WO2023221624A1 - 熔融盐制备三元正极材料的方法及其应用 - Google Patents

熔融盐制备三元正极材料的方法及其应用 Download PDF

Info

Publication number
WO2023221624A1
WO2023221624A1 PCT/CN2023/081688 CN2023081688W WO2023221624A1 WO 2023221624 A1 WO2023221624 A1 WO 2023221624A1 CN 2023081688 W CN2023081688 W CN 2023081688W WO 2023221624 A1 WO2023221624 A1 WO 2023221624A1
Authority
WO
WIPO (PCT)
Prior art keywords
salt
nickel
manganese
molten salt
cobalt
Prior art date
Application number
PCT/CN2023/081688
Other languages
English (en)
French (fr)
Inventor
余海军
谢英豪
李爱霞
张学梅
李长东
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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 filed Critical 广东邦普循环科技有限公司
Priority to GB2310923.4A priority Critical patent/GB2622915A/en
Priority to DE112023000016.6T priority patent/DE112023000016T5/de
Priority to MA61729A priority patent/MA61729A1/fr
Priority to ES202390117A priority patent/ES2957485A2/es
Priority to US18/371,465 priority patent/US20240014391A1/en
Publication of WO2023221624A1 publication Critical patent/WO2023221624A1/zh

Links

Classifications

    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/004—Oxides; Hydroxides; Oxyacids
    • C01G30/005—Oxides
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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 specifically relates to a method for preparing ternary cathode materials from molten salt and its application.
  • Lithium-ion batteries are widely used due to their good cycle performance, high capacity, low price, easy use, safety and environmental protection.
  • the synthesis methods of cathode materials include high-temperature solid phase method, sol-gel method, co-precipitation method, spray drying method, etc.
  • the high-temperature solid-phase method requires long roasting time, high energy consumption, uneven mixing, low efficiency, and easy mixing of impurities
  • the sol-gel method the use and evaporation of solvents require additional materials and energy consumption, and the synthesis process is long and complex.
  • the synthesis steps of the co-precipitation method are complex and time-consuming and laborious
  • the spray drying method can synthesize nanoscale primary particles, but the equipment is expensive.
  • the molten salt method is attracting widespread attention due to its simple process and short reaction time.
  • lithium salts such as LiCl, LiF, LiCO 3 , LiOH or LiNO 3 are generally used, which serve as solvents and provide lithium sources for the target products.
  • the main role of molten salt is to act as a "solvent" and diffusion medium throughout the reaction process.
  • the reaction raw materials generally have a certain solubility in the selected salt, so the reactants can achieve atomic-scale contact in the liquid phase; in addition, the reactants have a greater diffusion rate in the molten salt, such as ions in the molten salt
  • the migration rate is 1 ⁇ 10 -5 ⁇ 1 ⁇ 10 -8 cm 2 /s, while in the solid phase it is only 1 ⁇ 10 -8 cm 2 /s.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. For this reason, the present invention proposes melting A method for preparing ternary cathode materials from salt and its application.
  • the ternary cathode materials prepared by this method have good crystallinity and lattice pores, which can buffer the volume expansion of the material and improve the cycle stability of the material.
  • a method for preparing ternary cathode materials from molten salt includes the following steps:
  • S1 Mix nickel salt, cobalt salt, manganese salt, metal oxide and acid solution to prepare a mixed salt solution; wherein the metal oxide is an oxide of bismuth or an oxide of antimony;
  • the acid liquid is nitric acid. Further, the mass concentration of the nitric acid is 30-50%.
  • step S1 a nickel cobalt manganese metal liquid containing the nickel salt, cobalt salt, and manganese salt is first prepared, and then the metal oxide and the metal oxide are added to the nickel cobalt manganese metal liquid.
  • Acid liquid the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese metal liquid is 1.0-2.0 mol/L.
  • step S1 the ratio of the molar amount of bismuth or antimony in the mixed salt solution to the total molar amount of nickel, cobalt and manganese is (2-8):100.
  • the concentration of the sodium hydroxide solution is 4.0-10.0 mol/L.
  • step S2 the concentration of ammonia water is 6.0-12.0 mol/L.
  • the bottom liquid is a mixed liquid of sodium hydroxide and ammonia water, the pH of the bottom liquid is 10.8-11.5, and the ammonia concentration is 2.0-5.0g/L.
  • step S2 the temperature of the reaction is controlled to be 45°C-65°C, the pH is 10.8-11.5, and the ammonia concentration is 2.0-5.0g/L.
  • the target particle size D50 of the reaction material is 2.0 ⁇ m-15.0 ⁇ m.
  • the molten salt is at least one of sodium chloride or potassium chloride.
  • the lithium source is LiOH, and the amount of the lithium source is 1.02-1.08 times the total molar amount of nickel, cobalt and manganese in the precursor.
  • step S3 the amount of molten salt used is 4-5 times the total molar amount of nickel, cobalt and manganese in the precursor.
  • step S3 the roasting temperature is 800-900°C, and the roasting time is 12-36 hours. Further, the heating rate of the calcination is 2-5°C/min.
  • step S3 the ball milling time is 2-3 hours.
  • step S4 the drying temperature is 80-120°C, and the drying time is 2-5 hours.
  • step S4 the temperature of the annealing treatment is 650-700°C.
  • the invention also provides the application of the method in preparing lithium-ion batteries.
  • the present invention first prepares a bismuth/antimony-doped ternary precursor through a co-precipitation method, and further uses a molten salt method to sinter to prepare a ternary cathode material.
  • the low melting point property of the bismuth/antimony oxide is utilized. , melt the bismuth/antimony oxide doped in the precipitate into the molten salt, thereby achieving the separation of bismuth/antimony and nickel, cobalt and manganese, leaving atomic vacancies inside the crystal lattice, while further increasing the specific capacity of the material. It can effectively buffer the volume changes caused by subsequent charging and discharging of the ternary cathode material, and improve the cycle stability of the material.
  • the reaction principle is as follows:
  • Nitric acid dissolves bismuth/antimony oxide:
  • the remaining molten salt is removed by washing with water.
  • the remaining bismuth/antimony oxide undergoes further annealing reaction to form a coating layer on the surface of the cathode material, further improving the cycle performance of the material.
  • Figure 1 is an SEM image of the ternary cathode material prepared in Example 1 of the present invention.
  • a method for preparing ternary cathode materials from molten salt is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 8:1:1, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 1.0 mol/L. liquid metal;
  • Step 2 Add bismuth trioxide to the nickel-cobalt-manganese metal liquid, and add nitric acid with a mass concentration of 40% to completely dissolve it.
  • the total molar ratio of bismuth to nickel-cobalt-manganese is 5:100 to obtain a mixed salt solution;
  • Step 3 prepare 8.0mol/L sodium hydroxide solution
  • Step 4 Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent
  • Step 5 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.0 and an ammonia concentration of 4.0g/L) until it covers the bottom stirring paddle and start stirring;
  • Step 6 Add the mixed salt solution, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to be 55°C, the pH to be 11.0, and the ammonia concentration to be 4.0g/L;
  • Step 7 When the D50 of the material in the reaction kettle is detected to reach 5.0 ⁇ m, stop feeding;
  • Step 8 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 9 The washed materials are dried, screened, and demagnetized in order to obtain a bismuth-doped ternary cathode material precursor;
  • Step 10 Take LiOH and 5 times molten salt (composed of 60% potassium chloride and 40% sodium chloride in mass percentage) according to 1.05 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 9;
  • Step 11 Mix the mixture on a planetary ball mill for 3 hours, then heat it up to 850°C for 24 hours in an oxygen atmosphere at 3°C/min, and then naturally cool to room temperature;
  • Step 12 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 100°C for 4 hours;
  • Step 13 anneal the dried material at 700°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the appearance of the particles was detected by scanning electron microscopy as shown in Figure 1.
  • the material particle size D50 measured by a laser particle size analyzer was 4.0 ⁇ m.
  • a method for preparing ternary cathode materials from molten salt is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 6:2:2, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 2.0 mol/L. liquid metal;
  • Step 2 Add antimony trioxide to the nickel-cobalt-manganese metal liquid, and add nitric acid with a mass concentration of 40% to completely dissolve it.
  • the total molar ratio of antimony to nickel-cobalt-manganese is 2:100 to obtain a mixed salt solution;
  • Step 3 prepare 10.0mol/L sodium hydroxide solution
  • Step 4 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 5 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.5 and an ammonia concentration of 5.0g/L) until it covers the bottom stirring paddle and start stirring;
  • the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.5 and an ammonia concentration of 5.0g/L
  • Step 6 Add the mixed salt solution, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to be 65°C, the pH to be 11.5, and the ammonia concentration to be 5.0g/L;
  • Step 7 When the D50 of the material in the reaction kettle is detected to reach 2.0 ⁇ m, stop feeding;
  • Step 8 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 9 The washed materials are dried, screened, and demagnetized in order to obtain an antimony-doped ternary cathode material precursor;
  • Step 10 Take LiOH and 4 times molten salt (potassium chloride) 1.02 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 9;
  • Step 11 Mix the mixture on a planetary ball mill for 3 hours, then heat it to 800°C for 36 hours in an oxygen atmosphere at 5°C/min, and then naturally cool to room temperature;
  • Step 12 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 120°C for 2 hours;
  • Step 13 anneal the dried material at 650°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the material particle size D50 measured by a laser particle size analyzer was 4.5 ⁇ m.
  • a method for preparing ternary cathode materials from molten salt is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 5:2:3, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 1.5 mol/L. liquid metal;
  • Step 2 Add bismuth trioxide to the nickel-cobalt-manganese metal liquid, and add nitric acid with a mass concentration of 40% to completely dissolve it.
  • the total molar ratio of bismuth to nickel-cobalt-manganese is 8:100 to obtain a mixed salt solution;
  • Step 3 prepare 4.0mol/L sodium hydroxide solution
  • Step 4 Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent
  • Step 5 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 10.8 and an ammonia concentration of 2.0g/L) until it covers the bottom stirring paddle and start stirring;
  • Step 6 Add the mixed salt solution, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to 45°C, pH to 10.8, and ammonia concentration to 2.0g/L;
  • Step 7 When the D50 of the material in the reaction kettle is detected to reach 15.0 ⁇ m, stop feeding;
  • Step 8 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 9 The washed materials are dried, screened, and demagnetized in order to obtain a bismuth-doped ternary cathode material.
  • Step 10 Take LiOH and 5 times molten salt (composed of 50% potassium chloride and 50% sodium chloride in mass percentage) according to 1.08 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 9;
  • Step 11 Mix the mixture on a planetary ball mill for 2 hours, then heat it up to 900°C for 12 hours in an oxygen atmosphere at 5°C/min, and then naturally cool to room temperature;
  • Step 12 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 80°C for 5 hours;
  • Step 13 anneal the dried material at 700°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the material particle size D50 measured by a laser particle size analyzer was 16.6 ⁇ m.
  • a ternary cathode material was prepared in this comparative example.
  • the difference between Comparative Example 1 and Example 1 is that the precursor of Comparative Example 1 is not doped with bismuth trioxide.
  • the specific process is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 8:1:1, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 1.0 mol/L. liquid metal;
  • Step 2 prepare 8.0mol/L sodium hydroxide solution
  • Step 3 Prepare ammonia water with a concentration of 8.0 mol/L as a complexing agent
  • Step 4 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.0 and an ammonia concentration of 4.0g/L) until it covers the bottom stirring paddle and start stirring;
  • Step 5 Add the nickel-cobalt-manganese metal liquid, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to be 55°C, the pH to be 11.0, and the ammonia concentration to be 4.0g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 5.0 ⁇ m, stop feeding;
  • Step 7 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 8 The washed materials are dried, screened, and demagnetized in order to obtain the ternary cathode material precursor;
  • Step 9 Take LiOH and 5 times molten salt (composed of 60% potassium chloride and 40% sodium chloride in mass percentage) according to 1.05 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 8;
  • Step 10 Mix the mixture on a planetary ball mill for 3 hours, and then increase the temperature at 3°C/min in an oxygen atmosphere. Roast at 850°C for 24 hours, then cool to room temperature naturally;
  • Step 11 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 100°C for 4 hours;
  • Step 12 anneal the dried material at 700°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the material particle size D50 measured by a laser particle size analyzer was 4.0 ⁇ m.
  • a ternary cathode material was prepared in this comparative example.
  • the difference between Comparative Example 2 and Example 2 is that the precursor of Comparative Example 2 is not doped with antimony trioxide.
  • the specific process is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 6:2:2, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 2.0 mol/L. liquid metal;
  • Step 2 prepare 10.0mol/L sodium hydroxide solution
  • Step 3 Prepare ammonia water with a concentration of 12.0 mol/L as a complexing agent
  • Step 4 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 11.5 and an ammonia concentration of 5.0g/L) until it covers the bottom stirring paddle and start stirring;
  • Step 5 Add the nickel-cobalt-manganese metal liquid, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to be 65°C, the pH to be 11.5, and the ammonia concentration to be 5.0g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 2.0 ⁇ m, stop feeding;
  • Step 7 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 8 The washed materials are dried, screened, and demagnetized in order to obtain the ternary cathode material precursor;
  • Step 9 Take LiOH and 4 times molten salt (potassium chloride) 1.02 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 8;
  • Step 10 Mix the mixture on a planetary ball mill for 3 hours, then heat it up to 800°C for 36 hours in an oxygen atmosphere at 5°C/min, and then naturally cool to room temperature;
  • Step 11 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 120°C for 2 hours;
  • Step 12 anneal the dried material at 650°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the material particle size D50 measured by a laser particle size analyzer was 4.5 ⁇ m.
  • a ternary cathode material is prepared in this comparative example.
  • the difference between Comparative Example 3 and Example 3 is that the precursor of Comparative Example 3 is not doped with bismuth trioxide.
  • the specific process is:
  • Step 1 According to the required molar ratio of nickel, cobalt, and manganese elements, that is, 5:2:3, select nickel nitrate, cobalt nitrate, and manganese nitrate as raw materials respectively, and prepare nickel, cobalt, and manganese with a total metal ion concentration of 1.5 mol/L. liquid metal;
  • Step 2 prepare 4.0mol/L sodium hydroxide solution
  • Step 3 Prepare ammonia water with a concentration of 6.0 mol/L as a complexing agent
  • Step 4 Add the bottom liquid to the reaction kettle (the bottom liquid is a mixture of sodium hydroxide and ammonia water, with a pH value of 10.8 and an ammonia concentration of 2.0g/L) until it covers the bottom stirring paddle and start stirring;
  • Step 5 Add the nickel-cobalt-manganese metal liquid, sodium hydroxide solution and ammonia water into the reaction kettle in parallel flow for reaction. Control the reaction temperature in the kettle to be 45°C, the pH to be 10.8, and the ammonia concentration to be 2.0g/L;
  • Step 6 When the D50 of the material in the reaction kettle is detected to reach 15.0 ⁇ m, stop feeding;
  • Step 7 perform solid-liquid separation of the materials in the kettle, and wash the solid product with pure water
  • Step 8 The washed materials are dried, screened, and demagnetized in order to obtain the ternary cathode material precursor;
  • Step 9 Take LiOH and 5 times molten salt (composed of 50% potassium chloride and 50% sodium chloride in mass percentage) according to 1.08 times the sum of the molar amounts of nickel, cobalt and manganese, and mix them with the precursor obtained in step 8;
  • Step 10 Mix the mixture on a planetary ball mill for 2 hours, then heat it up to 900°C for 12 hours in an oxygen atmosphere at 5°C/min, and then naturally cool to room temperature;
  • Step 11 Wash the roasted product with deionized water to remove remaining molten salt, and dry it at 80°C for 5 hours;
  • Step 12 anneal the dried material at 700°C, crush, sieve, and remove iron to prepare the ternary cathode material.
  • the material particle size D50 measured by a laser particle size analyzer was 16.6 ⁇ m.
  • the positive electrode materials obtained in the Examples and Comparative Examples were formed into button batteries for electrochemical performance testing of lithium ion batteries.
  • the specific steps were: using N-methylpyrrolidone as the solvent, the positive electrode was mixed in a mass ratio of 8:1:1.
  • the active material is evenly mixed with acetylene black and PVDF, coated on aluminum foil, air dried at 80°C for 8 hours, and then vacuumed at 120°C. Dry for 12h.
  • 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, and the cycle performance is tested at a rate of 0.1C.
  • Table 1 The results are shown in Table 1.
  • the specific capacity and cycle performance of the embodiment are better than those of the corresponding comparative example. This is because the precursor of the embodiment is doped with bismuth/antimony, and the bismuth/antimony oxide is melted during the sintering process of the molten salt method. In the molten salt, atomic vacancies are left inside the crystal lattice, which can further increase the specific capacity of the material and effectively buffer the volume changes caused by subsequent charge and discharge of the ternary cathode material, thus improving the cycle stability of the material. At the same time, the coating layer formed by the annealing reaction of the remaining bismuth/antimony oxide after washing will further improve the material's cycle performance.

Abstract

一种熔融盐制备三元正极材料的方法及其应用，所述方法包括：将镍盐、钴盐、锰盐、金属氧化物和酸液混合，得混合盐溶液；向底液中并流加入混合盐溶液、氢氧化钠溶液和氨水进行反应得前驱体；将前驱体、锂源和熔盐混合焙烧，焙烧料经过水洗，再退火处理，得三元正极材料。先制备掺杂铋/锑的三元前驱体，再利用熔盐法烧结，期间铋/锑氧化物熔于熔盐中，经水洗除去剩余的熔盐，残留的铋/锑氧化物经退火反应在材料表面形成包覆层，提升材料的循环性能。

Description

熔融盐制备三元正极材料的方法及其应用 技术领域
本发明属于锂离子电池正极材料技术领域，具体涉及一种熔融盐制备三元正极材料的方法及其应用。
背景技术
锂离子电池因循环性能好、容量高、价格低廉、使用方便、安全和环保等优点而得到广泛应用。当今，随着市场对高能量密度等高性能电池需求的不断增长以及电动汽车的不断普及，电池正极材料的市场需求已呈现出快速增长态势。
目前，正极材料的合成方法有高温固相法、溶胶凝胶法、共沉淀法、喷雾干燥法等。其中，高温固相法焙烧时间长，能耗大，混合不均匀，效率低，易混入杂质；溶胶凝胶法中，溶剂的使用和蒸发需要附加材料和能量消耗，合成过程时间长且工艺复杂；共沉淀法合成步骤复杂，耗时费力；喷雾干燥法可以合成纳米尺度的一次粒子，但是设备昂贵。
熔盐法以其工艺简单，反应时间短等特点正引起广泛关注。合成这些含锂正极材料，一般采用的是如LiCl、LiF、LiCO3、LiOH或LiNO3等锂盐，它们既作为溶剂又为目标产物提供锂源。熔盐的主要作用是在整个反应过程中充当“溶剂”和扩散介质的作用。反应原料一般在所选择的盐中有一定的溶解度，因此可以使反应物在液相中实现原子尺度的接触；另外，反应物在熔盐中具有更大的扩散速率，如熔盐中的离子迁移速率为1×10-5～1×10-8cm2/s，而在固相中仅为1×10-8cm2/s，这两种效应可以实现在较短时间及较低温度下发生反应。现有熔盐法制备粉体材料能提高材料结晶度，改善材料的振实密度，从而改善电池循环性能和倍率性能，但目前针对熔盐法制备出性能高的三元正极材料的研究仍然较少。
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，本发明提出熔融 盐制备三元正极材料的方法及其应用，该方法制备的三元正极材料具有较好的结晶度和晶格孔隙，能够缓冲材料的体积膨胀，提高材料的循环稳定性。
根据本发明的一个方面，提出了一种熔融盐制备三元正极材料的方法，包括以下步骤：
S1：将镍盐、钴盐、锰盐、金属氧化物和酸液混合，配制成混合盐溶液；其中所述金属氧化物为铋的氧化物或锑的氧化物；
S2：向底液中并流加入所述混合盐溶液、氢氧化钠溶液和氨水进行反应，当反应物料达到目标粒径，固液分离得到前驱体；
S3：将所述前驱体、锂源和熔盐混合，所得混合物进行球磨，后于氧气氛围下焙烧，得到焙烧料；
S4：所述焙烧料经过水洗，烘干，再进行退火处理，即得所述三元正极材料。
在本发明的一些实施方式中，步骤S1中，所述酸液为硝酸。进一步地，所述硝酸的质量浓度为30-50％。
在本发明的一些实施方式中，步骤S1中，先配制含所述镍盐、钴盐、锰盐的镍钴锰金属液，再向所述镍钴锰金属液中加入所述金属氧化物和酸液，所述镍钴锰金属液中镍钴锰离子总浓度为1.0-2.0mol/L。
在本发明的一些实施方式中，步骤S1中，所述混合盐溶液中铋或锑的摩尔量与镍钴锰总的摩尔量之比为(2-8)：100。
在本发明的一些实施方式中，步骤S2中，所述氢氧化钠溶液的浓度为4.0-10.0mol/L。
在本发明的一些实施方式中，步骤S2中，所述氨水的浓度为6.0-12.0mol/L。
在本发明的一些实施方式中，步骤S2中，所述底液为氢氧化钠和氨水的混合液，所述底液的pH为10.8-11.5，氨浓度为2.0-5.0g/L。
在本发明的一些实施方式中，步骤S2中，控制所述反应的温度为45℃-65℃，pH为10.8-11.5，氨浓度为2.0-5.0g/L。
在本发明的一些实施方式中，步骤S2中，所述反应物料的目标粒径D50为 2.0μm-15.0μm。
在本发明的一些实施方式中，步骤S3中，所述熔盐为氯化钠或氯化钾中的至少一种。
在本发明的一些实施方式中，步骤S3中，所述锂源为LiOH，所述锂源的用量为述前驱体中镍钴锰总摩尔量的1.02-1.08倍。
在本发明的一些实施方式中，步骤S3中，所述熔盐的用量为所述前驱体中镍钴锰总摩尔量的4-5倍。
在本发明的一些实施方式中，步骤S3中，所述焙烧的温度为800-900℃，焙烧的时间为12-36h。进一步地，所述焙烧的升温速率为2-5℃/min。
在本发明的一些实施方式中，步骤S3中，所述球磨的时间为2-3h。
在本发明的一些实施方式中，步骤S4中，所述烘干的温度为80-120℃，烘干的时间为2-5h。
在本发明的一些实施方式中，步骤S4中，所述退火处理的温度为650-700℃。
本发明还提供所述的方法在制备锂离子电池中的应用。
根据本发明的一种优选的实施方式，至少具有以下有益效果：
1、本发明首先通过共沉淀法制备得到掺杂铋/锑的三元前驱体，并进一步利用熔盐法烧结制取三元正极材料，在烧结过程中利用铋/锑氧化物的低熔点性质，将掺杂在沉淀物中的铋/锑氧化物熔于熔盐中，从而实现铋/锑与镍钴锰的分离，使晶格内部留出原子空位，在进一步提高材料比容量的同时，能有效缓冲后续的三元正极材料充放电带来的体积变化，提高材料的循环稳定性。其反应原理如下：
硝酸溶解铋/锑氧化物:
Bi2O3+6HNO3→2Bi(NO3)3+3H2O
共沉淀反应时:
xNi2++yCo2++zMn2++2OH-→NixCoyMnz(OH)2
Bi3++3OH-→Bi(OH)3
熔盐烧结时：
4NixCoyMnz(OH)2+O2+4LiOH→4LiNixCoyMnzO2+6H2O
2Bi(OH)3→Bi2O3+3H2O
2、熔盐烧结后，经水洗除去剩余的熔盐，残留的铋/锑氧化物经进一步的退火反应，在正极材料表面形成包覆层，进一步提升材料的循环性能。
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制备的三元正极体材料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
一种熔融盐制备三元正极材料的方法，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即8：1：1，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为1.0mol/L的镍钴锰金属液；
步骤2，向镍钴锰金属液中加入三氧化二铋，并加入质量浓度为40％的硝酸，使其全部溶解，铋与镍钴锰总的摩尔比为5:100，得到混合盐溶液；
步骤3，配制8.0mol/L氢氧化钠溶液；
步骤4，配制浓度为8.0mol/L的氨水作为络合剂；
步骤5，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.0，氨浓度为4.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤6，将混合盐溶液、氢氧化钠溶液和氨水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11.0，氨浓度为4.0g/L；
步骤7，当检测到反应釜内物料的D50达到5.0μm时，停止进料；
步骤8，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤9，洗涤后的物料依次进行干燥、过筛、除磁，即得到掺杂铋的三元正极材料前驱体；
步骤10，按照镍钴锰摩尔量之和的1.05倍取LiOH、5倍取熔盐(由质量百分比60％氯化钾和40％氯化钠组成)，与步骤9得到的前驱体混合；
步骤11，将混合物进行放在行星球磨机上混合3h，后于氧气氛围下以3℃/min升温至850℃焙烧24h，自然冷却至室温；
步骤12，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于100℃下烘干4h；
步骤13，将烘干料在700℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。
通过扫描电镜检测颗粒外观如图1所见，激光粒度仪测得材料粒度D50为4.0μm。
实施例2
一种熔融盐制备三元正极材料的方法，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即6：2：2，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为2.0mol/L的镍钴锰金属液；
步骤2，向镍钴锰金属液中加入三氧化二锑，并加入质量浓度为40％的硝酸，使其全部溶解，锑与镍钴锰总的摩尔比为2:100，得到混合盐溶液；
步骤3，配制10.0mol/L氢氧化钠溶液；
步骤4，配制浓度为12.0mol/L的氨水作为络合剂；
步骤5，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.5，氨浓度为5.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤6，将混合盐溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为65℃，pH为11.5，氨浓度为5.0g/L；
步骤7，当检测到反应釜内物料的D50达到2.0μm时，停止进料；
步骤8，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤9，洗涤后的物料依次进行干燥、过筛、除磁，即得到掺杂锑的三元正极材料前驱体；
步骤10，按照镍钴锰摩尔量之和的1.02倍取LiOH、4倍取熔盐(氯化钾)，与步骤9得到的前驱体混合；
步骤11，将混合物进行放在行星球磨机上混合3h，后于氧气氛围下以5℃/min升温至800℃焙烧36h，自然冷却至室温；
步骤12，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于120℃下烘干2h；
步骤13，将烘干料在650℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。通过激光粒度仪测得材料粒度D50为4.5μm。
实施例3
一种熔融盐制备三元正极材料的方法，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即5：2：3，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为1.5mol/L的镍钴锰金属液；
步骤2，向镍钴锰金属液中加入三氧化二铋，并加入质量浓度为40％的硝酸，使其全部溶解，铋与镍钴锰总的摩尔比为8:100，得到混合盐溶液；
步骤3，配制4.0mol/L氢氧化钠溶液；
步骤4，配制浓度为6.0mol/L的氨水作为络合剂；
步骤5，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为10.8，氨浓度为2.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤6，将混合盐溶液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为45℃，pH为10.8，氨浓度为2.0g/L；
步骤7，当检测到反应釜内物料的D50达到15.0μm时，停止进料；
步骤8，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤9，洗涤后的物料依次进行干燥、过筛、除磁，即得到掺杂铋的三元正极材料 前驱体；
步骤10，按照镍钴锰摩尔量之和的1.08倍取LiOH、5倍取熔盐(由质量百分比50％氯化钾和50％氯化钠组成)，与步骤9得到的前驱体混合；
步骤11，将混合物进行放在行星球磨机上混合2h，后于氧气氛围下以5℃/min升温至900℃焙烧12h，自然冷却至室温；
步骤12，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于80℃下烘干5h；
步骤13，将烘干料在700℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。通过激光粒度仪测得材料粒度D50为16.6μm。
对比例1
本对比例制备了一种三元正极材料，对比例1与实施例1的区别在于，对比例1的前驱体未掺杂三氧化二铋，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即8：1：1，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为1.0mol/L的镍钴锰金属液；
步骤2，配制8.0mol/L氢氧化钠溶液；
步骤3，配制浓度为8.0mol/L的氨水作为络合剂；
步骤4，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.0，氨浓度为4.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤5，将镍钴锰金属液、氢氧化钠溶液和氨水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11.0，氨浓度为4.0g/L；
步骤6，当检测到反应釜内物料的D50达到5.0μm时，停止进料；
步骤7，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤8，洗涤后的物料依次进行干燥、过筛、除磁，即得到三元正极材料前驱体；
步骤9，按照镍钴锰摩尔量之和的1.05倍取LiOH、5倍取熔盐(由质量百分比60％氯化钾和40％氯化钠组成)，与步骤8得到的前驱体混合；
步骤10，将混合物进行放在行星球磨机上混合3h，后于氧气氛围下以3℃/min升 温至850℃焙烧24h，自然冷却至室温；
步骤11，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于100℃下烘干4h；
步骤12，将烘干料在700℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。通过激光粒度仪测得材料粒度D50为4.0μm。
对比例2
本对比例制备了一种三元正极材料，对比例2与实施例2的区别在于，对比例2的前驱体未掺杂三氧化二锑，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即6：2：2，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为2.0mol/L的镍钴锰金属液；
步骤2，配制10.0mol/L氢氧化钠溶液；
步骤3，配制浓度为12.0mol/L的氨水作为络合剂；
步骤4，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为11.5，氨浓度为5.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤5，将镍钴锰金属液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为65℃，pH为11.5，氨浓度为5.0g/L；
步骤6，当检测到反应釜内物料的D50达到2.0μm时，停止进料；
步骤7，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤8，洗涤后的物料依次进行干燥、过筛、除磁，即得到三元正极材料前驱体；
步骤9，按照镍钴锰摩尔量之和的1.02倍取LiOH、4倍取熔盐(氯化钾)，与步骤8得到的前驱体混合；
步骤10，将混合物进行放在行星球磨机上混合3h，后于氧气氛围下以5℃/min升温至800℃焙烧36h，自然冷却至室温；
步骤11，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于120℃下烘干2h；
步骤12，将烘干料在650℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。通过激光粒度仪测得材料粒度D50为4.5μm。
对比例3
本对比例制备了一种三元正极材料，对比例3与实施例3的区别在于，对比例3的前驱体未掺杂三氧化二铋，具体过程为：
步骤1，按照所需镍、钴、锰元素的摩尔比例，即5：2：3，分别选用硝酸镍、硝酸钴、硝酸锰为原料，配制金属离子总浓度为1.5mol/L的镍钴锰金属液；
步骤2，配制4.0mol/L氢氧化钠溶液；
步骤3，配制浓度为6.0mol/L的氨水作为络合剂；
步骤4，向反应釜中加入底液(底液为氢氧化钠和氨水的混合液，其pH值为10.8，氨浓度为2.0g/L)至漫过底层搅拌桨，启动搅拌；
步骤5，将镍钴锰金属液、氢氧化钠溶液和氨水并流加入到反应釜中进行反应，控制釜内反应温度为45℃，pH为10.8，氨浓度为2.0g/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；
步骤7，将釜内物料进行固液分离，将固体产物用纯水洗涤；
步骤8，洗涤后的物料依次进行干燥、过筛、除磁，即得到三元正极材料前驱体；
步骤9，按照镍钴锰摩尔量之和的1.08倍取LiOH、5倍取熔盐(由质量百分比50％氯化钾和50％氯化钠组成)，与步骤8得到的前驱体混合；
步骤10，将混合物进行放在行星球磨机上混合2h，后于氧气氛围下以5℃/min升温至900℃焙烧12h，自然冷却至室温；
步骤11，将焙烧产物用去离子水洗涤，去除剩余熔盐，并于80℃下烘干5h；
步骤12，将烘干料在700℃下进行退火处理，经破碎、过筛、除铁，制得三元正极材料。通过激光粒度仪测得材料粒度D50为16.6μm。
试验例
将实施例和对比例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)。充放电截止电压为2.7-4.3V，测试在0.1C倍率下的循环性能，结果如表1所示。
表1
由表1可见，实施例的比容量和循环性能均优于其对应的对比例，这是由于实施例的前驱体掺杂了铋/锑，在熔盐法烧结过程中铋/锑氧化物熔于熔盐中，使晶格内部留出原子空位，在进一步提高材料比容量的同时，能有效缓冲后续的三元正极材料充放电带来的体积变化，从而提高了材料的循环稳定性。同时水洗后残留的铋/锑氧化物经退火反应，形成的包覆层也会进一步提升材料的循环性能。
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. 一种熔融盐制备三元正极材料的方法，其特征在于，包括以下步骤：
    S1：将镍盐、钴盐、锰盐、金属氧化物和酸液混合，配制成混合盐溶液；其中所述金属氧化物为铋的氧化物或锑的氧化物；
    S2：向底液中并流加入所述混合盐溶液、氢氧化钠溶液和氨水进行反应，当反应物料达到目标粒径，固液分离得到前驱体；
    S3：将所述前驱体、锂源和熔盐混合，将所得混合物进行球磨，后于氧气氛围下焙烧，得到焙烧料；
    S4：所述焙烧料经过水洗，烘干，再进行退火处理，即得所述三元正极材料。
  2. 根据权利要求1所述的方法，其特征在于，步骤S1中，先配制含所述镍盐、钴盐、锰盐的镍钴锰金属液，再向所述镍钴锰金属液中加入所述金属氧化物和酸液，所述镍钴锰金属液中镍钴锰离子总浓度为1.0-2.0mol/L。
  3. 根据权利要求1所述的方法，其特征在于，步骤S1中，所述混合盐溶液中铋或锑的摩尔量与镍钴锰总的摩尔量之比为(5-15)：100。
  4. 根据权利要求1所述的方法，其特征在于，步骤S2中，所述底液为氢氧化钠和氨水的混合液，所述底液的pH为10.8-11.5，氨浓度为2.0-5.0g/L。
  5. 根据权利要求1所述的方法，其特征在于，步骤S2中，控制所述反应的温度为45℃-65℃，pH为10.8-11.5，氨浓度为2.0-5.0g/L。
  6. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述熔盐为氯化钠或氯化钾中的至少一种。
  7. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述熔盐的用量为所述前驱体中镍钴锰总摩尔量的4-5倍。
  8. 根据权利要求1所述的方法，其特征在于，步骤S3中，所述焙烧的温度为800-900℃，焙烧的时间为12-36h。
  9. 根据权利要求1所述的方法，其特征在于，步骤S4中，所述退火处理的温度为 650-700℃。
  10. 如权利要求1-9中任一项所述的方法在制备锂离子电池中的应用。
PCT/CN2023/081688 2022-05-19 2023-03-15 熔融盐制备三元正极材料的方法及其应用 WO2023221624A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB2310923.4A GB2622915A (en) 2022-05-19 2023-03-15 Method for preparing ternary cathode material from molten salt and use thereof
DE112023000016.6T DE112023000016T5 (de) 2022-05-19 2023-03-15 Verfahren zur Herstellung von ternärem Kathodenmaterial mit geschmolzenem Salz und Verwendung davon
MA61729A MA61729A1 (fr) 2022-05-19 2023-03-15 Méthode de préparation de matériau de cathode ternary avec du sel fondu et son utilisation
ES202390117A ES2957485A2 (es) 2022-05-19 2023-03-15 Metodo para preparar un material de catodo ternario con una sal fundida y su uso
US18/371,465 US20240014391A1 (en) 2022-05-19 2023-09-22 Method for preparing ternary cathode material with molten salt and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210546053.8 2022-05-19
CN202210546053.8A CN114853087B (zh) 2022-05-19 2022-05-19 熔融盐制备三元正极材料的方法及其应用

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/371,465 Continuation US20240014391A1 (en) 2022-05-19 2023-09-22 Method for preparing ternary cathode material with molten salt and use thereof

Publications (1)

Publication Number Publication Date
WO2023221624A1 true WO2023221624A1 (zh) 2023-11-23

Family

ID=82638613

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/081688 WO2023221624A1 (zh) 2022-05-19 2023-03-15 熔融盐制备三元正极材料的方法及其应用

Country Status (2)

Country Link
CN (1) CN114853087B (zh)
WO (1) WO2023221624A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114853087B (zh) * 2022-05-19 2023-06-13 广东邦普循环科技有限公司 熔融盐制备三元正极材料的方法及其应用
ES2957485A2 (es) * 2022-05-19 2024-01-19 Guangdong Brunp Recycling Technology Co Ltd Metodo para preparar un material de catodo ternario con una sal fundida y su uso
CN116443954B (zh) * 2023-06-12 2023-11-17 宜宾锂宝新材料有限公司 正极材料及其制备方法、正极以及锂离子电池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106299348A (zh) * 2016-08-25 2017-01-04 合肥国轩高科动力能源有限公司 一种复合材料包覆镍锰酸锂的方法
CN111533183A (zh) * 2020-05-09 2020-08-14 中伟新材料股份有限公司 一种熔融金属包覆型的三元前驱体及其制备方法
CN111682174A (zh) * 2020-06-10 2020-09-18 广东邦普循环科技有限公司 一种锑包覆的锂电池正极材料及其制备方法和应用
CN113130877A (zh) * 2021-06-18 2021-07-16 长沙理工大学 一种掺杂与浸渍包覆同步修饰的多晶正极材料及其固相制备方法与应用
WO2022062677A1 (zh) * 2020-09-24 2022-03-31 广东邦普循环科技有限公司 一种三元单晶正极材料及其制备方法和应用
CN114853087A (zh) * 2022-05-19 2022-08-05 广东邦普循环科技有限公司 熔融盐制备三元正极材料的方法及其应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107017402A (zh) * 2017-06-07 2017-08-04 长沙理工大学 一种金属离子掺杂的锂离子电池层状正极材料及其制备方法
WO2022006033A1 (en) * 2020-07-01 2022-01-06 University Of Washington High energy li batteries with lean lithium metal anodes and methods for prelithiation
CN113241433B (zh) * 2021-05-17 2022-06-07 浙江帕瓦新能源股份有限公司 一种双掺杂包覆复合改性的三元正极材料及其制备方法
CN113437377A (zh) * 2021-06-15 2021-09-24 昆明理工大学 一种废旧三元正极材料单晶化再生方法
CN113830841A (zh) * 2021-09-17 2021-12-24 天津市捷威动力工业有限公司 一种正极固溶体材料及其制备方法和应用
CN114426313A (zh) * 2022-01-07 2022-05-03 云南大学 一种高能量密度三元正极材料及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106299348A (zh) * 2016-08-25 2017-01-04 合肥国轩高科动力能源有限公司 一种复合材料包覆镍锰酸锂的方法
CN111533183A (zh) * 2020-05-09 2020-08-14 中伟新材料股份有限公司 一种熔融金属包覆型的三元前驱体及其制备方法
CN111682174A (zh) * 2020-06-10 2020-09-18 广东邦普循环科技有限公司 一种锑包覆的锂电池正极材料及其制备方法和应用
WO2022062677A1 (zh) * 2020-09-24 2022-03-31 广东邦普循环科技有限公司 一种三元单晶正极材料及其制备方法和应用
CN113130877A (zh) * 2021-06-18 2021-07-16 长沙理工大学 一种掺杂与浸渍包覆同步修饰的多晶正极材料及其固相制备方法与应用
CN114853087A (zh) * 2022-05-19 2022-08-05 广东邦普循环科技有限公司 熔融盐制备三元正极材料的方法及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QING REN‐PENG, SHI JI‐LEI, XIAO DONG‐DONG, ZHANG XU‐DONG, YIN YA‐XIA, ZHAI YUN‐BO, GU LIN, GUO YU‐GUO: "Enhancing the Kinetics of Li‐Rich Cathode Materials through the Pinning Effects of Gradient Surface Na + Doping", ADVANCED ENERGY MATERIALS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 6, no. 6, 1 March 2016 (2016-03-01), DE , XP093110214, ISSN: 1614-6832, DOI: 10.1002/aenm.201501914 *

Also Published As

Publication number Publication date
CN114853087B (zh) 2023-06-13
CN114853087A (zh) 2022-08-05

Similar Documents

Publication Publication Date Title
US11855285B2 (en) Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof
WO2023221624A1 (zh) 熔融盐制备三元正极材料的方法及其应用
WO2020043135A1 (zh) 三元正极材料及其制备方法、锂离子电池
CN102694167B (zh) 改性锰酸锂正极材料及其制备方法
CN110649252A (zh) 锂电池三元材料LiNi0.8Co0.1Mn0.1O2表面包覆Li2ZrO3的方法
CN109192972A (zh) 多元素混合掺杂包覆改性三元正极材料及其制备方法
CN112928253B (zh) 一种镍锰钛复合材料及其制备方法和应用
CN107978751A (zh) 一种高电化学活性三元正极材料及其制备方法
CN111564606B (zh) 一种锂离子电池用包覆型多元正极材料、其制备方法及用途
CN111180724B (zh) 一种三元单晶正极材料的制备方法
CN112299487B (zh) 一种层内阳离子无序的全锰或高锰基富锂层状正极材料及其制备方法
CN110391417B (zh) 一种类单晶富锂锰基正极材料的制备方法
CN106207158B (zh) 富锂锰酸锂正极材料的制备方法
CN102983326A (zh) 一种球形锂镍钴复合氧化物正极材料的制备方法
WO2023226554A1 (zh) 一种高电压镍钴锰酸锂正极材料及其制备方法和应用
WO2022089205A1 (zh) 一种掺杂型高镍三元材料及其制备方法
WO2023179048A1 (zh) 一种氟铝共掺杂的钴酸锂正极材料及其制备方法
WO2023173777A1 (zh) 一种锡基钴酸锂前驱体的制备方法及其应用
CN115939336A (zh) 一种钠离子电池正极材料、正极片以及二次电池
CN109888225A (zh) 正极材料及其制备方法和锂离子电池
CN109713251A (zh) 锂离子电池正极材料及其制备方法和应用
WO2023221625A1 (zh) 大粒径单晶三元正极材料及其制备方法和应用
TWI550938B (zh) 鋰離子電池正極材料及其製備方法
CN105958061A (zh) 一种镍钴铝三元正极材料的制备方法
CN103413928B (zh) 高容量高压实金属氧化物正极材料及其制备方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 202310923

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20230315

WWE Wipo information: entry into national phase

Ref document number: 112023000016

Country of ref document: DE

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

Ref document number: 23806584

Country of ref document: EP

Kind code of ref document: A1