WO2024060551A1 - Surface-modified positive electrode material precursor, preparation method therefor, and use thereof - Google Patents

Surface-modified positive electrode material precursor, preparation method therefor, and use thereof Download PDF

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WO2024060551A1
WO2024060551A1 PCT/CN2023/082862 CN2023082862W WO2024060551A1 WO 2024060551 A1 WO2024060551 A1 WO 2024060551A1 CN 2023082862 W CN2023082862 W CN 2023082862W WO 2024060551 A1 WO2024060551 A1 WO 2024060551A1
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cathode material
material precursor
modified cathode
nickel
solution
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PCT/CN2023/082862
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French (fr)
Chinese (zh)
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王涛
余海军
谢英豪
李爱霞
张学梅
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024060551A1 publication Critical patent/WO2024060551A1/en

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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
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/22—Magnesium silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
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    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • C01P2004/60—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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of lithium-ion battery cathode materials, and particularly relates to a surface-modified cathode material precursor and its preparation method and application.
  • Lithium-ion batteries are widely used in portable electronic products, electric vehicles, and energy storage systems due to their high specific energy, low self-discharge, high open circuit voltage, no memory effect, long cycle life, and low environmental pollution. field. As new energy vehicles have higher and higher requirements for cruising range, higher requirements have also been put forward for the energy density and cycle life of power lithium-ion batteries. Ternary materials have become a new type of lithium-ion battery cathode material that has attracted much attention due to its advantages such as high specific capacity, stable cycle performance, relatively low cost, and good safety performance.
  • ternary cathode materials mainly prepare hydroxide precursors through co-precipitation method.
  • nickel salts, cobalt salts, and manganese salts are used as raw materials.
  • spherical nickel, cobalt, and manganese are obtained.
  • the precursor is then mixed with lithium salt and sintered to obtain a ternary material.
  • ternary materials still has many problems and challenges, especially problems such as structural phase change at the interface with the electrolyte, dissolution of transition metals, oxygen evolution, and continuous oxidation and decomposition of the electrolyte, resulting in poor cycle performance of ternary materials. .
  • the present invention aims to solve at least one of the technical problems existing in the prior art.
  • the present invention proposes a surface-modified cathode material precursor and its preparation method and application, so that the cathode material precursor can be directionally coated after doping, thereby improving the cycle performance of subsequent sintering of the cathode material.
  • the surface-modified cathode material precursor is secondary particles formed by agglomeration of primary particles. particles, the particle size of the primary particles is 0.01-1.0 ⁇ m, and the particle size of the agglomerated secondary particles is 1.0-15.0 ⁇ m.
  • the silicon element in the surface-modified cathode material precursor only exists on the surface of primary particles.
  • a method for preparing a surface-modified cathode material precursor as described above including the following steps:
  • step (2) Perform solid-liquid separation on the mixed liquid obtained in step (1), wash the separated solids, and then dry them to obtain dry materials;
  • step (3) Mix the dry material obtained in step (2) with the silane coupling agent aqueous solution, dry it, and then calcine it in an oxygen atmosphere to obtain the surface-modified cathode material precursor.
  • the molar ratio of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese mixed salt solution is a:b:c.
  • the total concentration of nickel-cobalt-manganese ions in the nickel-cobalt-manganese mixed salt solution is 0.5-3.0 mol/L.
  • the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese mixed salt solution is 1.0-2.5 mol/L.
  • the precipitating agent is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the precipitating agent is 3.0-10.0 mol/L.
  • the concentration of the precipitating agent is 4.0-8.0 mol/L.
  • the complexing agent is ammonia water with a concentration of 5.0-15.0 mol/L.
  • the complexing agent is ammonia water with a concentration of 6.0-12.0 mol/L.
  • the soluble magnesium salt solution is at least one of magnesium sulfate solution, magnesium chloride solution and magnesium nitrate solution.
  • the concentration of the soluble magnesium salt solution is 0.5-3.0 mol/L.
  • the concentration of the soluble magnesium salt solution is 1.0-2.5 mol/L.
  • the alkaline bottom liquid is a mixed liquid of sodium hydroxide and ammonia water
  • the pH of the alkaline bottom liquid is 9.0-11.0
  • the ammonia water concentration in the alkaline bottom liquid is 1.0. -12.0g/L.
  • the pH of the alkaline bottom solution is 10.0-11.0, and the alkali
  • the ammonia concentration in the base solution is 2.0-10.0g/L.
  • the mixing method is to add the nickel, cobalt and manganese mixed salt solution, the precipitant, the complexing agent and the soluble magnesium salt solution to the alkaline bottom in parallel flow.
  • the pH of the mixed solution is controlled to be 10.0-11.0, and the ammonia concentration is controlled to be 2.0-10.0g/L.
  • the reaction temperature is 40-70°C.
  • reaction temperature is 45-65°C.
  • step (1) when it is detected that the particle size of the material in the mixed liquid reaches 1.0-15.0 ⁇ m, the feeding is stopped.
  • the washing method is to first wash with alkali solution and then wash with water.
  • the alkali solution is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the alkali solution is 0.5-2.5 mol/L.
  • the concentration of the alkali solution is 1-2.0 mol/L.
  • the drying temperature is 220-280°C, and the drying time is 1-2 hours.
  • the mass concentration of the silane coupling agent aqueous solution is 0.5%-2.5%.
  • the mass concentration of the silane coupling agent aqueous solution is 0.5%-2%.
  • the silane coupling agent in the silane coupling agent aqueous solution is N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, 3-glycidylpropyl At least one of trimethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane and vinyltrimethoxysilane.
  • the solid-to-liquid ratio of the dried material to the silane coupling agent aqueous solution is 1:(1-5) g/mL.
  • step (3) the dry material and the silane coupling agent are water-soluble.
  • the solid-liquid ratio g/mL of the liquid is 1: (1-3).
  • the drying temperature is 100-120°C, and the drying time is 2-3 hours.
  • the calcination temperature is 500-800°C, and the calcination time is 0.5-1 h.
  • a method for preparing a surface-modified cathode material precursor includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0-8.0 mol/L as a precipitant
  • Step 3 Prepare ammonia water with a concentration of 6.0-12.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium sulfate/magnesium chloride/magnesium nitrate solution with a concentration of 1.0-2.5 mol/L;
  • Step 5 Add alkaline bottom liquid to the reactor until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.0-11.0, and the concentration of ammonia water is 2.0-10.0 g/L;
  • Step 6 Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium sulfate/magnesium chloride/magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow.
  • control the reaction temperature in the kettle to 45-65°C, the pH to 10.0-11.0, and the ammonia concentration to be 2.0-10.0g/L; the flow rate of the magnesium sulfate/magnesium chloride/magnesium nitrate solution is 0.01-1 times the flow rate of the mixed salt solution.
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 1.0-15.0 ⁇ m, stop feeding;
  • Step 8 Separate the material in the kettle into solid and liquid, first wash it with 1-2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 220-280°C for 1-2 hours to obtain dry material;
  • Step 10 Prepare an aqueous solution of silane coupling agent with a mass concentration of 0.5%-2%.
  • the silane coupling agent is not limited to N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane and 3-glycidol.
  • Step 11 Mix the dry material with the silane coupling agent aqueous solution according to the solid-liquid ratio of 1g: (1-3) mL, and then dry it at 100-120°C for 2-3 hours to obtain the pretreated dry material;
  • Step 12 Calculate the pretreated dry material in an air or oxygen atmosphere at a temperature of 500-800°C for 0.5-1h to obtain a surface-modified cathode material precursor.
  • the surface-modified cathode material precursor prepared by the preparation method of the present invention has excellent cycle performance after being prepared into the cathode material. After 300 cycles, the cycle retention rate can reach more than 90.94%.
  • a nickel-cobalt-manganese mixed salt solution, a precipitant, a soluble magnesium salt and an alkaline bottom solution are used to perform a co-precipitation reaction under the complexation of a complexing agent.
  • a nickel-cobalt-manganese mixed salt solution, a precipitant, a soluble magnesium salt and an alkaline bottom solution are used to perform a co-precipitation reaction under the complexation of a complexing agent.
  • magnesium-doped nickel cobalt manganese hydroxide and dry it at low temperature (220-280°C), so that the nickel cobalt manganese hydroxide is dehydrated and decomposed into oxides, while the magnesium hydroxide is dried at this temperature
  • the silane coupling agent reacts with the hydroxide radicals on the surface of the drying material to selectively oxidize the hydroxide.
  • Magnesium is modified to form Mg-O-Si-R, while the nickel-cobalt-manganese oxide remains unchanged.
  • the remaining organic chains of the silane coupling agent are removed to form a magnesium silicate-type surface coating.
  • Silane coupling agent surface modification R 1 -Si(OR 2 ) 3 +3H 2 O ⁇ R 1 -Si(OH) 3 +3R 2 -OH R 1 -Si(OH) 3 +Mg(OH) 2 ⁇ R 1 -Si-O-Mg+H 2 O.
  • a silane coupling agent is selectively used to modify the magnesium hydroxide on the surface of the drying material, and the organic chains are removed by calcination to form a quasi-magnesium silicate.
  • the coating layer in the form can further improve the interface stability of the material, and the silane coupling agent will not react with nickel cobalt manganese oxide, avoiding the formation of nickel cobalt manganese silicate and making it difficult to form lithium nickel cobalt manganese oxide in subsequent sintering. question.
  • the decomposition of magnesium hydroxide is difficult for other hydroxides, and the nickel cobalt manganese hydroxide is selectively dehydrated to generate nickel cobalt manganese oxide.
  • the magnesium hydroxide alone reacts with the silane coupling agent to form a silicon-magnesium coating layer. Magnesium is doped on the surface of the particles. After combining with silicon, the coating layer formed is extremely stable and difficult to fall off. It can be further used during subsequent sintering of the cathode material. Improve the recycling performance of materials.
  • Figure 1 is an SEM image at 10,000 times magnification of the surface-modified cathode material precursor prepared in Example 1 of the present invention
  • Figure 2 is an SEM image at 50,000 times magnification of the surface-modified cathode material precursor prepared in Example 1 of the present invention.
  • a surface-modified cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.05MgO ⁇ 0.01SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0 ⁇ m, the particle size of the agglomerated secondary particles is 6.0 ⁇ m; silicon element only exists on the surface of the primary particles.
  • the SEM images of the surface-modified cathode material precursor are shown in Figures 1 and 2.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant
  • Step 3 Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
  • Step 6 Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle.
  • the reaction temperature is 58°C
  • the pH is 10.8, and the ammonia concentration is 8.0g/L
  • the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 6.0 ⁇ m, stop feeding;
  • Step 8 Separate the materials in the kettle from solid to liquid, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 280°C for 1 hour to obtain dry material
  • Step 10 Prepare an aqueous solution of vinyltrimethoxysilane with a mass concentration of 1%;
  • Step 11 Mix the dried material with an aqueous solution of vinyltrimethoxysilane at a solid-liquid ratio of 1 g:2 mL, and dry at 110° C. for 2.5 h to obtain a pretreated dried material;
  • Step 12 Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a surface-modified cathode material precursor.
  • a surface-modified cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.1MgO ⁇ 0.025SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0 ⁇ m, the particle size of the agglomerated secondary particles is 10.0 ⁇ m; silicon element only exists on the surface of the primary particles.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent
  • Step 3 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium chloride solution with a concentration of 2.5mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
  • Step 6 Add the nickel, cobalt and manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium chloride solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction in the kettle.
  • the temperature is 55°C
  • the pH is 10.2
  • the ammonia concentration is 4.0g/L
  • the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 10.0 ⁇ m, stop feeding;
  • Step 8 Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 220°C for 2 hours to obtain dry material
  • Step 10 Prepare an aqueous solution of vinyltriethoxysilane with a mass concentration of 2%;
  • Step 11 Mix the dry material with the aqueous solution of vinyltriethoxysilane according to the solid-to-liquid ratio of 1g:3mL, and then dry it at 120°C for 2 hours to obtain the pretreated dry material;
  • Step 12 Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 800°C for 0.5 h to obtain a surface-modified cathode material precursor.
  • a surface-modified cathode material precursor whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O ⁇ 0.02MgO ⁇ 0.0136SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0 ⁇ m, the particle size of the agglomerated secondary particles is 3.5 ⁇ m; silicon element only exists on the surface of the primary particles.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent
  • Step 3 Prepare 6.0 mol/L ammonia water as a complexing agent
  • Step 4 Prepare a magnesium nitrate solution with a concentration of 1.0mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
  • Step 6 Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3 and the magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle.
  • the reaction temperature is 48°C
  • the pH is 11.0
  • the ammonia concentration is 10.0g/L
  • the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 3.5 ⁇ m, stop feeding;
  • Step 8 Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 250°C for 1.5 hours to obtain dry material
  • Step 10 Prepare an aqueous solution of vinyl tris( ⁇ -methoxyethoxy)silane with a mass concentration of 0.5%;
  • Step 11 Dissolve the dry material and vinyl tris( ⁇ -methoxyethoxy)silane in water according to the solid-liquid ratio of 1g:1mL. After the liquid is mixed, it is dried at 100°C for 3 hours to obtain the pretreated dry material;
  • Step 12 Calculate the pretreated dry material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a surface-modified cathode material precursor.
  • Comparative Example 1 (Compared with Example 1, the precipitate was not dried, and the precipitate was directly treated with a silane coupling agent aqueous solution)
  • a surface-modified cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.05MgO ⁇ 0.0128SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0 ⁇ m, the particle size of the agglomerated secondary particles is 6.0 ⁇ m; silicon element only exists on the surface of the primary particles.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant
  • Step 3 Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
  • Step 6 Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle.
  • the reaction temperature is 58°C
  • the pH is 10.8, and the ammonia concentration is 8.0g/L
  • the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 6.0 ⁇ m, stop feeding;
  • Step 8 Perform solid-liquid separation of the materials in the kettle, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Prepare an aqueous solution of vinyltrimethoxysilane with a mass concentration of 1%;
  • Step 10 Mix the precipitate with the aqueous solution of vinyltrimethoxysilane according to the solid-liquid ratio of 1g:2mL, and then dry it at 110°C for 2.5h to obtain the pretreated dry material;
  • Step 11 Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a surface-modified cathode material precursor.
  • Comparative Example 2 (Compared with Example 2, the precipitate was not dried, and the precipitate was directly treated with a silane coupling agent aqueous solution)
  • a surface-modified cathode material precursor has a general chemical formula of Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.1MgO ⁇ 0.0308SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, the particle size of the primary particles is 0.01-1.0 ⁇ m, and the particle size of the agglomerated secondary particles is 10.0 ⁇ m; silicon element exists only on the surface of the primary particles.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent
  • Step 3 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 4 prepare a magnesium chloride solution with a concentration of 2.5 mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
  • Step 6 Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium chloride solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction in the kettle.
  • the temperature is 55°C
  • the pH is 10.2
  • the ammonia concentration is 4.0g/L
  • the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 10.0 ⁇ m, stop feeding;
  • Step 8 Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Prepare an aqueous solution of vinyltriethoxysilane with a mass concentration of 2%;
  • Step 10 Mix the precipitate with the aqueous solution of vinyltriethoxysilane according to a solid-to-liquid ratio of 1g:3mL, and then dry it at 120°C for 2 hours to obtain a pretreated dry material;
  • Step 11 Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 800°C for 0.5 h to obtain a surface-modified cathode material precursor.
  • Comparative Example 3 (Compared with Example 3, the precipitate was not dried and the precipitate was directly treated with a silane coupling agent aqueous solution)
  • a surface-modified cathode material precursor whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O ⁇ 0.02MgO ⁇ 0.00163SiO 2 ; It is a secondary particle formed by agglomeration of primary particles.
  • the particle size of the primary particles is 0.01-1.0 ⁇ m, and the particle size of the agglomerated secondary particles is 3.5 ⁇ m; Silicon Elements only exist on primary particle surfaces.
  • the preparation method of the surface-modified cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent
  • Step 3 Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium nitrate solution with a concentration of 1.0mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
  • Step 6 Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle.
  • the reaction temperature is 48°C
  • the pH is 11.0
  • the ammonia concentration is 10.0g/L
  • the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 3.5 ⁇ m, stop feeding;
  • Step 8 Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Prepare an aqueous solution of vinyl tris( ⁇ -methoxyethoxy)silane with a mass concentration of 0.5%;
  • Step 10 Mix the precipitate with the aqueous solution of vinyl tris( ⁇ -methoxyethoxy)silane according to the solid-liquid ratio of 1g:1mL, and then dry it at 100°C for 3 hours to obtain the pretreated dry material;
  • Step 11 Calculate the pretreated dry material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a surface-modified cathode material precursor.
  • a cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.05MgO; it is a secondary particle formed by agglomeration of primary particles.
  • the particle size of the primary particles is 0.01-1.0 ⁇ m, and the agglomerated secondary particles are The particle size of the particles is 6.0 ⁇ m.
  • the preparation method of the cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant
  • Step 3 Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
  • Step 6 Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle.
  • the reaction temperature is 58°C
  • the pH is 10.8, and the ammonia concentration is 8.0g/L
  • the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 6.0 ⁇ m, stop feeding;
  • Step 8 Separate the materials in the kettle from solid to liquid, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 280°C for 1 hour to obtain dry material
  • Step 10 Calculate the dried material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a cathode material precursor.
  • a cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O ⁇ 0.1MgO; it is a secondary particle formed by agglomeration of primary particles.
  • the particle size of the primary particles is 0.01-1.0 ⁇ m, and the agglomerated secondary particles are The particle size of the particles is 10.0 ⁇ m.
  • the preparation method of the cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent
  • Step 3 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 4 Prepare a magnesium chloride solution with a concentration of 2.5mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
  • Step 6 The nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2,
  • the ammonia water prepared in step 3 and the magnesium chloride solution prepared in step 4 are added to the reactor in parallel for reaction, and the reaction temperature in the reactor is controlled to be 55° C., the pH is 10.2, and the ammonia water concentration is 4.0 g/L; the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 10.0 ⁇ m, stop feeding;
  • Step 8 Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 220°C for 2 hours to obtain dry material
  • Step 10 Calculate the dried material in an oxygen atmosphere at a temperature of 800°C for 0.5 hours to obtain a cathode material precursor.
  • a cathode material precursor whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O ⁇ 0.02MgO; it is a secondary particle formed by agglomeration of primary particles.
  • the particle size of the primary particles is 0.01-1.0 ⁇ m, and the agglomerated secondary particles are The particle size of the particles is 3.5 ⁇ m.
  • the preparation method of the cathode material precursor as described above includes the following steps:
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent
  • Step 3 Prepare 6.0 mol/L ammonia water as a complexing agent
  • Step 4 Prepare a magnesium nitrate solution with a concentration of 1.0mol/L
  • Step 5 Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring.
  • the alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water.
  • the pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
  • Step 6 Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium nitrate solution prepared in step 4 to the reactor in parallel for reaction, and control the reaction temperature in the reactor to be 48° C., the pH to be 11.0, and the ammonia water concentration to be 10.0 g/L; the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
  • Step 7 When it is detected that the particle size of the material in the reaction kettle reaches 3.5 ⁇ m, stop feeding;
  • Step 8 Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
  • Step 9 Dry the precipitate at 250°C for 1.5 hours to obtain dry material
  • Step 10 Calculate the dried material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a cathode material precursor.
  • the cathode material precursors prepared in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 4 and Comparative Example 5 were mixed with lithium carbonate respectively according to a total molar ratio of lithium element to nickel cobalt manganese of 1.08:1. , mixed evenly, and calcined in an oxygen atmosphere at 850°C for 12 hours to obtain the corresponding cathode materials.
  • the cathode material precursors prepared in Example 3, Comparative Example 3 and Comparative Example 6 were mixed with lithium hydroxide according to the total molar ratio of lithium element to nickel cobalt manganese of 1.08:1, and mixed evenly in an oxygen atmosphere at 800°C. After calcination for 12 h, the corresponding cathode materials were obtained.
  • the positive electrode material obtained above was formulated into a button cell for electrochemical performance testing of lithium-ion batteries.
  • the specific steps are: using N-methylpyrrolidone as the solvent, the positive electrode active material (positive electrode) was added in a mass ratio of 8:1:1. Material), mixed evenly with acetylene black and PVDF, coated on aluminum foil, air dried at 80°C for 8 hours, and then vacuum dried at 120°C for 12 hours.
  • the cathode is a lithium metal sheet
  • the separator is a polypropylene film
  • the electrolyte is 1M LiPF6-EC/DMC (1:1, v/v).
  • the charge and discharge cut-off voltage is 2.7-4.3V.
  • the cycle performance at 1C current density was tested, and the results are shown in Table 1 below.
  • the surface-modified cathode material precursor prepared by the preparation method of the present invention has excellent electrochemical properties after being prepared into the cathode material, and its 0.1C discharge capacity can reach more than 182.9mAh/g for 300 cycles.
  • the post-discharge specific capacity can reach more than 172.0mAh/g, and after 300 cycles, the cycle retention rate can reach more than 90.94%.
  • Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be seen that during the preparation process of the cathode material precursor, the precipitate is not dried and the silane coupling agent is directly used. After the surface-modified cathode material precursor is prepared into the cathode material by treating the precipitate with the combined agent aqueous solution, the discharge capacity and cycle retention rate of the battery will decrease.
  • Example 1 Comparing Example 1 with Comparative Example 4, Example 2 with Comparative Example 5, and Example 3 with Comparative Example 6 respectively, it can be seen that during the preparation process of the cathode material precursor, the silane coupling agent aqueous solution is not used for surface modification treatment. , after the surface-modified cathode material precursor is prepared into a cathode material, the discharge capacity and cycle retention rate of the battery will decrease significantly.

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Abstract

Disclosed are a surface-modified positive electrode material precursor, a preparation method therefor, and use thereof. The chemical formula of the surface-modified positive electrode material precursor is: NiaCobMncO·xMgO·ySiO2, wherein 0≤a≤1, 0≤b≤1, 0≤c≤1, a+b+c=1, and 0<y<x≤0.1. The surface-modified positive electrode material precursor can improve the cycle performance of a subsequent sintered positive electrode material.

Description

一种表面改性的正极材料前驱体及其制备方法和应用A surface-modified cathode material precursor and its preparation method and application 技术领域Technical field
本发明属于锂离子电池正极材料技术领域，特别涉及一种表面改性的正极材料前驱体及其制备方法和应用。The invention belongs to the technical field of lithium-ion battery cathode materials, and particularly relates to a surface-modified cathode material precursor and its preparation method and application.
背景技术Background technique
锂离子电池(LIBs)因其比能量高、自放电小、开路电压高、无记忆效应、循环寿命长、环境污染小等众多优点而被广泛应用在便携式电子产品、电动汽车和储能系统等领域。随着新能源汽车对续航里程的要求越来越高，对动力型锂离子电池的能量密度、循环寿命也提出了更高的要求。三元材料因其具有高比容量、循环性能稳定、成本相对较低、安全性能较好等优点而成为目前备受关注的新型锂离子电池正极材料。Lithium-ion batteries (LIBs) are widely used in portable electronic products, electric vehicles, and energy storage systems due to their high specific energy, low self-discharge, high open circuit voltage, no memory effect, long cycle life, and low environmental pollution. field. As new energy vehicles have higher and higher requirements for cruising range, higher requirements have also been put forward for the energy density and cycle life of power lithium-ion batteries. Ternary materials have become a new type of lithium-ion battery cathode material that has attracted much attention due to its advantages such as high specific capacity, stable cycle performance, relatively low cost, and good safety performance.
目前三元正极材料主要是通过共沉淀法先制备氢氧化物前驱体，例如以镍盐、钴盐、锰盐为原料，在碱性环境下通过控制反应条件、反应速率，获得球形镍钴锰氢氧化物前驱体，其中镍钴锰的比例可以根据实际需要调整。然后将前驱体与锂盐混合后烧结得到三元材料。At present, ternary cathode materials mainly prepare hydroxide precursors through co-precipitation method. For example, nickel salts, cobalt salts, and manganese salts are used as raw materials. By controlling the reaction conditions and reaction rate in an alkaline environment, spherical nickel, cobalt, and manganese are obtained. Hydroxide precursor, in which the proportion of nickel, cobalt and manganese can be adjusted according to actual needs. The precursor is then mixed with lithium salt and sintered to obtain a ternary material.
但三元材料的应用还具有较多问题与挑战，尤其是与电解液界面处的结构相变、过渡金属溶解、氧析出、电解液持续氧化分解等问题，导致三元材料的循环性能较差。However, the application of ternary materials still has many problems and challenges, especially problems such as structural phase change at the interface with the electrolyte, dissolution of transition metals, oxygen evolution, and continuous oxidation and decomposition of the electrolyte, resulting in poor cycle performance of ternary materials. .
发明内容Contents of the invention
本发明旨在至少解决现有技术中存在的技术问题之一。为此，本发明提出一种表面改性的正极材料前驱体及其制备方法和应用，使正极材料前驱体掺杂后能够定向进行前驱体的包覆，提高后续烧结正极材料的循环性能。The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a surface-modified cathode material precursor and its preparation method and application, so that the cathode material precursor can be directionally coated after doping, thereby improving the cycle performance of subsequent sintering of the cathode material.
本发明的上述技术目的是通过以下技术方案得以实现的：The above technical objectives of the present invention are achieved through the following technical solutions:
一种表面改性的正极材料前驱体，所述表面改性的正极材料前驱体的化学式为：NiaCobMncO·xMgO·ySiO2，其中，0≤a≤1，0≤b≤1，0≤c≤1，a+b+c＝1，0＜y＜x≤0.1。A surface-modified cathode material precursor, the chemical formula of the surface-modified cathode material precursor is: Ni a Co b Mn c O·xMgO·ySiO 2 , where 0≤a≤1, 0≤b≤ 1, 0≤c≤1, a+b+c=1, 0<y<x≤0.1.
优选的，所述表面改性的正极材料前驱体是由一次颗粒团聚而成的二次颗 粒，其中一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为1.0-15.0μm。Preferably, the surface-modified cathode material precursor is secondary particles formed by agglomeration of primary particles. particles, the particle size of the primary particles is 0.01-1.0 μm, and the particle size of the agglomerated secondary particles is 1.0-15.0 μm.
优选的，所述表面改性的正极材料前驱体中的硅元素仅存在于一次颗粒表面。Preferably, the silicon element in the surface-modified cathode material precursor only exists on the surface of primary particles.
一种如上所述表面改性的正极材料前驱体的制备方法，包括以下步骤：A method for preparing a surface-modified cathode material precursor as described above, including the following steps:
(1)将镍钴锰混合盐溶液、沉淀剂、络合剂、可溶性镁盐溶液与碱性底液混合反应，得到混合液；(1) Mix and react a nickel-cobalt-manganese mixed salt solution, a precipitant, a complexing agent, a soluble magnesium salt solution and an alkaline bottom solution to obtain a mixed solution;
(2)将步骤(1)得到的混合液进行固液分离，将分离的固体物洗涤后，烘干，得到干燥料；(2) Perform solid-liquid separation on the mixed liquid obtained in step (1), wash the separated solids, and then dry them to obtain dry materials;
(3)将步骤(2)得到的干燥料与硅烷偶联剂水溶液混合，烘干，然后在有氧气氛下煅烧，得到所述表面改性的正极材料前驱体。(3) Mix the dry material obtained in step (2) with the silane coupling agent aqueous solution, dry it, and then calcine it in an oxygen atmosphere to obtain the surface-modified cathode material precursor.
优选的，步骤(1)中，所述镍钴锰混合盐溶液中镍元素、钴元素及锰元素的摩尔比为a:b:c。Preferably, in step (1), the molar ratio of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese mixed salt solution is a:b:c.
优选的，步骤(1)中，所述镍钴锰混合盐溶液中镍钴锰离子的总浓度为0.5-3.0mol/L。Preferably, in step (1), the total concentration of nickel-cobalt-manganese ions in the nickel-cobalt-manganese mixed salt solution is 0.5-3.0 mol/L.
进一步优选的，步骤(1)中，所述镍钴锰混合盐溶液中镍钴锰离子的总浓度为1.0-2.5mol/L。Further preferably, in step (1), the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese mixed salt solution is 1.0-2.5 mol/L.
优选的，步骤(1)中，所述沉淀剂为氢氧化钠溶液及氢氧化钾溶液中的至少一种，所述沉淀剂的浓度为3.0-10.0mol/L。Preferably, in step (1), the precipitating agent is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the precipitating agent is 3.0-10.0 mol/L.
进一步优选的，所述沉淀剂的浓度为4.0-8.0mol/L。Further preferably, the concentration of the precipitating agent is 4.0-8.0 mol/L.
优选的，步骤(1)中，所述络合剂为浓度为5.0-15.0mol/L的氨水。Preferably, in step (1), the complexing agent is ammonia water with a concentration of 5.0-15.0 mol/L.
进一步优选的，步骤(1)中，所述络合剂为浓度为6.0-12.0mol/L的氨水。Further preferably, in step (1), the complexing agent is ammonia water with a concentration of 6.0-12.0 mol/L.
优选的，步骤(1)中，所述可溶性镁盐溶液为硫酸镁溶液、氯化镁溶液及硝酸镁溶液中的至少一种。Preferably, in step (1), the soluble magnesium salt solution is at least one of magnesium sulfate solution, magnesium chloride solution and magnesium nitrate solution.
优选的，步骤(1)中，所述可溶性镁盐溶液的浓度为0.5-3.0mol/L。Preferably, in step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0 mol/L.
进一步优选的，步骤(1)中，所述可溶性镁盐溶液的浓度为1.0-2.5mol/L。Further preferably, in step (1), the concentration of the soluble magnesium salt solution is 1.0-2.5 mol/L.
优选的，步骤(1)中，所述碱性底液为氢氧化钠和氨水的混合液，所述碱性底液的pH为9.0-11.0，所述碱性底液中的氨水浓度为1.0-12.0g/L。Preferably, in step (1), the alkaline bottom liquid is a mixed liquid of sodium hydroxide and ammonia water, the pH of the alkaline bottom liquid is 9.0-11.0, and the ammonia water concentration in the alkaline bottom liquid is 1.0. -12.0g/L.
进一步优选的，步骤(1)中，所述碱性底液的pH为10.0-11.0，所述碱 性底液中的氨水浓度为2.0-10.0g/L。Further preferably, in step (1), the pH of the alkaline bottom solution is 10.0-11.0, and the alkali The ammonia concentration in the base solution is 2.0-10.0g/L.
优选的，步骤(1)中，所述混合的方式为将所述镍钴锰混合盐溶液、所述沉淀剂、所述络合剂及所述可溶性镁盐溶液并流加入所述碱性底液中，且加入过程中控制所述可溶性镁盐的流量为所述镍钴锰混合盐溶液流量的0.01-1倍，控制最终镁离子的加入量与镍钴锰离子的比例为Mg:Ni:Co:Mn＝x:a:b:c，并控制所述混合液的pH为9.0-11.0，氨水浓度为1.0-12.0g/L。Preferably, in step (1), the mixing method is to add the nickel, cobalt and manganese mixed salt solution, the precipitant, the complexing agent and the soluble magnesium salt solution to the alkaline bottom in parallel flow. liquid, and during the addition process, the flow rate of the soluble magnesium salt is controlled to be 0.01-1 times the flow rate of the nickel cobalt manganese mixed salt solution, and the ratio of the final added amount of magnesium ions to the nickel cobalt manganese ions is controlled to be Mg:Ni: Co:Mn=x:a:b:c, and the pH of the mixed solution is controlled to be 9.0-11.0, and the ammonia concentration is controlled to be 1.0-12.0g/L.
进一步优选的，控制所述混合液的pH为10.0-11.0，氨水浓度为2.0-10.0g/L。Further preferably, the pH of the mixed solution is controlled to be 10.0-11.0, and the ammonia concentration is controlled to be 2.0-10.0g/L.
优选的，步骤(1)中，所述反应的温度为40-70℃。Preferably, in step (1), the reaction temperature is 40-70°C.
进一步优选的，步骤(1)中，所述反应的温度为45-65℃。Further preferably, in step (1), the reaction temperature is 45-65°C.
优选的，步骤(1)中，当检测到所述混合液中的物料的粒度达到1.0-15.0μm时，停止进料。Preferably, in step (1), when it is detected that the particle size of the material in the mixed liquid reaches 1.0-15.0 μm, the feeding is stopped.
优选的，步骤(2)中，所述洗涤的方式为先用碱液洗涤，再用水洗。Preferably, in step (2), the washing method is to first wash with alkali solution and then wash with water.
优选的，所述碱液为氢氧化钠溶液及氢氧化钾溶液中的至少一种，所述碱液的浓度为0.5-2.5mol/L。Preferably, the alkali solution is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the alkali solution is 0.5-2.5 mol/L.
进一步优选的，所述碱液的浓度为1-2.0mol/L。Further preferably, the concentration of the alkali solution is 1-2.0 mol/L.
优选的，步骤(2)中，所述烘干的温度为220-280℃，烘干时间为1-2h。Preferably, in step (2), the drying temperature is 220-280°C, and the drying time is 1-2 hours.
优选的，步骤(3)中，所述硅烷偶联剂水溶液的质量浓度为0.5％-2.5％。Preferably, in step (3), the mass concentration of the silane coupling agent aqueous solution is 0.5%-2.5%.
进一步优选的，步骤(3)中，所述硅烷偶联剂水溶液的质量浓度为0.5％-2％。Further preferably, in step (3), the mass concentration of the silane coupling agent aqueous solution is 0.5%-2%.
优选的，步骤(3)中，所述硅烷偶联剂水溶液中的硅烷偶联剂为N-(β-氨乙基)-α-氨丙基三甲氧基硅烷、3-缩水甘油基丙基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三乙氧基硅烷及乙烯基三甲氧基硅烷中的至少一种。Preferably, in step (3), the silane coupling agent in the silane coupling agent aqueous solution is N-(β-aminoethyl)-α-aminopropyltrimethoxysilane, 3-glycidylpropyl At least one of trimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane and vinyltrimethoxysilane.
优选的，步骤(3)中，所述干燥料与所述硅烷偶联剂水溶液的固液比g/mL为1：(1-5)。Preferably, in step (3), the solid-to-liquid ratio of the dried material to the silane coupling agent aqueous solution is 1:(1-5) g/mL.
进一步优选的，步骤(3)中，所述干燥料与所述硅烷偶联剂水溶 液的固液比g/mL为1：(1-3)。Further preferably, in step (3), the dry material and the silane coupling agent are water-soluble. The solid-liquid ratio g/mL of the liquid is 1: (1-3).
优选的，步骤(3)中，所述烘干的温度为100-120℃，烘干时间为2-3h。Preferably, in step (3), the drying temperature is 100-120°C, and the drying time is 2-3 hours.
优选的，步骤(3)中，所述煅烧的温度为500-800℃，煅烧时间为0.5-1h。Preferably, in step (3), the calcination temperature is 500-800°C, and the calcination time is 0.5-1 h.
优选的，一种表面改性的正极材料前驱体的制备方法，包括以下步骤：Preferably, a method for preparing a surface-modified cathode material precursor includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝a:b:c，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为1.0-2.5mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=a:b:c, soluble salts of nickel, cobalt and manganese are selected as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total nickel-cobalt-manganese metal ion concentration of 1.0-2.5 mol/L;
步骤2.配制浓度为4.0-8.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 4.0-8.0 mol/L as a precipitant;
步骤3.配制浓度为6.0-12.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 6.0-12.0 mol/L as a complexing agent;
步骤4.配制浓度为1.0-2.5mol/L的硫酸镁/氯化镁/硝酸镁溶液；Step 4. Prepare a magnesium sulfate/magnesium chloride/magnesium nitrate solution with a concentration of 1.0-2.5 mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.0-11.0，氨水浓度为2.0-10.0g/L；Step 5. Add alkaline bottom liquid to the reactor until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.0-11.0, and the concentration of ammonia water is 2.0-10.0 g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硫酸镁/氯化镁/硝酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为45-65℃，pH为10.0-11.0，氨水浓度为2.0-10.0g/L；硫酸镁/氯化镁/硝酸镁溶液的流量为混合盐溶液的流量的0.01-1倍，并随着反应的进行任意调节，需控制最终镁离子的加入量与镍钴锰离子的比例为Mg:Ni:Co:Mn＝x:a:b:c；Step 6. Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium sulfate/magnesium chloride/magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow. For the reaction, control the reaction temperature in the kettle to 45-65°C, the pH to 10.0-11.0, and the ammonia concentration to be 2.0-10.0g/L; the flow rate of the magnesium sulfate/magnesium chloride/magnesium nitrate solution is 0.01-1 times the flow rate of the mixed salt solution. , and can be adjusted arbitrarily as the reaction progresses, the final amount of magnesium ions added and the ratio of nickel, cobalt and manganese ions need to be controlled to be Mg:Ni:Co:Mn=x:a:b:c;
步骤7.当检测到反应釜内物料的粒度达到1.0-15.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 1.0-15.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1-2.0mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the material in the kettle into solid and liquid, first wash it with 1-2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在220-280℃下烘干1-2h，得到干燥料；Step 9. Dry the precipitate at 220-280°C for 1-2 hours to obtain dry material;
步骤10.配制质量浓度为0.5％-2％的硅烷偶联剂的水溶液，硅烷偶联剂不限于N-(β-氨乙基)-α-氨丙基三甲氧基硅烷、3-缩水甘油基丙基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷中的一种或多种； Step 10. Prepare an aqueous solution of silane coupling agent with a mass concentration of 0.5%-2%. The silane coupling agent is not limited to N-(β-aminoethyl)-α-aminopropyltrimethoxysilane and 3-glycidol. One or more of vinylpropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane;
步骤11.按照固液比1g：(1-3)mL将干燥料与硅烷偶联剂水溶液混合后，在100-120℃下烘干2-3h，得到预处理干燥料；Step 11. Mix the dry material with the silane coupling agent aqueous solution according to the solid-liquid ratio of 1g: (1-3) mL, and then dry it at 100-120°C for 2-3 hours to obtain the pretreated dry material;
步骤12.将预处理干燥料，在空气或氧气氛围、温度为500-800℃下煅烧0.5-1h，得到表面改性的正极材料前驱体。Step 12. Calculate the pretreated dry material in an air or oxygen atmosphere at a temperature of 500-800°C for 0.5-1h to obtain a surface-modified cathode material precursor.
如上所述的表面改性的正极材料前驱体在制备锂离子电池中的应用。Application of the surface-modified cathode material precursor as described above in the preparation of lithium-ion batteries.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明的制备方法制备得到的表面改性的正极材料前驱体在制备成正极材料后具有优异的循环性能，其经过300次循环后，循环保持率能达到90.94％以上。(1) The surface-modified cathode material precursor prepared by the preparation method of the present invention has excellent cycle performance after being prepared into the cathode material. After 300 cycles, the cycle retention rate can reach more than 90.94%.
(2)本发明表面改性的正极材料前驱体的制备方法中，首先采用镍钴锰混合盐溶液、沉淀剂、可溶性镁盐及碱性底液在络合剂的络合下进行共沉淀反应，生成掺杂镁的镍钴锰氢氧化物，并在低温下(220-280℃)烘干，使其中的镍钴锰氢氧化物脱水并分解为氧化物，而氢氧化镁在此温度下仍以氢氧化物的形式存在，形成氢氧化镁掺杂的镍钴锰氧化物，通过硅烷偶联剂的定向改性，其与烘干料表面的氢氧根反应，选择性地将氢氧化镁改性生成Mg-O-Si-R，而镍钴锰氧化物保持不变，最后经进一步煅烧，将硅烷偶联剂残留的有机链去除，形成硅酸镁型的表面包覆物。其反应原理如下：(2) In the preparation method of the surface-modified cathode material precursor of the present invention, first, a nickel-cobalt-manganese mixed salt solution, a precipitant, a soluble magnesium salt and an alkaline bottom solution are used to perform a co-precipitation reaction under the complexation of a complexing agent. , generate magnesium-doped nickel cobalt manganese hydroxide, and dry it at low temperature (220-280°C), so that the nickel cobalt manganese hydroxide is dehydrated and decomposed into oxides, while the magnesium hydroxide is dried at this temperature Still exists in the form of hydroxide, forming magnesium hydroxide-doped nickel cobalt manganese oxide. Through the directional modification of the silane coupling agent, it reacts with the hydroxide radicals on the surface of the drying material to selectively oxidize the hydroxide. Magnesium is modified to form Mg-O-Si-R, while the nickel-cobalt-manganese oxide remains unchanged. Finally, after further calcination, the remaining organic chains of the silane coupling agent are removed to form a magnesium silicate-type surface coating. The reaction principle is as follows:
共沉淀反应：
aNi2++bCo2++cMn2++2OH-→NiaCobMnc(OH)2
Mg2++2OH-→Mg(OH)2 Co-precipitation reaction:
aNi 2+ +bCo 2+ +cMn 2+ +2OH - →Ni a Co b Mn c (OH) 2
Mg 2+ +2OH - →Mg(OH) 2
烘干脱水：
NiaCobMnc(OH)2→NiaCobMncODrying and dehydration:
Ni a Co b Mn c (OH) 2 → Ni a Co b Mn c O
硅烷偶联剂表面改性：
R1-Si(OR2)3+3H2O→R1-Si(OH)3+3R2-OH
R1-Si(OH)3+Mg(OH)2→R1-Si-O-Mg+H2O。Silane coupling agent surface modification:
R 1 -Si(OR 2 ) 3 +3H 2 O→R 1 -Si(OH) 3 +3R 2 -OH
R 1 -Si(OH) 3 +Mg(OH) 2 →R 1 -Si-O-Mg+H 2 O.
(3)本发明表面改性的正极材料前驱体的制备方法中，选择性地使用硅烷偶联剂对烘干料表面的氢氧化镁进行改性，经煅烧去除有机链后形成类硅酸镁形式的包覆层，可进一步提高材料的界面稳定性，且硅烷偶联剂不会与镍钴锰氧化物反应，避免了硅酸镍钴锰的形成导致后续烧结难以形成镍钴锰酸锂的问题。 (3) In the preparation method of the surface-modified cathode material precursor of the present invention, a silane coupling agent is selectively used to modify the magnesium hydroxide on the surface of the drying material, and the organic chains are removed by calcination to form a quasi-magnesium silicate. The coating layer in the form can further improve the interface stability of the material, and the silane coupling agent will not react with nickel cobalt manganese oxide, avoiding the formation of nickel cobalt manganese silicate and making it difficult to form lithium nickel cobalt manganese oxide in subsequent sintering. question.
(4)本发明表面改性的正极材料前驱体的制备方法中，利用氢氧化镁的分解难于其它氢氧化物的特性，选择性地将镍钴锰氢氧化物脱水生成镍钴锰氧化物，使氢氧化镁单独与硅烷偶联剂反应，形成硅镁包覆层，镁掺杂在颗粒表层，与硅结合后，形成的包覆层极为稳定，难以脱落，在后续烧结正极材料时可进一步提高材料的循环性能。(4) In the preparation method of the surface-modified cathode material precursor of the present invention, the decomposition of magnesium hydroxide is difficult for other hydroxides, and the nickel cobalt manganese hydroxide is selectively dehydrated to generate nickel cobalt manganese oxide. The magnesium hydroxide alone reacts with the silane coupling agent to form a silicon-magnesium coating layer. Magnesium is doped on the surface of the particles. After combining with silicon, the coating layer formed is extremely stable and difficult to fall off. It can be further used during subsequent sintering of the cathode material. Improve the recycling performance of materials.
附图说明Description of drawings
图1为本发明实施例1制备的表面改性的正极材料前驱体10000倍下的SEM图；Figure 1 is an SEM image at 10,000 times magnification of the surface-modified cathode material precursor prepared in Example 1 of the present invention;
图2为本发明实施例1制备的表面改性的正极材料前驱体50000倍下的SEM图。Figure 2 is an SEM image at 50,000 times magnification of the surface-modified cathode material precursor prepared in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施例对本发明做进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例1：Example 1:
一种表面改性的正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.05MgO·0.01SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为6.0μm；硅元素仅存在于一次颗粒表面，该表面改性的正极材料前驱体的SEM图如图1和图2所示。A surface-modified cathode material precursor, whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.01SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0 μm, the particle size of the agglomerated secondary particles is 6.0 μm; silicon element only exists on the surface of the primary particles. The SEM images of the surface-modified cathode material precursor are shown in Figures 1 and 2.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为2.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.0 mol/L. ;
步骤2.配制浓度为6.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant;
步骤3.配制浓度为8.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent;
步骤4.配制浓度为2.0mol/L的硫酸镁溶液；Step 4. Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.8，氨水浓度为8.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硫酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为58℃，pH为10.8，氨水浓度为8.0g/L；硫酸镁溶液的流量为混合盐溶液的流量的0.05倍； Step 6. Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle. The reaction temperature is 58°C, the pH is 10.8, and the ammonia concentration is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到6.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 6.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1.5mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the materials in the kettle from solid to liquid, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在280℃下烘干1h，得到干燥料；Step 9. Dry the precipitate at 280°C for 1 hour to obtain dry material;
步骤10.配制质量浓度为1％的乙烯基三甲氧基硅烷的水溶液；Step 10. Prepare an aqueous solution of vinyltrimethoxysilane with a mass concentration of 1%;
步骤11.按照固液比1g:2mL将干燥料与乙烯基三甲氧基硅烷的水溶液混合后，在110℃下烘干2.5h，得到预处理干燥料；Step 11. Mix the dried material with an aqueous solution of vinyltrimethoxysilane at a solid-liquid ratio of 1 g:2 mL, and dry at 110° C. for 2.5 h to obtain a pretreated dried material;
步骤12.将预处理干燥料，在氧气氛围、温度为650℃下煅烧1h，得到表面改性的正极材料前驱体。Step 12. Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a surface-modified cathode material precursor.
实施例2：Example 2:
一种表面改性的正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.1MgO·0.025SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为10.0μm；硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor, whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.025SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0μm, the particle size of the agglomerated secondary particles is 10.0μm; silicon element only exists on the surface of the primary particles.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为2.5mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.5 mol/L. ;
步骤2.配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent;
步骤3.配制浓度为12.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent;
步骤4.配制浓度为2.5mol/L的氯化镁溶液；Step 4. Prepare a magnesium chloride solution with a concentration of 2.5mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.2，氨水浓度为4.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的氯化镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为55℃，pH为10.2，氨水浓度为4.0g/L；氯化镁溶液的流量为混合盐溶液的流量的0.1倍；Step 6. Add the nickel, cobalt and manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium chloride solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction in the kettle. The temperature is 55°C, the pH is 10.2, and the ammonia concentration is 4.0g/L; the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到10.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 10.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用2.0mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物； Step 8. Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在220℃下烘干2h，得到干燥料；Step 9. Dry the precipitate at 220°C for 2 hours to obtain dry material;
步骤10.配制质量浓度为2％的乙烯基三乙氧基硅烷的水溶液；Step 10. Prepare an aqueous solution of vinyltriethoxysilane with a mass concentration of 2%;
步骤11.按照固液比1g:3mL将干燥料与乙烯基三乙氧基硅烷的水溶液混合后，在120℃下烘干2h，得到预处理干燥料；Step 11. Mix the dry material with the aqueous solution of vinyltriethoxysilane according to the solid-to-liquid ratio of 1g:3mL, and then dry it at 120°C for 2 hours to obtain the pretreated dry material;
步骤12.将预处理干燥料，在氧气氛围、温度为800℃下煅烧0.5h，得到表面改性的正极材料前驱体。Step 12. Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 800°C for 0.5 h to obtain a surface-modified cathode material precursor.
实施例3：Example 3:
一种表面改性的正极材料前驱体，其化学通式为Ni0.8Co0.1Mn0.1O·0.02MgO·0.0136SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为3.5μm；硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor, whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.0136SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0μm, the particle size of the agglomerated secondary particles is 3.5μm; silicon element only exists on the surface of the primary particles.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.8:0.1:0.1，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为1.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.8:0.1:0.1, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 1.0 mol/L. ;
步骤2.配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent;
步骤3.配制浓度为6.0mol/L的氨水作为络合剂；Step 3. Prepare 6.0 mol/L ammonia water as a complexing agent;
步骤4.配制浓度为1.0mol/L的硝酸镁溶液；Step 4. Prepare a magnesium nitrate solution with a concentration of 1.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为11.0，氨水浓度为10.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硝酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为48℃，pH为11.0，氨水浓度为10.0g/L；硝酸镁溶液的流量为混合盐溶液的流量的0.02倍；Step 6. Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3 and the magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle. The reaction temperature is 48°C, the pH is 11.0, and the ammonia concentration is 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到3.5μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 3.5 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在250℃下烘干1.5h，得到干燥料；Step 9. Dry the precipitate at 250°C for 1.5 hours to obtain dry material;
步骤10.配制质量浓度为0.5％的乙烯基三(β-甲氧乙氧基)硅烷的水溶液；Step 10. Prepare an aqueous solution of vinyl tris(β-methoxyethoxy)silane with a mass concentration of 0.5%;
步骤11.按照固液比1g:1mL将干燥料与乙烯基三(β-甲氧乙氧基)硅烷的水溶 液混合后，在100℃下烘干3h，得到预处理干燥料；Step 11. Dissolve the dry material and vinyl tris(β-methoxyethoxy)silane in water according to the solid-liquid ratio of 1g:1mL. After the liquid is mixed, it is dried at 100°C for 3 hours to obtain the pretreated dry material;
步骤12.将预处理干燥料，在空气氛围、温度为500℃下煅烧1h，得到表面改性的正极材料前驱体。Step 12. Calculate the pretreated dry material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a surface-modified cathode material precursor.
对比例1：(与实施例1相比未对沉淀物进行烘干，直接用硅烷偶联剂水溶液对沉淀物进行处理)Comparative Example 1: (Compared with Example 1, the precipitate was not dried, and the precipitate was directly treated with a silane coupling agent aqueous solution)
一种表面改性的正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.05MgO·0.0128SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为6.0μm；硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.0128SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, and the particle size of the primary particles is 0.01 -1.0μm, the particle size of the agglomerated secondary particles is 6.0μm; silicon element only exists on the surface of the primary particles.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为2.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.0 mol/L. ;
步骤2.配制浓度为6.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant;
步骤3.配制浓度为8.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent;
步骤4.配制浓度为2.0mol/L的硫酸镁溶液；Step 4. Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.8，氨水浓度为8.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硫酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为58℃，pH为10.8，氨水浓度为8.0g/L；硫酸镁溶液的流量为混合盐溶液的流量的0.05倍；Step 6. Add the nickel cobalt manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle. The reaction temperature is 58°C, the pH is 10.8, and the ammonia concentration is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到6.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 6.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1.5mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Perform solid-liquid separation of the materials in the kettle, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.配制质量浓度为1％的乙烯基三甲氧基硅烷的水溶液；Step 9. Prepare an aqueous solution of vinyltrimethoxysilane with a mass concentration of 1%;
步骤10.按照固液比1g:2mL将沉淀物与乙烯基三甲氧基硅烷的水溶液混合后，在110℃下烘干2.5h，得到预处理干燥料；Step 10. Mix the precipitate with the aqueous solution of vinyltrimethoxysilane according to the solid-liquid ratio of 1g:2mL, and then dry it at 110°C for 2.5h to obtain the pretreated dry material;
步骤11.将预处理干燥料，在氧气氛围、温度为650℃下煅烧1h，得到表面改性的正极材料前驱体。 Step 11. Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a surface-modified cathode material precursor.
对比例2：(与实施例2相比未对沉淀物进行烘干，直接用硅烷偶联剂水溶液对沉淀物进行处理)Comparative Example 2: (Compared with Example 2, the precipitate was not dried, and the precipitate was directly treated with a silane coupling agent aqueous solution)
一种表面改性的正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.1MgO·0.0308SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为10.0μm；硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor has a general chemical formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.0308SiO 2 ; it is a secondary particle formed by agglomeration of primary particles, the particle size of the primary particles is 0.01-1.0 μm, and the particle size of the agglomerated secondary particles is 10.0 μm; silicon element exists only on the surface of the primary particles.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为2.5mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.5 mol/L. ;
步骤2.配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent;
步骤3.配制浓度为12.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent;
步骤4.配制浓度为2.5mol/L的氯化镁溶液；Step 4. prepare a magnesium chloride solution with a concentration of 2.5 mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.2，氨水浓度为4.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的氯化镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为55℃，pH为10.2，氨水浓度为4.0g/L；氯化镁溶液的流量为混合盐溶液的流量的0.1倍；Step 6. Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium chloride solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction in the kettle. The temperature is 55°C, the pH is 10.2, and the ammonia concentration is 4.0g/L; the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到10.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 10.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用2.0mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.配制质量浓度为2％的乙烯基三乙氧基硅烷的水溶液；Step 9. Prepare an aqueous solution of vinyltriethoxysilane with a mass concentration of 2%;
步骤10.按照固液比1g:3mL将沉淀物与乙烯基三乙氧基硅烷的水溶液混合后，在120℃下烘干2h，得到预处理干燥料；Step 10. Mix the precipitate with the aqueous solution of vinyltriethoxysilane according to a solid-to-liquid ratio of 1g:3mL, and then dry it at 120°C for 2 hours to obtain a pretreated dry material;
步骤11.将预处理干燥料，在氧气氛围、温度为800℃下煅烧0.5h，得到表面改性的正极材料前驱体。Step 11. Calculate the pretreated dry material in an oxygen atmosphere at a temperature of 800°C for 0.5 h to obtain a surface-modified cathode material precursor.
对比例3：(与实施例3相比未对沉淀物进行烘干，直接用硅烷偶联剂水溶液对沉淀物进行处理)Comparative Example 3: (Compared with Example 3, the precipitate was not dried and the precipitate was directly treated with a silane coupling agent aqueous solution)
一种表面改性的正极材料前驱体，其化学通式为 Ni0.8Co0.1Mn0.1O·0.02MgO·0.00163SiO2；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为3.5μm；硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.00163SiO 2 ; It is a secondary particle formed by agglomeration of primary particles. The particle size of the primary particles is 0.01-1.0μm, and the particle size of the agglomerated secondary particles is 3.5μm; Silicon Elements only exist on primary particle surfaces.
如上所述的表面改性的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the surface-modified cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.8:0.1:0.1，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为1.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.8:0.1:0.1, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 1.0 mol/L. ;
步骤2.配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent;
步骤3.配制浓度为6.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent;
步骤4.配制浓度为1.0mol/L的硝酸镁溶液；Step 4. Prepare a magnesium nitrate solution with a concentration of 1.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为11.0，氨水浓度为10.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硝酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为48℃，pH为11.0，氨水浓度为10.0g/L；硝酸镁溶液的流量为混合盐溶液的流量的0.02倍；Step 6. Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium nitrate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle. The reaction temperature is 48°C, the pH is 11.0, and the ammonia concentration is 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到3.5μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 3.5 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.配制质量浓度为0.5％的乙烯基三(β-甲氧乙氧基)硅烷的水溶液；Step 9. Prepare an aqueous solution of vinyl tris(β-methoxyethoxy)silane with a mass concentration of 0.5%;
步骤10.按照固液比1g:1mL将沉淀物与乙烯基三(β-甲氧乙氧基)硅烷的水溶液混合后，在100℃下烘干3h，得到预处理干燥料；Step 10. Mix the precipitate with the aqueous solution of vinyl tris(β-methoxyethoxy)silane according to the solid-liquid ratio of 1g:1mL, and then dry it at 100°C for 3 hours to obtain the pretreated dry material;
步骤11.将预处理干燥料，在空气氛围、温度为500℃下煅烧1h，得到表面改性的正极材料前驱体。Step 11. Calculate the pretreated dry material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a surface-modified cathode material precursor.
对比例4：(与实施例1相比未使用硅烷偶联剂水溶液进行处理)Comparative Example 4: (Compared with Example 1, no silane coupling agent aqueous solution was used for treatment)
一种正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.05MgO；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为6.0μm。A cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO; it is a secondary particle formed by agglomeration of primary particles. The particle size of the primary particles is 0.01-1.0 μm, and the agglomerated secondary particles are The particle size of the particles is 6.0 μm.
如上所述的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为 原料，配制镍钴锰金属离子总浓度为2.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt and manganese as Raw materials: prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.0 mol/L;
步骤2.配制浓度为6.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 6.0 mol/L as a precipitant;
步骤3.配制浓度为8.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent;
步骤4.配制浓度为2.0mol/L的硫酸镁溶液；Step 4. Prepare a magnesium sulfate solution with a concentration of 2.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.8，氨水浓度为8.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.8, and the ammonia water concentration is 8.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硫酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为58℃，pH为10.8，氨水浓度为8.0g/L；硫酸镁溶液的流量为混合盐溶液的流量的0.05倍；Step 6. Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia solution prepared in step 3, and the magnesium sulfate solution prepared in step 4 into the reaction kettle in parallel flow for reaction, and control the reaction inside the kettle. The reaction temperature is 58°C, the pH is 10.8, and the ammonia concentration is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到6.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 6.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1.5mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the materials in the kettle from solid to liquid, first wash with 1.5 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在280℃下烘干1h，得到干燥料；Step 9. Dry the precipitate at 280°C for 1 hour to obtain dry material;
步骤10.将干燥料，在氧气氛围、温度为650℃下煅烧1h，得到正极材料前驱体。Step 10. Calculate the dried material in an oxygen atmosphere at a temperature of 650°C for 1 hour to obtain a cathode material precursor.
对比例5：(与实施例2相比未使用硅烷偶联剂水溶液进行处理)Comparative Example 5: (Compared with Example 2, no silane coupling agent aqueous solution was used for treatment)
一种正极材料前驱体，其化学通式为Ni0.6Co0.2Mn0.2O·0.1MgO；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为10.0μm。A cathode material precursor whose general chemical formula is Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO; it is a secondary particle formed by agglomeration of primary particles. The particle size of the primary particles is 0.01-1.0 μm, and the agglomerated secondary particles are The particle size of the particles is 10.0 μm.
如上所述的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.6:0.2:0.2，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为2.5mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.6:0.2:0.2, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 2.5 mol/L. ;
步骤2.配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitating agent;
步骤3.配制浓度为12.0mol/L的氨水作为络合剂；Step 3. Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent;
步骤4.配制浓度为2.5mol/L的氯化镁溶液；Step 4. Prepare a magnesium chloride solution with a concentration of 2.5mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为10.2，氨水浓度为4.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 10.2, and the ammonia water concentration is 4.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步 骤3配制的氨水以及步骤4配制的氯化镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为55℃，pH为10.2，氨水浓度为4.0g/L；氯化镁溶液的流量为混合盐溶液的流量的0.1倍；Step 6. The nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, The ammonia water prepared in step 3 and the magnesium chloride solution prepared in step 4 are added to the reactor in parallel for reaction, and the reaction temperature in the reactor is controlled to be 55° C., the pH is 10.2, and the ammonia water concentration is 4.0 g/L; the flow rate of the magnesium chloride solution is 0.1 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到10.0μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 10.0 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用2.0mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Perform solid-liquid separation of the materials in the kettle, first wash with 2.0 mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在220℃下烘干2h，得到干燥料；Step 9. Dry the precipitate at 220°C for 2 hours to obtain dry material;
步骤10.将干燥料，在氧气氛围、温度为800℃下煅烧0.5h，得到正极材料前驱体。Step 10. Calculate the dried material in an oxygen atmosphere at a temperature of 800°C for 0.5 hours to obtain a cathode material precursor.
对比例6：(与实施例3相比未使用硅烷偶联剂水溶液进行处理)Comparative Example 6: (Compared with Example 3, no silane coupling agent aqueous solution was used for treatment)
一种正极材料前驱体，其化学通式为Ni0.8Co0.1Mn0.1O·0.02MgO；其是由一次颗粒团聚而成的二次颗粒，一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为3.5μm。A cathode material precursor whose general chemical formula is Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO; it is a secondary particle formed by agglomeration of primary particles. The particle size of the primary particles is 0.01-1.0 μm, and the agglomerated secondary particles are The particle size of the particles is 3.5 μm.
如上所述的正极材料前驱体的制备方法，包括以下步骤：The preparation method of the cathode material precursor as described above includes the following steps:
步骤1.按照元素摩尔比Ni:Co:Mn＝0.8:0.1:0.1，选用镍、钴、锰可溶性盐为原料，配制镍钴锰金属离子总浓度为1.0mol/L的镍钴锰混合盐溶液；Step 1. According to the element molar ratio Ni:Co:Mn=0.8:0.1:0.1, select soluble salts of nickel, cobalt, and manganese as raw materials to prepare a nickel-cobalt-manganese mixed salt solution with a total concentration of nickel-cobalt-manganese metal ions of 1.0 mol/L. ;
步骤2.配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；Step 2. Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitating agent;
步骤3.配制浓度为6.0mol/L的氨水作为络合剂；Step 3. Prepare 6.0 mol/L ammonia water as a complexing agent;
步骤4.配制浓度为1.0mol/L的硝酸镁溶液；Step 4. Prepare a magnesium nitrate solution with a concentration of 1.0mol/L;
步骤5.向反应釜中加入碱性底液至漫过底层搅拌桨，启动搅拌，碱性底液为氢氧化钠和氨水的混合液，碱性底液的pH值为11.0，氨水浓度为10.0g/L；Step 5. Add the alkaline bottom liquid into the reaction kettle until it covers the bottom stirring paddle, and start stirring. The alkaline bottom liquid is a mixture of sodium hydroxide and ammonia water. The pH value of the alkaline bottom liquid is 11.0, and the ammonia water concentration is 10.0. g/L;
步骤6.将步骤1配制的镍钴锰混合盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水以及步骤4配制的硝酸镁溶液并流加入到反应釜中进行反应，控制釜内反应温度为48℃，pH为11.0，氨水浓度为10.0g/L；硝酸镁溶液的流量为混合盐溶液的流量的0.02倍；Step 6. Add the nickel-cobalt-manganese mixed salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, the ammonia water prepared in step 3, and the magnesium nitrate solution prepared in step 4 to the reactor in parallel for reaction, and control the reaction temperature in the reactor to be 48° C., the pH to be 11.0, and the ammonia water concentration to be 10.0 g/L; the flow rate of the magnesium nitrate solution is 0.02 times the flow rate of the mixed salt solution;
步骤7.当检测到反应釜内物料的粒度达到3.5μm时，停止进料；Step 7. When it is detected that the particle size of the material in the reaction kettle reaches 3.5 μm, stop feeding;
步骤8.将釜内物料进行固液分离，先用1mol/L的氢氧化钠溶液洗涤，再用纯水洗涤沉淀物；Step 8. Separate the materials in the kettle from solid to liquid, first wash with 1mol/L sodium hydroxide solution, and then wash the precipitate with pure water;
步骤9.将沉淀物在250℃下烘干1.5h，得到干燥料； Step 9. Dry the precipitate at 250°C for 1.5 hours to obtain dry material;
步骤10.将干燥料，在空气氛围、温度为500℃下煅烧1h，得到正极材料前驱体。Step 10. Calculate the dried material in an air atmosphere at a temperature of 500°C for 1 hour to obtain a cathode material precursor.
试验例：Test example:
将实施例1、实施例2、对比例1、对比例2、对比例4及对比例5制备得到的正极材料前驱体，分别与碳酸锂按照锂元素与镍钴锰总摩尔比为1.08：1，混合均匀，在氧气氛围、850℃下煅烧12h，分别得到对应的正极材料。The cathode material precursors prepared in Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 4 and Comparative Example 5 were mixed with lithium carbonate respectively according to a total molar ratio of lithium element to nickel cobalt manganese of 1.08:1. , mixed evenly, and calcined in an oxygen atmosphere at 850°C for 12 hours to obtain the corresponding cathode materials.
将实施例3、对比例3及对比例6制备得到的正极材料前驱体，分别与氢氧化锂按照锂元素与镍钴锰总摩尔比为1.08：1，混合均匀，在氧气氛围、800℃下煅烧12h，分别得到对应的正极材料。The cathode material precursors prepared in Example 3, Comparative Example 3 and Comparative Example 6 were mixed with lithium hydroxide according to the total molar ratio of lithium element to nickel cobalt manganese of 1.08:1, and mixed evenly in an oxygen atmosphere at 800°C. After calcination for 12 h, the corresponding cathode materials were obtained.
将以上得到的正极材料配成扣式电池进行锂离子电池电化学性能测试，其具体步骤为：以N-甲基吡咯烷酮为溶剂，按照质量比8︰1︰1的比例将正极活性物质(正极材料)与乙炔黑、PVDF混合均匀，涂覆于铝箔上，经80℃鼓风干燥8h后，于120℃真空干燥12h。在氩气保护的手套箱中装配电池，负极为金属锂片，隔膜为聚丙烯膜，电解液为1M LiPF6-EC/DMC(1︰1，v/v)。电流密度为1C＝160mA/g，充放电截止电压为2.7-4.3V。测试在1C电流密度下的循环性能，结果如下表1所示。The positive electrode material obtained above was formulated into a button cell for electrochemical performance testing of lithium-ion batteries. The specific steps are: using N-methylpyrrolidone as the solvent, the positive electrode active material (positive electrode) was added in a mass ratio of 8:1:1. Material), mixed evenly with acetylene black and PVDF, coated on aluminum foil, air dried at 80°C for 8 hours, and then vacuum dried at 120°C for 12 hours. Assemble the battery in an argon-protected glove box. The cathode is a lithium metal sheet, the separator is a polypropylene film, and the electrolyte is 1M LiPF6-EC/DMC (1:1, v/v). The current density is 1C=160mA/g, and the charge and discharge cut-off voltage is 2.7-4.3V. The cycle performance at 1C current density was tested, and the results are shown in Table 1 below.
表1：电池性能测试结果
Table 1: Battery performance test results
由表1可知，本发明的制备方法制备得到的表面改性的正极材料前驱体在制备成正极材料后具有优异的电化学性能，其0.1C放电容量能达到182.9mAh/g以上，300次循环后放电比容量能达到172.0mAh/g以上，其经过300次循环后，循环保持率能达到90.94％以上。As can be seen from Table 1, the surface-modified cathode material precursor prepared by the preparation method of the present invention has excellent electrochemical properties after being prepared into the cathode material, and its 0.1C discharge capacity can reach more than 182.9mAh/g for 300 cycles. The post-discharge specific capacity can reach more than 172.0mAh/g, and after 300 cycles, the cycle retention rate can reach more than 90.94%.
同时分别对比实施例1与对比例1、实施例2与对比例2、实施例3与对比例3可知，当在正极材料前驱体的制备过程中，不对沉淀物进行烘干，直接用硅烷偶联剂水溶液对沉淀物进行处理，制得的表面改性的正极材料前驱体在制备成正极材料后，电池的放电容量及循环保持率均会下降。At the same time, comparing Example 1 with Comparative Example 1, Example 2 with Comparative Example 2, and Example 3 with Comparative Example 3, it can be seen that during the preparation process of the cathode material precursor, the precipitate is not dried and the silane coupling agent is directly used. After the surface-modified cathode material precursor is prepared into the cathode material by treating the precipitate with the combined agent aqueous solution, the discharge capacity and cycle retention rate of the battery will decrease.
分别对比实施例1与对比例4、实施例2与对比例5、实施例3与对比例6可知，当在正极材料前驱体的制备过程中，不使用硅烷偶联剂水溶液进行表面改性处理，制得的表面改性的正极材料前驱体在制备成正极材料后，电池的放电容量及循环保持率均会大幅度下降。Comparing Example 1 with Comparative Example 4, Example 2 with Comparative Example 5, and Example 3 with Comparative Example 6 respectively, it can be seen that during the preparation process of the cathode material precursor, the silane coupling agent aqueous solution is not used for surface modification treatment. , after the surface-modified cathode material precursor is prepared into a cathode material, the discharge capacity and cycle retention rate of the battery will decrease significantly.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。 The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, etc. may be made without departing from the spirit and principles of the present invention. All simplifications should be equivalent substitutions, and are all included in the protection scope of the present invention.

Claims (10)

  1. 一种表面改性的正极材料前驱体，其特征在于：所述表面改性的正极材料前驱体的化学式为：NiaCobMncO·xMgO·ySiO2，其中，0≤a≤1，0≤b≤1，0≤c≤1，a+b+c＝1，0＜y＜x≤0.1。A surface-modified cathode material precursor, characterized in that: the chemical formula of the surface-modified cathode material precursor is: Ni a Co b Mn c O·xMgO·ySiO 2 , where 0≤a≤1, 0≤b≤1, 0≤c≤1, a+b+c=1, 0＜y＜x≤0.1.
  2. 根据权利要求1所述的一种表面改性的正极材料前驱体，其特征在于：所述表面改性的正极材料前驱体是由一次颗粒团聚而成的二次颗粒，其中一次颗粒的粒度为0.01-1.0μm，团聚的二次颗粒的粒度为1.0-15.0μm。A surface-modified cathode material precursor according to claim 1, characterized in that: the surface-modified cathode material precursor is secondary particles formed by agglomeration of primary particles, wherein the particle size of the primary particles is 0.01-1.0μm, the particle size of the agglomerated secondary particles is 1.0-15.0μm.
  3. 根据权利要求1所述的一种表面改性的正极材料前驱体，其特征在于：所述表面改性的正极材料前驱体中的硅元素仅存在于一次颗粒表面。A surface-modified cathode material precursor according to claim 1, characterized in that: the silicon element in the surface-modified cathode material precursor only exists on the surface of primary particles.
  4. 一种如权利要求1至3任一项所述的表面改性的正极材料前驱体的制备方法，其特征在于：包括以下步骤：A method for preparing a surface-modified cathode material precursor according to any one of claims 1 to 3, characterized in that it includes the following steps:
    (1)将镍钴锰混合盐溶液、沉淀剂、络合剂、可溶性镁盐溶液与碱性底液混合反应，得到混合液；(1) Mix and react a nickel-cobalt-manganese mixed salt solution, a precipitant, a complexing agent, a soluble magnesium salt solution and an alkaline bottom solution to obtain a mixed solution;
    (2)将步骤(1)得到的混合液进行固液分离，将分离的固体物洗涤后，烘干，得到干燥料；(2) Perform solid-liquid separation on the mixed liquid obtained in step (1), wash the separated solids, and then dry them to obtain dry materials;
    (3)将步骤(2)得到的干燥料与硅烷偶联剂水溶液混合，烘干，然后在有氧气氛下煅烧，得到所述表面改性的正极材料前驱体。(3) Mix the dry material obtained in step (2) with the silane coupling agent aqueous solution, dry it, and then calcine it in an oxygen atmosphere to obtain the surface-modified cathode material precursor.
  5. 根据权利要求4所述的一种表面改性的正极材料前驱体的制备方法，其特征在于：步骤(1)中，所述镍钴锰混合盐溶液中镍元素、钴元素及锰元素的摩尔比为a:b:c。A method for preparing a surface-modified cathode material precursor according to claim 4, characterized in that: in step (1), the moles of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese mixed salt solution The ratio is a:b:c.
  6. 根据权利要求4所述的一种表面改性的正极材料前驱体的制备方法，其特征在于：步骤(1)中，所述可溶性镁盐溶液的浓度为0.5-3.0mol/L。The method for preparing a surface-modified cathode material precursor according to claim 4, characterized in that in step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0 mol/L.
  7. 根据权利要求4所述的一种表面改性的正极材料前驱体的制备方法，其特征在于：步骤(1)中，所述碱性底液为氢氧化钠和氨水的混合液，所述碱性底液的pH为9.0-11.0，所述碱性底液中的氨水浓度为1.0-12.0g/L。A method for preparing a surface-modified cathode material precursor according to claim 4, characterized in that: in step (1), the alkaline bottom liquid is a mixed liquid of sodium hydroxide and ammonia water, and the alkali The pH of the alkaline bottom liquid is 9.0-11.0, and the ammonia concentration in the alkaline bottom liquid is 1.0-12.0g/L.
  8. 根据权利要求4所述的一种表面改性的正极材料前驱体的制备方法，其特征在于：步骤(2)中，所述烘干的温度为220-280℃，烘干时间为1-2h。The method for preparing a surface-modified cathode material precursor according to claim 4, characterized in that in step (2), the drying temperature is 220-280°C, and the drying time is 1-2 hours .
  9. 根据权利要求4所述的一种表面改性的正极材料前驱体的制备方法，其特征在于：步骤(3)中，所述硅烷偶联剂水溶液中的硅烷偶联剂为N-(β-氨乙 基)-α-氨丙基三甲氧基硅烷、3-缩水甘油基丙基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、乙烯基三乙氧基硅烷及乙烯基三甲氧基硅烷中的至少一种。The method for preparing a surface-modified cathode material precursor according to claim 4, characterized in that in step (3), the silane coupling agent in the silane coupling agent aqueous solution is N-(β- Ammonia B methyl)-α-aminopropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane and vinyltrimethyl At least one of the oxysilanes.
  10. 权利要求1至3任一项所述的表面改性的正极材料前驱体在制备锂离子电池中的应用。 Application of the surface-modified cathode material precursor according to any one of claims 1 to 3 in the preparation of lithium-ion batteries.
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