WO2023202203A1 - 掺杂钨的四氧化三钴的制备方法及其应用 - Google Patents

掺杂钨的四氧化三钴的制备方法及其应用 Download PDF

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WO2023202203A1
WO2023202203A1 PCT/CN2023/077220 CN2023077220W WO2023202203A1 WO 2023202203 A1 WO2023202203 A1 WO 2023202203A1 CN 2023077220 W CN2023077220 W CN 2023077220W WO 2023202203 A1 WO2023202203 A1 WO 2023202203A1
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tungsten
solution
preparation
concentration
sodium
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PCT/CN2023/077220
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English (en)
French (fr)
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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
湖南邦普汽车循环有限公司
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Priority to HU2400117A priority Critical patent/HUP2400117A1/hu
Priority to DE112023000017.4T priority patent/DE112023000017T5/de
Priority to ES202390116A priority patent/ES2957119A2/es
Priority to US18/233,879 priority patent/US20230382761A1/en
Publication of WO2023202203A1 publication Critical patent/WO2023202203A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—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 battery cathode material precursors, and specifically relates to a preparation method and application of tungsten-doped cobalt tetroxide.
  • Lithium cobalt oxide cathode materials have important application directions in the digital field. As electronic products have increasingly stringent performance requirements for lithium batteries, the update and iteration of lithium cobalt oxide cathode materials is particularly important.
  • the performance of lithium cobalt oxide cathode material depends largely on the performance of the precursor.
  • the application of cobalt tetroxide in the field of lithium ion batteries is mainly as the precursor of lithium cobalt oxide. Its performance is a key factor affecting the electrochemical performance of lithium cobalt oxide.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for preparing tungsten-doped cobalt tetroxide and its application.
  • the cobalt tetroxide obtained by this method has high structural stability, and the prepared cathode material has good cycle performance.
  • a method for preparing tungsten-doped cobalt tetroxide which includes the following steps:
  • step S1 the concentration of the alkali solution is 4.0-10.0 mol/L.
  • the alkali solution is sodium hydroxide solution.
  • step S1 the molar ratio of tungsten element and molybdenum element in the mixed solution is 3: (1-3); the total concentration of tungsten element and molybdenum element in the mixed solution is 0.01 -1.0mol/L.
  • the tungsten-containing compound in step S1, is sodium tungstate, sodium metatungstate, ammonium tungstate, ammonium metatungstate, potassium tungstate, lithium tungstate, tungsten trioxide or tungsten One or more acids.
  • the molybdenum-containing compound is sodium molybdate, sodium metamolybdate, ammonium molybdate, ammonium metamolybdate, potassium molybdate, lithium molybdate, molybdenum trioxide or molybdic acid. one or more of them.
  • the concentration of the cobalt salt solution is 1.0-2.0 mol/L.
  • the cobalt salt solution is at least one of cobalt sulfate, cobalt nitrate or cobalt chloride solution.
  • the complexing agent in step S2, is ammonia water with a concentration of 6.0-12.0 mol/L.
  • step S2 the pH value of the bottom liquid is 10-11, and the ammonia concentration is 5.0-10.0g/L.
  • step S2 the pH of the reaction is controlled to be 10-11, the temperature in the kettle is 55-65°C, and the ammonia concentration is 5-10g/L.
  • step S2 the reaction is carried out at a stirring speed of 200-500 r/min.
  • step S2 before the aging, the D50 of the target particle size of the reaction material is 2.0-15.0 ⁇ m.
  • step S2 the aging time is 1-2 h.
  • step S3 the precipitate is washed and dried before roasting.
  • the drying temperature is 100-120°C and the drying time is 4-6 hours.
  • the roasting temperature is 500-750°C, and the roasting time is 2-6 hours.
  • the oxygen-containing atmosphere is air or oxygen.
  • step S4 the volume ratio (solid-liquid ratio) of the mass of the roasted material to the sodium sulfide solution is 1g: (1-5) mL, and the concentration of the sodium sulfide solution is 0.1-1mol/L.
  • the soaking temperature is 70-80°C. Further, the soaking time is 1-3h.
  • step S4 sodium hydroxide or sodium bisulfate is used to adjust the pH of the solution.
  • step S4 after the solid-liquid separation, the tungsten-doped cobalt tetroxide is also washed and dried with water.
  • the drying temperature is 80-120°C, and the drying time is 2- 4h.
  • the present invention also proposes the application of the tungsten-doped cobalt tetroxide prepared by the preparation method in the preparation of lithium cobalt oxide or lithium-ion batteries.
  • the present invention at least has the following beneficial effects:
  • the present invention carries out co-precipitation reaction with an alkali solution containing tungsten and molybdenum and a complexing agent to prepare cobalt hydroxide doped with tungsten and molybdenum.
  • an alkali solution containing tungsten and molybdenum and a complexing agent to prepare cobalt hydroxide doped with tungsten and molybdenum.
  • the cobalt exists in the form of cobalt tetraoxide
  • molybdenum and Tungsten is doped inside cobalt tetroxide in the form of trioxide.
  • it is dissolved by sodium sulfide, and the molybdenum element is selectively removed by controlling the pH, leaving the tungsten element with a larger radius, thereby obtaining tungsten-doped cobalt tetroxide.
  • the reaction equation is as follows:
  • the present invention replaces the hydroxide anions inside the cobalt hydroxide by co-doping the hexavalent elements of tungstate and molybdate, and uses the larger atomic radii of tungsten and molybdenum to stabilize its internal structure and expand the ions.
  • Channel, in the soaking process the principle of different binding abilities of tungsten and molybdenum with sulfur at different pH is used to selectively remove molybdenum with a slightly smaller atomic radius, leaving tungsten with a larger radius, which not only stabilizes the internal crystal lattice of the material, Atomic vacancies are also provided, further increasing the specific capacity of the material.
  • tungsten stabilizes the lattice structure and further improves the material's cycle performance. At the same time, it expands the ion channel and improves the migration efficiency of lithium ions; the atomic vacancies left due to the reduction of molybdenum atoms further The specific capacity of the material is increased.
  • Figure 1 is an SEM image of tungsten-doped cobalt tetroxide prepared in Example 1 of the present invention.
  • tungsten-doped cobalt tetroxide is prepared.
  • the specific process is:
  • Step 1 prepare a cobalt sulfate solution with a concentration of 1.0 mol/L;
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitant, and add sodium tungstate and sodium molybdate according to the molar ratio of tungsten to molybdenum to 3:1 until it is clear and free of precipitation to obtain a mixed solution.
  • the total concentration of tungsten and molybdenum elements in the mixed solution is 0.01mol/L;
  • Step 3 Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent
  • Step 4 Add pure water to the reaction kettle until it covers the bottom stirring paddle, and then add a certain amount of the mixture prepared in Step 2. Combine the solution and the ammonia solution prepared in step 3 to form the bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is 10.7 and the ammonia concentration is 5.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the mixed solution prepared in step 2, and the ammonia water prepared in step 3 into the reactor in parallel flow for reaction. Control the stirring speed of the reactor to 200 r/min, the pH to 10.7, and the reaction in the reactor. The temperature is 55°C and the ammonia concentration is 5g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 11.0 ⁇ m, stop feeding and age for 2 hours;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 100°C for 6 hours, and roast it for 6 hours in an air atmosphere at a roasting temperature of 500°C to obtain the roasted material;
  • Step 8 Add the roasted material to a 1 mol/L sodium sulfide solution and soak it for 3 hours according to the solid-liquid ratio of 1g:1mL; during the soaking period, adjust the pH of the solution to 7.2-8.5 by adding sodium hydroxide or sodium bisulfate, and adjust the soaking temperature to 7.2-8.5. is 70°C;
  • Step 9 After solid-liquid separation, wash the solid with deionized water. After washing is completed, dry it at 80°C for 4 hours to prepare tungsten-doped cobalt tetroxide.
  • tungsten-doped cobalt tetroxide is prepared.
  • the specific process is:
  • Step 1 prepare a cobalt nitrate solution with a concentration of 1.5mol/L;
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 8.0 mol/L as a precipitant, and add ammonium tungstate and ammonium molybdate according to the molar ratio of tungsten to molybdenum to 3:2 until it is clear and free of precipitation to obtain a mixed solution. ;
  • the total concentration of hexavalent elements in the mixed solution is 0.5mol/L;
  • Step 3 Prepare ammonia water with a concentration of 8.0mol/L as a complexing agent
  • Step 4 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the mixed solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is 10.5.
  • Ammonia concentration is 8.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the mixed solution prepared in step 2, and the ammonia water prepared in step 3 into the reactor in parallel flow for reaction. Control the stirring speed of the reactor to 350 r/min, the pH to 10.5, and the reaction in the reactor. The temperature is 60°C and the ammonia concentration is 8g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 9.0 ⁇ m, stop feeding and age for 2 hours;
  • Step 7 Separate the materials in the kettle from solid and liquid, then wash the precipitate with pure water, dry it at 110°C for 5 hours, and Under oxygen atmosphere, roast for 4 hours at a roasting temperature of 600°C to obtain roasted material;
  • Step 8 According to the solid-to-liquid ratio of 1g:3mL, add the roasted material to 0.5mol/L sodium sulfide solution and soak it for 2 hours; during the soaking period, adjust the pH of the solution to 7.2-8.5 by adding sodium hydroxide or sodium bisulfate, and soak The temperature is 75°C;
  • Step 9 After solid-liquid separation, the solid is washed with deionized water. After washing, it is dried at 100°C for 3 hours to prepare tungsten-doped cobalt tetroxide.
  • tungsten-doped cobalt tetroxide is prepared.
  • the specific process is:
  • Step 1 Prepare a cobalt chloride solution with a concentration of 2.0 mol/L
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 10.0 mol/L as a precipitant, and add potassium tungstate and potassium molybdate according to the molar ratio of tungsten to molybdenum to 3:3 until it is clear and free of precipitation to obtain a mixed solution. ;
  • the total concentration of hexavalent elements in the mixed solution is 1.0mol/L;
  • Step 3 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 4 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the mixed solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is 10.
  • Ammonia concentration is 10.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the mixed solution prepared in step 2, and the ammonia water prepared in step 3 into the reactor in parallel flow for reaction. Control the stirring speed of the reactor to 500 r/min, the pH to 10, and the reaction in the reactor. The temperature is 65°C and the ammonia concentration is 10g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 15.0 ⁇ m, stop feeding and age for 1 hour;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 120°C for 4 hours, and roast it for 2 hours in an oxygen atmosphere at a roasting temperature of 750°C to obtain the roasted material;
  • Step 8 According to the solid-to-liquid ratio of 1g:5mL, add the roasted material to the 0.1mol/L sodium sulfide solution and soak it for 3 hours; during the soaking period, adjust the pH of the solution to 7.2-8.5 by adding sodium hydroxide or sodium bisulfate, and soak The temperature is 80°C;
  • Step 9 After solid-liquid separation, wash the solid with deionized water. After washing is completed, dry it at 80°C for 4 hours to prepare tungsten-doped cobalt tetroxide.
  • This comparative example prepared a kind of tricobalt tetroxide.
  • the difference between Comparative Example 1 and Example 1 is that Comparative Example 1 does not add sodium tungstate and sodium molybdate.
  • the specific process is:
  • Step 1 prepare a cobalt sulfate solution with a concentration of 1.0 mol/L;
  • 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 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the sodium hydroxide solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is: 10.7, ammonia concentration is 5.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the ammonia water prepared in step 3 into the reaction kettle in parallel flow for reaction. Control the stirring speed of the reaction kettle to 200 r/min, and the pH to 10.7. The temperature in the kettle is 55°C and the ammonia concentration is 5g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 11.0 ⁇ m, stop feeding and age for 2 hours;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 100°C for 6 hours, and roast it for 6 hours in an air atmosphere at a roasting temperature of 500°C to obtain non-doped cobalt tetroxide.
  • This comparative example prepared a kind of tricobalt tetroxide.
  • the difference between Comparative Example 2 and Example 2 is that Comparative Example 2 does not add ammonium tungstate and ammonium molybdate.
  • the specific process is:
  • Step 1 prepare a cobalt nitrate solution with a concentration of 1.5mol/L;
  • 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 8.0mol/L as a complexing agent
  • Step 4 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the sodium hydroxide solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is: 10.5, ammonia concentration is 8.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the ammonia water prepared in step 3 into the reaction kettle in parallel flow for reaction. Control the stirring speed of the reaction kettle to 350 r/min, and the pH to 10.5. inside the cauldron The temperature is 60°C and the ammonia concentration is 8g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 9.0 ⁇ m, stop feeding and age for 2 hours;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 110°C for 5 hours, and roast it for 4 hours in an oxygen atmosphere at a roasting temperature of 600°C to obtain non-doped cobalt tetroxide.
  • This comparative example prepared a kind of tricobalt tetroxide.
  • the difference between Comparative Example 3 and Example 3 is that Comparative Example 3 does not add potassium tungstate and potassium molybdate.
  • the specific process is:
  • Step 1 Prepare a cobalt chloride solution with a concentration of 2.0 mol/L
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 10.0 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 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the sodium hydroxide solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is: 10.
  • Ammonia concentration is 10.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the sodium hydroxide solution prepared in step 2, and the ammonia water prepared in step 3 into the reaction kettle in parallel flow for reaction. Control the stirring speed of the reaction kettle to 500r/min, and the pH to 10, The temperature in the kettle is 65°C and the ammonia concentration is 10g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 15.0 ⁇ m, stop feeding and age for 1 hour;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 120°C for 4 hours, and roast it for 2 hours in an oxygen atmosphere at a roasting temperature of 750°C to obtain non-doped cobalt tetroxide.
  • This comparative example prepared a kind of tricobalt tetroxide.
  • the difference between Comparative Example 4 and Example 1 is that no sodium molybdate was added in Comparative Example 4.
  • the specific process is:
  • Step 1 prepare a cobalt sulfate solution with a concentration of 1.0 mol/L;
  • Step 2 Prepare a sodium hydroxide solution with a concentration of 4.0 mol/L as a precipitant, and add sodium tungstate until it is clear and free of precipitation to obtain a mixed solution.
  • concentration of tungsten element in the mixed solution is 0.0075 mol/L;
  • Step 3 Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent
  • Step 4 Add pure water to the reaction kettle until it covers the bottom stirring paddle, then add a certain amount of the mixed solution prepared in step 2 and the ammonia water prepared in step 3 to form a bottom liquid for starting the reaction.
  • the pH value of the bottom liquid is 10.7.
  • Ammonia concentration is 5.0g/L;
  • Step 5 Add the cobalt salt solution prepared in step 1, the mixed solution prepared in step 2, and the ammonia water prepared in step 3 into the reactor in parallel flow for reaction. Control the stirring speed of the reactor to 200 r/min, the pH to 10.7, and the reaction in the reactor. The temperature is 55°C and the ammonia concentration is 5g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 11.0 ⁇ m, stop feeding and age for 2 hours;
  • Step 7 Separate the materials in the kettle from solid to liquid, then wash the precipitate with pure water, dry it at 100°C for 6 hours, and roast it for 6 hours in an air atmosphere at a roasting temperature of 500°C to obtain tungsten-doped cobalt tetroxide.
  • the tricobalt tetroxide obtained in Examples 1-3 and Comparative Examples 1-4 was mixed with lithium carbonate respectively, and the molar ratio of Li:Co was controlled to 1.06. It was placed in a push plate kiln for high-temperature solid-phase sintering at a sintering temperature of 1000°C. The sintering time is 12h, and the lithium cobalt oxide cathode material is obtained respectively;
  • the lithium cobalt oxide material obtained in Examples 1-3 and Comparative Examples 1-4 was used as the active material, acetylene black was used as the conductive agent, and PVDF was used as the binder.
  • the active material, conductive agent, and The binder is added with a certain amount of organic solvent NMP, stirred and then coated on aluminum foil to make a positive electrode sheet.
  • the negative electrode is made of metal lithium sheet, and a CR2430 button battery is made in a glove box filled with argon.

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Abstract

本发明公开了一种掺杂钨的四氧化三钴的制备方法及其应用，该方法包括以下步骤：将含钨化合物和含钼化合物溶于碱液中，得到混合溶液；向底液中并流加入混合溶液、钴盐溶液和络合剂进行反应；将所得沉淀物置于含氧气氛下焙烧；将焙烧料置于硫化钠溶液中浸泡，即得掺杂钨的四氧化三钴。本发明掺杂了钨，钨具有较大的原子半径，稳定了材料内部结构，扩大了离子通道，提高了材料循环性能，同时经过浸泡工序中除去钼，提供了原子空位，进一步提高了材料的比容量。

Description

掺杂钨的四氧化三钴的制备方法及其应用 技术领域
本发明属于锂电池正极材料前驱体技术领域，具体涉及一种掺杂钨的四氧化三钴的制备方法及其应用。
背景技术
随着数码领域产品的迭代升级以及各种高端航模、无人机等新兴电子产品的快速发展，对锂电池的轻量化以及电池容量要求越来越高。钴酸锂正极材料在数码领域具有重要的应用方向，随着电子产品对锂电池的性能要求越来越严格，钴酸锂正极材料的更新迭代显得尤为重要。钴酸锂正极材料的性能很大程度上取决于前驱体的性能，四氧化三钴在锂离子电池领域的应用主要是作为钴酸锂的前驱体，它的性能是影响钴酸锂电化学性能的关键因素。但传统的钴酸锂在充电过程中，由于锂离子的脱出，晶格会发生改变，限制了材料的容量。如何进一步提高电池容量，特别是锂电池在高电压下的充放电性能，便成为当下需要解决的重要问题。研究表明，对材料进行部分元素掺杂不仅能够提高主体材料晶格的稳定性，而且还可以大幅度提高电池材料的循环性能。
因此，对四氧化三钴材料进行掺杂以改进正极材料结构稳定性并且不影响其电性能是目前值得关注的问题。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种掺杂钨的四氧化三钴的制备方法及其应用，该方法得到的四氧化三钴具有较高的结构稳定性，制备得到的正极材料具有良好的循环性能。
根据本发明的一个方面，提出了一种掺杂钨的四氧化三钴的制备方法，包括以下步骤：
S1：将含钨化合物和含钼化合物溶于碱液中，得到混合溶液；
S2：向底液中并流加入所述混合溶液、钴盐溶液和络合剂进行反应，待反应物料达 到目标粒径，进行陈化，固液分离得到沉淀物，所述底液含有所述混合溶液和氨水；
S3：将所述沉淀物置于含氧气氛下焙烧，得到焙烧料；
S4：将所述焙烧料置于硫化钠溶液中浸泡，浸泡期间调节溶液pH为7.2-8.5，固液分离，即得所述掺杂钨的四氧化三钴。
在本发明的一些实施方式中，步骤S1中，所述碱液的浓度为4.0-10.0mol/L。
在本发明的一些实施方式中，步骤S1中，所述碱液为氢氧化钠溶液。
在本发明的一些实施方式中，步骤S1中，所述混合溶液中钨元素与钼元素的摩尔比为3：(1-3)；所述混合溶液中钨元素与钼元素的总浓度为0.01-1.0mol/L。
在本发明的一些实施方式中，步骤S1中，所述含钨化合物为钨酸钠、偏钨酸钠、钨酸铵、偏钨酸铵、钨酸钾、钨酸锂、三氧化钨或钨酸中的一种或多种。
在本发明的一些实施方式中，步骤S1中，诉述含钼化合物为钼酸钠、偏钼酸钠、钼酸铵、偏钼酸铵、钼酸钾、钼酸锂、三氧化钼或钼酸中的一种或多种。
在本发明的一些实施方式中，步骤S2中，所述钴盐溶液的浓度为1.0-2.0mol/L。
在本发明的一些实施方式中，步骤S2中，所述钴盐溶液为硫酸钴、硝酸钴或氯化钴溶液中的至少一种。
在本发明的一些实施方式中，步骤S2中，所述络合剂为浓度6.0-12.0mol/L的氨水。
在本发明的一些实施方式中，步骤S2中，所述底液的pH值为10-11，氨浓度为5.0-10.0g/L。
在本发明的一些实施方式中，步骤S2中，控制所述反应的pH为10-11，釜内温度为55-65℃，氨浓度为5-10g/L。
在本发明的一些实施方式中，步骤S2中，所述反应在200-500r/min的搅拌速度下进行。
在本发明的一些实施方式中，步骤S2中，所述陈化前，反应物料的目标粒径的D50为2.0-15.0μm。
在本发明的一些实施方式中，步骤S2中，所述陈化的时间为1-2h。
在本发明的一些实施方式中，步骤S3中，所述沉淀物在焙烧前，还进行水洗和烘干，所述烘干的温度为100-120℃，烘干的时间为4-6h。
在本发明的一些实施方式中，步骤S3中，所述焙烧的温度为500-750℃，焙烧的时间为2-6h。进一步的，所述含氧气氛为空气或氧气。
在本发明的一些实施方式中，步骤S4中，所述焙烧料的质量与所述硫化钠溶液的体积比(固液比)为1g：(1-5)mL，所述硫化钠溶液的浓度为0.1-1mol/L。
在本发明的一些实施方式中，步骤S4中，所述浸泡的温度为70-80℃。进一步的，所述浸泡的时间为1-3h。
在本发明的一些实施方式中，步骤S4中，所述调节溶液pH采用氢氧化钠或硫酸氢钠。
在本发明的一些实施方式中，步骤S4中，所述固液分离后，还包括将所述掺杂钨的四氧化三钴进行水洗和干燥，干燥的温度为80-120℃，干燥的时间为2-4h。
本发明还提出所述的制备方法制得的所述掺杂钨的四氧化三钴在制备钴酸锂或锂离子电池中的应用。
根据本发明的一种优选的实施方式，本发明至少具有以下有益效果：
1、本发明以钴盐与含钨和钼的碱溶液、络合剂进行共沉淀反应，制备掺杂有钨和钼的氢氧化钴，经煅烧后，钴以四氧化三钴的形式存在，而钼与钨则以三氧化物的形式掺杂在四氧化三钴内部，最后，经硫化钠溶解，通过控制pH，选择性的去除钼元素，保留半径较大的钨元素，从而得到掺杂钨的四氧化三钴。其反应方程式如下：
共沉淀反应时：
Co2++2OH-→Co(OH)2；
Co2++xWO4 2-+(1-x)MoO4 2-→Co(WO4)x(MoO4)(1-x)；
煅烧反应时：
6Co(OH)2+O2→2Co3O4+6H2O
6Co(WO4)x(MoO4)(1-x)+O2→2Co3O4+6xWO3+(6-6x)MoO3；
浸泡反应时：
MoO3+4S2-+3H2O→MoS4 2-+6OH-。
2、本发明通过钨酸根、钼酸根六价元素的共掺杂，使氢氧化钴内部的氢氧根阴离子被取代，利用钨与钼较大的原子半径，稳定了其内部结构、扩大了离子通道，在浸泡工序中，利用钨与钼在不同pH下与硫的结合能力不同的原理，选择性地除去原子半径稍小的钼，留下半径较大的钨，不但稳定材料内部晶格，还提供了原子空位，进一步提高了材料的比容量。在后续制备正极材料钴酸锂时，钨稳定了晶格结构，进一步提高材料循环性能，同时，扩大了离子通道，提高了锂离子的迁移效率；由于钼原子减少而留下的原子空位，进一步提高了材料的比容量。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明实施例1制备的掺杂钨的四氧化三钴SEM图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例制备了一种掺杂钨的四氧化三钴，具体过程为：
步骤1，配制浓度为1.0mol/L的硫酸钴溶液；
步骤2，配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂，并按照钨与钼的元素摩尔比为3:1，加入钨酸钠和钼酸钠，直至澄清无沉淀，得到混合溶液，混合溶液中钨与钼元素的总浓度为0.01mol/L；
步骤3，配制浓度为6.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的混 合溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10.7，氨浓度为5.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的混合溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为200r/min、pH为10.7、釜内温度为55℃、氨浓度为5g/L；
步骤6，当检测到反应釜内物料的D50达到11.0μm时，停止进料，并陈化2h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在100℃下烘干6h，在空气气氛下，焙烧6h，焙烧温度500℃，得到焙烧料；
步骤8，按照固液比1g:1mL，将焙烧料加入到1mol/L的硫化钠溶液中浸泡3h；浸泡期间，通过加入氢氧化钠或硫酸氢钠，调节溶液pH为7.2-8.5，浸泡温度为70℃；
步骤9，固液分离后，将固体用去离子水洗涤，洗涤完成后在80℃下干燥4h，制得掺杂钨的四氧化三钴。
实施例2
本实施例制备了一种掺杂钨的四氧化三钴，具体过程为：
步骤1，配制浓度为1.5mol/L的硝酸钴溶液；
步骤2，配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂，并按照钨与钼的元素摩尔比为3:2，加入钨酸铵和钼酸铵，直至澄清无沉淀，得到混合溶液；混合溶液中六价元素的总浓度为0.5mol/L；
步骤3，配制浓度为8.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的混合溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10.5，氨浓度为8.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的混合溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为350r/min、pH为10.5、釜内温度为60℃、氨浓度为8g/L；
步骤6，当检测到反应釜内物料的D50达到9.0μm时，停止进料，并陈化2h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在110℃下烘干5h，在 氧气气氛下，焙烧4h，焙烧温度600℃，得到焙烧料；
步骤8，按照固液比1g:3mL，将焙烧料加入到0.5mol/L的硫化钠溶液中浸泡2h；浸泡期间，通过加入氢氧化钠或硫酸氢钠，调节溶液pH为7.2-8.5，浸泡温度为75℃；
步骤9，固液分离后，将固体用去离子水洗涤，洗涤完成后在100℃下干燥3h，制得掺杂钨的四氧化三钴。
实施例3
本实施例制备了一种掺杂钨的四氧化三钴，具体过程为：
步骤1，配制浓度为2.0mol/L的氯化钴溶液；
步骤2，配制浓度为10.0mol/L的氢氧化钠溶液作为沉淀剂，并按照钨与钼的元素摩尔比为3:3，加入钨酸钾和钼酸钾，直至澄清无沉淀，得到混合溶液；混合溶液中六价元素的总浓度为1.0mol/L；
步骤3，配制浓度为12.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的混合溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10，氨浓度为10.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的混合溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为500r/min、pH为10、釜内温度为65℃、氨浓度为10g/L；
步骤6，当检测到反应釜内物料的D50达到15.0μm时，停止进料，并陈化1h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在120℃下烘干4h，在氧气气氛下，焙烧2h，焙烧温度750℃，得到焙烧料；
步骤8，按照固液比1g:5mL，将焙烧料加入到0.1mol/L的硫化钠溶液中浸泡3h；浸泡期间，通过加入氢氧化钠或硫酸氢钠，调节溶液pH为7.2-8.5，浸泡温度为80℃；
步骤9，固液分离后，将固体用去离子水洗涤，洗涤完成后在80℃下干燥4h，制得掺杂钨的四氧化三钴。
对比例1
本对比例制备了一种四氧化三钴，对比例1与实施例1的区别在于，对比例1不加入钨酸钠和钼酸钠，具体过程为：
步骤1，配制浓度为1.0mol/L的硫酸钴溶液；
步骤2，配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂；
步骤3，配制浓度为6.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的氢氧化钠溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10.7，氨浓度为5.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为200r/min、pH为10.7、釜内温度为55℃、氨浓度为5g/L；
步骤6，当检测到反应釜内物料的D50达到11.0μm时，停止进料，并陈化2h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在100℃下烘干6h，在空气气氛下，焙烧6h，焙烧温度500℃，得到非掺杂的四氧化三钴。
对比例2
本对比例制备了一种四氧化三钴，对比例2与实施例2的区别在于，对比例2不加入钨酸铵和钼酸铵，具体过程为：
步骤1，配制浓度为1.5mol/L的硝酸钴溶液；
步骤2，配制浓度为8.0mol/L的氢氧化钠溶液作为沉淀剂；
步骤3，配制浓度为8.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的氢氧化钠溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10.5，氨浓度为8.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为350r/min、pH为10.5、釜内 温度为60℃、氨浓度为8g/L；
步骤6，当检测到反应釜内物料的D50达到9.0μm时，停止进料，并陈化2h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在110℃下烘干5h，在氧气气氛下，焙烧4h，焙烧温度600℃，得到非掺杂的四氧化三钴。
对比例3
本对比例制备了一种四氧化三钴，对比例3与实施例3的区别在于，对比例3不加入钨酸钾和钼酸钾，具体过程为：
步骤1，配制浓度为2.0mol/L的氯化钴溶液；
步骤2，配制浓度为10.0mol/L的氢氧化钠溶液作为沉淀剂；
步骤3，配制浓度为12.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的氢氧化钠溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10，氨浓度为10.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的氢氧化钠溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为500r/min、pH为10、釜内温度为65℃、氨浓度为10g/L；
步骤6，当检测到反应釜内物料的D50达到15.0μm时，停止进料，并陈化1h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在120℃下烘干4h，在氧气气氛下，焙烧2h，焙烧温度750℃，得到非掺杂的四氧化三钴。
对比例4
本对比例制备了一种四氧化三钴，对比例4与实施例1的区别在于，对比例4不加入钼酸钠，具体过程为：
步骤1，配制浓度为1.0mol/L的硫酸钴溶液；
步骤2，配制浓度为4.0mol/L的氢氧化钠溶液作为沉淀剂，加入钨酸钠，直至澄清无沉淀，得到混合溶液，混合溶液中钨元素的浓度为0.0075mol/L；
步骤3，配制浓度为6.0mol/L氨水作为络合剂；
步骤4，向反应釜中加入纯水至漫过底层搅拌桨，再加入一定量的步骤2配制的混合溶液和步骤3配制的氨水，形成反应开机的底液，底液的pH值为10.7，氨浓度为5.0g/L；
步骤5，将步骤1配制的钴盐溶液、步骤2配制的混合溶液、步骤3配制的氨水并流加入到反应釜中进行反应，控制反应釜搅拌速度为200r/min、pH为10.7、釜内温度为55℃、氨浓度为5g/L；
步骤6，当检测到反应釜内物料的D50达到11.0μm时，停止进料，并陈化2h；
步骤7，将釜内物料进行固液分离，再用纯水洗涤沉淀物，在100℃下烘干6h，在空气气氛下，焙烧6h，焙烧温度500℃，得到掺杂钨的四氧化三钴。
试验例
将实施例1-3与对比例1-4得到的四氧化三钴分别与碳酸锂进行配料，控制Li:Co的摩尔比为1.06，置于推板窑中进行高温固相烧结，烧结温度为1000℃，烧结时间为12h，分别得钴酸锂正极材料；
以实施例1-3和对比例1-4得到的钴酸锂材料为活性材料，乙炔黑为导电剂，PVDF为粘结剂，以92:4:4的比例称取活性材料、导电剂、粘结剂，并加入一定量的有机溶剂NMP，搅拌后涂覆于铝箔上制成正极片，负极采用金属锂片，在充满氩气的手套箱内制成CR2430型纽扣电池。在CT2001A型蓝电测试系统进行电性能测试。测试条件：3.0-4.48V，在0.1C下测试温度为25±1℃。测试结果如表1所示。
表1钴酸锂的电化学性能

从表1可见，实施例的放电容量和循环性能均比对比例高，这是由于实施例掺杂了钨，钨具有较大的原子半径，稳定了材料内部结构，扩大了离子通道，提高了材料循环性能；同时经过浸泡工序中除去钼，提供了原子空位，进一步提高了材料的比容量。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种掺杂钨的四氧化三钴的制备方法，其特征在于，包括以下步骤：
    S1：将含钨化合物和含钼化合物溶于碱液中，得到混合溶液；
    S2：向底液中并流加入所述混合溶液、钴盐溶液和络合剂进行反应，待反应物料达到目标粒径，进行陈化，固液分离得到沉淀物，所述底液含有所述混合溶液和氨水；
    S3：将所述沉淀物置于含氧气氛下焙烧，得到焙烧料；
    S4：将所述焙烧料置于硫化钠溶液中浸泡，浸泡期间调节溶液pH为7.2-8.5，固液分离，即得所述掺杂钨的四氧化三钴。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述碱液的浓度为4.0-10.0mol/L。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述混合溶液中钨元素与钼元素的摩尔比为3：(1-3)；所述混合溶液中钨元素与钼元素的总浓度为0.01-1.0mol/L。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述含钨化合物为钨酸钠、偏钨酸钠、钨酸铵、偏钨酸铵、钨酸钾、钨酸锂、三氧化钨或钨酸中的一种或多种。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述含钼化合物为钼酸钠、偏钼酸钠、钼酸铵、偏钼酸铵、钼酸钾、钼酸锂、三氧化钼或钼酸中的一种或多种。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述钴盐溶液的浓度为1.0-2.0mol/L。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述底液的pH值为10-11，氨浓度为5.0-10.0g/L。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述焙烧料与所述硫化钠溶液的固液比为1g：(1-5)mL，所述硫化钠溶液的浓度为0.1-1mol/L。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤S4中，所述浸泡的温度为70-80℃。
  10. 如权利要求1-9中任一项所述的制备方法制得的所述掺杂钨的四氧化三钴在制备钴酸锂或锂离子电池中的应用。
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