WO2020007176A1 - Hydroxyde de nickel-cobalt-manganèse à particules de très petite taille de et son procédé de préparation - Google Patents

Hydroxyde de nickel-cobalt-manganèse à particules de très petite taille de et son procédé de préparation Download PDF

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Publication number
WO2020007176A1
WO2020007176A1 PCT/CN2019/091008 CN2019091008W WO2020007176A1 WO 2020007176 A1 WO2020007176 A1 WO 2020007176A1 CN 2019091008 W CN2019091008 W CN 2019091008W WO 2020007176 A1 WO2020007176 A1 WO 2020007176A1
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Prior art keywords
cobalt
preparation
solution
nickel
reaction kettle
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PCT/CN2019/091008
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English (en)
Chinese (zh)
Inventor
王娟
高炯信
邱天
梁二倩
沈震雷
朱玉华
周勤俭
陈要忠
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Huayou New Energy Technology (quzhou) Co Ltd
Zhejiang Huayou Cobalt Co Ltd
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Huayou New Energy Technology (quzhou) Co Ltd
Zhejiang Huayou Cobalt Co Ltd
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Publication of WO2020007176A1 publication Critical patent/WO2020007176A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/11—Powder tap density
    • 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
    • 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
    • C01P2006/80—Compositional purity

Definitions

  • the invention belongs to the field of precursors of ternary cathode materials for lithium ion batteries, in particular to an ultra-small particle size nickel cobalt manganese hydroxide and a preparation method thereof.
  • Lithium-ion batteries as a new type of green power source, have been widely used in 3C digital electronic products, electric tools, electric vehicles, energy storage and other fields.
  • nickel-cobalt-manganate lithium exhibits excellent comprehensive performance in terms of energy density, discharge voltage, cycle performance, thermal stability, self-discharge, and cost, and has gradually become the mainstream cathode material for lithium-ion batteries for electric vehicles.
  • the most widely used nickel-cobalt lithium manganate cathode materials are secondary spherical particles formed by agglomeration of small grains. Due to the existence of a certain gap between the small grains, the material has low compaction and secondary spherical particles.
  • the cathode materials have problems such as fragile particles and low lithium ion transfer efficiency during battery manufacturing, which affect the electrochemical performance of the battery.
  • the single crystal nickel-cobalt-lithium-manganate cathode material has a higher lithium ion transfer efficiency, reduces the interface reaction between the material and the electrolyte, thereby improving the rate performance and cycle performance of the battery.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and to provide a method for preparing a nickel-cobalt-manganese hydroxide with D50 ⁇ 2 ⁇ m and good dispersibility.
  • the obtained nickel-cobalt-manganese hydroxide can be used for preparing high-power single crystals.
  • Ternary cathode material is used for preparing high-power single crystals.
  • the present invention adopts the following technical solution: a method for preparing an ultra-small-diameter nickel-cobalt-manganese hydroxide, comprising the steps:
  • step 3 3) Turn on the stirring, and add the mixed solution of the mixed metal salt solution and the ammonia-free nitrogen complexing agent and the sodium hydroxide solution configured in step 1 into the reactor in parallel to carry out the reaction, and adjust the flow of the sodium hydroxide solution to make the pH value 10.50 ⁇ 12.50, temperature is 45 ⁇ 70 °C; when the D50 of the material in the reaction kettle is detected to be 1.4 ⁇ 2.0 ⁇ m, stop feeding and continue stirring and aging for 1 ⁇ 2 hours;
  • the aged material is added to a suction filtration washing device equipped with a microporous precision filter tube for suction filtration washing.
  • the washed material is filtered to remove moisture, and then dried, sieved and demagnetized to obtain ⁇ 2 ⁇ m spherical particles of nickel cobalt manganese hydroxide.
  • the specific washing process is as follows: first, washing with a NaOH solution having a concentration of 0 to 0.5 mol / L, controlling the sulfur content to be less than 500 ppm, and then washing with pure water.
  • the soluble salt is one or more of sulfate, nitrate, and chloride; the total metal ion concentration in the mixed metal salt solution is 1 to 2.5 mol / L, and most preferably It is 1.5 to 2.0 mol / L.
  • the ammonia-free nitrogen complexing agent includes, but is not limited to, citric acid, sodium citrate, potassium citrate, oxalic acid, sodium oxalate, potassium oxalate, acetic acid, sodium acetate, potassium acetate, salicylic acid, One or more of sodium salicylate, sulfosalicylic acid, and sodium sulfosalicylate, most preferably citric acid, sodium citrate, and salicylic acid.
  • the molar ratio of the ammonia-free nitrogen complexing agent to the metal ion in the mixed metal salt solution is 0.005 to 1.000: 1, and most preferably 0.05 to 0.3. :1.
  • the concentration of the sodium hydroxide solution of the precipitating agent is 5 to 7 mol / L, and most preferably 6 mol / L.
  • the reaction kettle is a sealed reaction kettle with a stirring and temperature control device, the effective volume of the reaction kettle is 50 to 5000 L, and the volume of the bottom liquid is 1/5 to 1 of the effective volume of the reaction kettle.
  • the stirring speed of the reaction kettle is 150 to 800 r / min, and most preferably 650 to 700 r / min.
  • the bottom liquid is an aqueous solution having a complexing agent concentration of 0.006 to 0.760 mol / L, a pH value of 10.5 to 12.5, and a temperature of 45 to 70 ° C.
  • the pH of the aqueous solution can be adjusted with a sodium hydroxide solution.
  • the temperature of the NaOH solution is 45-60 ° C, and the washing time is 1-10 hours, and most preferably 3-4 hours; the temperature of pure water is 45-60 ° C, and the washing time is 1 -10 hours, most preferably 3-6 hours.
  • Another object of the present invention is to provide an ultra-small particle size nickel-cobalt-manganese hydroxide obtained by the above preparation method, and the particle size D50 is less than 2 ⁇ m.
  • a nickel-cobalt-manganese hydroxide with ultra-small particle size (D50 ⁇ 2 ⁇ m, S ⁇ 500 ppm) with ultra-low sulfur content is prepared, and the particles have good dispersibility and sphericity.
  • the present invention uses an ammonia-free nitrogen complexing agent to prepare a nickel cobalt manganese hydroxide precursor with an ultra-small particle diameter through co-precipitation reaction.
  • the present invention has the following advantages: 1
  • the precursor D50 can reach below 2.0 ⁇ m and maintain high dispersibility On the one hand, it can be used to prepare high-power single-crystal ternary cathode materials, and on the other hand, it can be used to prepare ultra-small particle size secondary spherical particles ternary cathode materials for small and large particle blending systems; 2 ammonia is not used in the product preparation process On the one hand, it reduces the use of flammable and explosive materials and improves the production safety; on the other hand, it avoids the production of irritating gases, which greatly improves the production environment and reduces environmental pollution; 3 the precursor can be washed with very low concentration of lye or even pure water It can reduce the sulfur content to less than 500ppm, reaching the leading level in the industry, which is greatly beneficial to the performance of the cathode material. The washing process of the material is beneficial to reduce the manufacturing cost of the material.
  • Example 1 is a particle size distribution curve diagram of nickel-cobalt-manganese hydroxide particles in Example 1 of the present invention
  • Example 2 is a FESEM photograph of nickel-cobalt-manganese hydroxide particles at 3000 times in Example 1 of the present invention
  • Example 3 is a particle size distribution curve diagram of nickel-cobalt-manganese hydroxide particles in Example 2 of the present invention.
  • Example 4 is a FESEM photograph of nickel-cobalt-manganese hydroxide particles at 3000 times in Example 2 of the present invention.
  • Example 5 is a particle size distribution curve diagram of nickel-cobalt-manganese hydroxide particles in Example 3 of the present invention.
  • FIG. 6 is a FESEM photograph of nickel-cobalt-manganese hydroxide particles at 3000 times in Example 3 of the present invention.
  • the aged slurry is added to a suction filtration washing device equipped with a microporous precision filter tube for suction filtration washing, washing with pure water at a temperature of 55 ° C, and the washing time is 6 hours;
  • the material was filtered to remove moisture, and then placed in an oven at 110 ° C for 20 hours to dry.
  • the dried material was sieved through a 200-mesh screen and demagnetized to obtain Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 .
  • tap density 1.16 g / cm 3
  • specific surface area 132.29 m 2 / g
  • sulfur content is 430 ppm
  • the particle size distribution curve of the product is shown in Figure 1, and the morphological characteristics are shown in Figure 2.
  • the particle size distribution curve of the product is shown in Figure 3, and the morphological characteristics are shown in Figure 4.
  • the particle size distribution curve of the product is shown in Figure 5, and the morphological characteristics are shown in Figure 6.

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

Abstract

L'invention concerne un hydroxyde de nickel-cobalt-manganèse à particules de très petite taille et son procédé de préparation. Le procédé comprend : la préparation d'une solution de sel métallique mixte et l'ajout d'un agent complexant contenant de l'azote et exempt d'ammoniac à la solution de sel métallique mixte ; la préparation d'une solution d'hydroxyde de sodium en tant qu'agent de précipitation ; l'ajout d'une solution de base à une cuve de réaction, l'introduction d'azote gazeux pour mettre en œuvre une protection atmosphérique et le maintien de l'azote gazeux de protection les pendant tout le processus de réaction ; le début de l'agitation et l'ajout simultané de la solution mixte préparée de sel métallique et d'agent complexant contenant de l'azote et exempt d'ammoniac et la solution d'hydroxyde d'azote à la cuve de réaction pour la réaction. La D50 obtenue du précurseur peut atteindre 2,0 μm ou moins et maintenir une dispersibilité élevée, et le précurseur peut être utilisé pour préparer un matériau monocristallin d'électrode positive ternaire de haute puissance, et peut également être utilisée pour préparer un matériau d'électrode positive ternaire de particules sphériques secondaires de particules très petites pouvant être utilisé dans un système de mélange de grosses particules et de petites particules.
PCT/CN2019/091008 2018-07-03 2019-06-13 Hydroxyde de nickel-cobalt-manganèse à particules de très petite taille de et son procédé de préparation Ceased WO2020007176A1 (fr)

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CN201810711813.X 2018-07-03
CN201810711813.XA CN108946827B (zh) 2018-07-03 2018-07-03 一种超小粒径镍钴锰氢氧化物及其制备方法

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EP4089055A3 (fr) * 2021-09-02 2023-03-08 XTC New Energy Materials (Xiamen) Ltd. Matériau ternaire positif de grandes particules de type monocristal, procédé de préparation de celui-ci, et batterie au lithium-ion comprenant le materiau
CN116924484A (zh) * 2023-07-19 2023-10-24 荆门市格林美新材料有限公司 一种富锂锰基前驱体材料及其制备方法和用途
CN117509751A (zh) * 2023-10-28 2024-02-06 芜湖佳纳新能源材料有限公司 正极材料前驱体及其制备方法和应用
CN119284992A (zh) * 2024-11-22 2025-01-10 安徽得壹能源科技有限公司 一种镍铁锰氢氧化物的制备方法

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CN111170375A (zh) * 2020-01-07 2020-05-19 万华化学集团股份有限公司 一种三元正极材料前驱体及其制备方法
CN114644368B (zh) * 2020-12-18 2024-03-26 中国石油化工股份有限公司 正极材料前驱体及其制备方法和正极材料及其应用
CN112694137A (zh) * 2020-12-24 2021-04-23 荆门市格林美新材料有限公司 小粒径无钴富锂锰基固溶体与钒酸锂复合材料及制备方法
CN115771914A (zh) * 2021-09-07 2023-03-10 浙江海创锂电科技有限公司 一种掺杂型小粒径高镍前驱体的制备方法
CN116986636A (zh) * 2023-07-04 2023-11-03 华友新能源科技（衢州）有限公司 钠离子电池及其铁基多元正极材料和前驱体与制备方法
CN116621234B (zh) * 2023-07-20 2023-11-07 宜宾光原锂电材料有限公司 一种钠离子正极材料前驱体及制备方法和正极材料
CN116969521B (zh) * 2023-07-31 2025-06-10 中国科学院过程工程研究所 一种钠离子电池正极材料前驱体及其制备方法和应用
WO2025107211A1 (fr) * 2023-11-23 2025-05-30 广东邦普循环科技有限公司 Précurseur ternaire, procédé de synthèse s'y rapportant et utilisation associée
CN117699867A (zh) * 2023-12-25 2024-03-15 中国科学院宁波材料技术与工程研究所 富锰氢氧化物前驱体、正极材料和电池以及制备方法

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EP4089055A3 (fr) * 2021-09-02 2023-03-08 XTC New Energy Materials (Xiamen) Ltd. Matériau ternaire positif de grandes particules de type monocristal, procédé de préparation de celui-ci, et batterie au lithium-ion comprenant le materiau
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CN117509751A (zh) * 2023-10-28 2024-02-06 芜湖佳纳新能源材料有限公司 正极材料前驱体及其制备方法和应用
CN119284992A (zh) * 2024-11-22 2025-01-10 安徽得壹能源科技有限公司 一种镍铁锰氢氧化物的制备方法

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