WO2026001026A1 - 电极材料的制备方法、电极材料、电极片、电池及用电装置 - Google Patents

电极材料的制备方法、电极材料、电极片、电池及用电装置

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Publication number
WO2026001026A1
WO2026001026A1 PCT/CN2025/078581 CN2025078581W WO2026001026A1 WO 2026001026 A1 WO2026001026 A1 WO 2026001026A1 CN 2025078581 W CN2025078581 W CN 2025078581W WO 2026001026 A1 WO2026001026 A1 WO 2026001026A1
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Prior art keywords
coating layer
electrode
mixed solution
electrode material
preparation
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PCT/CN2025/078581
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English (en)
French (fr)
Inventor
邱嵩
覃卫峰
杨静芳
冉坤
赵雷
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BYD Co Ltd
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BYD Co Ltd
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Publication of WO2026001026A1 publication Critical patent/WO2026001026A1/zh
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Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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

  • This disclosure relates to the field of battery technology, and in particular to a method for preparing an electrode material, an electrode material, an electrode sheet, a battery, and an electrical device.
  • This disclosure provides a new technical solution for the preparation method of electrode materials.
  • a method for preparing an electrode material includes: mixing a transition metal oxide with raw materials of lithium manganese iron phosphate and performing a first calcination to obtain a first material; mixing the first material, a core, and a first conductive agent to obtain a second material, the second material comprising a core and a first coating layer covering the core; and forming a second coating layer outside the first coating layer, the second coating layer comprising a conductive agent.
  • the formation of a second coating layer outside the first coating layer, the second coating layer comprising a conductive agent includes:
  • the second carbon-containing organic compound and the second material are mixed and calcined a second time to obtain the electrode material, which includes a core, a first coating layer covering the core, and a second coating layer covering the first coating layer.
  • the raw materials for the lithium manganese iron phosphate material include: lithium source, manganese source, iron source and phosphorus source.
  • the molar ratio of manganese to iron in the manganese source and the iron source is x:(1-x), where x is any value from 0.3 to 0.9.
  • the process of mixing the transition metal oxide with the raw materials of lithium manganese iron phosphate and performing a first calcination to obtain a first material includes: dissolving a lithium source, a manganese source, an iron source, and a phosphorus source in a first solvent to obtain a first mixed solution; dissolving the transition metal oxide and a first carbon-containing organic compound in the first mixed solution to obtain a second mixed solution; and performing a first calcination on the second mixed solution to obtain the first material.
  • the molar ratio of the transition metal oxide to lithium manganese iron phosphate is a, and the molar ratio of the first carbon-containing organic compound to lithium manganese iron phosphate is a/3, where a is any value from 0.03 to 0.2.
  • the temperature of the first calcination is 400°C to 950°C, and the temperature is held for 1 hour to 3 hours after reaching the whole number of degrees.
  • mixing the first material, the core, and the first conductive agent to obtain the second material includes: dissolving a portion of the first material, the nickel-cobalt-manganese material, and the first conductive agent in a second solvent and mixing them to obtain a third mixed solution; and drying the mixed third mixed solution.
  • the method further includes: adding another portion of the first material, the product of the dried third mixed solution, and the second conductive agent to a third solvent and mixing them to obtain a fourth mixed solution; and drying the mixed fourth mixed solution to obtain the second material.
  • the second carbon-containing organic compound and the second material are mixed and then calcined a second time to obtain the electrode material, wherein the molar ratio of the second carbon-containing organic compound to the second material is b, and b is any value from 0.01 to 0.15.
  • the temperature of the second calcination is 700°C to 1000°C, and the temperature is maintained for 0.5 to 1.5 hours when the temperature rise is an integer multiple of 100°C.
  • This electrode material is prepared according to the preparation method described above.
  • the electrode sheet includes a sheet body and the aforementioned electrode material, wherein the electrode material is disposed on the surface of the sheet body.
  • the battery includes the electrode plates described above.
  • This electrical device includes one of the following: the battery described above, the electrode sheet described above, or the electrode material described above.
  • the preparation method is simple to operate and the resulting electrode material has stable properties.
  • the electrode material prepared by this method includes a core and two coating layers covering the core.
  • the two coating layers effectively reduce the contact between the electrolyte and the nickel-cobalt-manganese material, improving the surface stability of the electrode material and effectively suppressing the exothermic reaction between the electrolyte and the nickel-cobalt-manganese material under abuse conditions such as overcharging, short circuits, heating, and needle penetration, thereby improving the cycle stability and safety performance of the electrode material.
  • the conductive agent can improve the conductivity of the electrode material and reduce the internal resistance of the battery.
  • Figure 1 is a schematic diagram of the structure of a cathode material according to some embodiments.
  • Figure 2 is a magnified view of a portion of Figure 1.
  • any value should be interpreted as merely exemplary and not as a limitation. Therefore, other examples in some embodiments may have different values.
  • the positive electrode of lithium-ion batteries typically includes nickel-cobalt-manganese ternary materials. These nickel-cobalt-manganese ternary materials have poor stability during use, are prone to failure, and have high internal resistance.
  • some embodiments of this disclosure provide a method for preparing an electrode material.
  • the method includes: mixing a transition metal oxide with raw materials of lithium manganese iron phosphate and performing a first calcination to obtain a first material; mixing the first material, a core, and a first conductive agent to obtain a second material, the second material comprising a core and a first coating layer 2 covering the core; and forming a second coating layer 3 outside the first coating layer 2, the second coating layer comprising a conductive agent.
  • the core 1 is a ternary material, such as nickel-cobalt-manganese material.
  • the ternary material includes at least one of NCM111, NCM523, NCM622, and NCM811.
  • the core 1 is a powder with a particle size in the micrometer range.
  • the particle size of kernel 1 is less than or equal to 5 ⁇ m.
  • the particle size of kernel 1 is 0.5 ⁇ m to 1 ⁇ m.
  • the particle size of kernel 1 is 0.5 ⁇ m, 0.6 ⁇ m, 0.8 ⁇ m to 1 ⁇ m.
  • core 1 exhibits high activity and high electrochemical stability.
  • a first coating layer 2 is applied to the core 1 using a physical coating method, and a second coating layer 3 is applied to the first coating layer 2.
  • Transition metal-doped lithium manganese iron phosphate ( LiMnPO4 , abbreviated as LMP) materials combine the stability and high voltage characteristics of an olivine-type phosphate structure. By doping with different transition metal oxides, lithium manganese iron phosphate materials can achieve better electrochemical performance, such as high structural stability, conductivity, and cycling performance.
  • the lithium source includes at least one selected from lithium hydroxide, lithium carbonate, lithium chloride, and lithium oxide.
  • the manganese source includes at least one selected from manganese dioxide, manganese tetroxide, and manganese sulfate.
  • the iron source includes at least one selected from ferrous sulfate, ferric nitrate, ferric oxide, iron powder, ferrous oxalate, and ferric phosphate.
  • the phosphorus source includes at least one selected from phosphoric acid, ammonium dihydrogen phosphate, or diammonium hydrogen phosphate.
  • transition metal oxides are used to provide transition metal elements. Transition metal oxides are introduced during the preparation of lithium manganese iron phosphate materials. These oxides can act as dopant and modifiers, improving the ionic conductivity of lithium manganese iron phosphate materials.
  • transition metal oxides also form nano-metal oxides on the surface of lithium manganese iron phosphate materials.
  • the transition metal oxides react with residual lithium carbonate, lithium hydroxide, and other substances on the surface of the lithium manganese iron phosphate material to form lithium-ion conductors, thereby reducing the residual alkali content of the lithium manganese iron phosphate material, improving its ability to conduct lithium ions, and enhancing the bonding force between the first coating layer 2 and the second coating layer 3.
  • a transition metal-doped lithium manganese iron phosphate material namely the first material, can be formed.
  • the first material, the core 1, and the first conductive agent are mixed to obtain the second material, which includes the core 1 and a first coating layer 2 covering the core 1.
  • the particle size of core 1 is less than or equal to 5 ⁇ m.
  • the particle size of core 1 is 0.5 ⁇ m to 1 ⁇ m.
  • the first material is particulate, and the particle size of the first material is in the nanometer range, for example, the particle size of the first material is less than or equal to 100 ⁇ m. Since the particle size of core 1 is larger than the particle size of the first material, the first material can adhere to the surface of core 1 during the mixing process. For example, the particle size of the first material is greater than or equal to 40 ⁇ m. This particle size range not only facilitates the coating of the first coating layer 2 on the core, but also facilitates the coating of the second coating layer 3 on the first coating layer 2.
  • the raw materials for the lithium manganese iron phosphate material also include a first carbon-containing organic compound.
  • the first carbon-containing organic compound includes at least one of glucose, sucrose, fructose, cellulose, starch, etc.
  • the first solvent includes at least one of a ketone, an alcohol, and water.
  • Ketones include acetone, methyl ethyl ketone, butanone, cyclohexanone, etc.
  • Alcohols include methanol, ethanol, propanol, ethylene glycol, etc.
  • the above materials are added to the first solvent and mixed. Mixing may be performed using methods such as ultrasonic dispersion or mechanical stirring.
  • the mixed liquid undergoes a first calcination in a muffle furnace.
  • the calcination atmosphere is nitrogen or an inert gas. After calcination, a first material is obtained.
  • the formation of a second coating layer 3 outside the first coating layer 2, the second coating layer 3 comprising a conductive agent includes: mixing a second carbon-containing organic compound and a second material, and performing a second calcination to obtain the electrode material, the electrode material comprising a core 1, a first coating layer 2 covering the core 1, and a second coating layer 3 covering the first coating layer 2.
  • the second carbon-containing organic compound includes at least one selected from glucose, sucrose, fructose, cellulose, starch, etc. This substance can encapsulate the second material.
  • the second carbon-containing organic compound forms a conductive agent, which forms a second coating layer 3, covering the outside of the first coating layer 2.
  • the conductive agent is granular.
  • the particle size of the conductive agent is 20 ⁇ m to 35 ⁇ m.
  • the particle size of the conductive agent is smaller than that of the first material, therefore the second coating layer 3 can cover the outside of the first coating layer 2.
  • the molar ratio of manganese to iron in the manganese source and the iron source is x:(1-x), where x is any value from 0.3 to 0.9.
  • x is 0.3, 0.5, 0.75, or 0.9.
  • the general formula of lithium manganese iron phosphate material is LiMn x Fe 1-x PO 4.
  • x is 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9.
  • the manganese content in the first coating layer 2 is further reduced, thereby reducing manganese leaching and ensuring the stability of the performance of the first coating layer 2.
  • the step of mixing a lithium source, a manganese source, an iron source, a phosphorus source, a transition metal oxide, and a first carbon-containing organic compound in a first solvent and then performing a first calcination to obtain a first material includes: dissolving the lithium source, manganese source, iron source, and phosphorus source in the first solvent to obtain a first mixed solution; dissolving the transition metal oxide and the first carbon-containing organic compound in the first mixed solution to obtain a second mixed solution; and performing a first calcination on the second mixed solution to obtain the first material.
  • multiple raw materials are added in steps.
  • lithium source, manganese source, iron source and phosphorus source are added to a first solvent to dissolve and obtain a first mixed solution.
  • the above materials are relatively easy to disperse in the first solvent, so lithium source, manganese source, iron source and phosphorus source are added to the first solvent to dissolve at room temperature.
  • the transition metal oxides and the first carbon-containing organic compounds are not easily dispersed in the first mixed solution. Therefore, under heating conditions, the transition metal oxides and the first carbon-containing organic compounds are dispersed in the first mixed solution to obtain a second mixed solution.
  • the heating temperature is 60°C.
  • the ultrasonic dispersion time is 0.5 hours to 1 hour.
  • the heating temperature is not limited to 60°C; it can also be 50°C, 70°C, 80°C, etc. Those skilled in the art can set the temperature according to actual needs.
  • the first material is mixed by a multi-step dispersion process, resulting in a material with uniform quality.
  • the molar ratio of the transition metal oxide, the first carbon-containing organic compound, and lithium manganese iron phosphate is 3a:a:3, for example, a is any value from 0.03 to 0.2 (e.g., 0.03, 0.05, 0.1, 0.15, or 0.2).
  • transition metal oxides can effectively dope and modify lithium manganese iron phosphate, and the first carbon-containing organic compound can enable the transition metal-doped lithium manganese iron phosphate material to form nanomaterials.
  • the temperature of the first calcination is 400°C to 950°C (e.g., 400°C, 500°C, 600°C, 700°C, 800°C, or 900°C, etc.), and the temperature is held for 1 hour to 3 hours (e.g., 1 hour, 2 hours, or 3 hours, etc.) when the temperature rises to a whole number of 100°C.
  • the first sintering temperature allows transition metal-doped lithium manganese iron phosphate materials to form nanomaterials.
  • the temperature is held for 1 to 3 hours after reaching a whole number of degrees.
  • heat preservation ensures that the transition metal oxide, the first carbon-containing organic compound, and lithium manganese iron phosphate have sufficient time to undergo a complete chemical reaction at the set high temperature, forming the desired compound phase.
  • Heat preservation promotes the growth of the crystal lattice in the transition metal-doped lithium manganese iron phosphate material, increasing the material's crystallinity. High crystallinity facilitates rapid lithium-ion diffusion.
  • heat preservation helps form a more stable crystal structure, effectively improving the material's electrochemical performance and cycle stability. Heat preservation also reduces thermal stress caused by rapid cooling, reduces microstructural defects in the crystal structure, reduces thermal decomposition at high temperatures, and maintains the material's chemical stability.
  • the duration of heat preservation can control the material's microstructure, including grain size and shape. Heat preservation also helps increase the density of the sintered body, reduce porosity, and improve the battery's energy density and power density.
  • the temperature for the first sintering is 800°C.
  • the temperature is gradually increased to 800°C at a rate of 5°C/minute.
  • the first material is obtained.
  • the temperature steps are performed in multiple steps with critical values in whole hundredths such as 200°C to 400°C.
  • the temperature range is 25°C ⁇ 200°C ⁇ 400°C ⁇ 600°C ⁇ 800°C.
  • Each temperature step is maintained at this constant temperature for 2 hours. That is, the temperature is maintained at 200°C, 400°C, 600°C, and 800°C for 2 hours each.
  • the resulting transition metal-doped lithium manganese iron phosphate material exhibits good crystal structure, few defects, low thermal stress, high material density, good chemical stability, and high energy and power density.
  • insulation can be performed at 100°C, 300°C, 500°C, 700°C, or 800°C.
  • insulation can be performed at 200°C, 300°C, 600°C, 700°C, or 800°C.
  • the insulation temperature can be set according to actual needs.
  • mixing the first material, core 1, and first conductive agent to obtain the second material includes: dissolving a portion of the first material, the nickel-cobalt-manganese material, and the first conductive agent in a second solvent, and mixing them by ultrasonic dispersion to obtain a third mixed solution; ball milling the third mixed solution; and spray drying the ball-milled third mixed solution.
  • the nickel-cobalt-manganese material includes at least one of NCM111, NCM523, NCM622, and NCM811.
  • the first conductive agent may be, but is not limited to, carbon materials 2-3.
  • the second solvent includes at least one of ketones, alcohols, and water.
  • the first material, nickel-cobalt-manganese material, and first conductive agent are added to the second solvent and mixed using methods such as mechanical stirring and ultrasonic dispersion.
  • the mixed solution is then dried using methods such as spray drying and heat drying. After drying, the second material is obtained.
  • the second solvent is ethanol.
  • a portion of the first material, the nickel-cobalt-manganese material, and the first conductive agent are added to ethanol for dissolution.
  • ultrasonic dispersion is performed at 60°C for 0.5 to 1 hour to finally obtain the third mixed solution.
  • the third mixed solution is ball milled.
  • the third mixed solution is added to a ball mill jar and ball milled for 2 hours.
  • the ball milling speed is 300 rpm to 600 rpm (e.g., 300 rpm, 400 rpm, 500 rpm, or 600 rpm), and the number of ball milling cycles is 2 or 3.
  • Ball milling reduces the particle size of the raw material powder through mechanical force, forming fine primary particles. This helps increase the specific surface area of the material, thereby increasing the diffusion rate of lithium ions and improving the charge and discharge rate of the battery. Ball milling can promote solid-state reactions, especially in the second calcination, increasing the reaction rate and facilitating the synthesis of electrode materials with specific structures and properties. Ball milling can increase the compaction density of the electrode material, reducing interparticle voids and contributing to improved battery energy density. Furthermore, ball milling introduces more defects and grain boundaries, which can act as rapid diffusion channels for lithium ions, improving the conductivity of the electrode material.
  • the ball-milled third mixed solution is spray-dried.
  • spray-drying parameters such as spray speed, hot air temperature, and drying rate
  • the particle morphology and size of the resulting electrode material powder can be controlled, thereby affecting the charge-discharge performance of the electrode material.
  • Spray-dried particles typically have smaller size and higher specific surface area, which helps to improve the diffusion rate of lithium ions, thus enhancing the charge-discharge efficiency of the battery.
  • Spray drying can produce electrode materials with excellent electrochemical performance, such as high capacity, high rate performance, and excellent cycle stability.
  • the method further includes: adding another portion of the first material, the second material, and the second conductive agent to a third solvent, mixing them by ultrasonic dispersion to obtain a fourth mixed solution; ball milling the fourth mixed solution; and spray drying the ball-milled fourth mixed solution.
  • the second conductive agent includes carbon materials 2-3.
  • the third solvent includes at least one of ketones, alcohols, and water. Another portion of the first material, the second material, and the second conductive agent are added to the third solvent and then mixed using methods such as mechanical stirring or ultrasonic dispersion. The mixed solution is then dried using methods such as spray drying or heat drying. After drying, the second material is obtained.
  • a fourth mixed solution another portion of the first material, the second material, and the second conductive agent are added to a third solvent and mixed using ultrasonic dispersion.
  • the third solvent is ethanol.
  • the first material, the second material, and the second conductive agent are dissolved in ethanol.
  • the mixture is then ultrasonically dispersed at 60°C for 1 to 2 hours to finally obtain the fourth mixed solution.
  • the fourth mixed solution is ball milled.
  • the fourth mixed solution is added to a ball mill jar and ball milled for 2 hours.
  • the ball milling speed is 300 to 600 rpm, and the number of milling cycles is 2 or 3.
  • the ball-milled fourth mixed solution is spray dried to obtain the second material.
  • the second coating layer 3 can be made to form a high-concentration layer 2-1 and a low-concentration layer 2-2.
  • the second carbon-containing organic compound and the second material are mixed and then calcined a second time to obtain the electrode material, wherein the molar ratio of the second carbon-containing organic compound to the second material is b, and b is any value from 0.01 to 0.15.
  • the second carbon-containing organic compound includes at least one of glucose, sucrose, fructose, cellulose, starch, etc.
  • the fourth solvent includes at least one of ketones, alcohols, and water.
  • Ketones include acetone, methyl ethyl ketone, butanone, cyclohexanone, etc.
  • Alcohols include methanol, ethanol, propanol, ethylene glycol, etc.
  • the second material and the second carbon-containing organic compound are added to the fourth solvent and then mixed using mechanical stirring, ultrasonic dispersion, or other methods.
  • the mixed solution is then added to a muffle furnace and calcined a second time under an inert gas or nitrogen atmosphere. After the second calcination, the electrode materials in some embodiments of this disclosure are obtained.
  • the second carbon-containing organic compound is glucose.
  • the fourth solvent is ethanol.
  • the solution of the second material, the second carbon-containing organic compound, and the fourth solvent is ultrasonically dispersed at 60°C for 1 to 2 hours. Then, the ultrasonically dispersed solution is placed in a muffle furnace for a second calcination.
  • the molar ratio of the second carbon-containing organic compound to the second material is b, where b is any value from 0.01 to 0.15.
  • the molar ratio of glucose to the second material is 0.01 to 0.15.
  • Glucose is converted into carbon material 2-3 during high-temperature calcination.
  • Carbon material 2-3 serves as a conductive agent, i.e., the second coating layer 3.
  • the thickness of the second coating layer 3 is uniform with few defects.
  • the second coating layer 3 significantly improves the conductivity of the electrode material, thereby reducing the internal resistance of the battery.
  • the second coating layer 3 can also act as a protective layer, reducing side reactions between the electrode material and the electrolyte during charging and discharging, thereby improving the cycle stability of the battery.
  • the second coating layer 3 helps to form a stable chemical and electrochemical reaction interface on the surface of the electrode material, reducing electrolyte decomposition.
  • the second coating layer 3 can also buffer the volume changes of the electrode material during charging and discharging, reducing structural stress and improving the structural stability of the electrode material.
  • the temperature of the second calcination is 700°C to 1000°C (e.g., 700°C, 800°C, 900°C, or 1000°C, etc.), and the holding time is 0.5 hours to 1.5 hours (e.g., 0.5 hours, 1 hour, or 1.5 hours, etc.) when the temperature rise is an integer multiple of 100°C.
  • the calcination atmosphere in the muffle furnace is nitrogen, and the temperature is increased to 700°C in steps at a rate of 5°C/min. This temperature is then held at 700°C. After natural cooling, the electrode material is obtained.
  • the temperature rises as follows: 25°C ⁇ 100°C ⁇ 200°C ⁇ 300°C ⁇ 400°C ⁇ 500°C ⁇ 600°C ⁇ 700°C.
  • the temperature is held constant for 1 hour, ultimately yielding the electrode material.
  • the final electrode material obtained has a core-shell structure containing a nickel-cobalt-manganese core 1, a transition metal-doped lithium manganese iron phosphate material as the first coating layer 2, and a conductive agent as the second coating layer 3.
  • the heating temperature during ultrasonic dispersion is not limited to 60°C, but can also be 50°C, 70°C, 80°C, etc. Those skilled in the art can set it according to actual needs.
  • nano-sized lithium manganese iron phosphate is prepared by first calcining a lithium source, a manganese source, an iron source, a phosphorus source, a transition metal oxide, and a first carbon-containing organic compound.
  • a lithium source a manganese source
  • an iron source a phosphorus source
  • a transition metal oxide a transition metal oxide
  • a first carbon-containing organic compound for example, manganese and iron exist in the form of divalent ions.
  • the anion is phosphate.
  • no reduction process is required, reducing structural defects in the electrode material caused by the reduction of Mn and Fe during electrode material preparation.
  • Transition metal oxides were introduced during the preparation of lithium manganese iron phosphate materials. These oxides can dope and modify the materials, thereby improving their ionic conductivity.
  • transition metal oxides can also form nano-metal oxides on the surface of lithium manganese iron phosphate materials.
  • the transition metal oxides react with residual lithium carbonate, lithium hydroxide, and other substances on the surface of the lithium manganese iron phosphate material to form lithium-ion conductors, thereby reducing the residual alkali content of the lithium manganese iron phosphate material, improving its ability to conduct lithium ions, and enhancing the bonding force between the first coating layer 2 and the second coating layer 3.
  • a conductive agent is filled in the gap between the transition metal oxide-doped lithium manganese iron phosphate material and the nickel cobalt manganese material.
  • the conductive agent can improve the ionic conductivity of the electrode material, and at the same time, it can effectively avoid direct contact between the transition metal oxide-doped lithium manganese iron phosphate material and the nickel cobalt manganese material, prevent spontaneous redox reactions between them, and improve the interfacial structural stability of the electrode material.
  • the above structure can isolate moisture, reducing the sensitivity of nickel-cobalt-manganese materials to environmental humidity and improving the storage and processing performance of electrode materials during use.
  • first coating layer 2 and the second coating layer 3 can effectively reduce the contact between the electrolyte and the nickel-cobalt-manganese material, improve the stability of the surface structure of the electrode material, and effectively suppress the exothermic reaction between the electrolyte and the nickel-cobalt-manganese material under conditions such as overcharging, short circuit, heating and needle penetration, thereby improving the cycle and safety performance of the electrode material.
  • secondary coating using mechanical processing can achieve a uniform and dense coating of transition metal oxide-doped lithium manganese iron phosphate material on the surface of nickel-cobalt-manganese material.
  • This preparation method is simple, efficient, and suitable for industrial production.
  • an electrode material is provided.
  • This electrode material is prepared according to the preparation method described above.
  • the electrode material includes a core 1 containing nickel-cobalt-manganese material, a first coating layer 2 covering the core 1, and a second coating layer 3 covering the first coating layer 2.
  • the first coating layer 2 comprises lithium manganese iron phosphate material doped with a transition metal
  • the second coating layer 3 comprises a conductive agent.
  • This electrode material serves as the positive electrode material. It has a core-shell structure.
  • the core 1 is a ternary material, namely nickel-cobalt-manganese.
  • the ternary material includes at least one of NCM111, NCM523, NCM622, and NCM811.
  • the first coating layer 2 covers the core 1.
  • Transition metal-doped lithium manganese iron phosphate ( LiMnPO4 , LMP) materials combine the stability of an olivine-type phosphate structure with high voltage characteristics. By doping with different transition metal oxides, LMP materials can achieve better electrochemical performance, such as high structural stability, conductivity, and cycling performance.
  • the second coating layer 3 is a conductive agent.
  • Conductive agents are used to increase electrical conductivity, thereby increasing the electron conduction path within the electrode material, reducing internal battery resistance, improving charge and discharge efficiency, and enhancing rate performance and cycle stability. Conductive agents also help reduce electrode reaction polarization, decrease energy loss, and increase the battery's operating voltage.
  • the electrode material is granular.
  • the average particle size of the core-shell structure is less than or equal to 10 ⁇ m. Within this range, the core-shell structure exhibits high structural strength and excellent electrochemical performance. For example, the average particle size is between 200 nm and 2 ⁇ m, and the electrochemical performance of the electrode material is even better within this range.
  • the electrode material includes a core 1 and two coating layers covering the core 1.
  • the two coating layers effectively reduce the contact between the electrolyte and the nickel-cobalt-manganese material, improving the surface stability of the electrode material and effectively suppressing exothermic reactions between the electrolyte and the nickel-cobalt-manganese material under abuse conditions such as overcharging, short circuits, heating, and needle penetration, thereby improving the cycle stability and safety performance of the electrode material.
  • the conductive agent improves the conductivity of the electrode material and reduces the internal resistance of the battery.
  • the first coating layer 2 includes a conductive agent, and the transition metal-doped lithium manganese iron phosphate material is mixed with the conductive agent.
  • transition metal-doped lithium manganese iron phosphate material is formed into particles.
  • a conductive agent is filled in the gaps between the particles. This conductive agent can further increase the electron conduction path within the electrode material, reduce the battery's internal resistance, improve the battery's charge/discharge efficiency, and enhance the battery's rate performance and cycle stability.
  • the conductive agent comprises carbon material 2-3.
  • Carbon material 2-3 has good electrical conductivity and can form good bonds with nickel-cobalt-manganese materials and transition metal-doped lithium manganese iron phosphate materials.
  • conductive agents are not limited to carbon materials 2-3, but can also be conductive polymers, etc. Those skilled in the art can configure them according to actual needs.
  • the dotted carbon material 2-3 includes at least one of carbon black, acetylene black, Ketjen black, and conductive graphite.
  • the linear carbon material 2-3 includes at least one of carbon fiber and carbon nanotubes.
  • the linear carbon material 2-3 has high strength and toughness, which can improve the mechanical properties of the electrode material and prevent deformation or breakage of the electrode material during charging and discharging.
  • the addition of the dotted carbon material 2-3 can also further enhance the structural stability of the electrode material.
  • carbon material 2-3 includes dot-shaped carbon material 2-3 and linear carbon material 2-3. Due to the excellent electrical conductivity of linear carbon material 2-3 and dot-shaped carbon material 2-3, mixing them together can effectively reduce the internal resistance of the electrode material, improve the charge and discharge efficiency of the battery, and increase the energy density of the battery.
  • carbon materials 2-3 are not limited to the above embodiments, and those skilled in the art can make settings according to actual needs.
  • the concentration of the transition metal-doped lithium manganese iron phosphate material in the first coating layer 2 gradually decreases from the side closer to the core 1 to the side closer to the second coating layer 3.
  • the concentration of transition metal-doped lithium manganese iron phosphate material in the first coating layer 2 gradually decreases from the inside to the outside.
  • the concentration of the conductive agent in the first coating layer 2 gradually increases from the inside to the outside. In this way, the closer the first coating layer 2 is to the outer layer, the better the electron transport performance, thereby effectively improving the conductivity of the electrode material.
  • the portion of the first coating layer 2 near the core 1 forms a high-concentration layer 2-1, while the portion near the second coating layer 3 forms a low-concentration layer 2-2.
  • the high-concentration layer 2-1 has a high concentration of transition metal-doped lithium manganese iron phosphate material, while the low-concentration layer 2-2 has a low concentration of transition metal-doped lithium manganese iron phosphate material.
  • This electrode material can more effectively balance high energy density and high conductivity.
  • the transition metal oxide includes a divalent transition metal oxide.
  • the divalent transition metal oxide introduced into the lithium manganese iron phosphate material can play a doping modification role, thereby significantly improving the ionic conductivity of the lithium manganese iron phosphate material.
  • divalent transition metal-doped lithium manganese iron phosphate (LMP) materials form nano-sized metal oxides, such as nano-sized divalent transition metal oxides, on the surface of LMP.
  • these nano-sized divalent transition metal oxides react with residual lithium carbonate, lithium hydroxide, and other materials on the surface of the LMP material to form lithium-ion conductors. This reduces the residual alkali content of the LMP material and improves its ability to conduct lithium ions, thereby enhancing the bonding force between the first coating layer 2 and the second coating layer 3.
  • the divalent transition metal oxide includes at least one of beryllium oxide, magnesium oxide, and calcium oxide.
  • the above materials all have good stability, can effectively reduce the residual alkali content of lithium manganese iron phosphate materials, improve the lithium ion conduction capacity of lithium manganese iron phosphate materials, and enhance the bonding force between the first coating layer 2 and the second coating layer 3.
  • the molar ratio of manganese to iron is x:(1-x), for example, x is any value from 0.3 to 0.9.
  • the general formula for lithium manganese iron phosphate materials is LiMnxFe1 -xPO4 .
  • x can be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9. Within this range, the manganese content in the first coating layer 2 is further reduced, decreasing manganese leaching and ensuring the stable performance of the first coating layer 2.
  • the molar ratio of the transition metal to the lithium manganese iron phosphate material is any value from 0.1% to 10%.
  • divalent transition metal oxides can effectively reduce the residual alkali content of lithium manganese iron phosphate materials, improve the lithium-ion conduction capacity of lithium manganese iron phosphate materials, and enhance the bonding force between the first coating layer 2 and the second coating layer 3.
  • an electrode sheet includes a sheet body and the electrode material described above, the electrode material being disposed on the surface of the sheet body.
  • the sheet body is a metal foil.
  • the material of the sheet body is copper, aluminum, nickel, etc.
  • Electrode materials of some embodiments of this disclosure are coated onto the surface of the metal foil by a coating method.
  • the electrode sheet has stable physicochemical properties.
  • a battery is provided.
  • the battery includes the electrode plates described above.
  • this electrode sheet is a positive electrode sheet.
  • the active material of the negative electrode sheet is graphite.
  • a separator is disposed between the positive and negative electrode sheets. The positive electrode sheet, separator, and negative electrode sheet are combined together by stacking or winding.
  • This battery features stable performance, high energy density, and long service life.
  • an electrical device includes the battery described above, or the electrode sheet described above, or the electrode material described above.
  • This electrical device is characterized by stable performance and long service life.

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Abstract

一种电极材料的制备方法、电极材料、电极片、电池及用电装置。该制备方法包括：将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料；将第一材料、内核以及第一导电剂混合，以得到第二材料，所述第二材料包括内核以及包覆在内核外的第一包覆层；在所述第一包覆层外形成第二包覆层，所述第二包覆层包括导电剂。

Description

电极材料的制备方法、电极材料、电极片、电池及用电装置
本申请要求于2024年06月28日提交的、申请号为202410869507.4的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及电池技术领域，尤其涉及一种电极材料的制备方法、电极材料、电极片、电池及用电装置。
背景技术
随着电化学储能装置的快速发展，高安全高稳定的锂离子储能系统如锂离子电池是电力行业发展的必然选择。锂离子电池是一种二次电池，包括电极材料，且主要通过电极材料中的锂离子在正极和负极之间往复移动来工作。
发明内容
本公开提供一种电极材料的制备方法的新技术方案。
第一方面，提供了一种电极材料的制备方法。该制备方法包括：将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料；将第一材料、内核以及第一导电剂混合，以得到第二材料，所述第二材料包括内核以及包覆在内核外的第一包覆层；以及在所述第一包覆层外形成第二包覆层，所述第二包覆层包括导电剂。
在一些实施例中，所述在所述第一包覆层外形成第二包覆层，所述第二包覆层包括导电剂，包括：
将第二含碳有机物、第二材料混合，并进行第二次煅烧，以得到所述电极材料，所述电极材料包括内核、包覆在所述内核外的第一包覆层以及包覆在所述第一包覆层外的第二包覆层。
在一些实施例中，所述磷酸锰铁锂材料的原料包括：锂源、锰源、铁源和磷源。
在一些实施例中，在所述锰源和所述铁源中，锰和铁的摩尔比为x:(1-x)，x为0.3至0.9中的任一值。
在一些实施例中，所述将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料，包括：将锂源、锰源、铁源和磷源加入第一溶剂中进行溶解，得到第一混合溶液；将过渡金属氧化物、第一含碳有机物在所述第一混合溶液中溶解，以得到第二混合溶液；以及将所述第二混合溶液进行第一次煅烧，以得到所述第一材料。
在一些实施例中，过渡金属氧化物与磷酸锰铁锂的摩尔比为a，第一含碳有机物与磷酸锰铁锂的摩尔比为a/3，a为0.03至0.2中的任一值。
在一些实施例中，第一次煅烧的温度为400℃至950℃，在温度升至整百温度时保温1小时至3小时。
在一些实施例中，所述将第一材料、内核以及第一导电剂混合，以得到第二材料，包括：将所述第一材料的一部分、镍钴锰材料、第一导电剂溶解在第二溶剂中混合，以得到第三混合溶液；以及将混合后的所述第三混合溶液进行干燥。
在一些实施例中，所述方法还包括：将所述第一材料的另一部分、所述第三混合溶液干燥后的产物、第二导电剂加入第三溶剂中混合，以得到第四混合溶液；以及将混合后的所述第四混合溶液进行干燥，以得到第二材料。
在一些实施例中，所述将第二含碳有机物、第二材料混合，并进行第二次煅烧，以得到所述电极材料中，第二含碳有机物与第二材料的摩尔比为b，b为0.01至0.15中的任一值。
在一些实施例中，所述第二次煅烧的温度为700℃至1000℃，在温度升值100的整数倍时，保温0.5小时至1.5小时。
第二方面，提供了一种电极材料。该电极材料根据上述的制备方法制备而成。
第三方面，提供了一种电极片。该电极片包括片材本体和上述的电极材料，所述电极材料设置在所述片材本体的表面。
第四方面，提供了一种电池。该电池包括上述的电极片。
第五方面，提供了一种用电装置。该用电装置包括以下之一：上述的电池，上述的电极片，或上述的电极材料。
根据本公开的一些实施例，该制备方法的操作简单，形成的电极材料性质稳定。该制备方法制备的电极材料包括内核以及包覆在内核外的两个包覆层。两个包覆层能有效地减少电解液与镍钴锰材料接触，提高了电极材料的表面稳定性，有效地抑制了电解液与镍钴锰材料之间在过充、短路、加热和针刺等滥用情况下的放热反应，从而提高了电极材料的循环稳定性和安全性能。导电剂能提高电极材料的导电性能降低电池的内阻。
通过以下参照附图对本公开的一些实施例的详细描述，本公开的其它特征及其优点将会变得清楚。
附图说明
被结合在说明书中并构成说明书的一部分的附图示出了本公开的一些实施例，并且连同其说明一起用于解释本公开的原理。
图1是根据一些实施例的正极材料的结构示意图。
图2是图1的局部放大图。
附图标记：
1、内核；2、第一包覆层；2-1、高浓度层；2-2、低浓度层；2-3、碳材料；3、第二包覆层。
具体实施方式
现在将参照附图来详细描述本公开的一些实施例。应注意到：除非另外说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本公开的范围。
以下对至少一个实施例的描述实际上仅仅是说明性的，决不作为对本公开及其应用或使用的任何限制。
对于相关领域普通技术人员已知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为说明书的一部分。
在这里示出和讨论的所有例子中，任何取值应被解释为仅仅是示例性的，而不是作为限制。因此，一些实施例中的其它例子可以具有不同的值。
应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。
相关技术中，锂离子电池的正极通常包括镍钴锰三元材料，这些镍钴锰三元材料在使用过程中稳定性差，容易失效，并且，镍钴锰三元材料的内阻较大。
基于此，本公开的本公开一些实施例提供了一种电极材料的制备方法。该制备方法包括：将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料；将第一材料、内核以及第一导电剂混合，以得到第二材料，所述第二材料包括内核以及包覆在内核外的第一包覆层2；以及在所述第一包覆层2外形成第二包覆层3，所述第二包覆层包括导电剂。
在本公开一些实施例中，如图1所示，内核1为三元材料，例如镍钴锰材料。
在一些实施例中，三元材料包括NCM111、NCM523、NCM622、NCM811中的至少一种。内核1为粉料，内核1的粒径为微米级。
在一些实施例中，内核1的粒径为小于或等于5μm。例如，内核1的粒径为0.5μm至1μm。例如，内核1的粒径为0.5μ、0.6μm、0.8μm至1μm。
可以理解的是，在该范围内，内核1的活性高，电化学稳定性高。
采用物理包覆的方式在内核1外包覆第一包覆层2以及在第一包覆层2外包覆第二包覆层3。过渡金属掺杂的磷酸锰铁锂(LiMnPO4，简称LMP)材料结合了橄榄石型磷酸盐结构的稳定性和高电压特性。通过掺杂不同的过渡金属氧化物，磷酸锰铁锂材料可以获得更好的电化学性能，例如高的结构稳定性、导电性能以及循环性能。
第二包覆层3为导电剂。导电剂用于导电，能够增加电极材料内部的电子传导路径，减少电池内阻，提高电池的充放电效率，还可以改善电池的倍率性能和循环稳定性。导电剂有助于降低电极反应的极化，减少能量损耗，提高电池的工作电压。该制备方法的工艺简单，能够形成性质稳定的电极材料。
在一些实施例中，所述在所述内核1外包覆形成第一包覆层2，所述第一包覆层2包括过渡金属掺杂的磷酸锰铁锂材料，包括：将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料；以及将第一材料、内核1以及第一导电剂混合，以得到第二材料，所述第二材料包括内核1以及包覆在内核1外的第一包覆层2。
在一些实施例中，磷酸锰铁锂材料的原料包括锂源、锰源、铁源和磷源。
在一些实施例中，锂源包括氢氧化锂、碳酸锂、氯化锂和氧化锂中的至少一种。锰源包括二氧化锰、四氧化三锰和硫酸锰中的至少一种。铁源包括硫酸亚铁、硝酸铁、氧化铁、铁粉、草酸亚铁和磷酸铁中的至少一种。磷源为包括磷酸、磷酸二氢铵或磷酸氢二铵中的至少一种。
可以理解的是，过渡金属氧化物用于提供过渡金属元素。在制备磷酸锰铁锂材料过程中引入了过渡金属氧化物。过渡金属氧化物可对磷酸锰铁锂材料起到掺杂、改性的作用，提高了磷酸锰铁锂材料的离子电导。
此外，过渡金属氧化物还会在磷酸锰铁锂材料的表面形成纳米金属氧化物。在退火处理时，过渡金属氧化物与磷酸锰铁锂材料表面残余的碳酸锂、氢氧化锂等物质反应形成锂离子导体，从而降低了磷酸锰铁锂材料的残碱含量，提高了磷酸锰铁锂材料传导锂离子的能力，增强了第一包覆层2与第二包覆层3的结合力。经过第一次煅烧，能够形成过渡金属掺杂的磷酸锰铁锂材料，即第一材料。
在包覆时，将第一材料、内核1以及第一导电剂混合，以得到第二材料，所述第二材料包括内核1以及包覆在内核1外的第一包覆层2。
需要说明的是，内核1的粒径为小于或等于5μm。例如，内核1的粒径为0.5μm至1μm。第一材料为颗粒料，且第一材料的粒径为纳米级，例如，第一材料的粒径小于或等于100μm。由于内核1的粒径比第一材料的粒径大，故在混合过程中，第一材料能够附着在内核1的表面。例如，第一材料的粒径大于或等于40μm。该粒径范围不仅便于第一包覆层2在内核的包覆，还便于第二包覆层3在第一包覆层2的包覆。
例如，为了提高第一材料的导电性能。磷酸锰铁锂材料的原料还包括第一含碳有机物。第一含碳有机物包括葡萄糖、蔗糖、果糖、纤维素、淀粉等中的至少一种。为了混合均匀磷酸锰铁锂材料的原料被添加到第一溶剂中。第一溶剂包括酮、醇、水中的至少一种。酮包括丙酮、甲乙酮、丁酮、环己酮等。醇包括甲醇、乙醇、丙醇、乙二醇等。在进行制备时，上述材料被添加到第一溶剂中，并进行混合。例如采用超声分散、机械搅拌等方式进行混合。
最后，混合后的液体在马弗炉中进行第一次煅烧。例如，煅烧的气氛为氮气或惰性气体。煅烧后得到第一材料。
在一些实施例中，所述在所述第一包覆层2外形成第二包覆层3，所述第二包覆层3包括导电剂，包括：将第二含碳有机物、第二材料混合，并进行第二次煅烧，以得到所述电极材料，所述电极材料包括内核1、包覆在所述内核1外的第一包覆层2以及包覆在所述第一包覆层2外的第二包覆层3。
在一些实施例中，第二含碳有机物包括葡萄糖、蔗糖、果糖、纤维素、淀粉等中的至少一种。上述物质能对第二材料形成包裹。在第二次煅烧后，第二含碳有机物形成导电剂，导电剂形成第二包覆层3，第二包覆层3包覆在第一包覆层2外。导电剂为颗粒料。导电剂的粒径为20μm至35μm。导电剂的粒径小于第一材料的粒径，故第二包覆层3能包覆在第一包覆层2的外侧。
在一些实施例中，在所述锰源和所述铁源中中，锰和铁的摩尔比为x:(1-x)，x为0.3至0.9中的任一值。例如，x为0.3、0.5、0.75或0.9。
在一些实施例中，磷酸锰铁锂材料的通式为LiMnxFe1-xPO4。例如，x为0.3、0.4、0.5、0.6、0.7、0.8、0.9。在该范围内，进一步降低了第一包覆层2中锰含量，减少锰溶出量，保证第一包覆层2的性能稳定。
在一些实施例中，所述将锂源、锰源、铁源、磷源、过渡金属氧化物、第一含碳有机物加入第一溶剂中进行混合，并进行第一次煅烧，以得到第一材料，包括：将锂源、锰源、铁源和磷源加入第一溶剂中进行溶解，得到第一混合溶液；将过渡金属氧化物、第一含碳有机物在所述第一混合溶液中溶解，以得到第二混合溶液；以及将所述第二混合溶液进行第一次煅烧，以得到第一材料。
在一些实施例中，多种原料分步进行添加。例如，在将锂源、锰源、铁源和磷源加入第一溶剂中进行溶解，得到第一混合溶液中，上述材料在第一溶剂中的分散较为容易，故在常温下将锂源、锰源、铁源和磷源加入所述第一溶剂中进行溶解。
在将锂源、锰源、铁源和磷源加入第一溶剂中进行溶解，得到第一混合溶液中，过渡金属氧化物、第一含碳有机物在第一混合溶液中不易分散，故在加热的条件下，将过渡金属氧化物、第一含碳有机物分散在第一混合溶液中，以得到第二混合溶液。
例如，加热温度为60℃。超声分散的时间为0.5小时至1小时。当然，加热温度不限于60℃，还可以是50℃、70℃、80℃等。本领域技术人员可以根据实际需要进行设置。
最后，第二混合溶液被加入马弗炉内进行第一次煅烧。
通过多步骤分散的方式进行混合，最终得到的第一材料的质量均匀。
在一些实施例中，过渡金属氧化物、第一含碳有机物与磷酸锰铁锂的摩尔比为3a:a:3，例如，a为0.03至0.2中的任一值(例如，0.03、0.05、0.1、0.15或0.2)。
在该范围内，过渡金属氧化物能够有效地对磷酸锰铁锂进行掺杂、改性，并且第一含碳有机物能够使得过渡金属掺杂的磷酸锰铁锂材料形成纳米材料。
在一些实施例中，第一次煅烧的温度为400℃至950℃(例如，400℃，500℃，600℃，700℃，800℃，或900等)，在温度升至整百温度时保温1小时至3小时(例如，1小时，2小时或3小时等)。
例如，第一次烧结温度在该范围内，能使得过渡金属掺杂的磷酸锰铁锂材料形成纳米材料。马弗炉在升温过程中，在温度升至整百温度时保温1小时至3小时。
可以理解的是，保温可以确保过渡金属氧化物、第一含碳有机物与磷酸锰铁锂在设定的高温下有足够的时间进行充分的化学反应，形成所需的化合物相。通过保温能够促进过渡金属掺杂的磷酸锰铁锂材料的晶格的生长，提高材料的结晶度，高的结晶度有助于锂离子的快速扩散。并且，保温有助于形成更加稳定的晶体结构，能有效地提高材料的电化学性能和循环稳定性。保温还能够减少由于快速冷却导致的热应力，减少的晶体结构的微观结构缺陷，减少材料在高温下的热分解，保持材料的化学稳定性。保温时间的长短可以控制材料的微观结构，包括晶粒的大小和形状等。保温还有助于提高烧结体的密度，减少孔洞，提高了电池的能量密度和功率密度。
例如，第一次烧结的温度为800℃。在烧结过程中，在氮气氛围下，以5℃/分钟的温升速率阶梯升温至800℃。经自然冷却后得到第一材料，例如，温度阶梯以200℃至400℃等的整百温度数为临界值，分多步进行保温。
例如，室温为25℃→200℃→400℃→600℃→800℃。在每个阶梯处各恒温保持2小时。即，在200℃、400℃、600℃、800℃各保温2小时。通过这种方式，生成的过渡金属掺杂的磷酸锰铁锂材料的晶型良好，缺陷少、热应力小、材料的密度致密、化学稳定性良好、能量密度和功率密度高。
例如，也可以是在100℃、300℃、500℃、700℃、800℃进行保温。也可以是，在200℃、300℃、600℃、700℃、800℃进行保温。保温的温度可以根据实际需要进行设置。
当然，第一次煅烧的温度和保温工艺不限于上述实施例，本领域技术人员可以根据实际需要进行设置。
在一些实施例中，所述将第一材料、内核1以及第一导电剂混合，以得到第二材料包括：将所述第一材料的一部分、镍钴锰材料、第一导电剂溶解在第二溶剂中，并采用超声分散的方式进行混合，以得到第三混合溶液；将所述第三混合溶液进行球磨；以及将球磨后的所述第三混合溶液进行喷雾干燥。
在一些实施例中，镍钴锰材料包括NCM111、NCM523、NCM622、NCM811中的至少一种。第一导电剂可以是但不限于碳材料2-3。第二溶剂包括酮、醇、水中的至少一种。
第一材料、镍钴锰材料、第一导电剂加入第二溶剂后，采用机械搅拌、超声分散等方式进行混合。混合后的溶液采用喷雾干燥、加热干燥等方式进行干燥。干燥后得到第二材料。
在将所述第一材料的一部分、镍钴锰材料、第一导电剂溶解在第二溶剂中，并采用超声分散的方式进行混合，以得到第三混合溶液步骤中，第二溶剂为乙醇。部分所述第一材料的一部分、镍钴锰材料、第一导电剂加入乙醇中进行溶解。例如，在60℃下，超声分散0.5小时至1小时，最终得到第三混合溶液。
在将所述第三混合溶液进行球磨步骤中，对第三混合溶液进行球磨。例如，将第三混合溶液加入球磨罐中，球磨2小时。球磨转速为300rpm至600rpm(例如，300rpm、400rpm、500rpm或600rpm)。，球磨次数为2或3次。
球磨通过机械力作用减小上述原料粉末的粒径，形成细小的初级颗粒，这有助于提高材料的比表面积，从而增加锂离子的扩散速率，提高了电池的充放电速率。球磨可以促进固态反应的发生，特别是在第二次煅烧中，球磨可以提高反应速率，有助于合成具有特定结构和性能的电极材料。球磨可以提高电极材料的压实密度，减少颗粒间的空隙，有助于提高电池的能量密度。通过球磨可以引入更多的缺陷和晶界，这些缺陷和晶界可以作为锂离子的快速扩散通道，提高电极材料的导电性。
最后，将球磨后的所述第三混合溶液进行喷雾干燥。通过调整喷雾干燥的参数，例如喷雾速度、热风温度、干燥速率等，能够控制得到的电极材料粉末的颗粒形态和尺寸，从而影响电极材料的充放电性能。喷雾干燥产生的颗粒通常具有较小的尺寸和较高的比表面积，有助于提高锂离子的扩散速率，从而提升电池的充放电效率。喷雾干燥能够制备出具有良好电化学性能的电极材料，例如高容量、高倍率性能和优异的循环稳定性。
在一些实施例中，该方法还包括：将另一部分所述第一材料的另一部分、所述第二材料、第二导电剂加入第三溶剂中，采用超声分散的方式进行混合，以得到第四混合溶液；将所述第四混合溶液进行球磨；以及将球磨后的所述第四混合溶液进行喷雾干燥。
例如，第二导电剂包括碳材料2-3。第三溶剂包括酮、醇、水中的至少一种。所述第一材料的另一部分、所述第二材料、第二导电剂加入第三溶剂后采用机械搅拌、超声分散等方式进行混合。混合后的溶液采用喷雾干燥、加热干燥等方式进行干燥。干燥后得到第二材料。
在将所述第一材料的另一部分、所述第二材料、第二导电剂加入第三溶剂中，采用超声分散的方式进行混合，以得到第四混合溶液中，第三溶剂为乙醇。将第一材料、第二材料、第二导电剂加入乙醇中进行溶解。在60℃条件下，超声分散1小时至2小时，最终得到第四混合溶液。
在将所述第四混合溶液进行球磨中，将第四混合溶液进行球磨。例如，将第四混合溶液加入球磨罐中，球磨2小时。球磨转速为300至600rpm，球磨次数为2或3次。
在将球磨后的所述第四混合溶液进行喷雾干燥中，将球磨后的所述第四混合溶液进行喷雾干燥，以得到第二材料。
在一些实施例中，如图2所示，通过将第一材料分两次添加，能够使得第二包覆层3形成高浓度层2-1和低浓度层2-2。
当然，可以通过更多次添加第一材料，以形成更多梯度的浓度层。
在一些实施例中，所述将第二含碳有机物、第二材料混合，并进行第二次煅烧，以得到所述电极材料中，第二含碳有机物与第二材料的摩尔比为b，b为0.01至0.15中的任一值。
例如，第二含碳有机物包括葡萄糖、蔗糖、果糖、纤维素、淀粉等中的至少一种。第四溶剂包括酮、醇、水中的至少一种。酮包括丙酮、甲乙酮、丁酮、环己酮等。醇包括甲醇、乙醇、丙醇、乙二醇等。
第二材料、第二含碳有机物加入第四溶剂后，采用机械搅拌、超声分散等方式进行混合。混合后的溶液加入到马弗炉中，在惰性气体或氮气分为中进行第二次煅烧。第二次煅烧后得到本公开一些实施例中的电极材料。
例如，第二含碳有机物为葡萄糖。第四溶剂为乙醇。例如，第二材料、第二含碳有机物和第四溶剂混合后的溶液在60℃下，超声分散1小时至2小时。然后，超声分散后的溶液被放置到马弗炉中进行第二次煅烧。
在一些实施例中，第二含碳有机物与第二材料的摩尔比为b，b为0.01至0.15中的任一值。例如葡萄糖与第二材料的摩尔比例为0.01至0.15。葡萄糖在高温煅烧过程中转化为碳材料2-3。
碳材料2-3作为导电剂，即第二包覆层3。在该范围内，第二包覆层3的厚度均匀，缺陷少。例如，厚度在上述厚度范围内，第二包覆层3显著提高了电极材料的电导率，从而降低电池的内阻。第二包覆层3可以作为保护层，减少了电极材料在充放电过程中与电解液的副反应，从而提高电池的循环稳定性。
第二包覆层3有助于在电极材料表面形成稳定的化学和电化学反应界面，减少了电解液的分解。第二包覆层3还可以缓冲电极材料在充放电过程中的体积变化，减少结构应力，提高电极材料的结构稳定性。
在一些实施例中，所述第二次煅烧的温度为700℃至1000℃(例如，700℃，800℃，900或1000℃等)，在温度升值100的整数倍时，保温0.5小时至1.5小时(例如，0.5小时，1小时，或1.5小时等)。
例如，马弗炉的煅烧气氛为氮气，以5℃/min的温升速率阶梯升温至700℃。在700℃下进行保温。经自然冷却后得到电极材料。在第二次煅烧过程中，例如，室温为25℃。升温过程为25℃→100℃→200℃→300℃→400℃→500℃→600℃→700℃，在每个阶梯处，即100℃、200℃、300℃、400℃、500℃、600℃、700℃下，各恒温保持1小时，最终得到电极材料。
可以理解的是，通过第二次煅烧，最终得到含有镍钴锰材料的内核1、过渡金属掺杂的磷酸锰铁锂材料作为第一包覆层2、导电剂作为第二包覆层3的核壳结构的电极材料。
当然，在上述步骤中，在进行超声分散时，加热温度不限于60℃，还可以是50℃、70℃、80℃等。本领域技术人员可以根据实际需要进行设置。
在本公开一些实施例中，将锂源、锰源、铁源、磷源、过渡金属氧化物和第一含碳有机物经第一次煅烧，制备得到纳米化的磷酸锰铁锂，例如，锰和铁以二价离子的形式存在。阴离子为磷酸根。在烧结过程中，无需进行还原过程，减少了电极材料制备过程因为Mn和Fe还原而造成电极材料的结构缺陷。
在制备磷酸锰铁锂材料过程中引入了过渡金属氧化物。过渡金属氧化物可对磷酸锰铁锂材料起到掺杂、改性的作用，提高了磷酸锰铁锂材料的离子电导。
此外，过渡金属氧化物还会在磷酸锰铁锂材料的表面形成纳米金属氧化物。在退火处理时，过渡金属氧化物与磷酸锰铁锂材料表面残余的碳酸锂、氢氧化锂等物质反应形成锂离子导体，从而降低了磷酸锰铁锂材料的残碱含量，提高了磷酸锰铁锂材料传导锂离子的能力，增强了第一包覆层2与第二包覆层3的结合力。
过渡金属氧化物掺杂的磷酸锰铁锂材料和镍钴锰材料之间的间隙内填充有导电剂。导电剂能够提高电极材料的离子电导，同时能够有效避免过渡金属氧化物掺杂的磷酸锰铁锂材料和镍钴锰材料之间的直接接触，防止二者之间自发的氧化还原反应，提高了电极材料的界面结构稳定性。
同时，上述结构能够隔离水分，使得镍钴锰材料对环境湿度的敏感性降低，改善了电极材料在使用过程中的存储和加工性能。
此外，第一包覆层2和第二包覆层3能够有效电减少电解液与镍钴锰材料的接触，提高了电极材料表面结构的稳定性，有效抑制了电解液与镍钴锰材料之间在过充、短路、加热和针刺等情况下的放热反应，从而提高电极材料的循环和安全性能。
此外，采用机械加工的方式进行二次包覆，能够实现过渡金属氧化物掺杂的磷酸锰铁锂材料在镍钴锰材料表面形成均匀、紧密的包覆。该制备方法的工艺简单、高效、适合工业化生产。
根据本公开的一些实施例，提供了一种电极材料。该电极材料根据上述的制备方法制备而成。如图1和图2所示，该电极材料包括含有镍钴锰材料的内核1、包覆在所述内核1外的第一包覆层2以及包覆在所述第一包覆层2外的第二包覆层3，所述第一包覆层2包括过渡金属掺杂的磷酸锰铁锂材料，所述第二包覆层3包括导电剂。
该电极材料作为正极材料。该电极材料为核壳结构。内核1为三元材料，即镍钴锰材料。
在一些实施例中，三元材料包括NCM111、NCM523、NCM622、NCM811中的至少一种。第一包覆层2包覆在内核1外。
过渡金属掺杂的磷酸锰铁锂(LiMnPO4，简称LMP)材料结合了橄榄石型磷酸盐结构的稳定性和高电压特性。通过掺杂不同的过渡金属氧化物，磷酸锰铁锂材料可以获得更好的电化学性能，例如高的结构稳定性、导电性能以及循环性能。第二包覆层3为导电剂。
导电剂用于导电，能够增加电极材料内部的电子传导路径，减少电池内阻，提高电池的充放电效率，还可以改善电池的倍率性能和循环稳定性。导电剂有助于降低电极反应的极化，减少能量损耗，提高电池的工作电压。
电极材料呈颗粒状。核壳结构的平均粒径小于或等于10μm。在该范围内，核壳结构的结构强度高，电化学性能优良。例如，平均粒径为200nm至2μm，在该范围内，电极材料的电化学性能更加优良。
第一包覆层2的厚度为1nm至100nm，例如为10nm至80nm。第二包覆层3的厚度为10nm至50nm，例如为20nm至35nm。在上述范围内，两个包覆层对内核1形成了良好的保护作用。
在本公开一些实施例中，电极材料包括内核1以及包覆在内核1外的两个包覆层。两个包覆层能有效地减少电解液与镍钴锰材料接触，提高了电极材料的表面稳定性，有效地抑制了电解液与镍钴锰材料之间在过充、短路、加热和针刺等滥用情况下的放热反应，从而提高了电极材料的循环稳定性和安全性能。导电剂能提高电极材料的导电性能，降低电池的内阻。
在一些实施例中，所述第一包覆层2包括导电剂，所述过渡金属掺杂的磷酸锰铁锂材料与所述导电剂混合在一起。
在一些实施例中，过渡金属掺杂的磷酸锰铁锂材料形成颗粒。颗粒之间的间隙内填充有导电剂。该导电剂能够进一步增加电极材料内部的电子传导路径，减少电池内阻，提高电池的充放电效率，改善电池的倍率性能和循环稳定性。
例如，作为内核1的镍钴锰材料形成颗粒。在颗粒之间同样填充有导电剂。这种设置方式能够进一步减少电池内阻，提高电池的充放电效率，改善电池的倍率性能和循环稳定性。
在一些实施例中，所述导电剂包括碳材料2-3。碳材料2-3具有良好的导电性能，并且能与镍钴锰材料和过渡金属掺杂的磷酸锰铁锂材料形成良好的结合。
当然，导电剂不限于碳材料2-3也可以导电聚合物等。本领域技术人员可以根据实际需要进行设置。
在一些实施例中，所述碳材料2-3包括点状碳材料2-3、线状碳材料2-3中的至少一种。
在一些实施例中，点状碳材料2-3包括炭黑、乙炔黑、科琴黑和导电石墨中的至少一种。线状碳材料2-3包括碳纤维和碳纳米管中的至少一种。线状碳材料2-3具有很高的强度和韧性，能够提升电极材料的机械性能，防止在充放电过程中电极材料的变形或断裂。点状碳材料2-3的加入也能进一步增强电极材料的结构稳定性。
例如，碳材料2-3包括点状碳材料2-3和线状碳材料2-3。由于线状碳材料2-3和点状碳材料2-3的导电性能优异，混合在一起能够有效地减小电极材料的内阻，提高电池的充放电效率，增加电池的能量密度。
当然，碳材料2-3不限于上述实施例，本领域技术人员可以根据实际需要进行设置。
在一些实施例中，沿所述电极材料的厚度方向，所述过渡金属掺杂的磷酸锰铁锂材料在第一包覆层2中的浓度由靠近内核1一侧向靠近第二包覆层3一侧逐渐减小。
在一些实施例中，过渡金属掺杂的磷酸锰铁锂材料在第一包覆层2中的浓度由内到外逐渐减小。导电剂在第一包覆层2中的浓度由内到外逐渐增大。通过这种方式，第一包覆层2越靠近外层，则电子传输性能越好，从而有效地提高了电极材料的导电性能。第一包覆层2越靠近内层，则磷酸锰铁锂材料的浓度越高，能量密度越高。通过这种方式，该电极材料能有效地兼顾高的能量密度以及高的导电性能。
例如，如图1至图2所示，第一包覆层2靠近内核1的部分形成高浓度层2-1，靠近第二包覆层3的部分形成低浓度层2-2。高浓度层2-1中过渡金属掺杂的磷酸锰铁锂材料的浓度高。低浓度层2-2中过渡金属掺杂的磷酸锰铁锂材料的浓度低。该电极材料能更有效地兼顾高的能量密度以及高的导电性能。
在一些实施例中，所述过渡金属氧化物包括二价过渡金属氧化物。
在一些实施例中，磷酸锰铁锂材料中引入的二价过渡金属氧化物，能对磷酸锰铁锂材料起到掺杂改性作用，使得磷酸锰铁锂材料的离子导电性能显著提高。
此外，二价过渡金属掺杂的磷酸锰铁锂材料会在磷酸锰铁锂表面形成纳米金属氧化物，例如纳米尺寸的二价过渡金属氧化物。在退火处理时，纳米尺寸的二价过渡金属氧化物与磷酸锰铁锂材料表面残余的碳酸锂、氢氧化锂等材料反应形成锂离子导体，从而降低了磷酸锰铁锂材料的残碱含量，并提高了磷酸锰铁锂材料传导锂离子的能力，增强了第一包覆层2与第二包覆层3的结合力。
在一些实施例中，所述二价过渡金属氧化物包括氧化铍、氧化镁和氧化钙中的至少一种。
在一些实施例中，上述材料均具有良好的稳定性，能有效地降低磷酸锰铁锂材料的残碱含量，提高磷酸锰铁锂材料传导锂离子的能力，增强第一包覆层2与第二包覆层3的结合力。
在一些实施例中，锰和铁的摩尔比为x:(1-x)，例如，x为0.3至0.9中的任一值。
例如，磷酸锰铁锂材料的通式为LiMnxFe1-xPO4。例如，x为0.3、0.4、0.5、0.6、0.7、0.8、0.9。在该范围内，进一步降低了第一包覆层2中锰含量，减少了锰溶出量，保证第一包覆层2的性能稳定。
在一些实施例中，所述过渡金属掺杂的磷酸锰铁锂材料中，过渡金属与磷酸锰铁锂材料的摩尔比为0.1％至10％中的任一值。
在该范围内，二价过渡金属氧化物能有效地降低磷酸锰铁锂材料的残碱含量，提高磷酸锰铁锂材料传导锂离子的能力，增强第一包覆层2与第二包覆层3的结合力。
根据本公开的一些实施例，提供了一种电极片。该电极片包括片材本体和上述的电极材料，所述电极材料设置在所述片材本体的表面。
片材本体为金属箔。片材本体的材质为铜、铝、镍等。通过涂覆的方式将本公开一些实施例的电极材料涂覆到金属箔的表面。该电极片的物理化学性质稳定。
根据本公开的一些实施例，提供了一种电池。该电池包括上述的电极片。
例如，该电极片为正极片。在使用时，负极片的电极活性物质为石墨。正极片和负极片之间设置有隔离膜。正极片、隔离膜和负极片通过层叠的方式或者卷绕的方式组合在一起。
该电池具有性能稳定、能量密度高、使用寿命长的特点。
根据本公开的一些实施例，提供了一种用电装置。该用电装置包括上述的电池，或上述的电极片，或上述的电极材料。
该用电装置具有性能稳定、使用寿命长的特点。
上文一些实施例中重点描述的是各个实施例之间的不同，各个实施例之间不同的优化特征只要不矛盾，均可以组合形成新的实施例，考虑到行文简洁，在此则不再赘述。
虽然已经通过例子对本公开的一些实施例进行了详细说明，但是本领域的技术人员应该理解，以上例子仅是为了进行说明，而不是为了限制本公开的范围。本领域的技术人员应该理解，可在不脱离本公开的范围和精神的情况下，对以上实施例进行修改。本公开的范围由所附权利要求来限定。

Claims (15)

  1. 一种电极材料的制备方法，包括：
    将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料；
    将所述第一材料、内核以及第一导电剂混合，以得到第二材料；其中，所述第二材料包括所述内核以及包覆在所述内核外的第一包覆层；以及
    在所述第一包覆层外形成第二包覆层，所述第二包覆层包括导电剂。
  2. 根据权利要求1所述的制备方法，其中，所述在所述第一包覆层外形成第二包覆层，所述第二包覆层包括导电剂，包括：
    将第二含碳有机物、所述第二材料混合，并进行第二次煅烧，以得到所述电极材料；其中，所述电极材料包括所述内核、包覆在所述内核外的所述第一包覆层以及包覆在所述第一包覆层外的所述第二包覆层。
  3. 根据权利要求1或2所述的制备方法，其中，所述磷酸锰铁锂材料的原料包括：锂源、锰源、铁源和磷源。
  4. 根据权利要求3所述的制备方法，其中，在所述锰源和所述铁源中，锰和铁的摩尔比为x:(1-x)，其中，x为0.3至0.9中的任一值。
  5. 根据权利要求3或4所述的制备方法，其中，所述将过渡金属氧化物与磷酸锰铁锂材料的原料混合，并进行第一次煅烧，以得到第一材料，包括：
    将所述锂源、所述锰源、所述铁源和所述磷源加入第一溶剂中进行溶解，以得到第一混合溶液；
    将所述过渡金属氧化物、第一含碳有机物在所述第一混合溶液中溶解，以得到第二混合溶液；以及
    将所述第二混合溶液进行所述第一次煅烧，以得到所述第一材料。
  6. 根据权利要求5所述的制备方法，其中，所述过渡金属氧化物与所述磷酸锰铁锂的摩尔比为a，所述第一含碳有机物与所述磷酸锰铁锂的摩尔比为a/3，其中，a为0.03至0.2中的任一值。
  7. 根据权利要求1-6中任一项所述的制备方法，其中，所述第一次煅烧的温度为400℃至950℃；在温度升至整百温度时保温1小时至3小时。
  8. 根据权利要求1-7中任一项所述的制备方法，其中，所述将所述第一材料、内核以及第一导电剂混合，以得到第二材料，包括：
    将所述第一材料的一部分、镍钴锰材料、所述第一导电剂溶解在第二溶剂中混合，以得到第三混合溶液；以及
    将混合后的所述第三混合溶液进行干燥。
  9. 根据权利要求8所述的制备方法，还包括：
    将所述第一材料的另一部分、所述第三混合溶液干燥后的产物、第二导电剂加入第三溶剂中混合，以得到第四混合溶液；以及
    将混合后的所述第四混合溶液进行干燥，以得到所述第二材料。
  10. 根据权利要求2-9中任一项所述的制备方法，其中，在所述将第二含碳有机物、第二材料混合，并进行第二次煅烧，以得到所述电极材料中，所述第二含碳有机物与所述第二材料的摩尔比为b；其中，b为0.01至0.15中的任一值。
  11. 根据权利要求2-10中任一项所述的制备方法，其中，所述第二次煅烧的温度为700℃至1000℃；在温度升值100的整数倍时，保温0.5小时至1.5小时。
  12. 一种电极材料，根据权利要求1至11中的任一项所述的制备方法制备而成。
  13. 一种电极片，包括片材本体和根据权利要求12所述的电极材料，所述电极材料设置在所述片材本体的表面。
  14. 一种电池，包括根据权利要求13所述的电极片。
  15. 一种用电装置，包括以下之一：
    根据权利要求14所述的电池；、
    根据权利要求13所述的电极片；或
    根据权利要求12所述的电极材料。
PCT/CN2025/078581 2024-06-28 2025-02-21 电极材料的制备方法、电极材料、电极片、电池及用电装置 Pending WO2026001026A1 (zh)

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CN114447322A (zh) * 2022-01-25 2022-05-06 欣旺达电动汽车电池有限公司 一种磷酸锰铁锂改性正极材料及其制备方法
CN117276509A (zh) * 2023-10-10 2023-12-22 楚能新能源股份有限公司 一种掺混正极材料及其制备方法和应用

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* Cited by examiner, † Cited by third party
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CN114447322A (zh) * 2022-01-25 2022-05-06 欣旺达电动汽车电池有限公司 一种磷酸锰铁锂改性正极材料及其制备方法
CN117276509A (zh) * 2023-10-10 2023-12-22 楚能新能源股份有限公司 一种掺混正极材料及其制备方法和应用

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