WO2023016427A1 - Preparation method for al and zr doped cobalt-free precursor with high specific surface area - Google Patents

Preparation method for al and zr doped cobalt-free precursor with high specific surface area Download PDF

Info

Publication number
WO2023016427A1
WO2023016427A1 PCT/CN2022/110997 CN2022110997W WO2023016427A1 WO 2023016427 A1 WO2023016427 A1 WO 2023016427A1 CN 2022110997 W CN2022110997 W CN 2022110997W WO 2023016427 A1 WO2023016427 A1 WO 2023016427A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
metal salt
zirconium
surface area
salt solution
Prior art date
Application number
PCT/CN2022/110997
Other languages
French (fr)
Chinese (zh)
Inventor
许开华
吴凯飞
吕志
刘坤
王登登
邹书文
Original Assignee
荆门市格林美新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 荆门市格林美新材料有限公司 filed Critical 荆门市格林美新材料有限公司
Publication of WO2023016427A1 publication Critical patent/WO2023016427A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 synthesis of new energy battery material precursors, and in particular relates to a method for preparing an Al, Zr doped high specific surface area cobalt-free precursor.
  • ternary materials With the development of new energy vehicles, the research on ternary materials has become more and more in-depth in recent years.
  • the ternary materials are developing towards high nickel and cobalt-free.
  • Co in ternary materials can inhibit the mixing of Li and Ni and improve the rate performance.
  • the presence of Co is beneficial to enhance the structural stability and thermal safety performance of crystalline materials.
  • the global reserves of Co are relatively small, expensive, and easily affected by geopolitics. Therefore, it is of great significance to study cobalt-free precursors.
  • the resistivity of the battery material will increase, and the rate performance, cycle performance, and stability will all decrease.
  • Materials with a large specific surface area have a large contact area with the electrolyte, and the diffusion path of lithium ions becomes shorter, which is beneficial to the intercalation and extraction of lithium ions in the battery material and improves the rate performance of the material.
  • the cyclability and stability of the material can be improved by incorporating some other elements. Therefore, increasing the specific surface area of the upstream precursor material and doping some other elements is beneficial to solve the defects caused by cobalt deficiency.
  • the cobalt-free precursor material prepared by doping technology rarely mentions the specific surface area.
  • the ammonia concentration is high in the synthesis process, and the ammonia water consumption is large in the production process, which is not conducive to environmental protection.
  • the present invention provides a cobalt-free precursor with high specific surface area doped with Al and Zr that is completely cobalt-free, can reduce the cost of raw materials, consumes less ammonia water, is environmentally friendly and easy to control, and is suitable for mass production. Preparation.
  • the present invention adopts following technical scheme:
  • a method for preparing an Al, Zr-doped high specific surface area cobalt-free precursor characterized in that the method comprises the following steps:
  • preparation concentration is the sodium metaaluminate solution of 5g/L-70g/L;
  • the preparation method of the high specific surface area cobalt-free precursor of above-mentioned Al, Zr doping it is characterized in that, the nickel-manganese metal salt solution concentration containing zirconium in step (2) is 20g/L-120g/L;
  • the preparation method of the above-mentioned Al, Zr doped high specific surface area cobalt-free precursor it is characterized in that the pH of the bottom liquid in step (4) is 8.0-12.0, and the ammonia concentration of the bottom liquid is 1.0g/L-15.0 g/L.
  • the flow rate of nitrogen gas in step (4) is 0.5m 3 /h-5.0m 3 /h.
  • the concentration of liquid caustic soda in step (4) is 10%-50%, and the concentration of ammonia water is 10%-50%;
  • the feed flow rates of zirconium-containing nickel-manganese metal salt solution, sodium metaaluminate solution, liquid caustic soda, and ammonia water into the reactor are 30L/h-300L/h, 5L/h-50L/h, 10L/h- 100L/h, 3L/h-30L/h.
  • the preparation method of the above-mentioned Al, Zr-doped high specific surface area cobalt-free precursor it is characterized in that in step (4), the nickel-manganese metal salt solution containing zirconium, sodium metaaluminate solution, liquid caustic soda, and ammoniacal liquor are simultaneously
  • the reaction conditions for adding to a reaction kettle for reaction are as follows: the reaction temperature is 20°C-90°C, the reaction time is 15h-100h, and the stirring speed is 50r/min-400r/min.
  • the present invention adopts a low-ammonia process, which greatly reduces the amount of ammonia water, produces waste water containing less ammonia nitrogen, and has low recovery and treatment costs, which is in line with the national concept of low-carbon environmental protection.
  • the high surface area enhances the lithium ion intercalation and extraction capabilities of downstream battery materials and improves the rate performance of the material.
  • elements such as Al and Zr are added to the material. Al, to a certain extent, inhibits the mixing of cations when lithium ions are extracted, and improves the cycle performance and stability of the material.
  • the ion radius of Zr 4+ is higher than that of Ni 3+ , which can increase the
  • the large unit cell expands the lithium ion transmission channel, significantly improves the electrical conductivity, and improves the rate performance of the material.
  • Zr will form ZrO 2 during the sintering process of the positive electrode material, which has the characteristics of high melting point and low thermal conductivity, and can enhance the high temperature chemical stability of the material.
  • the product prepared by the method of the invention is completely cobalt-free, reduces the cost of raw materials, and consumes less ammonia water, is environmentally friendly and easy to control, and is suitable for mass production.
  • Fig. 1 is a schematic flow sheet of the present invention
  • Fig. 2 is the SEM figure of the high specific surface area cobalt-free precursor of Al, Zr doping obtained in embodiment 1;
  • Example 3 is a cross-sectional SEM image of the Al, Zr doped high specific surface area cobalt-free precursor obtained in Example 1.
  • the preparation method of Zr-doped high specific surface area cobalt-free precursor of the present invention comprises the following steps:
  • Soluble nickel salts include nickel sulfate, nickel nitrate, nickel chloride, and nickel acetate
  • soluble manganese salts include sulfate, nitrate, chloride, and acetate.
  • the pH of the bottom liquid is 8.0-12.0, and the ammonia concentration of the bottom liquid is 1.0g/L-15.0g/L.
  • the flow rate of nitrogen gas is 0.5m 3 /h-5.0m 3 /h.
  • the concentration of liquid caustic soda is 10%-50%, the concentration of ammonia water is 10%-50%; 30L/h-300L/h, 5L/h-50L/h, 10L/h-100L/h, 3L/h-30L/h.
  • the reaction conditions are: reaction temperature 20°C-90°C, reaction time 15h-100h, stirring The speed is 50r/min-400r/min.
  • nickel sulfate and manganese sulfate respectively into a preparation tank equipped with pure water to prepare a nickel-manganese sulfate solution with a concentration of 90 g/L for later use.
  • aluminum sulfate to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 30g/L for later use, prepare a liquid caustic soda with a mass fraction of 43%, and prepare an ammonia solution with a mass fraction of 22%.
  • zirconium sulfate to the nickel-manganese sulfate solution to prepare a zirconium-containing nickel-manganese sulfate solution with a zirconium content of 10,000 ppm and a concentration of 90/L.
  • the pH of the whole system is maintained between 9.0-11.5, the ammonia concentration is maintained between 2.5g/L-7.3g/L, and the stirring speed of the stirring blade is 200r/min by regulating the flow rate of liquid caustic soda and ammonia water.
  • the reaction temperature of the system is 50°C, and the reaction time is 70h.
  • the feed is stopped to end the reaction, and the precursor material with the structural formula Ni 0.85 Mn 0.10 Al 0.04 Zr 0.01 (OH) 2 is obtained. .
  • the material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 25.19m 2 /g is obtained , and finally pack the material to get the finished product.
  • nickel nitrate and manganese nitrate respectively into a preparation tank equipped with pure water to prepare a nickel manganese nitrate solution with a concentration of 20 g/L for later use.
  • zirconium nitrate to the nickel-manganese nitrate solution to prepare a zirconium-containing nickel-manganese nitrate solution with a zirconium content of 1000ppm and a concentration of 20g/L; zirconium ions and nickel-manganese metal salts in the zirconium-containing nickel-manganese nitrate solution
  • the material is discharged into the aging tank, and after washing and removing impurities, dehydration, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 28.07m 2 /g is obtained , and finally pack the material to get the finished product.
  • nickel chloride and manganese chloride respectively into a preparation tank equipped with pure water to prepare a nickel manganese chloride salt solution with a concentration of 120g/L for subsequent use.
  • aluminum chloride to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 70g/L for use, prepare a liquid caustic soda with a mass fraction of 50%, and prepare an ammonia solution with a mass fraction of 40%.
  • Zirconium chloride is added to the nickel-manganese chloride salt solution to prepare a zirconium-containing nickel-manganese metal salt solution with a zirconium content of 10,000 ppm and a concentration of 120 g/L;
  • the pH of the whole system is maintained between 10.0-12.0, the ammonia concentration is maintained between 5.0g/L-10.0g/L, and the stirring speed of the stirring blade is 200r/min by regulating the flow rate of liquid caustic soda and ammonia water.
  • the reaction temperature of the system is 60°C, and the reaction time is 30h.
  • the feed is stopped to end the reaction, and the precursor material with the structural formula Ni 0.60 Mn 0.34 Al 0.05 Zr 0.01 (OH) 2 is obtained. .
  • the material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 15.12m 2 /g is obtained , and finally pack the material to get the finished product.
  • nickel acetate and manganese acetate respectively into a preparation tank equipped with pure water to prepare a nickel-manganese acetate solution with a concentration of 80 g/L for subsequent use.
  • Aluminum acetate to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 40g/L for use, prepare a liquid caustic soda with a mass fraction of 35%, and prepare an ammonia solution with a mass fraction of 20%.
  • Zirconium acetate is added to the nickel-manganese acetate solution to prepare a zirconium-containing nickel-manganese acetate solution with a zirconium content of 5000ppm and a concentration of 80g/L; zirconium ions and nickel in the zirconium-containing nickel-manganese salt solution
  • the pH of the whole system is maintained between 10.0-11.0, the ammonia concentration is maintained between 1.0g/L-5.0g/L, and the stirring speed of the stirring blade is 50r/min by regulating the flow rate of liquid caustic soda and ammonia water.
  • the reaction temperature of the system is 70°C, the reaction time is 85h, stop feeding after D50 reaches 3.2um, and stop the reaction to obtain a precursor material with the structural formula Ni 0.80 Mn 0.19 Al 0.005 Zr 0.005 (OH) 2 .
  • the material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 20.89m 2 /g is obtained , and finally pack the material to get the finished product.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A preparation method for an Al and Zr doped cobalt-free precursor with a high specific surface area, comprising the following steps: preparing a nickel-manganese metal salt solution from soluble nickel salt and soluble manganese salt; adding soluble zirconium salt into the nickel-manganese metal salt solution to prepare a zirconium-containing nickel-manganese metal salt solution; preparing a sodium metaaluminate solution with the aluminum content of 5 g/L-70 g/L; adding pure water, ammonia water and liquid caustic soda into a reaction kettle to prepare a base solution, introducing nitrogen into the base solution, starting the reaction kettle for stirring, and simultaneously adding the zirconium-containing nickel-manganese metal salt solution, the sodium metaaluminate solution, the liquid caustic soda and the ammonia water into the reaction kettle for reaction to obtain a precursor material; and washing, filtering and drying the precursor material to obtain the Al and Zr doped cobalt-free precursor with the high specific surface area of 10 m2/g-30 m2/g. The method is completely cobalt-free, can reduce the cost of raw materials, is less in ammonia water consumption, is environment-friendly and easy to control, and is suitable for mass production.

Description

一种Al、Zr掺杂的高比表面积无钴前驱体的制备方法A kind of preparation method of Al, Zr doped high specific surface area cobalt-free precursor 技术领域technical field
本发明属于新能源电池材料前驱体合成领域，具体涉及一种Al、Zr掺杂的高比表面积无钴前驱体的制备方法。The invention belongs to the field of synthesis of new energy battery material precursors, and in particular relates to a method for preparing an Al, Zr doped high specific surface area cobalt-free precursor.
背景技术Background technique
随着新能源汽车的发展，近年来三元材料的研究越来越深，三元材料朝着高镍化和无钴化发展，三元材料中Co能抑制Li、Ni混排，改善倍率性能和循环性能，Co的存在有利于增强晶体材料结构稳定性和热安全性能，然而Co全球储量相对较少，价格昂贵，容易受地缘政治影响，因此研究无钴前驱体具有十分重要的意义。With the development of new energy vehicles, the research on ternary materials has become more and more in-depth in recent years. The ternary materials are developing towards high nickel and cobalt-free. Co in ternary materials can inhibit the mixing of Li and Ni and improve the rate performance. The presence of Co is beneficial to enhance the structural stability and thermal safety performance of crystalline materials. However, the global reserves of Co are relatively small, expensive, and easily affected by geopolitics. Therefore, it is of great significance to study cobalt-free precursors.
由于没有Co的存在，电池材料的阻抗性会增加，倍率性能、循环性能和稳定性都会随之降低。比表面积大的材料与电解液的接触面积大，锂离子的扩散路径变短，有利于锂离子在电池材料的嵌脱，提高材料倍率性能。通过掺入一些其它元素能改善材料的循环性和稳定性。因此提高上游前驱体材料的比表面积和掺入一些其它元素有利于解决缺钴带来的缺陷。现有技术中采用掺杂技术制得的无钴前驱体材料对于比表面积问题少有提到，合成过程中氨浓度高，生产过程中氨水用量大，不利于环保。Due to the absence of Co, the resistivity of the battery material will increase, and the rate performance, cycle performance, and stability will all decrease. Materials with a large specific surface area have a large contact area with the electrolyte, and the diffusion path of lithium ions becomes shorter, which is beneficial to the intercalation and extraction of lithium ions in the battery material and improves the rate performance of the material. The cyclability and stability of the material can be improved by incorporating some other elements. Therefore, increasing the specific surface area of the upstream precursor material and doping some other elements is beneficial to solve the defects caused by cobalt deficiency. In the prior art, the cobalt-free precursor material prepared by doping technology rarely mentions the specific surface area. The ammonia concentration is high in the synthesis process, and the ammonia water consumption is large in the production process, which is not conducive to environmental protection.
发明内容Contents of the invention
针对现有技术中的问题，本发明提供一种完全无钴化、能够降低原料成本、氨水用量少、环保易控、适合量产的Al、Zr掺杂的高比表面积无钴前驱体的制备方法。In view of the problems in the prior art, the present invention provides a cobalt-free precursor with high specific surface area doped with Al and Zr that is completely cobalt-free, can reduce the cost of raw materials, consumes less ammonia water, is environmentally friendly and easy to control, and is suitable for mass production. Preparation.
本发明采用以下技术方案：The present invention adopts following technical scheme:
一种Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，所述方法包括以下步骤：A method for preparing an Al, Zr-doped high specific surface area cobalt-free precursor, characterized in that the method comprises the following steps:
(1)将可溶性镍盐与可溶性锰盐按照摩尔比为Ni:Mn＝x 1:y 1配制成镍锰金属盐溶液，其中，0.60≤x 1≤0.85，0.10≤y 1≤0.35，x 1+y 1<1，镍锰金属盐溶液的浓度为20g/L-120g/L； (1) The soluble nickel salt and the soluble manganese salt are prepared into a nickel-manganese metal salt solution according to the molar ratio of Ni:Mn=x 1 :y 1 , wherein, 0.60≤x 1 ≤0.85, 0.10≤y 1 ≤0.35, x 1 +y 1 <1, the concentration of nickel manganese metal salt solution is 20g/L-120g/L;
(2)将可溶性锆盐加入到镍锰金属盐溶液中，配制成含锆的镍锰金属盐溶液，含锆的镍锰金属盐溶液中锆含量为1000ppm-10000ppm；(2) adding the soluble zirconium salt into the nickel-manganese metal salt solution to prepare a zirconium-containing nickel-manganese metal salt solution, and the zirconium content in the zirconium-containing nickel-manganese metal salt solution is 1000ppm-10000ppm;
(3)配制浓度为5g/L-70g/L的偏铝酸钠溶液；(3) preparation concentration is the sodium metaaluminate solution of 5g/L-70g/L;
(4)向反应釜中加入纯水、氨水、液碱配制成底液，向底液中通入氮气，将反应釜开启搅拌，将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应， 得到结构式为Ni xMn yAl mZr n(OH) 2的前驱体材料，其中x+y+m+n＝1，0.60≤x≤0.85，0.10≤y≤0.35，0.005≤m≤0.05，0.001≤n≤0.01； (4) add pure water, ammoniacal liquor, liquid caustic soda to be mixed with bottom liquid in the reaction kettle, feed nitrogen into the bottom liquid, the reaction kettle is opened and stirred, and the nickel-manganese metal salt solution containing zirconium, sodium metaaluminate solution, Liquid caustic soda and ammonia water are added to the reaction kettle at the same time for reaction, and a precursor material with a structural formula of Ni x Mn y Al m Zr n (OH) 2 is obtained, wherein x+y+m+n=1, 0.60≤x≤0.85, 0.10≤y≤0.35, 0.005≤m≤0.05, 0.001≤n≤0.01;
(5)将物料排入陈化槽，经过洗涤、除杂、脱水、烘干、混批、筛分、除铁后包装，得到比表面积为10m 2/g-30m 2/g的Al、Zr掺杂的高比表面积无钴前驱体成品。 (5) Put the material into the aging tank, and pack after washing, impurity removal, dehydration, drying, batch mixing, screening, and iron removal to obtain Al and Zr with a specific surface area of 10m 2 /g-30m 2 /g Doped high surface area cobalt-free precursor finished product.
根据上述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(2)中含锆的镍锰金属盐溶液浓度为20g/L-120g/L；含锆的镍锰金属盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Zr：Ni：Mn＝(0.001-0.01):(0.60-0.85):(0.10-0.35)。According to the preparation method of the high specific surface area cobalt-free precursor of above-mentioned Al, Zr doping, it is characterized in that, the nickel-manganese metal salt solution concentration containing zirconium in step (2) is 20g/L-120g/L; The molar ratio of zirconium ions in the nickel-manganese metal salt solution to metal ions in the nickel-manganese metal salt solution is Zr:Ni:Mn=(0.001-0.01):(0.60-0.85):(0.10-0.35).
根据上述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中底液的pH为8.0-12.0，底液的氨浓度为1.0g/L-15.0g/L。According to the preparation method of the above-mentioned Al, Zr doped high specific surface area cobalt-free precursor, it is characterized in that the pH of the bottom liquid in step (4) is 8.0-12.0, and the ammonia concentration of the bottom liquid is 1.0g/L-15.0 g/L.
根据上述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中氮气的通入流量为0.5m 3/h-5.0m 3/h。 According to the above-mentioned preparation method of Al, Zr doped high specific surface area cobalt-free precursor, it is characterized in that the flow rate of nitrogen gas in step (4) is 0.5m 3 /h-5.0m 3 /h.
根据上述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中液碱的浓度为10％-50％，氨水的浓度为10％-50％；含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水加入到反应釜中的进料流量分别为30L/h-300L/h、5L/h-50L/h、10L/h-100L/h、3L/h-30L/h。According to the preparation method of the above-mentioned Al, Zr doped high specific surface area cobalt-free precursor, it is characterized in that the concentration of liquid caustic soda in step (4) is 10%-50%, and the concentration of ammonia water is 10%-50%; The feed flow rates of zirconium-containing nickel-manganese metal salt solution, sodium metaaluminate solution, liquid caustic soda, and ammonia water into the reactor are 30L/h-300L/h, 5L/h-50L/h, 10L/h- 100L/h, 3L/h-30L/h.
根据上述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应的反应条件为：反应温度为20℃-90℃、反应时间为15h-100h、搅拌转速为50r/min-400r/min。According to the preparation method of the above-mentioned Al, Zr-doped high specific surface area cobalt-free precursor, it is characterized in that in step (4), the nickel-manganese metal salt solution containing zirconium, sodium metaaluminate solution, liquid caustic soda, and ammoniacal liquor are simultaneously The reaction conditions for adding to a reaction kettle for reaction are as follows: the reaction temperature is 20°C-90°C, the reaction time is 15h-100h, and the stirring speed is 50r/min-400r/min.
本发明的有益技术效果：本发明采用一种低氨工艺，大大减少了氨水的用量，产生的废水含氨氮少，回收处理成本低，符合国家低碳环保的理念，制备出的前驱体材料比表面积高，增强了下游电池材料锂离子的嵌脱能力，提高材料的倍率性能。本发明在材料中添加了Al、Zr等元素，Al在一定程度上抑制了锂离子脱出时阳离子混排，提高材料的循环性能和稳定性，Zr 4+离子半径高于Ni 3+，可以增大晶胞，扩充锂离子传输通道，显著提高电导率，提高材料的倍率性能。此外Zr在正极材料烧结过程中会在形成ZrO 2，具有高熔点、低热导率的特点，可以增强材料的高温化学稳定性。本发明方法制备的产品完全无钴化，降低了原料成本，并且氨水用量少，环保易控，适合量产。 Beneficial technical effects of the present invention: the present invention adopts a low-ammonia process, which greatly reduces the amount of ammonia water, produces waste water containing less ammonia nitrogen, and has low recovery and treatment costs, which is in line with the national concept of low-carbon environmental protection. The high surface area enhances the lithium ion intercalation and extraction capabilities of downstream battery materials and improves the rate performance of the material. In the present invention, elements such as Al and Zr are added to the material. Al, to a certain extent, inhibits the mixing of cations when lithium ions are extracted, and improves the cycle performance and stability of the material. The ion radius of Zr 4+ is higher than that of Ni 3+ , which can increase the The large unit cell expands the lithium ion transmission channel, significantly improves the electrical conductivity, and improves the rate performance of the material. In addition, Zr will form ZrO 2 during the sintering process of the positive electrode material, which has the characteristics of high melting point and low thermal conductivity, and can enhance the high temperature chemical stability of the material. The product prepared by the method of the invention is completely cobalt-free, reduces the cost of raw materials, and consumes less ammonia water, is environmentally friendly and easy to control, and is suitable for mass production.
附图说明Description of drawings
图1为本发明的流程示意图；Fig. 1 is a schematic flow sheet of the present invention;
图2为实施例1中得到的Al、Zr掺杂的高比表面积无钴前驱体的SEM图；Fig. 2 is the SEM figure of the high specific surface area cobalt-free precursor of Al, Zr doping obtained in embodiment 1;
图3为实施例1中得到的Al、Zr掺杂的高比表面积无钴前驱体的剖面SEM图。3 is a cross-sectional SEM image of the Al, Zr doped high specific surface area cobalt-free precursor obtained in Example 1.
具体实施方式Detailed ways
参见图1，本发明的一种Al、Zr掺杂的高比表面积无钴前驱体的制备方法，包括以下步骤：Referring to Fig. 1, a kind of Al, the preparation method of Zr-doped high specific surface area cobalt-free precursor of the present invention comprises the following steps:
(1)将可溶性镍盐与可溶性锰盐按照摩尔比为Ni:Mn＝x 1:y 1配制成镍锰金属盐溶液，其中，0.60≤x 1≤0.85，0.10≤y 1≤0.35，x 1+y 1<1，镍锰金属盐溶液的浓度为20g/L-120g/L。可溶性镍盐包括硫酸镍、硝酸镍、氯化镍、醋酸镍，可溶性锰盐包括硫酸盐、硝酸盐、氯化盐、醋酸盐。 (1) The soluble nickel salt and the soluble manganese salt are prepared into a nickel-manganese metal salt solution according to the molar ratio of Ni:Mn=x 1 :y 1 , wherein, 0.60≤x 1 ≤0.85, 0.10≤y 1 ≤0.35, x 1 +y 1 <1, the concentration of nickel manganese metal salt solution is 20g/L-120g/L. Soluble nickel salts include nickel sulfate, nickel nitrate, nickel chloride, and nickel acetate, and soluble manganese salts include sulfate, nitrate, chloride, and acetate.
(2)将可溶性锆盐加入到镍锰金属盐溶液中，配制成锆含量为1000ppm-10000ppm、浓度为20g/L-120g/L的含锆的镍锰金属盐溶液；含锆的镍锰金属盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Zr：Ni：Mn＝(0.001-0.01):(0.60-0.85):(0.10-0.35)。(2) Add the soluble zirconium salt into the nickel-manganese metal salt solution to prepare a zirconium-containing nickel-manganese metal salt solution with a zirconium content of 1000ppm-10000ppm and a concentration of 20g/L-120g/L; zirconium-containing nickel-manganese metal salt solution The molar ratio of zirconium ions in the salt solution to metal ions in the nickel-manganese metal salt solution is Zr:Ni:Mn=(0.001-0.01):(0.60-0.85):(0.10-0.35).
(3)将可溶性铝盐加入到NaOH溶液中，配制浓度为5g/L-70g/L的偏铝酸钠溶液；(3) soluble aluminum salt is added in the NaOH solution, and preparation concentration is the sodium metaaluminate solution of 5g/L-70g/L;
(4)向反应釜中加入纯水、氨水、液碱配制成底液，向底液中通入氮气，将反应釜开启搅拌，升高温度，待达到预定温度后，将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应，得到结构式为Ni xMn yAl mZr n(OH) 2的前驱体材料，其中x+y+m+n＝1，0.60≤x≤0.85，0.10≤y≤0.35，0.005≤m≤0.05，0.001≤n≤0.01。底液的pH为8.0-12.0，底液的氨浓度为1.0g/L-15.0g/L。氮气的通入流量为0.5m 3/h-5.0m 3/h。液碱的浓度为10％-50％，氨水的浓度为10％-50％；含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水加入到反应釜中的进料流量分别为30L/h-300L/h、5L/h-50L/h、10L/h-100L/h、3L/h-30L/h。将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应的反应条件为：反应温度为20℃-90℃、反应时间为15h-100h、搅拌转速为50r/min-400r/min。 (4) Add pure water, ammonia water, and liquid caustic soda to the reaction kettle to prepare the bottom liquid, feed nitrogen into the bottom liquid, start the reaction kettle to stir, raise the temperature, and after reaching the predetermined temperature, the nickel-manganese containing zirconium Metal salt solution, sodium metaaluminate solution, liquid caustic soda, and ammonia water are added to the reaction kettle at the same time for reaction, and a precursor material with a structural formula of Ni x Mn y Al m Zr n (OH) 2 is obtained, wherein x+y+m+ n=1, 0.60≤x≤0.85, 0.10≤y≤0.35, 0.005≤m≤0.05, 0.001≤n≤0.01. The pH of the bottom liquid is 8.0-12.0, and the ammonia concentration of the bottom liquid is 1.0g/L-15.0g/L. The flow rate of nitrogen gas is 0.5m 3 /h-5.0m 3 /h. The concentration of liquid caustic soda is 10%-50%, the concentration of ammonia water is 10%-50%; 30L/h-300L/h, 5L/h-50L/h, 10L/h-100L/h, 3L/h-30L/h. Add zirconium-containing nickel-manganese metal salt solution, sodium metaaluminate solution, liquid caustic soda, and ammonia water into the reaction kettle at the same time. The reaction conditions are: reaction temperature 20°C-90°C, reaction time 15h-100h, stirring The speed is 50r/min-400r/min.
(5)将物料排入陈化槽，经过洗涤除杂、脱水、烘干、混批、筛分、除铁后包装，得到比表面积为10m 2/g-30m 2/g的Al、Zr掺杂的高比表面积无钴前驱体成品。 (5) Put the material into the aging tank, wash and remove impurities, dehydrate, dry, mix batches, sieve, and pack after iron removal to obtain Al, Zr mixed with a specific surface area of 10m 2 /g-30m 2 /g Complex high specific surface area cobalt-free precursor products.
实施例1Example 1
分别将硫酸镍、硫酸锰加入到装有纯水的配制槽中，配制出浓度为90g/L的镍锰硫酸盐溶液备用。将硫酸铝加入到装有NaOH溶液的配制槽中，配制出浓度为30g/L的偏铝酸钠溶液备用，配制质量分数为43％的液碱，配制质量分数为22％的氨水溶液。Add nickel sulfate and manganese sulfate respectively into a preparation tank equipped with pure water to prepare a nickel-manganese sulfate solution with a concentration of 90 g/L for later use. Add aluminum sulfate to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 30g/L for later use, prepare a liquid caustic soda with a mass fraction of 43%, and prepare an ammonia solution with a mass fraction of 22%.
将硫酸锆加入到镍锰硫酸盐溶液中，配制成锆含量为10000ppm、浓度为90/L的含锆的镍锰硫酸盐溶液，含锆的镍锰金属盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为 Ni：Mn：Zr＝0.85:0.10:0.01。Add zirconium sulfate to the nickel-manganese sulfate solution to prepare a zirconium-containing nickel-manganese sulfate solution with a zirconium content of 10,000 ppm and a concentration of 90/L. Zirconium ions and nickel-manganese metal salts in the zirconium-containing nickel-manganese metal salt solution The molar ratio of metal ions in the solution is Ni:Mn:Zr=0.85:0.10:0.01.
在反应釜中加入4.5m 3纯水、45L质量分数22％的氨水、35L质量分数为43％的液碱，配制成pH值为11.0-11.8、氨浓度为5.0g/L-9.0/L的底液，向反应釜中以1.5m 3/h的流量通入氮气，将底液加热至47℃，通过计量泵分别将含锆的镍锰硫酸盐溶液以300L/h、偏铝酸钠溶液以50L/h的流量同时加入体积为7m 3的反应釜中；同时在反应釜中加入质量分数为43％的液碱和质量分数为22％的氨水，流量分别为100L/h和15L/h。当反应釜中物料液位上升至溢流口后开启与浓缩机之间物料循环。反应过程中通过调控液碱和氨水的流量，使整个体系的pH维持在9.0-11.5之间，氨浓度维持在2.5g/L-7.3g/L之间，搅拌桨的搅拌速度为200r/min-400r/min之间，体系的反应温度为50℃、反应时间为70h，D50达到3.2um后停止进料结束反应，得到结构式为Ni 0.85Mn 0.10Al 0.04Zr 0.01(OH) 2的前驱体材料。 Add 4.5m 3 of pure water, 45L of ammonia water with a mass fraction of 22%, and 35L of liquid caustic soda with a mass fraction of 43% in the reaction kettle to prepare a solution with a pH value of 11.0-11.8 and an ammonia concentration of 5.0g/L-9.0/L. For the bottom liquid, feed nitrogen into the reaction kettle at a flow rate of 1.5m 3 /h, heat the bottom liquid to 47°C, and pump the zirconium-containing nickel-manganese sulfate solution at 300L/h, sodium metaaluminate solution, and Add 50L/h flow into a reactor with a volume of 7m 3 at the same time; add liquid caustic soda with a mass fraction of 43% and ammonia water with a mass fraction of 22% in the reactor at the same time, and the flow rates are 100L/h and 15L/h respectively . When the liquid level of the material in the reactor rises to the overflow port, the material circulation with the concentrator is started. During the reaction process, the pH of the whole system is maintained between 9.0-11.5, the ammonia concentration is maintained between 2.5g/L-7.3g/L, and the stirring speed of the stirring blade is 200r/min by regulating the flow rate of liquid caustic soda and ammonia water. Between -400r/min, the reaction temperature of the system is 50°C, and the reaction time is 70h. After the D50 reaches 3.2um, the feed is stopped to end the reaction, and the precursor material with the structural formula Ni 0.85 Mn 0.10 Al 0.04 Zr 0.01 (OH) 2 is obtained. .
将物料排入陈化槽，经过洗涤除杂、脱水、烘干、混批、筛分、除铁后，得到比表面积为25.19m 2/g的Al、Zr掺杂高比表面积无钴前驱体，最后将物料进行包装得到成品。 The material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 25.19m 2 /g is obtained , and finally pack the material to get the finished product.
实施例2Example 2
分别将硝酸镍、硝酸锰加入到装有纯水的配制槽中，配制出浓度为20g/L的镍锰硝酸盐溶液备用。将硝酸铝加入到装有NaOH溶液的配制槽中，配制出浓度为10g/L的偏铝酸钠溶液备用，配制质量分数为10％的液碱，配制质量分数为10％的氨水溶液。Add nickel nitrate and manganese nitrate respectively into a preparation tank equipped with pure water to prepare a nickel manganese nitrate solution with a concentration of 20 g/L for later use. Add aluminum nitrate to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 10g/L for use, prepare a liquid caustic soda with a mass fraction of 10%, and prepare an ammonia solution with a mass fraction of 10%.
将硝酸锆加入到镍锰硝酸盐溶液中，配制成锆含量为1000ppm、浓度为20g/L的含锆的镍锰硝酸盐溶液；含锆的镍锰硝酸盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Ni：Mn：Zr＝0.75:0.24:0.001。Add zirconium nitrate to the nickel-manganese nitrate solution to prepare a zirconium-containing nickel-manganese nitrate solution with a zirconium content of 1000ppm and a concentration of 20g/L; zirconium ions and nickel-manganese metal salts in the zirconium-containing nickel-manganese nitrate solution The molar ratio of metal ions in the solution is Ni:Mn:Zr=0.75:0.24:0.001.
在反应釜中加入3.5m 3纯水、70L质量分数10％的氨水、45L质量分数为10％的液碱，配制成pH值为10.0-12.0、氨浓度为1.0g/L-3.5g/L的底液，向反应釜中以5.0m 3/h的流量通入氮气，将底液加热至40℃，通过计量泵分别将含锆的镍锰硝酸盐溶液以100L/h、偏铝酸钠溶液以5L/h的流量同时加入体积为7m 3的反应釜中；同时在反应釜中加入质量分数为10％的液碱和质量分数为10％的氨水，流量分别为10L/h和3L/h。当反应釜中物料液位上升至溢流口后开启与浓缩机之间物料循环。反应过程中通过调控液碱和氨水的流量，使整个体系的pH维持在8.0-11.0之间，氨浓度维持在1.0g/L-3.5g/L之间，搅拌桨的搅拌速度为150r/min-300r/min之间，体系的反应温度为40℃、反应时间为100h，D50达到3.2um后停止进料结束反应，得到结构式为Ni 0.75Mn 0.24Al 0.009Zr 0.001(OH) 2的前驱体材料。 Add 3.5m 3 pure water, 70L ammonia water with a mass fraction of 10%, and 45L liquid caustic soda with a mass fraction of 10% in the reaction kettle to prepare a pH value of 10.0-12.0 and an ammonia concentration of 1.0g/L-3.5g/L Nitrogen gas is introduced into the reactor at a flow rate of 5.0m 3 /h, the bottom liquid is heated to 40°C, and the nickel-manganese nitrate solution containing zirconium is fed to 100L/h, sodium metaaluminate The solution is added into the reactor with a volume of 7m3 at the same time at a flow rate of 5L/h; at the same time, the mass fraction of 10% liquid caustic soda and 10% ammonia water are added into the reactor, and the flow rates are 10L/h and 3L/h respectively. h. When the liquid level of the material in the reactor rises to the overflow port, the material circulation with the concentrator is started. During the reaction process, by adjusting the flow rate of liquid caustic soda and ammonia water, the pH of the whole system is maintained between 8.0-11.0, the ammonia concentration is maintained between 1.0g/L-3.5g/L, and the stirring speed of the stirring blade is 150r/min Between -300r/min, the reaction temperature of the system is 40°C, and the reaction time is 100h. After the D50 reaches 3.2um, the feed is stopped to end the reaction, and the precursor material with the structural formula Ni 0.75 Mn 0.24 Al 0.009 Zr 0.001 (OH) 2 is obtained. .
将物料排入陈化槽，经过洗涤除杂、脱水、烘干、混批、筛分、除铁后，得到比表面积 为28.07m 2/g的Al、Zr掺杂高比表面积无钴前驱体，最后将物料进行包装得到成品。 The material is discharged into the aging tank, and after washing and removing impurities, dehydration, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 28.07m 2 /g is obtained , and finally pack the material to get the finished product.
实施例3Example 3
分别将氯化镍、氯化锰加入到装有纯水的配制槽中，配制出浓度为120g/L的氯化镍锰盐溶液备用。将氯化铝加入到装有NaOH溶液的配制槽中，配制出浓度为70g/L的偏铝酸钠溶液备用，配制质量分数为50％的液碱，配制质量分数为40％的氨水溶液。Add nickel chloride and manganese chloride respectively into a preparation tank equipped with pure water to prepare a nickel manganese chloride salt solution with a concentration of 120g/L for subsequent use. Add aluminum chloride to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 70g/L for use, prepare a liquid caustic soda with a mass fraction of 50%, and prepare an ammonia solution with a mass fraction of 40%.
将氯化锆加入到氯化镍锰盐溶液中，配制成锆含量为10000ppm、浓度为120g/L的含锆的镍锰金属盐溶液；含锆的镍锰金属盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Ni：Mn：Zr＝0.60:0.34:0.01。Zirconium chloride is added to the nickel-manganese chloride salt solution to prepare a zirconium-containing nickel-manganese metal salt solution with a zirconium content of 10,000 ppm and a concentration of 120 g/L; The molar ratio of metal ions in the metal salt solution is Ni:Mn:Zr=0.60:0.34:0.01.
在反应釜中加入5.0m 3纯水、35L质量分数40％的氨水、25L质量分数为50％的液碱，配制成pH值为11.0-12.0、氨浓度为10.0g/L-15.0/L的底液，向反应釜中以0.5m 3/h的流量通入氮气，将底液加热至60℃，通过计量泵分别将含锆的镍锰金属盐溶液以200L/h、偏铝酸钠溶液以50L/h的流量同时加入体积为7m 3的反应釜中；同时在反应釜中加入质量分数为50％的液碱和质量分数为40％的氨水，流量分别为70L/h和30L/h。当反应釜中物料液位上升至溢流口后开启与浓缩机之间物料循环。反应过程中通过调控液碱和氨水的流量，使整个体系的pH维持在10.0-12.0之间，氨浓度维持在5.0g/L-10.0g/L之间，搅拌桨的搅拌速度为200r/min-300r/min之间，体系的反应温度为60℃、反应时间为30h，D50达到3.2um后停止进料结束反应，得到结构式为Ni 0.60Mn 0.34Al 0.05Zr 0.01(OH) 2的前驱体材料。 Add 5.0m3 of pure water, 35L of ammonia water with a mass fraction of 40%, and 25L of liquid caustic soda with a mass fraction of 50% in the reaction kettle to prepare a solution with a pH value of 11.0-12.0 and an ammonia concentration of 10.0g/L-15.0/L. For the bottom liquid, feed nitrogen gas into the reactor at a flow rate of 0.5m 3 /h, heat the bottom liquid to 60°C, and feed the zirconium-containing nickel-manganese metal salt solution at 200L/h, sodium metaaluminate solution, and Add 50L/h flow into the reactor with a volume of 7m 3 at the same time; add liquid caustic soda with a mass fraction of 50% and ammonia water with a mass fraction of 40% in the reactor at the same time, and the flow rates are 70L/h and 30L/h respectively . When the liquid level of the material in the reactor rises to the overflow port, the material circulation with the concentrator is started. During the reaction process, the pH of the whole system is maintained between 10.0-12.0, the ammonia concentration is maintained between 5.0g/L-10.0g/L, and the stirring speed of the stirring blade is 200r/min by regulating the flow rate of liquid caustic soda and ammonia water. Between -300r/min, the reaction temperature of the system is 60°C, and the reaction time is 30h. After the D50 reaches 3.2um, the feed is stopped to end the reaction, and the precursor material with the structural formula Ni 0.60 Mn 0.34 Al 0.05 Zr 0.01 (OH) 2 is obtained. .
将物料排入陈化槽，经过洗涤除杂、脱水、烘干、混批、筛分、除铁后，得到比表面积为15.12m 2/g的Al、Zr掺杂高比表面积无钴前驱体，最后将物料进行包装得到成品。 The material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 15.12m 2 /g is obtained , and finally pack the material to get the finished product.
实施例4Example 4
分别将醋酸镍、醋酸锰加入到装有纯水的配制槽中，配制出浓度为80g/L的镍锰醋酸盐溶液备用。将醋酸铝加入到装有NaOH溶液的配制槽中，配制出浓度为40g/L的偏铝酸钠溶液备用，配制质量分数为35％的液碱，配制质量分数为20％的氨水溶液。Add nickel acetate and manganese acetate respectively into a preparation tank equipped with pure water to prepare a nickel-manganese acetate solution with a concentration of 80 g/L for subsequent use. Add aluminum acetate to the preparation tank equipped with NaOH solution, prepare a sodium metaaluminate solution with a concentration of 40g/L for use, prepare a liquid caustic soda with a mass fraction of 35%, and prepare an ammonia solution with a mass fraction of 20%.
将醋酸锆加入到镍锰醋酸盐溶液中，配制成锆含量为5000ppm、浓度为80g/L的含锆的镍锰醋酸盐溶液；含锆的镍锰酸盐盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Ni：Mn：Zr＝0.80:0.19:0.005。Zirconium acetate is added to the nickel-manganese acetate solution to prepare a zirconium-containing nickel-manganese acetate solution with a zirconium content of 5000ppm and a concentration of 80g/L; zirconium ions and nickel in the zirconium-containing nickel-manganese salt solution The molar ratio of metal ions in the manganese metal salt solution is Ni:Mn:Zr=0.80:0.19:0.005.
在反应釜中加入4.5m 3纯水、50L质量分数20％的氨水、10L质量分数为35％的液碱，配制成pH值为10.5-11.5、氨浓度为1.0g/L-5.0/L的底液，向反应釜中以2.0m 3/h的流量通入氮气，将底液加热至90℃，通过计量泵分别将含锆的镍锰酸盐盐溶液以150L/h、偏铝酸钠溶 液以25L/h的流量同时加入体积为7m 3的反应釜中；同时在反应釜中加入质量分数为35％的液碱和质量分数为20％的氨水，流量分别为50L/h和15L/h。当反应釜中物料液位上升至溢流口后开启与浓缩机之间物料循环。反应过程中通过调控液碱和氨水的流量，使整个体系的pH维持在10.0-11.0之间，氨浓度维持在1.0g/L-5.0g/L之间，搅拌桨的搅拌速度为50r/min-250r/min之间，体系的反应温度为70℃、反应时间为85h，D50达到3.2um后停止进料结束反应，得到结构式为Ni 0.80Mn 0.19Al 0.005Zr 0.005(OH) 2的前驱体材料。 Add 4.5m3 of pure water, 50L of ammonia water with a mass fraction of 20%, and 10L of liquid caustic soda with a mass fraction of 35% in the reaction kettle, and prepare a solution with a pH value of 10.5-11.5 and an ammonia concentration of 1.0g/L-5.0/L. For the bottom liquid, feed nitrogen into the reactor at a flow rate of 2.0m 3 /h, heat the bottom liquid to 90°C, and feed zirconium-containing nickel manganese salt solution at 150L/h, sodium metaaluminate The solution is simultaneously added into a reactor with a volume of 7m at a flow rate of 25L/h; at the same time, adding a mass fraction of 35% liquid caustica and 20% ammonia in the reactor, the flow rate is 50L/h and 15L/h respectively h. When the liquid level of the material in the reactor rises to the overflow port, the material circulation with the concentrator is started. During the reaction process, the pH of the whole system is maintained between 10.0-11.0, the ammonia concentration is maintained between 1.0g/L-5.0g/L, and the stirring speed of the stirring blade is 50r/min by regulating the flow rate of liquid caustic soda and ammonia water. Between -250r/min, the reaction temperature of the system is 70°C, the reaction time is 85h, stop feeding after D50 reaches 3.2um, and stop the reaction to obtain a precursor material with the structural formula Ni 0.80 Mn 0.19 Al 0.005 Zr 0.005 (OH) 2 .
将物料排入陈化槽，经过洗涤除杂、脱水、烘干、混批、筛分、除铁后，得到比表面积为20.89m 2/g的Al、Zr掺杂高比表面积无钴前驱体，最后将物料进行包装得到成品。 The material is discharged into the aging tank, and after washing and removing impurities, dehydrating, drying, batch mixing, screening, and iron removal, an Al and Zr doped high specific surface area cobalt-free precursor with a specific surface area of 20.89m 2 /g is obtained , and finally pack the material to get the finished product.

Claims (6)

  1. 一种Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，所述方法包括以下步骤：A method for preparing an Al, Zr-doped high specific surface area cobalt-free precursor, characterized in that the method comprises the following steps:
    (1)将可溶性镍盐与可溶性锰盐按照摩尔比为Ni:Mn＝x 1:y 1配制成镍锰金属盐溶液，其中，0.60≤x 1≤0.85，0.10≤y 1≤0.35，x 1+y 1<1，镍锰金属盐溶液的浓度为20g/L-120g/L； (1) The soluble nickel salt and the soluble manganese salt are prepared into a nickel-manganese metal salt solution according to the molar ratio of Ni:Mn=x 1 :y 1 , wherein, 0.60≤x 1 ≤0.85, 0.10≤y 1 ≤0.35, x 1 +y 1 <1, the concentration of nickel manganese metal salt solution is 20g/L-120g/L;
    (2)将可溶性锆盐加入到镍锰金属盐溶液中，配制成含锆的镍锰金属盐溶液，含锆的镍锰金属盐溶液中锆含量为1000ppm-10000ppm；(2) adding the soluble zirconium salt into the nickel-manganese metal salt solution to prepare a zirconium-containing nickel-manganese metal salt solution, and the zirconium content in the zirconium-containing nickel-manganese metal salt solution is 1000ppm-10000ppm;
    (3)配制浓度为5g/L-70g/L的偏铝酸钠溶液；(3) preparation concentration is the sodium metaaluminate solution of 5g/L-70g/L;
    (4)向反应釜中加入纯水、氨水、液碱配制成底液，向底液中通入氮气，将反应釜开启搅拌，将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应，得到结构式为Ni xMn yAl mZr n(OH) 2的前驱体材料，其中x+y+m+n＝1，0.60≤x≤0.85，0.10≤y≤0.35，0.005≤m≤0.05，0.001≤n≤0.01； (4) add pure water, ammoniacal liquor, liquid caustic soda to be mixed with bottom liquid in the reaction kettle, feed nitrogen into the bottom liquid, the reaction kettle is opened and stirred, and the nickel-manganese metal salt solution containing zirconium, sodium metaaluminate solution, Liquid caustic soda and ammonia water are added to the reaction kettle at the same time for reaction to obtain a precursor material with a structural formula of Ni x Mn y Al m Zr n (OH) 2 , wherein x+y+m+n=1, 0.60≤x≤0.85, 0.10≤y≤0.35, 0.005≤m≤0.05, 0.001≤n≤0.01;
    (5)将物料排入陈化槽，经过洗涤、除杂、脱水、烘干、混批、筛分、除铁后包装，得到比表面积为10m 2/g-30m 2/g的Al、Zr掺杂的高比表面积无钴前驱体成品。 (5) Put the material into the aging tank, and pack after washing, impurity removal, dehydration, drying, batch mixing, screening, and iron removal to obtain Al and Zr with a specific surface area of 10m 2 /g-30m 2 /g Doped high surface area cobalt-free precursor finished product.
  2. 根据权利要求1所述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(2)中含锆的镍锰金属盐溶液浓度为20g/L-120g/L；含锆的镍锰金属盐溶液中锆离子和镍锰金属盐溶液中的金属离子摩尔比为Zr：Ni：Mn＝(0.001-0.01):(0.60-0.85):(0.10-0.35)。The preparation method of Al, Zr-doped high specific surface area cobalt-free precursor according to claim 1, characterized in that the concentration of the nickel-manganese metal salt solution containing zirconium in step (2) is 20g/L-120g/L The molar ratio of zirconium ions in the nickel-manganese metal salt solution containing zirconium to the metal ion in the nickel-manganese metal salt solution is Zr:Ni:Mn=(0.001-0.01):(0.60-0.85):(0.10-0.35).
  3. 根据权利要求1所述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中底液的pH为8.0-12.0，底液的氨浓度为1.0g/L-15.0g/L。The preparation method of the high specific surface area cobalt-free precursor doped with Al and Zr according to claim 1, characterized in that the pH of the bottom liquid in step (4) is 8.0-12.0, and the ammonia concentration of the bottom liquid is 1.0g /L-15.0g/L.
  4. 根据权利要求1所述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中氮气的通入流量为0.5m 3/h-5.0m 3/h。 The preparation method of Al, Zr-doped high specific surface area cobalt-free precursor according to claim 1, characterized in that the flow rate of nitrogen gas in step (4) is 0.5m 3 /h-5.0m 3 /h .
  5. 根据权利要求1所述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中液碱的浓度为10％-50％，氨水的浓度为10％-50％；含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水加入到反应釜中的进料流量分别为30L/h-300L/h、5L/h-50L/h、10L/h-100L/h、3L/h-30L/h。The preparation method of Al, Zr-doped high specific surface area cobalt-free precursor according to claim 1, characterized in that the concentration of liquid caustic soda in step (4) is 10%-50%, and the concentration of ammonia water is 10% -50%; the feed flow rates of zirconium-containing nickel-manganese metal salt solution, sodium metaaluminate solution, liquid caustic soda, and ammonia water into the reactor are 30L/h-300L/h, 5L/h-50L/h, 10L/h-100L/h, 3L/h-30L/h.
  6. 根据权利要求5所述的Al、Zr掺杂的高比表面积无钴前驱体的制备方法，其特征在于，步骤(4)中将含锆的镍锰金属盐溶液、偏铝酸钠溶液、液碱、氨水同时加入到反应釜中进行反应的反应条件为：反应温度为20℃-90℃、反应时间为15h-100h、搅拌转速为50r/min-400r/min。The preparation method of Al, Zr doped high specific surface area cobalt-free precursor according to claim 5, is characterized in that, in step (4), the nickel-manganese metal salt solution containing zirconium, sodium metaaluminate solution, liquid The reaction conditions of adding alkali and ammonia water into the reaction kettle at the same time are as follows: the reaction temperature is 20°C-90°C, the reaction time is 15h-100h, and the stirring speed is 50r/min-400r/min.
PCT/CN2022/110997 2021-08-13 2022-08-09 Preparation method for al and zr doped cobalt-free precursor with high specific surface area WO2023016427A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110933003.0A CN113735189A (en) 2021-08-13 2021-08-13 Preparation method of Al and Zr doped cobalt-free precursor with high specific surface area
CN202110933003.0 2021-08-13

Publications (1)

Publication Number Publication Date
WO2023016427A1 true WO2023016427A1 (en) 2023-02-16

Family

ID=78731109

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/110997 WO2023016427A1 (en) 2021-08-13 2022-08-09 Preparation method for al and zr doped cobalt-free precursor with high specific surface area

Country Status (2)

Country Link
CN (1) CN113735189A (en)
WO (1) WO2023016427A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735189A (en) * 2021-08-13 2021-12-03 荆门市格林美新材料有限公司 Preparation method of Al and Zr doped cobalt-free precursor with high specific surface area
CN114988491A (en) * 2022-05-27 2022-09-02 荆门市格林美新材料有限公司 Bimetal alternately-doped nickel-manganese precursor and preparation method and application thereof
CN115676919A (en) * 2022-12-28 2023-02-03 河南科隆电源材料有限公司 Modified cobalt-free precursor material and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109686970A (en) * 2018-12-27 2019-04-26 四川万邦胜辉机械设备有限公司 A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof
CN109970106A (en) * 2019-03-28 2019-07-05 广东迈纳科技有限公司 A kind of large-scale producing method of nickelic no cobalt precursor and positive electrode
US20190341598A1 (en) * 2016-12-22 2019-11-07 Posco Positive electrode active material, method for preparing same, and lithium secondary battery comprising same
CN112382734A (en) * 2020-08-25 2021-02-19 万向一二三股份公司 Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material
CN112939095A (en) * 2021-01-29 2021-06-11 陕西煤业化工技术研究院有限责任公司 Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof
CN113735189A (en) * 2021-08-13 2021-12-03 荆门市格林美新材料有限公司 Preparation method of Al and Zr doped cobalt-free precursor with high specific surface area
CN113745494A (en) * 2021-07-30 2021-12-03 格林美股份有限公司 Preparation method of cobalt-free cathode material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111422920A (en) * 2019-12-26 2020-07-17 蜂巢能源科技有限公司 Cobalt-free cathode material of lithium ion battery, preparation method of cobalt-free cathode material and lithium ion battery
CN112582599B (en) * 2020-12-10 2022-08-05 万华化学(四川)有限公司 Cobalt-free high-nickel quaternary positive electrode material, and preparation method and application thereof
CN113161548B (en) * 2021-03-29 2023-02-10 广东邦普循环科技有限公司 Cobalt-free nickel-manganese cathode material and preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190341598A1 (en) * 2016-12-22 2019-11-07 Posco Positive electrode active material, method for preparing same, and lithium secondary battery comprising same
CN109686970A (en) * 2018-12-27 2019-04-26 四川万邦胜辉机械设备有限公司 A kind of no cobalt richness lithium tertiary cathode material NMA and preparation method thereof
CN109970106A (en) * 2019-03-28 2019-07-05 广东迈纳科技有限公司 A kind of large-scale producing method of nickelic no cobalt precursor and positive electrode
CN112382734A (en) * 2020-08-25 2021-02-19 万向一二三股份公司 Lithium ion battery positive plate using cobalt-free high-nickel positive electrode material
CN112939095A (en) * 2021-01-29 2021-06-11 陕西煤业化工技术研究院有限责任公司 Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof
CN113745494A (en) * 2021-07-30 2021-12-03 格林美股份有限公司 Preparation method of cobalt-free cathode material
CN113735189A (en) * 2021-08-13 2021-12-03 荆门市格林美新材料有限公司 Preparation method of Al and Zr doped cobalt-free precursor with high specific surface area

Also Published As

Publication number Publication date
CN113735189A (en) 2021-12-03

Similar Documents

Publication Publication Date Title
WO2023016427A1 (en) Preparation method for al and zr doped cobalt-free precursor with high specific surface area
CN110048118B (en) High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material
WO2019104473A1 (en) Ternary precursor material and preparation method therefor
CN103606694B (en) Preparation method for commercial vanadium battery electrolyte
CN113443640B (en) Method for preparing battery-grade lithium carbonate and battery-grade iron phosphate by using waste positive and negative electrode powder of lithium iron phosphate battery
CN102544472B (en) Spherical aluminum-doped manganous-manganic oxide and preparation method thereof
CN112624076A (en) Preparation method and application of iron phosphate
CN109179359A (en) A method of extracting lithium and ferric phosphate from LiFePO4 waste material
CN109216817A (en) A kind of element recovery method of waste and old nickle cobalt lithium manganate cell positive material
CN110759384A (en) Method for preparing spheroidal manganous manganic oxide by manganese sulfate solution
CN113072048B (en) Sewage treatment and slag recycling process for producing iron phosphate by sodium method
CN104084598A (en) Production method for solar cell high-density monodisperse silver powder
WO2023142672A1 (en) Preparation method for high-purity iron phosphate and use thereof
CN104070180A (en) Production method for high-density silver powder for solar cell conductive silver paste
WO2023197483A1 (en) Hydrothermal synthesis method for nano lithium manganese iron phosphate
CN114348984A (en) Method for preparing nano iron phosphate and nano ferrous phosphate by using titanium dioxide byproduct
CN112357971A (en) Preparation method of aluminum-doped large-particle-size cobalt carbonate for battery
CN115663128A (en) Method for reducing residual alkali on surface of high-nickel ternary electrode material through gas-liquid two-phase washing
CN108682849A (en) A kind of preparation method for mixing aluminium cobalt acid lithium
WO2023207247A1 (en) Porous spherical cobalt oxide particle and preparation method therefor
WO2023160016A1 (en) Method for preparing ternary precursor from microbubbles by pre-oxidation and application of ternary precursor
CN114773617B (en) Core-shell gradient ternary precursor and preparation method and application thereof
TWI696309B (en) Method for preparing and purifying lithium carbonate from waste lithium battery
CN110311114B (en) Method for preparing ternary precursor of lithium battery through circular electrolysis
CN113845156A (en) Preparation method of low-sodium-sulfur ultrahigh-nickel quaternary precursor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22855408

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE