CN110642299B - Preparation method of aluminum-doped cobalt hydroxide applied to high-voltage LCO (liquid Crystal on oxide) coating material - Google Patents

Preparation method of aluminum-doped cobalt hydroxide applied to high-voltage LCO (liquid Crystal on oxide) coating material Download PDF

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CN110642299B
CN110642299B CN201910881593.XA CN201910881593A CN110642299B CN 110642299 B CN110642299 B CN 110642299B CN 201910881593 A CN201910881593 A CN 201910881593A CN 110642299 B CN110642299 B CN 110642299B
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aluminum
cobalt
doped
cobalt hydroxide
solution
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CN110642299A (en
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张荣洲
田礼平
刘人生
虞颖
熊铜兴
游小龙
傅江浩
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Quzhou Huayou Cobalt New Material Co ltd
Zhejiang Huayou Cobalt Co Ltd
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Quzhou Huayou Cobalt New Material Co ltd
Zhejiang Huayou Cobalt Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

Abstract

The invention belongs to the technical field of preparation of lithium battery anode materials, and particularly relates to a preparation method of cobalt hydroxide. The invention provides a preparation method of aluminum-doped cobalt hydroxide applied to a high-voltage LCO coating material, which comprises the steps of carrying out wet coprecipitation reaction on a cobalt-aluminum mixed solution and liquid caustic soda, adding an antioxidant in the process to protect 2-valent cobalt from being oxidized into 3-valent cobalt, and improving the particle dispersibility by controlling the reaction rate and the crystal nucleus growth rate. The synthesized slurry is subjected to filter pressing, washing and low-temperature drying, and is crushed by an airflow mill, and finally the aluminum-doped cobalt hydroxide finished product with the D50 less than 1 mu m and without agglomeration is obtained. The aluminum-doped cobalt hydroxide prepared by the method has a wide aluminum-doped range which can reach 0.1-1%.

Description

Preparation method of aluminum-doped cobalt hydroxide applied to high-voltage LCO (liquid Crystal on oxide) coating material
Technical Field
The invention belongs to the technical field of preparation of lithium battery anode materials, and particularly relates to a preparation method of cobalt hydroxide.
Background
Lithium Cobaltate (LCO) is superior to other ternary cathode materials such as lithium manganate, lithium iron phosphate and the like in the aspects of compaction density, high voltage, high capacity, high temperature resistance and the like, and is always the first choice of cathode materials of batteries of consumer electronic products (3C electronics for short) such as mobile phones, notebook computers, digital cameras and the like. With the development of 3C electronic products, people have higher and higher requirements for the capacity of batteries, and researchers improve the specific capacity of lithium cobaltate by increasing the charge cut-off voltage of LCO and allowing more ions to participate in charging and discharging. Currently, the LCO with the high voltage of 4.45V is gradually released, and a positive electrode material manufacturer adopts a coating mode of doping elements such as Al, Mg, Zr, Ti, Ni, Mn and the like in a wet synthesis stage of a cobaltosic oxide precursor to produce the LCO, namely doping cobaltosic oxide and lithium carbonate to carry out solid-phase reaction. Because the surface contains excessive lithium after the solid-phase reaction, the lithium cobaltate after the first burning needs to be coated and burned by superfine cobalt hydroxide, and the excessive lithium on the surface of the lithium cobaltate is consumed. In order to ensure the stability of the LCO surface under a higher voltage platform, the corresponding requirements of the coating material are also greatly improved.
The coating of lithium cobaltate is to coat various electrochemically active or non-electrochemically active materials, such as metal oxides, phosphates, conductive polymers and the like, on the surface of the lithium cobaltate, and the lithium cobaltate can be coated by a liquid phase or solid phase method, so that the anode material is prevented from being directly contacted with electrolyte, the dissolution of cobalt ions is slowed down, and the cycle life of the lithium cobaltate can be effectively prolonged. The coating of the non-electrochemically active substance can reduce the capacity of the lithium cobaltate, and the mainstream technical route is to form a layer of doped lithium cobaltate microparticles on the surface of the lithium cobaltate, wherein the microparticles not only have electrochemical activity, but also can protect an internal main material from being in direct contact with an electrolyte and enhance the stability of the material. And coating and burning the primarily burnt lithium cobaltate by adopting the aluminum-doped cobalt hydroxide to finally form a nano-scale aluminum-doped lithium cobaltate coating layer on the surface of the lithium cobaltate, thereby conforming to the development direction of the mainstream technology.
The aluminum-doped cobalt hydroxide has the following difficulties: 1. when the particle size D50 of cobalt hydroxide is less than 1 μm, the surface energy of the particles is highly unstable and easy to agglomerate spontaneously, and the particles are easy to agglomerate in the drying process, so that D50 is enlarged; 2. the aluminum hydroxide is doped with the cobalt hydroxide, the aluminum hydroxide generated by the reaction is a common colloid floccule, can stably exist and has a huge surface area, the adsorption capacity is strong, the cobalt hydroxide can be adsorbed to deepen the agglomeration of particles, meanwhile, the colloid causes the mobility of the slurry to be poor, the local stirring strength in the slurry is weakened, and after the aluminum is doped, the nano-scale cobalt hydroxide particles are more difficult to disperse, so that the aluminum-doped cobalt hydroxide D50 becomes larger.
Disclosure of Invention
The invention provides a preparation method of aluminum-doped cobalt hydroxide, which aims at the technical problem of aluminum-doped cobalt hydroxide, wherein the aluminum-doped range is 0.1-1%, particles are free from agglomeration, and D50 is less than 1 mu m (laser granularity in a non-ultrasonic state).
The invention provides a preparation method of aluminum-doped cobalt hydroxide applied to a high-voltage LCO coating material, which comprises the following steps:
1. preparing a cobalt-aluminum mixed salt solution: adding a certain amount of aluminum salt into a cobalt salt solution, wherein the mass ratio of aluminum to cobalt is 0.001-0.017: 1;
2. preparing an alkali solution: diluting industrial liquid caustic soda with water to prepare an aqueous alkali solution with the concentration of 40-80 g/L;
3. and (3) synthesis reaction: pure water is used as a base solution, and the amount of the base solution is more than or equal to 30 percent of the effective volume of the reaction kettle; adding an antioxidant, wherein the mass ratio of the antioxidant to Co is 1-2%; starting stirring, simultaneously adding the cobalt-aluminum mixed salt solution and the alkali solution in the steps 1 and 2 at normal temperature, wherein the flow rate of the cobalt-aluminum mixed salt solution is 1000-2000L/h, the pH value in the reaction process is strictly controlled to be more than 12.0 through the flow rate of the alkali solution, the feeding reaction time is controlled to be 4-8 h, the temperature of the reaction system is increased to 40-60 ℃ after the cobalt-aluminum mixed salt solution is added, and stirring for 0.2-0.4 h after the temperature reaches the requirement to form and disperse particles;
4. the synthesized aluminum-doped cobalt hydroxide is subjected to filter pressing, washing, low-temperature drying and crushing by adopting an airflow mill, and finally, a nano-scale aluminum-doped cobalt hydroxide finished product with the D50 of less than 1 mu m and without agglomeration is obtained. D50 herein refers to the laser particle size in the non-ultrasonic state, which is the standard for testing the particle size of nano-sized cobalt hydroxide in the industry.
Preferably, the cobalt salt in the step 1 is one of cobalt chloride, cobalt sulfate and cobalt nitrate, the cobalt ion concentration is 80-160 g/L, and the aluminum salt and the cobalt salt anion are the same.
Preferably, the antioxidant in step 3 is one or more of sodium borohydride, acetoxime, hydrazine hydrate and carbohydrazide. The antioxidant is added in the reaction process mainly for preventing the 2-valent cobalt from being oxidized into 3-valent cobalt, because the oxygen concentration in the slurry is increased under the condition that the reaction kettle is opened and stirred, the 2-valent cobalt hydroxide is easily oxidized into 3-valent cobalt under the condition of high pH, and after the antioxidant is added, the antioxidant and oxygen are subjected to redox reaction, most of the oxygen in the system is consumed, and therefore the protection effect is achieved.
As the nano-scale cobalt hydroxide is easy to spontaneously agglomerate, and colloidal cobalt hydroxide generated after aluminum is doped in the wet synthesis stage makes the dispersion of particles in a system more difficult, and the agglomeration is more serious as the aluminum doping amount is higher, the invention solves the problems through the following two key points: firstly, the amount of the base solution is more than or equal to 30 percent of the effective volume of the reaction kettle, so that the solid content in a reaction system can be reduced, and the collision probability between particles is reduced, thereby reducing agglomeration; secondly, the synthesis time is prolonged to 4-8 h, so that the crystal nuclei of the nano aluminum hydroxide and the nano cobalt hydroxide can grow up, the generation of colloidal aluminum hydroxide is inhibited to a certain extent, and the effect of reducing agglomeration is achieved. Meanwhile, the invention does not adopt complexing agent to complex with Co ions in the wet synthesis stage, thereby simplifying the process and effectively reducing the production cost. The aluminum-doped cobalt hydroxide prepared by the method has wide aluminum-doped range of 0.1-1%, strong process applicability and can be matched with all common cobaltosic oxide-doped precursors in the current market for use.
Drawings
FIG. 1 is a scanning electron microscope image of a product obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a product obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a product obtained in example 3 of the present invention;
FIG. 4 is a PSD graph of the particle size of the product obtained in example 1 of the present invention;
FIG. 5 is a PSD graph of the particle size of the product obtained in example 2 of the present invention;
FIG. 6 is a PSD graph of the particle size of the product obtained in example 3 of the present invention.
Detailed Description
Example 1
1. Preparing 80g/L cobalt chloride solution, adding into each 1m34.614kg of aluminum chloride is added into the cobalt solution, and the mixture is stirred uniformly;
2. adding water to dilute the industrial liquid caustic soda to prepare a sodium hydroxide solution with the concentration of 40 g/L;
3. adding 3m into a reaction kettle3Pure water beaterAdding sodium borohydride accounting for 1 percent of the mass of Co; starting stirring, simultaneously adding the cobalt-aluminum mixed salt solution and the sodium hydroxide solution obtained in the steps 1 and 2 at normal temperature, wherein the flow rate of the cobalt-aluminum mixed salt solution is 1000L/h, the pH value in the reaction process is strictly controlled to be more than 12.0 through the flow rate of the sodium hydroxide solution, the feeding reaction time is controlled to be 8h, after 8h, feeding is stopped, the temperature of the reaction system is raised to 40 ℃, and after the temperature reaches the requirement, stirring for 0.2h is carried out to form and disperse particles;
4. and carrying out filter pressing, washing and low-temperature drying on the synthesized aluminum-doped cobalt hydroxide, and crushing by adopting an airflow mill to finally obtain the finished product of the aluminum-doped cobalt hydroxide.
The detection indexes of the aluminum-doped cobalt hydroxide are as follows: co content 62.35%, median particle diameter D50: 0.133 μm (as shown in fig. 4), and 0.4052% aluminum loading (aluminum loading was measured by ICP emission spectrometer), were well dispersed without large agglomerated particles (as shown in fig. 1).
Example 2
1. Preparing 120g/L cobalt sulfate solution, wherein each 1m cobalt sulfate solution316.845kg of aluminum sulfate is added into the cobalt solution, and the mixture is uniformly stirred;
2. adding water to dilute the industrial liquid caustic soda to prepare a sodium hydroxide solution with the concentration of 60 g/L;
3. adding 3.5m into the reaction kettle3Priming with pure water, and adding acetone oxime with the mass of 1.5 percent of Co; starting stirring, simultaneously adding the cobalt-aluminum mixed salt solution and the sodium hydroxide solution obtained in the steps 1 and 2 at normal temperature, wherein the flow rate of the cobalt-aluminum mixed salt solution is 1500L/h, the pH value in the reaction process is strictly controlled to be more than 12.0 through the flow rate of the sodium hydroxide solution, the feeding reaction time is controlled to be 5.5h, after 5.5h, stopping feeding, heating the reaction system to 50 ℃, and stirring for 0.3h after the temperature reaches the requirement to form and disperse particles;
4. and carrying out filter pressing, washing and low-temperature drying on the synthesized aluminum-doped cobalt hydroxide, and crushing by adopting an airflow mill to finally obtain the finished product of the aluminum-doped cobalt hydroxide.
The detection indexes of the aluminum-doped cobalt hydroxide are as follows: co content 61.73%, median particle diameter D50: 0.335 μm (as shown in fig. 5), and 0.7013% aluminum loading (aluminum loading was measured by ICP emission spectrometer), dispersed well without bulk agglomerated particles (as shown in fig. 2).
Example 3
1. Preparing 160g/L cobalt nitrate solution, adding into each 1m322.769kg of aluminum nitrate is added into the cobalt solution and stirred uniformly;
2. adding water to dilute the industrial liquid caustic soda to prepare a sodium hydroxide solution with the concentration of 80 g/L;
3. adding 4m into a reaction kettle3Priming with pure water, and adding hydrazine hydrate accounting for 2% of the mass of Co; starting stirring, simultaneously adding the cobalt-aluminum mixed salt solution and the sodium hydroxide solution obtained in the steps 1 and 2 at normal temperature, wherein the flow rate of the cobalt-aluminum mixed salt solution is 2000L/h, the pH value in the reaction process is strictly controlled to be more than 12.0 through the flow rate of the sodium hydroxide solution, the feeding reaction time is controlled to be 4h, after 4h, feeding is stopped, the temperature of the reaction system is raised to 60 ℃, and after the temperature reaches the requirement, stirring for 0.4h is carried out to enable particles to be formed and dispersed;
4. and carrying out filter pressing, washing and low-temperature drying on the synthesized aluminum-doped cobalt hydroxide, and crushing by adopting an airflow mill to finally obtain the finished product of the aluminum-doped cobalt hydroxide.
The detection indexes of the aluminum-doped cobalt hydroxide are as follows: co content 60.86%, median particle diameter D50: 0.653 μm (as shown in fig. 6) and 0.9986% aluminum loading (aluminum loading was measured by ICP emission spectrometer) were well dispersed without large agglomerated particles (as shown in fig. 3).
EXAMPLES results characterization
Item Co/％ Al/％ D50/μm
Example 1 62.35 0.4052 0.133
Example 2 61.73 0.7013 0.335
Example 3 60.86 0.9986 0.653
From the above results, it can be seen that the cobalt hydroxide of the present invention does not agglomerate significantly with the increase of the aluminum doping amount, and the particle size of the cobalt hydroxide can still reach < 1 μm when the aluminum doping amount is close to 1%.

Claims (3)

1. A preparation method of aluminum-doped cobalt hydroxide applied to a high-voltage LCO coating material comprises the steps of taking pure water as a base solution in a reaction kettle; starting stirring, adding an alkali solution and other solutions at normal temperature, performing filter pressing, washing and low-temperature drying on a synthesized product, and crushing by adopting an airflow mill to obtain a finished product, wherein the method comprises the following steps: adding aluminum salt into the cobalt salt solution, wherein the mass ratio of aluminum to cobalt is 0.001-0.017: 1; the aqueous alkali is prepared by diluting industrial liquid alkali with water to prepare an aqueous alkali with the concentration of 40-80 g/L; the amount of the base solution is not less than 30% of the effective volume of the reaction kettle, an antioxidant is further added into the base solution, and the mass ratio of the antioxidant to Co is 1-2: 100; controlling the flow of the cobalt-aluminum mixed salt solution to be 1000-2000L/h in the feeding process, strictly controlling the pH value to be more than 12.0 in the reaction process through the flow of the alkali solution, and controlling the feeding reaction time to be 4-8 h; after the cobalt-aluminum mixed salt solution is added, heating the reaction system to 40-60 ℃, and stirring for 0.2-0.4 h after the temperature reaches the requirement to form and disperse particles; the obtained finished product is nano-grade aluminum-doped cobalt hydroxide without agglomeration, and the D50 is less than 1 mu m.
2. The method of claim 1, wherein the aluminum-doped cobalt hydroxide is applied to the high voltage LCO coating material, and the method comprises the following steps: the cobalt salt is one of cobalt chloride, cobalt sulfate and cobalt nitrate, the concentration of cobalt ions is 20-160g/L, and the aluminum salt and the cobalt salt have the same anion.
3. The method of claim 1, wherein the aluminum-doped cobalt hydroxide is applied to the high voltage LCO coating material, and the method comprises the following steps: the antioxidant is one or more of sodium borohydride, acetone oxime, hydrazine hydrate and carbohydrazide.
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CN112537802B (en) * 2020-12-08 2022-11-22 衢州华友钴新材料有限公司 Preparation method of high-voltage lithium battery precursor doped with cobalt hydroxide
CN113501553A (en) * 2021-05-25 2021-10-15 中南大学 High-voltage lithium cobaltate coating material aluminum-doped cobalt hydroxide and preparation method thereof
CN113896249B (en) * 2021-09-29 2023-03-24 衢州华友钴新材料有限公司 Cobalt oxide for coating lithium battery positive electrode material and preparation method thereof
CN113816436B (en) * 2021-09-30 2024-02-02 湖南中伟新能源科技有限公司 Amorphous highly-doped cobalt aluminum hydroxide, and preparation method and application thereof

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