水的添加量为反应总体积量的10-30％。 The method for synthesizing a precursor of a nickel-manganese-based cathode material according to claim 1, wherein the amount of metal powder or metal oxide added is nickel determined by the stoichiometric formula of the precursor Ni 1-xy Mn x T y (OH) 2 , 0.01-5% of the number of moles of manganese; the added amount of pure water is 10-30% of the total volume of the reaction.
  7. 如权利要求1所述镍锰基正极材料前驱体的合成方法，其特征在于所述共沉淀反应的条件为：保温温度40-100℃、搅拌0.5-3.0h，陈化0.5-2.0h。The method for synthesizing the nickel-manganese-based cathode material precursor according to claim 1, wherein the conditions of the co-precipitation reaction are: holding temperature 40-100° C., stirring for 0.5-3.0 h, and aging for 0.5-2.0 h.
  8. 利用权利要求1所述合成方法制备得到的镍锰基正极材料前驱体进一步合成镍锰基正极材料的方法，其特征在于包括以下步骤：A method for further synthesizing a nickel-manganese-based positive electrode material using the nickel-manganese-based positive electrode material precursor prepared by the synthesis method of claim 1, characterized in that it comprises the following steps:
    将前驱体与锂源充分混合，在通氧条件下的管式炉中进行预焙烧5-15h，然后升温在氧气气氛中进行烧结10-30h，取出，研磨，即为镍锰基正极材料。The precursor is fully mixed with the lithium source, pre-baked in a tube furnace under oxygen flow for 5-15h, then heated in an oxygen atmosphere for sintering for 10-30h, taken out, and ground to form a nickel-manganese-based cathode material.
  9. 如权利要求8所述的方法，其特征在于：所述的锂源为氢氧化锂或碳酸锂。8. The method of claim 8, wherein the lithium source is lithium hydroxide or lithium carbonate.
  10. 如权利要求8所述的方法，其特征在于：预焙烧的温度为500-650℃，升温至750-900℃煅烧。The method according to claim 8, wherein the temperature of the pre-calcination is 500-650°C, and the temperature is increased to 750-900°C for calcination.
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