WO2023124544A1 - 负极材料及其制备方法、负极极片、电池及用电设备 - Google Patents

负极材料及其制备方法、负极极片、电池及用电设备 Download PDF

Info

Publication number
WO2023124544A1
WO2023124544A1 PCT/CN2022/130296 CN2022130296W WO2023124544A1 WO 2023124544 A1 WO2023124544 A1 WO 2023124544A1 CN 2022130296 W CN2022130296 W CN 2022130296W WO 2023124544 A1 WO2023124544 A1 WO 2023124544A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
graphitization
treatment
electrode material
powder
Prior art date
Application number
PCT/CN2022/130296
Other languages
English (en)
French (fr)
Inventor
黄健
黄家骏
彭晗
冯先杰
张宝瑄
杨书展
任建国
Original Assignee
贝特瑞新材料集团股份有限公司
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 贝特瑞新材料集团股份有限公司 filed Critical 贝特瑞新材料集团股份有限公司
Priority to EP22913807.8A priority Critical patent/EP4283724A1/en
Publication of WO2023124544A1 publication Critical patent/WO2023124544A1/zh

Links

Images

Classifications

    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the application belongs to the technical field of negative electrode materials, and in particular relates to a negative electrode material and a preparation method thereof, a negative electrode sheet, a battery and electrical equipment.
  • Graphitization is an important link in the production of negative electrode materials.
  • the existing graphitization process is generally carried out in a batch-type graphite furnace.
  • the batch-type graphite furnace does not move after the material is loaded into the furnace, and the power is cut off after heating, graphitization, and cooling.
  • the graphitization cycle of the batch graphite furnace is long and the cost is high.
  • the dust generated during the operation and the flue gas emission at high temperature are likely to cause environmental pollution.
  • the continuous high-temperature furnace has a short production cycle and can save production costs.
  • the existing continuous high-temperature furnaces are usually used to produce carbon/graphite products such as recarburizers that have low requirements for carbon content and degree of graphitization.
  • the particle size has high requirements, and it is impossible to process the powder.
  • the continuous high-temperature furnace of the existing technology does not have a corresponding graphite preparation process, which cannot meet the performance requirements of the graphite anode industry. Therefore, there is an urgent need for a continuous graphitization preparation process capable of processing powder materials and negative electrode materials with a high degree of graphitization.
  • the present application provides a negative electrode material and its preparation method, negative electrode sheet, battery and electrical equipment, which solves the problem that the traditional vertical graphite furnace cannot process and produce powder raw materials.
  • the present application provides a method for preparing an anode material, comprising the following steps:
  • the precursor is continuously fed to the inlet of the graphitization device, the precursor moves from the inlet to the direction close to the high temperature zone, undergoes preheating and graphitization in turn, and then continuously from the outlet of the graphitization device discharge to obtain the negative electrode material.
  • the preparation method includes at least one of the following technical features (1) to (8):
  • the precursor can be pulverized and restored to a powder during the graphitization treatment, and the ratio of the median particle diameter of the pulverized and restored powder to the median particle diameter of the powder raw material is 1 to 4: 1;
  • the movement mode of the precursor in the graphitization equipment includes at least one of rotation, rolling, spiral descent, vertical fall and horizontal movement;
  • the movement mode of the precursor in the graphitization equipment is self-rolling and spiral descent.
  • the heating method of the graphitization equipment includes at least one of arc heating, plasma heating and resistance heating;
  • the graphitization equipment is a vertical structure
  • the graphitization equipment also includes an exhaust device, the exhaust device is arranged on the furnace cover of the graphitization equipment and communicates with the interior of the graphitization equipment;
  • the graphitization equipment also includes an exhaust device, and the gravity of the precursor is greater than the adsorption force produced by the exhaust device;
  • the graphitization equipment further includes an exhaust device, and the frequency of the main fan of the exhaust device is 10Hz-20Hz.
  • the preparation method includes at least one of the following technical features (1) to (6):
  • the powder raw material includes coke powder and/or graphite
  • the powder raw material includes coke powder, and the coke powder includes at least one of petroleum coke, pitch coke, needle coke, green coke, semi-calcined coke and calcined coke;
  • the powder raw material includes graphite, and the graphite includes at least one of flake graphite, microcrystalline graphite and spherical graphite;
  • the median particle size of the powder raw material is 5 ⁇ m to 25 ⁇ m;
  • the carbon content of the powder raw material is greater than 80%;
  • the volatile content of the powder raw material is less than 15%.
  • the preparation method includes at least one of the following technical features (1) to (8):
  • the pressure of the molding treatment is 5MPa ⁇ 100MPa
  • the average particle diameter of the precursor is 5 mm to 100 mm;
  • the bulk density of the precursor is 0.8g/cc ⁇ 1.2g/cc;
  • the mass of the precursor described in a single block is 5g to 100g;
  • the powder tap density of the powder raw material is T1
  • the powder tap density of the precursor is T2, wherein T1-T2 ⁇ 0.03g/cc;
  • the equipment for forming treatment includes at least one of a molding press, a four-column hydraulic press, a screw extruder, a double-roll extruder, a pellet extruder, and a briquetting machine.
  • the step of mixing the powder raw material with a binder and a solvent is also included before the molding process.
  • the preparation method includes at least one of the following technical features (1) to (14):
  • the binder is converted into at least one of carbon and graphite substances after the graphitization treatment
  • the binder includes heavy oil, mineral oil, coal tar, asphalt, petroleum resin, phenolic resin, epoxy resin, coumarone resin, potato starch, wheat starch, corn starch, sweet potato starch, arrowroot powder and tapioca at least one of powder;
  • the solvent includes at least one of water, ethanol, acetone, benzene, toluene, quinoline, tetrahydrofuran and carbon tetrachloride;
  • the mixing includes mechanical mixing and/or mechanical fusion
  • the mixing includes mechanical mixing, and the rotating speed of the mechanical mixing is 100r/min ⁇ 500r/min;
  • said mixing comprises mechanical mixing, and the time of said mechanical mixing is 10min ⁇ 100min;
  • the mixing includes mechanical fusion, and the rotating speed of the mechanical fusion is 200r/min ⁇ 1000r/min;
  • said mixing includes mechanical fusion, and the time of said mechanical fusion is 10min ⁇ 80min;
  • a drying treatment step is also included, and the equipment for the drying treatment includes a tunnel dryer, a tumble dryer, a mesh belt dryer and a box dryer at least one of;
  • drying treatment step After the forming treatment and before the continuous feeding, a drying treatment step is also included, and the drying treatment time is 4 hours to 20 hours.
  • the step of pre-charging the precursor is also included before the continuous feeding, and the preparation method includes at least one of the following technical features (1) to (6):
  • the equipment for the pre-carbonization includes at least one of a roller kiln, a pusher kiln, a mesh belt kiln, a high sand kiln and a rotary kiln;
  • the temperature of the pre-carbonization treatment is 700°C to 1500°C;
  • the pre-carbonization treatment is performed in a first protective atmosphere for anti-oxidation, and the first protective atmosphere includes at least one of nitrogen, argon, neon and xenon.
  • the preparation method includes at least one of the following technical features (1) to (5):
  • the graphitization treatment is carried out in a second protective atmosphere for anti-oxidation, and the second protective atmosphere includes at least one of nitrogen, argon, neon and xenon;
  • the power of the graphitization treatment is greater than or equal to 500KW;
  • the holding temperature of the graphitization treatment is 2800°C to 3500°C;
  • the holding time of the graphitization treatment is 2h-4h.
  • the present application provides a negative electrode material, the negative electrode material includes graphite, and the negative electrode material satisfies at least one of the following characteristics (1) to (8):
  • the crystal orientation index OI value of the negative electrode material is 1.0 to 3.0;
  • the median particle size of the negative electrode material is 10 ⁇ m to 20 ⁇ m;
  • the tap density of the negative electrode material is 0.90g/cm 3 to 1.20g/cm 3 ;
  • the specific surface area of the negative electrode material is 0.5m 2 /g ⁇ 5.0m 2 /g;
  • the specific capacity of the negative electrode material is 330mAh/g ⁇ 370mAh/g;
  • the powder compacted density of the negative electrode material is 1.50g/cm 3 ⁇ 2.10g/cm 3 ;
  • D10 of the negative electrode material is 5 ⁇ m to 10 ⁇ m
  • the D90 of the negative electrode material is 15 ⁇ m to 35 ⁇ m.
  • the present application provides a negative electrode sheet, including the negative electrode material prepared by the preparation method described in the first aspect;
  • the present application provides a battery, including the negative electrode material prepared by the preparation method according to the first aspect or the negative electrode material according to the second aspect.
  • the present application provides an electrical device, including the negative electrode material prepared by the preparation method according to the first aspect or the negative electrode material according to the second aspect.
  • the negative electrode material is obtained by molding the powder raw material and then performing continuous graphitization treatment, so that the shape of the material can undergo powder-block-powder transformation.
  • the recovery of the shape of the negative electrode material solves the problem that the traditional vertical graphite furnace cannot process and produce powder raw materials, and greatly reduces the production cycle and cost of the negative electrode material; with continuous graphitization treatment, the temperature and time of all materials passing through the high temperature zone are uniform Similarly, there is no problem of uneven heating of materials caused by temperature gradients, and it can improve the orientation and fast charging performance of negative electrode materials, and can meet products with high requirements for graphitization and meet the production requirements of the graphite negative electrode industry.
  • Fig. 1 is the preparation method flowchart of the negative electrode material of the present application
  • Fig. 2 is the SEM picture of the negative electrode material that the application embodiment 1 provides;
  • FIG. 3 is a first charge and discharge curve of a button battery made of the negative electrode material provided in Example 1 of the present application.
  • first and second are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • the embodiment of the present application provides a method for preparing an anode material, as shown in FIG. 1 , which is a flow chart of the method for preparing an anode material in this embodiment, including the following steps:
  • Step S100 molding the powder raw material to obtain a precursor
  • Step S200 continuously feeding the precursor to the inlet of the graphitization equipment, the precursor moves from the inlet to the direction close to the high temperature zone, undergoes preheating treatment and graphitization treatment in sequence, and then continuously discharges from the outlet of the graphitization equipment to obtain a negative electrode Material.
  • Molding treatment refers to extruding the powder raw material, so that multiple particles are squeezed together to form a block with a larger particle size and single mass than the powder raw material.
  • block shape refers to the non-powder form formed by extruding powder raw materials together, which is used to distinguish from the particle size and single mass of powder, but there is no limitation on the shape, and the shape of the block can be It is spherical, ellipsoid, rod, flake and other regular shapes or other irregular shapes.
  • the precursor undergoes the preheating treatment in the movement stage before reaching the high temperature zone, and the precursor undergoes graphitization treatment in the movement stage in the high temperature zone. After the precursor undergoes graphitization treatment in the high-temperature zone, it can be crushed and restored to a powder form.
  • Continuous feeding means that in each production cycle, from the beginning of feeding to the end of feeding, continuous feeding is carried out throughout the whole process.
  • Continuous discharge means that in each production cycle, from the beginning of the discharge to the end of the discharge, the discharge is carried out continuously and uninterrupted throughout the entire process.
  • the interior of the graphitization equipment is filled with materials, therefore, the material is continuously fed from the inlet of the graphitization equipment, and the precursor body inside the graphitization equipment will be released from the inlet of the graphitization equipment.
  • Continuous movement towards the high temperature zone of the graphitization equipment, and at the same time, the pulverized and restored powder form materials after graphitization treatment in the high temperature zone will be continuously discharged from the outlet of the graphitization equipment.
  • the material at each moment will repeat the trajectory of the material at the previous moment, so that all the precursors fed at different times are graphitized The temperature and time are the same.
  • the precursor is obtained by molding the powder raw material, and then the precursor is entered into the graphitization equipment for graphitization treatment and continuously discharged to obtain the negative electrode material.
  • the preparation method of the application enables the shape of the material to be powder-block-
  • this application adopts the method of crushing and restoring the negative electrode material after graphitization treatment, which solves the problem that the traditional vertical graphite furnace cannot carry out continuous graphitization production of powder raw materials.
  • this application adopts the method that the precursors continuously enter and exit the graphitization equipment, so that the temperature and time for graphitization of all precursors are the same, and there is no problem of uneven heating of materials caused by temperature gradients, which greatly reduces the negative electrode.
  • the production cycle and cost of materials are used to reduce the production cycle and cost of materials.
  • Step S100 molding the powder raw material to obtain a precursor.
  • the powder raw material includes coke-like powder and/or graphite. It can be understood that the powder raw material can be a single coke-like powder or graphite, or a mixture of coke-like powder and graphite.
  • the coke powder includes at least one of petroleum coke, pitch coke, needle coke, green coke, semi-calcined coke and calcined coke.
  • the graphite includes at least one of flake graphite, microcrystalline graphite, and spherical graphite. It can be understood that the graphite may be natural graphite or artificial graphite, and the present application does not limit the type of graphite.
  • the median particle size of the powder raw material is 5 ⁇ m to 25 ⁇ m, and the specific median particle size can be 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, and 25 ⁇ m, etc., of course, can also be other values within the above range, which are not limited here. Controlling the median particle size of the powder raw material within the above range is beneficial for subsequent processing and molding.
  • the median particle size of the powder raw material is 7 ⁇ m ⁇ 15 ⁇ m.
  • the median particle size is D50, which means the particle size corresponding to the mass of particles smaller than this particle size on the particle size distribution curve accounting for 50% of the total mass of the particles.
  • the carbon content of the powder raw material is greater than 80%, specifically, the carbon content of the powder raw material can be 82%, 85%, 88%, 90%, 93% and 95%, etc., of course It can be other values within the above range, which is not limited here.
  • the carbon content of powder raw materials is greater than 90%.
  • the volatile content of the powder raw material is less than 15%, specifically, the volatile content of the powder raw material can be 5%, 8%, 10% and 13%, etc., of course, it can also be other values within the above range , is not limited here.
  • Volatile matter refers to the amount of volatile gas that escapes when the powder material is heated in an air-isolated state.
  • the volatile gas is generally water, carbon dioxide, etc.
  • the volatile matter in graphite volatilizes when heated. Holes are left in the graphite structure, and when encountering severe temperature changes, the loose structure is difficult to withstand such thermal shocks and is easy to crack. Therefore, it is necessary to control the volatile content of the powder raw materials within the range defined in this application.
  • the equipment for molding treatment includes at least one of a molding press, a four-column hydraulic press, a screw extruder, a counter-roll extruder, a pellet extruder, and a ball press.
  • the molding equipment is a four-column Hydraulic press
  • the mold aperture size of the four-column hydraulic press is ⁇ (10mm ⁇ 500mm) ⁇ (200mm ⁇ 1000mm)
  • the specific aperture size can be ⁇ 10mm ⁇ 200mm, ⁇ 50mm ⁇ 500mm, ⁇ 100mm ⁇ 200mm, ⁇ 300mm ⁇ 600mm, ⁇ 500mm ⁇ 200mm, ⁇ 500mm ⁇ 1000mm , exemplarily ⁇ 10mm ⁇ 300mm ⁇ 200mm ⁇ 600mm.
  • the pressure of the molding treatment is 5MPa-100MPa
  • the pressure of the molding treatment can be 5MPa, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa, 80MPa, 90MPa and 100MPa, etc.
  • the molding pressure is greater than 100MPa, the bulk density and strength of the formed pellets will be too high, which is not conducive to the recovery of the shape of the subsequent molding material; if the molding pressure is less than 5MPa, the strength of the pellets will be too low, which is not conducive to the process of continuous graphitization. Production .
  • the pressure of the molding treatment is 5MPa-50MPa.
  • the holding time of the molding treatment is 10s to 60s, and the holding time of the molding treatment can be 10s, 20s, 30s, 40s, 50s, and 60s, etc., of course, it can also be other values within the above range, It is not limited here.
  • the pressure and holding time of the powder raw material for molding treatment are controlled within the above range, which is beneficial to the continuous graphitization process production; at the same time, it is beneficial to the recovery of the shape of the subsequent molding material to form the final powder material.
  • the average particle size of the precursor is 5 mm to 100 mm, and the specific average particle size can be 5 mm, 10 mm, 15 mm, 20 mm, 30 mm, 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm and 100 mm, etc., of course It can be other values within the above range, which is not limited here.
  • the average particle size means that for an actual particle group composed of particles with different sizes and shapes, compared with an imaginary particle group composed of uniform spherical particles, if the particle diameters of the two have the same overall length, it is called this
  • the diameter of spherical particles is the average particle diameter of the actual particle group.
  • the bulk density of the precursor is 0.8g/cc ⁇ 1.2g/cc
  • the specific bulk density can be 0.8g/cc, 0.85g/cc, 0.9g/cc, 0.95g/cc, 1.0g/cc cc, 1.05g/cc, 1.1g/cc, 1.15g/cc, and 1.2g/cc, etc., of course, can also be other values within the above range, which are not limited here.
  • the powder tap density of the powder raw material is T1
  • the powder tap density of the precursor is T2, wherein T1-T2 ⁇ 0.03g/cc, specifically, the tap density of the powder raw material
  • T1-T2 ⁇ 0.03g/cc specifically, the tap density of the powder raw material
  • the difference between T1 and the powder tap density T2 of the precursor material can be 0.01g/cc, 0.02g/cc, and 0.03g/cc, etc. Of course, it can also be other values within the above range, which is not limited here. Within the above range, the tap density difference between the precursor material and the raw material powder is not large, indicating that the precursor after molding treatment is recoverable, that is, the precursor after molding treatment can be restored to powder after crushing, and the molding treatment It does not constitute damage to the powder form of the powder raw material.
  • It also includes a step of mixing powder raw materials with binders and solvents before the molding process.
  • the binder is added before the forming process, so that the formed particles form secondary particles through the binder, and the secondary particles formed after the forming process have high bonding strength and high density.
  • the binder is transformed into at least one of carbon and graphitic substances after graphitization.
  • the binder is substantially completely converted after graphitization, eg, greater than 90%, greater than 95%, or greater than 99% of the binder is converted. It is understood that the binder may start to transform at the very beginning of the graphitization process, or may start to transform in the middle of the graphitization process.
  • the binder can be basically completely converted during the graphitization treatment, or can be basically completely converted at the end of the graphitization treatment.
  • binders include heavy oils, mineral oils, coal tar, pitch, petroleum resins, phenolic resins, epoxy resins, coumarone resins, potato starch, wheat starch, corn starch, sweet potato starch, arrowroot and tapioca At least one of them, the binder selected in the present application, can be converted into carbon or graphite-like substances under the high temperature of graphitization treatment, and will not pollute the final product.
  • the solvent can completely evaporate after the graphitization treatment. It can be understood that the solvent may start to volatilize at the beginning of the graphitization treatment, or start to volatilize in the middle of the graphitization treatment. In addition, the solvent may be completely volatilized during the graphitization process, or may be completely volatilized at the end of the graphitization process.
  • the solvent includes at least one of water, ethanol, acetone, benzene, toluene, quinoline, tetrahydrofuran and carbon tetrachloride, and the function of the solvent is mainly to mix the binder and the powder raw material to facilitate subsequent molding Treatment, the solvent selected in this application can be volatilized at high temperature and will not cause secondary pollution to the material.
  • the mass ratio of powder raw material, binder and solvent is (10-100):1:(5-60), specifically, the mass ratio of powder raw material, binder and solvent can be 10:1:5, 20:1:5, 30:1:60, 50:1:50, 80:1:10 and 100:1:5, etc.
  • the mass ratio of powder raw material, binder and solvent is ( 10 ⁇ 50): 1: (5 ⁇ 30).
  • mixing includes mechanical mixing and/or mechanical fusion.
  • Mechanical mixing refers to dispersing materials into one another but not blending them together, and mechanical fusion refers to merging materials into one another.
  • the equipment for mechanical mixing can be a VC mixer, horizontal ribbon mixer, three-dimensional mixer, conical mixer, etc., for example, a horizontal ribbon mixer, and the equipment for mechanical fusion can be Mechanical fusion machine, heating fusion machine, etc.
  • the speed of mechanical mixing is 100r/min ⁇ 500r/min, and the specific speed can be 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min , 450r/min, and 500r/min, etc., of course, can also be other values within the above range, which are not limited here.
  • the rotational speed of mechanical mixing is 200r/min.
  • the time for mechanical mixing is 10 min to 100 min.
  • the specific mixing time can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, and 100 min. value, which is not limited here.
  • the time for mechanical mixing is 30 minutes.
  • the rotation speed of mechanical fusion is 200r/min ⁇ 1000r/min
  • the specific rotation speed can be 200r/min, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min, 800r/min , 900r/min, and 1000r/min, etc., of course, can also be other values within the above range, which are not limited here.
  • the rotating speed of mechanical mixing is 500r/min.
  • the time for mechanical fusion is 10 min to 80 min, and the specific mixing time can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, and 80 min, etc. Of course, it can also be other values within the above range, here No limit.
  • the time for mechanical fusion is 20 minutes.
  • the coke raw materials and/or graphite are coated with binder, and the mechanical mixing and/or mechanical fusion process is adopted to make the binder more uniformly dispersed, so as to achieve the ideal molding effect.
  • a drying treatment step is also included.
  • the purpose of drying is to volatilize the solvent and avoid pollution to the material.
  • the equipment used for the drying treatment includes at least one of a tunnel dryer, a tumble dryer, a mesh belt dryer, and a box dryer, and is exemplarily a tunnel dryer.
  • the temperature of the drying treatment is 100°C to 300°C, and the specific temperatures are 100°C, 120°C, 170°C, 200°C, 230°C, 250°C, 280°C, and 300°C, etc.
  • the temperature of the drying treatment is 100°C-200°C.
  • the drying time is 4h to 20h, and the specific drying time can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, etc., of course, can also be other values within the above range, which are not limited here.
  • the drying treatment time is 4h-10h.
  • a material with high strength and high density is obtained by molding the powder raw material, and the powder material is formed by mixing and molding the powder raw material and the binder, and the material coated in the liquid phase is added with a solvent Good uniformity of coating, high degree of particle recombination after granulation, and excellent orientation.
  • Step S200 continuously feed the precursor to the inlet of the graphitization equipment, the precursor moves from the inlet to the direction close to the high temperature zone, undergoes preheating treatment and graphitization treatment in turn, and then continuously discharges from the outlet of the graphitization equipment to obtain the negative electrode material .
  • the pre-carbonization treatment removes the volatile matter in the precursor, which can reduce the pressure on the graphitization equipment in subsequent production; when the powder raw material is mixed with the binder, the binder can be placed between the precursor particles after pre-carbonization It forms a bridge to achieve the effect of secondary granulation, which replaces the secondary granulation process of the traditional graphite negative electrode using a mixing heating kettle.
  • the equipment used in the pre-carbonization treatment includes at least one of a roller kiln, a pusher kiln, a mesh belt kiln, a high sand kiln, and a rotary kiln.
  • the temperature of the pre-carbonization treatment is 700°C to 1500°C, specifically, the temperature of the pre-carbonization treatment can be 700°C, 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C, 1400°C °C, 1500°C, etc., of course, can also be other values within the above range, which are not limited here.
  • the time for the pre-carbonization treatment is 900°C-1300°C.
  • the pre-carbonization treatment time is 10h to 80h, specifically 10h, 20h, 30h, 40h, 50h, 60h, 70h and 80h, etc. Of course, it can also be other values within the above range, here No limit.
  • the time for the pre-carbonization treatment is 20h-50h.
  • the holding time of the highest temperature experienced by the pre-carbonization treatment is greater than 1h, and the specific holding time of the highest temperature experienced by the pre-carbonization treatment can be 1.5h, 2h, 3h and 4h, etc., of course, it can also be other within the above range. value, which is not limited here.
  • the holding time of the highest temperature experienced by the pre-carbonization treatment is greater than 2 hours. It can be understood that the highest temperature experienced by the pre-carbonization treatment can be any value in the pre-carbonization treatment temperature (that is, any value in 700 ° C ⁇ 1500 ° C) , the temperature during the pre-carbonization process can fluctuate or remain unchanged.
  • the highest temperature experienced by the pre-carbonization process is the temperature maintained during the reaction process. During the pre-carbonization process, the temperature is mostly maintained at the experienced The highest carbonization temperature is conducive to the removal of volatile impurities in the precursor, which is beneficial to the subsequent graphitization and reduces the pollution of the final prepared negative electrode material.
  • the pre-carbonization treatment is performed in a first protective atmosphere for anti-oxidation.
  • the first protective atmosphere includes at least one of nitrogen, argon, neon and xenon.
  • the holding temperature of the graphitization treatment is 2800°C to 3500°C. It can be other values within the above range, which is not limited here. Controlling the graphitization temperature within the above range is beneficial to the graphitization of the material, improves the particle shape and tap density of the final negative electrode material, and is beneficial to subsequent processing. If the temperature of continuous graphitization treatment is lower than 2800°C, it is not conducive to the discharge of impurities and trace elements, and if the temperature of graphitization treatment is higher than 3500°C, it will lead to the gasification of carbon/graphite material. Optionally, the temperature of the graphitization treatment is 3000°C-3500°C.
  • the graphitization device is a vertical structure.
  • the movement of the precursor in the graphitization device includes at least one of rotation, rolling, spiral descent, vertical fall and horizontal movement. Since the precursor is a shaped block or granular substance, it performs at least one of the motion states of rotation, rolling, spiral descent, vertical fall and horizontal movement at the entrance of the graphitization equipment to reach the designated position in the furnace. The precursor is unloaded in the graphitization equipment smoothly and with high efficiency.
  • the motion of the precursor in the graphitization device is self-rolling and spiral-down.
  • the heating method of the graphitization equipment includes at least one of arc heating, plasma heating and resistance heating. Arc and form a high-temperature thermal field, thereby ensuring the necessary temperature conditions for graphitization of the negative electrode.
  • the graphitization equipment also includes an exhaust device, which is arranged on the furnace cover of the graphitization equipment and communicates with the inside of the graphitization equipment, or is arranged around the furnace cover and communicates with the inside of the graphitization equipment. Communication, for example, the gas inside the graphitization equipment is extracted through the exhaust device and processed through the desulfurization device, which better solves the problem of environmental pollution caused by the gas emission of the traditional open graphitization equipment.
  • Arranging the exhaust device close to the furnace cover has at least the following advantages: firstly, the exhaust device is located at a high place of the graphitization equipment, which is conducive to air extraction; at the same time, the exhaust device is kept away from the high-temperature area, so as to avoid the influence of the exhaust device on the temperature of the high-temperature area; In addition, the exhaust device is also kept away from the reaction materials, so as to avoid affecting the yield by taking away the powder materials.
  • the gravity of the precursor is greater than the adsorption force generated by the air exhaust device, the mass of a single precursor is maintained at 5g-100g, and the fan frequency of the air exhaust device is 10Hz-20Hz. Within the above-mentioned fan frequency range, the precursor does not It will be drawn away due to excessive air volume.
  • the temperature of the inlet cover of the graphitization equipment is 500°C to 1600°C
  • the temperature of the inlet cover of the graphitization equipment can be, for example, 500°C, 600°C, 700°C, 800°C, 900°C, 1000°C °C, 1100 °C, 1200 °C, 1300 °C, 1400 °C, 1500 °C and 1600 °C, etc., within the above temperature range, it is beneficial to control the heat balance in the graphite equipment.
  • the continuous production time in the graphitization equipment is 8h to 50h, and the continuous production time in the specific graphitization equipment can be 8h, 9h, 10h, 15h, 20h, 30h, 40h and 50h, etc., of course It can also be other values within the above range, which is not limited here.
  • the time for continuous production and treatment in the graphitization equipment is 8 hours to 20 hours.
  • the continuous production process in the graphitization equipment includes a heating section, a heat preservation section and a cooling section; among them, the heating section refers to the preheating treatment, the holding section refers to the graphitization treatment, and the cooling section refers to the recovery of the powder after leaving the high temperature.
  • the cooling process experienced after the zone is an example:
  • Heating section the temperature of the precursor is raised to 2800°C to 3500°C within 3h to 6h;
  • Insulation section maintain at 2800°C ⁇ 3500°C for 2h ⁇ 4h;
  • Cooling section after the end of the heat preservation, the temperature is lowered to 100°C-200°C within 3h-6h.
  • the equipment for graphitization treatment is a continuous graphitization furnace.
  • the graphitization treatment is performed in a second protective atmosphere for anti-oxidation.
  • the second protective atmosphere includes at least one of nitrogen, argon, neon, and xenon.
  • the power of the graphitization treatment is greater than or equal to 500KW, and the specific power can be 500KW, 600KW, 700KW, 800KW, 900KW, 1000KW and 1100KW, etc. Of course, it can also be other values within the above range, which is not limited here .
  • the power of the graphitization treatment is greater than or equal to 800KW.
  • the discharge rate of graphitization treatment is 1kg/min ⁇ 20kg/min, and the specific discharge rate can be 1kg/min, 2kg/min, 3kg/min, 4kg/min, 5kg/min, 6kg/min min. 7kg/min. 8kg/min. 9kg/min. 10kg/min. 12kg/min. 15kg/min. limited.
  • the discharge rate of the graphitization treatment is 1 kg/min ⁇ 10 kg/min. Controlling the output speed within the above range is beneficial to the stability of the graphitization process.
  • cooling treatment is also included.
  • the cooling treatment adopts multi-stage water jacket circulating water cooling, so that the material can be rapidly cooled to near room temperature during the cooling process, so as to ensure the continuous and stable operation of the furnace under high temperature conditions.
  • the graphitization treatment temperature, power and discharge speed are controlled within the above range, the graphitization treatment time of the present application is far lower than the existing graphitization treatment time, and all materials are processed by the high temperature of the graphitization treatment.
  • the temperature and time of the zone are the same, and there is no problem of uneven heating or temperature gradient. It can improve the capacity and powder compaction density of the negative electrode material, and the material consistency is good.
  • the equipment for pulverization treatment includes at least one of a jet pulverizer, a mechanical pulverizer, and a grinder.
  • the pulverization adopts Mechanical grinder.
  • the mechanical pulverizer includes at least one of a tooth pulverizer, a hammer pulverizer, a turbine pulverizer, a press mill pulverizer, a knife pulverizer and a mill pulverizer.
  • the median particle size of the powder raw material is 5 ⁇ m to 25 ⁇ m
  • the median particle size of the negative electrode material obtained by pulverization after graphitization treatment is 10 ⁇ m to 20 ⁇ m.
  • the particle size range of the precursor is restored to the particle size range of the powder raw material after graphitization treatment and crushing.
  • the precursor can be crushed and restored to a powder after graphitization treatment and crushing, and the middle
  • the ratio of the median particle size to the median particle size of the powder raw material is 1 to 4:1, and the specific ratio can be 1:1, 2:1, 3:1 and 4:1, etc., of course, it can also be within the above range Other values are not limited here.
  • the preparation method of the negative electrode material of this application adopts the powder raw material to carry out molding processing to obtain the precursor.
  • the precursor can be restored to powder after graphitization treatment and pulverization in the above-mentioned ways, and the molding treatment will not damage the powder form of the powder raw material.
  • the anode material particle shape obtained after continuous graphitization of the above precursor is good, the tap density is high, and the cost is low, which can meet the needs of high-end power or 3C products.
  • the embodiment of the present application provides a negative electrode material, which includes graphite, and can be prepared by the preparation method of the negative electrode material provided in the above embodiment.
  • the I 004 /I 110 value of the negative electrode material is 1.0 ⁇ 3.0.
  • the area ratio of the negative electrode material is obtained by integrating the XRD peak
  • I 004 refers to the (004) crystal plane diffraction peak intensity of the negative electrode material
  • I 110 refers to the negative electrode material (110) crystal plane diffraction peak intensity
  • the /I 110 value is the crystal orientation index OI value of the graphite negative electrode material.
  • the OI value of the negative electrode material may specifically be 1.0, 1.2, 1.8, 2.0, 2.5, 3.0, etc., of course, may also be other values within the above range, which are not limited here.
  • the negative electrode material mainly includes secondary particles, and the secondary particles include a plurality of primary particles.
  • primary particles in this application refer to particles that exist alone without forming aggregates.
  • Secondary particles refer to particles in which the above-mentioned primary particles are aggregated or bonded.
  • the median particle size of the negative electrode material is 10 ⁇ m to 20 ⁇ m, and the specific median particle size can be 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m and 20 ⁇ m, etc., of course, it can also be are other values within the above range, and are not limited here.
  • the median particle size of the negative electrode material is 12 ⁇ m to 18 ⁇ m, and controlling the median particle size of the negative electrode material within the above range is beneficial to the improvement of the cycle performance of the negative electrode material.
  • the D10 of the negative electrode material is 5 ⁇ m to 10 ⁇ m, specifically D10 can be 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, and 10 ⁇ m, etc. Of course, it can also be other values within the above range, which is not limited here.
  • D10 represents the particle size corresponding to 10% of the total mass of the particles on the particle size distribution curve where the mass of particles smaller than the particle size accounts for 10%.
  • the D90 of the negative electrode material is 15 ⁇ m to 35 ⁇ m, and the specific D90 can be 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, 21 ⁇ m, 22 ⁇ m, 23 ⁇ m, 24 ⁇ m, 25 ⁇ m, 26 ⁇ m, 27 ⁇ m, 28 ⁇ m, 29 ⁇ m, 30 ⁇ m , 31 ⁇ m, 32 ⁇ m, 33 ⁇ m, 34 ⁇ m, and 35 ⁇ m, etc., of course, can also be other values within the above range, which are not limited here.
  • D90 represents the particle size corresponding to the mass of particles smaller than this particle size on the particle size distribution curve accounting for 90% of the total mass of the particles.
  • the tap density of the negative electrode material is 0.90 g/cm 3 to 1.20 g/cm 3 , specifically the tap density is 0.90 g/cm 3 , 0.95 g/cm 3 , 1.00 g/cm 3 , 1.05 g/cm 3 , or 1.05 g/cm 3 . /cm 3 , 1.10g/cm 3 , 1.15g/cm 3 , and 1.20g/cm 3 , etc., of course, can also be other values within the above range, which are not limited here.
  • the median particle size of the negative electrode material is 0.95g/cm 3 -1.10g/cm 3 .
  • the specific surface area of the negative electrode material is 0.5m 2 /g ⁇ 5.0m 2 /g
  • the specific surface area of the negative electrode material is 0.5m 2 /g, 0.8m 2 / g, 1.0m 2 / g, 1.5 m 2 /g, 2.0m 2 /g, 2.5m 2 /g , 3.0m 2 /g, 4.0m 2 /g and 5.0m 2 /g, etc., of course, can also be other values within the above range, not here Do limited. Controlling the specific surface area of the negative electrode material within the above range is conducive to improving the initial efficiency and output characteristics of the negative electrode material.
  • the specific surface area of the negative electrode material is 0.8m 2 /g ⁇ 3.0m 2 /g.
  • the specific capacity of the negative electrode material is 330mAh/g to 370mAh/g, and the specific capacity of the negative electrode material can be 330mAh/g, 340mAh/g, 350mAh/g, 360mAh/g and 370mAh/g, etc., of course It can also be other values within the above range, which is not limited here.
  • the specific capacity of the negative electrode material is 340mAh/g-360mAh/g.
  • the powder compacted density of the negative electrode material is 1.50 g/cm 3 to 2.10 g/cm 3
  • the specific powder compacted density of the negative electrode material can be 1.50 g/cm 3 , 1.60 g/cm 3 , 1.70g/cm 3 , 1.80g/cm 3 , 1.90g/cm 3 , 2.0g/cm 3 , and 2.1g/cm 3 , etc., of course, can also be other values within the above range, which are not limited here.
  • the powder compacted density of the negative electrode material is 1.70g/cm 3 -2.05g/cm 3 .
  • the embodiment of the present application provides a negative electrode sheet, including the negative electrode material provided in the above embodiment.
  • the negative electrode sheet includes a current collector and a negative active material layer.
  • the negative active material layer includes a negative active material, a conductive agent and a binder.
  • the negative electrode active material includes the above-mentioned negative electrode materials.
  • the current collector of the negative electrode sheet may include at least one of copper foil, aluminum foil, nickel foil, or fluorocarbon current collector.
  • the binder of the negative electrode sheet can include carboxymethylcellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, polystyrene butadiene rubber, At least one of epoxy resin, polyester resin, polyurethane resin or polyfluorene.
  • the conductive agent of the negative electrode sheet can include at least one of conductive carbon black, Ketjen black, acetylene black, carbon nanotubes, VGCF (Vapor Grown Carbon Fiber, vapor phase grown carbon fiber) or graphene.
  • the present application provides a battery, including the negative electrode material provided in the above embodiment.
  • batteries can be lithium-ion batteries, sodium-ion batteries, etc.
  • the battery can be a button battery, a pouch battery, a square battery, etc.
  • the battery is a lithium-ion battery
  • the lithium-ion battery includes a positive pole piece, the above-mentioned negative pole piece, and a separator disposed between the positive pole piece and the negative pole piece.
  • the positive active material layer may include a positive active material, a conductive agent, and a binder.
  • Al foil can be used as the positive electrode current collector, and other positive electrode current collectors commonly used in this field can also be used.
  • the conductive agent of the positive electrode sheet may include at least one of conductive carbon black, graphite flakes, graphene or carbon nanotubes.
  • the binder in the positive pole piece can include polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, styrene-acrylate copolymer, styrene-butadiene copolymer, polyamide, polyacrylonitrile, Polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene at least one of the
  • the positive electrode active material includes but is not limited to at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganate, lithium nickel manganese oxide, lithium nickel cobalt oxide, lithium iron phosphate, lithium nickel cobalt alumina
  • the isolation film includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, or aramid.
  • polyethylene includes at least one selected from high-density polyethylene, low-density polyethylene, or ultra-high molecular weight polyethylene.
  • the thickness of the isolation film is in the range of about 5 ⁇ m to 500 ⁇ m.
  • the lithium-ion battery may also include an electrolyte.
  • electrolytes include, but are not limited to, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), At least two of propyl propionate (PP).
  • the electrolytic solution may additionally include at least one of vinylene carbonate (VC), fluoroethylene carbonate (FEC), or dinitrile compounds as an electrolytic solution additive.
  • the electrolyte also includes a lithium salt.
  • the positive pole piece, separator, and negative pole piece are wound or stacked in order to form an electrode piece, and then packed into an aluminum-plastic film for packaging, injected with electrolyte, formed, and packaged to form a lithium-ion battery. Then, perform performance test and cycle test on the prepared lithium-ion battery.
  • the present application provides an electrical device, including the negative electrode material provided in the above embodiment.
  • the electric device can be in various forms, for example, mobile phone, portable device, notebook computer, battery car, electric car, ship, spacecraft, electric toy, electric tool and so on.
  • spacecraft include, for example, airplanes, rockets, space shuttles and spaceships, etc.
  • electric toys for example, include fixed or mobile electric toys, such as game consoles, electric car toys, electric boat toys and electric airplane toys, etc.
  • Electric tools include, for example, metal cutting electric tools, grinding electric tools, assembly electric tools, and electric power tools for railways, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, impact drills, concrete vibrators, and electric planers.
  • preheating treatment and graphitization treatment are all carried out under protective atmosphere
  • the carbon content of coke raw materials is >99%, the carbon content of natural graphite is >95%, the ash content of various binders is ⁇ 0.1%, and the coking value of heavy oil and tar is 10%.
  • step (2) The material obtained after the mixing treatment in step (1) was formed by a four-column hydraulic press (pressure 10MPa, mold hole diameter ⁇ 250 ⁇ 500mm, pressure holding time 20s) to obtain a precursor, and the mass of a single precursor was 25g.
  • the bulk density is 1.01g/cc.
  • step (4) The material obtained from step (4) pre-carbonization is continuously fed to the inlet of the graphitization equipment, and the material obtained from the pre-carbonization moves from the inlet to the direction close to the high-temperature zone and is graphitized in the high-temperature zone.
  • the electric power is controlled at 1000KW, and the feeding speed is controlled at 10kg/min, so that the pre-carbonized material is heated to 3100°C in 4 hours, kept at 3100°C for 3 hours, and cooled to about 200°C for 3 hours after heat preservation.
  • the gas in the furnace is extracted and processed by a desulfurization device.
  • the fan frequency is controlled to 14Hz.
  • the obtained material is continuously discharged from the outlet of the graphitization equipment, and then pulverized by a turbine pulverizer to obtain the graphite negative electrode of the present application. Material.
  • step (2) The material obtained after the mixing treatment in step (1) is molded by a briquetting machine (the mold hole diameter is ⁇ 50 ⁇ 40mm, and the holding time is 10s) to obtain a precursor, the pressure is 10MPa, and the mass of a single precursor is 10g .
  • the bulk density is 1.03g/cc.
  • step (4) The material obtained from step (4) pre-carbonization is continuously fed to the inlet of the graphitization equipment, and the material obtained from the pre-carbonization moves from the inlet to the direction close to the high-temperature zone and is graphitized in the high-temperature zone.
  • the electric power is controlled at 1000KW, and the feeding speed is controlled at 10kg/min, so that the pre-carbonized material is heated to 3100°C in 4 hours, kept at 3100°C for 3 hours, and cooled to about 200°C for 3 hours after heat preservation.
  • the gas in the furnace is extracted and processed by a desulfurization device.
  • the fan frequency is controlled to 14 Hz. After being treated in a continuous graphitization furnace, it is pulverized by a turbine pulverizer to obtain the graphite negative electrode material of the present application.
  • step (2) The material obtained after the mixing treatment in step (1) is passed through a pellet extruder (the die aperture is ⁇ 20 ⁇ 45mm, and the holding time is 10s), and the precursor is obtained by molding treatment, the pressure is 10MPa, and the mass of a single precursor is It is 8g.
  • the bulk density is 1.05g/cc.
  • step (4) The material obtained from step (4) pre-carbonization is continuously fed to the inlet of the graphitization equipment, and the material obtained from the pre-carbonization moves from the inlet to the direction close to the high-temperature zone and is graphitized in the high-temperature zone.
  • the electric power is controlled at 1000KW, and the feeding speed is controlled at 10kg/min, so that the pre-carbonized material is heated to 3100°C in 4 hours, kept at 3100°C for 3 hours, and cooled to about 200°C for 3 hours after heat preservation.
  • the gas in the furnace is extracted and processed by a desulfurization device.
  • the fan frequency is controlled to 15 Hz. After being treated in a continuous graphitization furnace, it is pulverized by a turbine pulverizer to obtain the graphite negative electrode material of the present application.
  • step (2) The material obtained after the mixing treatment in step (1) is molded by a double-roll extruder (the die diameter is ⁇ 20 ⁇ 40mm, and the holding time is 10s) to obtain a precursor, the pressure is 10MPa, and the mass of a single precursor is It is 6g.
  • the bulk density is 1.06g/cc.
  • step (4) The material obtained from step (4) pre-carbonization is continuously fed to the inlet of the graphitization equipment, and the material obtained from the pre-carbonization moves from the inlet to the direction close to the high-temperature zone and is graphitized in the high-temperature zone.
  • the electric power is controlled at 900KW, and the feeding speed is controlled at 8kg/min, so that the pre-carbonized material is heated up to 3100°C in 4 hours, kept at 3100°C for 3 hours, and cooled to about 200°C for 3 hours after heat preservation.
  • the gas in the furnace is extracted and processed by a desulfurization device.
  • the fan frequency is controlled to 15 Hz. After being treated in a continuous graphitization furnace, it is pulverized by a turbine pulverizer to obtain the graphite negative electrode material of the present application.
  • step (2) The material obtained after the mixing treatment in step (1) is molded by a screw extruder (the die diameter is ⁇ 15 ⁇ 40mm, and the holding time is 10s) to obtain a precursor, the pressure is 10MPa, and the mass of a single precursor is 6g.
  • the bulk density is 1.14g/cc.
  • step (4) The material obtained from step (4) pre-carbonization is continuously fed to the inlet of the graphitization equipment, and the material obtained from the pre-carbonization moves from the inlet to the direction close to the high-temperature zone and is graphitized in the high-temperature zone.
  • the electric power is controlled at 1000KW, and the feeding speed is controlled at 10kg/min, so that the pre-carbonized material is heated to 3100°C in 4 hours, kept at 3100°C for 3 hours, and cooled to about 200°C for 3 hours after heat preservation.
  • the gas in the furnace is extracted and processed by a desulfurization device.
  • the fan frequency is controlled to 14 Hz. After being treated in a continuous graphitization furnace, it is pulverized by a turbine pulverizer to obtain the graphite negative electrode material of the present application.
  • the heat preservation temperature in step (5) is 2600°C.
  • the heat preservation temperature in step (5) is 2800°C.
  • the heat preservation temperature in step (5) is 3300°C.
  • the heat preservation temperature in step (5) is 3500°C.
  • the incubation time in step (5) is 1.5h.
  • the incubation time in step (5) is 2h.
  • the incubation time in step (5) is 4h.
  • the incubation time in step (5) is 4.5h.
  • Example 1 The difference from Example 1 is that the molding pressure in step (2) is 4MPa, and the bulk density of the obtained precursor is 0.72g/cc.
  • Example 1 The difference from Example 1 is that the molding pressure in step (2) is 5 MPa, and the bulk density of the obtained precursor is 0.87 g/cc.
  • Example 1 The difference from Example 1 is that the molding pressure in step (2) is 30MPa, and the bulk density of the obtained precursor is 1.02g/cc.
  • Example 1 The difference from Example 1 is that the molding pressure in step (2) is 50 MPa, and the bulk density of the obtained precursor is 1.10 g/cc.
  • Example 1 The difference from Example 1 is that the molding pressure in step (2) is 100 MPa, and the bulk density of the obtained precursor is 1.12 g/cc.
  • the molding pressure in step (2) is 110MPa, and the bulk density of the obtained precursor is 1.23g/cc.
  • Example 1 The difference from Example 1 is that the mass ratio of powder raw material, binder and solvent in step (1) is 9:1:4.
  • Example 1 The difference from Example 1 is that the mass ratio of powder raw material, binder and solvent in step (1) is 10:1:5.
  • Example 1 The difference from Example 1 is that the mass ratio of powder raw material, binder and solvent in step (1) is 100:1:60.
  • Example 1 The difference from Example 1 is that the mass ratio of powder raw material, binder and solvent in step (1) is 105:1:63.
  • step (1) the petroleum coke raw material with a D 50 of 8 ⁇ m is directly used for molding treatment by a four-column hydraulic press.
  • Example 2 The difference from Example 1 is that the median particle size D50 of the petroleum coke raw material is 3 ⁇ m.
  • Example 2 The difference from Example 1 is that the median particle diameter D50 of the petroleum coke raw material is 5 ⁇ m.
  • Example 2 The difference from Example 1 is that the median particle diameter D50 of the petroleum coke raw material is 15 ⁇ m.
  • Example 2 The difference from Example 1 is that the median particle size D50 of the petroleum coke raw material is 25 ⁇ m.
  • Example 2 The difference from Example 1 is that the median particle diameter D50 of the petroleum coke raw material is 28 ⁇ m.
  • step (5) the fourth precursor is loaded into the Acheson furnace (the highest temperature is 3100 ° C, and the highest temperature is kept for 3 hours) for graphitization treatment, and the recycled material is pulverized by a turbine pulverizer to obtain Negative material.
  • step (5) the fourth precursor is loaded into the Acheson furnace (the highest temperature is 3100 ° C, and the highest temperature is kept for 3 hours) for graphitization treatment, and the recycled material is pulverized by a turbine pulverizer to obtain Negative material.
  • the negative electrode material samples, conductive carbon black, and PVDF prepared in Examples 1-29 and Comparative Examples 1-3 were magnetically stirred in N-methylpyrrolidone solution (NMP, AR) at a mass ratio of 91.6:1.8:6.6 for 8h, Mix it well.
  • NMP N-methylpyrrolidone solution
  • the slurry obtained by mixing was coated on a copper foil, dried under vacuum at 60° C. and used as a working electrode.
  • Metal lithium is used as the counter electrode and reference electrode, the diaphragm is Celgard2325, and the electrolyte is 1mol L -1 LiPF 6 -EC (ethylene carbonate)/DMC (dimethyl carbonate)/EMC (ethyl methyl carbonate) (volume The ratio is 1:1:1), and the CR2016 button battery was assembled in a glove box filled with high-purity argon, and 4 batteries were prepared for each group of samples.
  • the specific surface area of the material is tested by a Tristar 3000 automatic specific surface area and porosity analyzer from Mike Instrument Company of the United States.
  • the particle size (D10, D50 and D90) of the negative electrode material and the particle size (D50) of the raw material particles were tested by a Malvern laser particle size tester MS3000.
  • the tap density of the material is tested by the Konta tap density tester.
  • the first discharge capacity/first discharge efficiency test is carried out on the LAND battery tester, and the charging and discharging conditions are as follows:
  • the SEM image of the negative electrode material provided in Example 1 is shown in FIG. 2 .
  • Figure 3 shows the initial charge and discharge curves of the button battery made of the electrode material provided in Example 1.
  • Curve 1 in Fig. 3 is the discharge curve
  • curve 2 in Fig. 3 is the charge curve. According to Figure 3, it can be seen that the battery made of the negative electrode material prepared in the embodiment of the present application has a higher charge-discharge specific capacity and first-time efficiency.
  • test data of embodiment 1 ⁇ 29 and comparative examples 1 ⁇ 3 are shown in table 1 below:
  • the negative electrode materials prepared in Examples 1 to 29 of the present application have little difference between the powder tap density T1 of the powder raw material and the tap density T2 of the precursor powder, which shows that the precursor powder after the molding treatment of the application
  • the powder is recoverable, and the preparation method of the present application does not damage the powder form of the material.
  • this application covers the powder raw materials in liquid phase and performs molding treatment, transforms the powder into granules or blocks and then performs pre-carbonization treatment, so as to achieve the purpose of pipeline transportation of materials. After the adhesive is pre-carbonized It can form a bridge between the particles to achieve the effect of secondary granulation.
  • the particle shape of the material obtained is good, the tap density is high, and the processing performance is excellent. Since the graphitization process in this application is a continuous operation, the temperature and time of all materials passing through the high temperature zone are the same, and there is no problem of uneven heating or temperature gradient, so that the prepared negative electrode material has good product consistency, high capacity, The advantages of high purity and low cost can meet the needs of high-end power or 3C lithium battery products.
  • the graphitization temperature is too low (Example 6), resulting in poor graphitization degree and capacity performance of the negative electrode material, large crystal orientation index OI value, poor isotropic performance of the material, and negative electrode material
  • the tap density of the material and the compacted density of the powder also decreased to a certain extent.
  • the time of graphitization treatment was too short (Example 10), resulting in poor graphitization degree and capacity performance of the material, large crystal orientation index OI value, and the isotropy of the material The performance is poor, and the tap density and powder compaction density of the negative electrode material also decrease to a certain extent. If the graphitization treatment time is too long (Example 13), the performance indicators such as tap density, powder compacted density, degree of graphitization, capacity performance and crystal orientation index of the material will no longer be effectively improved or even decreased.
  • molding treatment pressure is too little (embodiment 14), causes the strength of granule to reduce, causes the negative electrode material first efficiency and degree of graphitization to be slightly worse; Forming pressure is too big (embodiment 19), the volume density of the negative electrode material is too high and the specific surface area is small, which is not conducive to the recovery of the powder form of the negative electrode material, and the tap density of the negative electrode material also decreases to a certain extent.
  • the mass ratio of the powder raw material and the solvent to the binder is too small (Example 20), and the specific surface area is small, which is not conducive to the recovery of the powder form of the negative electrode material.
  • the crystal orientation index is relatively large; the mass ratio of the powder raw material and the solvent to the binder is too large (embodiment 23), and the specific surface area is small, which is not conducive to the recovery of the powder form of the negative electrode material, and the crystal orientation index is relatively large. big.
  • Example 24 In the negative electrode material prepared in Example 24, no binder and solvent were added, and the raw material of petroleum coke was directly used for molding treatment, resulting in a small specific surface area of the negative electrode material, which was not conducive to the recovery of the powder form of the negative electrode material; and the crystal orientation index was relatively low. Large, the isotropic performance of the material is poor.
  • the D50 of the powder raw materials is too small (Example 25), resulting in poor capacity performance of the material, large crystal orientation index, and the tap density and powder compaction of the negative electrode material The solid density also declined to a certain extent; the D50 of the powder raw material was too large (Example 28), and performance indicators such as capacity performance and crystal orientation index of the material were no longer effectively improved.
  • the tap density, specific surface area, first reversible capacity, degree of graphitization and other indicators of negative electrode material examples 1-5 prepared by the method described in this application are all close to those of comparative examples 1-3, while those of examples 1-5 of this application
  • the OI value (I 004 /I 110 ) is obviously smaller than that of Comparative Examples 1-3, which shows that the orientation of the negative electrode material prepared by the preparation method of the present application is better.
  • Comparative example 2 and comparative example 3 are not processed through the continuous feed, preheating and graphitization in the graphitization equipment, but replaced by pulverizing after graphitization in the Acheson furnace, the OI value (I 004 /I 110 ) is obviously higher, and the powder orientation is poor, which is not conducive to the intercalation and migration of lithium ions.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本申请涉及一种负极材料及其制备方法、负极极片、电池及用电设备，包括以下步骤：将粉体原料进行成型处理得到前驱体；将所述前驱体连续加料至石墨化设备的入口，所述前驱体自所述入口向靠近高温区的方向运动，依次经历预热处理和石墨化处理，之后从石墨化设备的出口连续排出，得到负极材料。本申请的制备方法使得材料的形状能够进行粉-块状-粉的转变，本申请采用石墨化处理后可粉碎复原的方式使得负极材料的形态复原，解决了传统立式石墨炉无法加工生产粉体原料的问题。

Description

负极材料及其制备方法、负极极片、电池及用电设备
交叉引用
本申请要求享有于2021年12月31日提交的名称为“负极材料的制备方法、锂离子电池”的第2021116627709号中国专利申请的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请属于负极材料技术领域，特别涉及一种负极材料及其制备方法、负极极片、电池及用电设备。
背景技术
石墨化是负极材料生产中的重要环节，现有的石墨化工艺一般在间歇式石墨炉中进行，间歇式石墨炉在物料装炉后不移动，经过升温、石墨化、降温等过程后断电出炉，间歇式石墨炉的石墨化周期较长，成本高，同时，作业过程中产生的粉尘及高温下的烟气排放等容易造成环境污染。
连续式高温炉生产周期短，可以节约生产成本，但是现有的连续式高温炉通常多用于生产增碳剂等对碳量、石墨化度要求较低的碳/石墨产品，其对物料状态及颗粒大小有较高要求，无法实现对粉料的加工，另一方面，目前，现有技术的连续式高温炉没有对应配套的石墨制备工艺，无法满足石墨负极行业的性能要求。因此，目前急需一种可以对粉体材料进行加工的连续石墨化制备工艺及石墨化度高的负极材料。
发明内容
本申请为了克服上述缺陷，提供一种负极材料及其制备方法、负极极片、电池及用电设备，解决了传统立式石墨炉无法加工生产粉体原料的问题。
第一方面，本申请提供一种负极材料的制备方法，包括以下步骤：
将粉体原料进行成型处理得到前驱体；
将所述前驱体连续加料至石墨化设备的入口，所述前驱体自所述入口向靠近高温区的方向运动，依次经历预热处理和石墨化处理，之后从所述石墨化设备的出口连续排出，得到负极材料。
结合第一方面，所述制备方法包括如下技术特征(1)～(8)中的至少一种：
(1)所述前驱体在所述石墨化处理可粉碎复原成粉体，并且粉碎复原后的粉体的中值粒径与所述粉体原料的中值粒径之比为1～4:1；
(2)所述前驱体在所述石墨化设备中的运动方式包括旋转、滚动、螺旋下降、垂直下落和水平移动中的至少一种；
(3)所述前驱体在所述石墨化设备中的运动方式为自滚动且螺旋下降。
(4)所述石墨化设备的加热方式包括电弧加热、等离子体加热和电阻加热中的至少一种；
(5)所述石墨化设备为立式结构；
(6)所述石墨化设备还包括抽风装置，所述抽风装置设置于所述石墨化设备的炉盖上并与所述石墨化设备的内部连通；
(7)所述石墨化设备还包括抽风装置，所述前驱体的重力大于所述抽风装置产生的吸附力；
(8)所述石墨化设备还包括抽风装置，所述抽风装置主风机的频率为10Hz～20Hz。
结合第一方面，所述制备方法包括如下技术特征(1)～(6)中的至少一种：
(1)所述粉体原料包括焦类粉料和/或石墨；
(2)所述粉体原料包括焦类粉料，所述焦类粉料包括石油焦、沥青焦、针状焦、生焦、半煅焦和煅后焦中的至少一种；
(3)所述粉体原料包括石墨，所述石墨包括鳞片石墨、微晶石墨和球形石墨中的至少一种；
(4)所述粉体原料的中值粒径为5μm～25μm；
(5)所述粉体原料的含碳量大于80％；
(6)所述粉体原料的挥发分小于15％。
结合第一方面，所述制备方法包括如下技术特征(1)～(8)中的至少一种：
(1)所述成型处理的压力为5MPa～100MPa；
(2)所述成型处理的保压时间为10s～60s；
(3)所述前驱体的平均粒径为5mm～100mm；
(4)所述前驱体的体积密度为0.8g/cc～1.2g/cc；
(5)单块所述前驱体的质量为5g～100g；
(6)所述粉体原料的粉体振实密度为T1，所述前驱体的粉体振实密度为T2，其中，T1-T2≤0.03g/cc；
(7)所述成型处理的设备包括模压机、四柱液压机、螺旋挤压机、对辊挤压机、颗粒挤压机和压球机中的至少一种。
结合第一方面，在所述成型处理之前还包括将粉体原料与粘合剂和溶剂混合的步骤。
结合第一方面，所述制备方法包括如下技术特征(1)～(14)中的至少一种：
(1)所述粘合剂在所述石墨化处理后转化为炭和石墨类物质中的至少一种；
(2)所述粘合剂包括重油、矿物质油、煤焦油、沥青、石油树脂、酚醛树脂、环氧树脂、古玛隆树脂、土豆淀粉、小麦淀粉、玉米淀粉、红薯淀粉、葛粉和木薯粉中的至少一种；
(3)所述溶剂能够在所述石墨化处理后挥发完全；
(4)所述溶剂包括水、乙醇、丙酮、苯、甲苯、喹啉、四氢呋喃和四氯化碳中的至少一种；
(5)所述粉体原料、所述粘合剂和所述溶剂的质量比为(10～100)：1：(5～60)；
(6)所述混合包括机械混合和/或机械融合；
(7)所述混合包括机械混合，所述机械混合的转速为100r/min～500r/min；
(8)所述混合包括机械混合，所述机械混合的时间为10min～100min；
(9)所述混合包括机械融合，所述机械融合的转速为200r/min～1000r/min；
(10)所述混合包括机械融合，所述机械融合的时间为10min～80min；
(11)所述成型处理后且所述连续加料前还包括干燥处理的步骤；
(12)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的设备包括隧道式干燥机、滚筒式烘干机、网带式干燥机和箱式烘干机中的至少一种；
(13)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的温度为100℃～300℃；
(14)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的时间为4h～20h。
结合第一方面，所述连续加料前还包括对所述前驱体进行预炭化处理的步骤，所述制备方法包括如下技术特征(1)～(6)中的至少一种：
(1)所述预炭化的设备包括辊道窑、推板窑、网带窑、高砂窑和回转窑中的至少一种；
(2)所述预炭化处理的温度为700℃～1500℃；
(3)所述预炭化处理的时间为10h～80h；
(4)所述预炭化处理经历的最高温度的保温时间大于1h；
(5)所述预炭化处理在用于抗氧化的第一保护性氛围中进行；
(6)所述预炭化处理在用于抗氧化的第一保护性氛围中进行，所述第一保护性氛围包括氮气、氩气、氖气和氙气中的至少一种。
结合第一方面，所述制备方法包括如下技术特征(1)～(5)中的至少一种：
(1)所述石墨化处理在用于抗氧化的第二保护性氛围中进行；
(2)所述石墨化处理在用于抗氧化的第二保护性氛围中进行，所述第二保护性氛围包括氮气、氩气、氖气和氙气中的至少一种；
(3)所述石墨化处理的功率大于等于500KW；
(4)所述石墨化处理的保温温度为2800℃～3500℃；
(5)所述石墨化处理的保温时间为2h～4h。
第二方面，本申请提供一种负极材料，所述负极材料包括石墨，所述负极材料满足如下特征(1)～(8)中的至少一种：
(1)所述负极材料的晶向指数OI值为1.0～3.0；
(2)所述负极材料的中值粒径为10μm～20μm；
(3)所述负极材料的振实密度为0.90g/cm 3～1.20g/cm 3；
(4)所述负极材料的比表面积为0.5m 2/g～5.0m 2/g；
(5)所述负极材料的比容量为330mAh/g～370mAh/g；
(6)所述负极材料的粉体压实密度为1.50g/cm 3～2.10g/cm 3；
(7)所述负极材料的D10为5μm～10μm；
(8)所述负极材料的D90为15μm～35μm。
第三方面，本申请提供一种负极极片，包括如第一方面所述的制备方法制得的负极材料；
或者
如第二方面所述的负极材料。
第四方面，本申请提供一种电池，包括如第一方面所述的制备方法制得的负极材料或者如第二方面所述的负极材料。
第五方面，本申请提供一种用电设备，包括如第一方面所述的制备方法制得的负极材料或者如第二方面所述的负极材料。
本申请的技术方案至少具有以下有益的效果：
本申请通过对粉体原料进行成型处理再进行连续的石墨化处理得到负极材料，使得材料的 形状能够进行粉-块状-粉的转变，本申请采用上述石墨化处理后可粉碎复原的方式使得负极材料的形态复原，解决了传统立式石墨炉无法加工生产粉体原料的问题，大大降低了负极材料的生产周期及成本；采用连续的石墨化处理，所有物料通过高温区的温度及时间均相同，不存在温度梯度所造成的物料受热不均匀的问题，能够提升负极材料的取向及快充性能，能够满足石墨化程度要求高的产品，满足石墨负极行业的生产要求。
附图说明
为了更清楚的说明本申请实施例或现有技术的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单的介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请负极材料的制备方法流程图；
图2为本申请实施例1提供的负极材料的SEM图；
图3为本申请实施例1提供的负极材料制成扣式电池的首次充放电曲线图。
具体实施方式
1为了更好的理解本申请的技术方案，下面结合附图对本申请实施例进行详细描述。
应当明确，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本申请保护的范围。
本申请中，关于“和/或”的描述，如“特征1和/或特征2”，均是指可以单独地为“特征1”、单独地为“特征2”、“特征1”加“特征2”，该三种情况。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
第一方面，本申请实施例提供一种负极材料的制备方法，如图1所示，为本实施例负极材料制备方法的流程图，包括以下步骤：
步骤S100、将粉体原料进行成型处理得到前驱体；
步骤S200、将前驱体连续加料至石墨化设备的入口，前驱体自该入口向靠近高温区的方向运动，依次经历预热处理和石墨化处理，之后从石墨化设备的出口连续排出，得到负极材料。
成型处理是指将粉体原料进行挤压成型，使得多个颗粒挤压在一起，形成粒径和单颗质量比粉体原料更大的块状。本申请中，块状表示粉体原料挤压在一起形成的非粉体形态，其用于和粉体的粒径和单颗质量进行区分，但是对形状不产生限定，该块体的形状可以是球状、椭球状、棒状、片状等规则形状或者其他不规则形状。
前驱体自石墨化设备入口向靠近高温区的方向运动的过程中，前驱体在到达高温区之前的运动阶段经历该预热处理，前驱体在高温区内的运动阶段经历石墨化处理。前驱体在高温区内经历石墨化处理后，可被粉碎复原为粉体形态。
连续加料是指在每一个生产周期内，从开始加料到结束加料，整个过程中连续不间断地进行加料。
连续排出是指在每一个生产周期内，从开始排料到结束排料，整个过程中连续不间断地进行排料。
由于在石墨化设备中进行连续化生产的过程中，石墨化设备内部是填充有物料的状态，因 此，从石墨化设备入口连续进料，此时石墨化设备内部的前驱体会自石墨化设备入口向靠近石墨化设备高温区的方向连续运动，同时经过高温区石墨化处理后粉碎复原粉末形态的物料会从石墨化设备的出口连续排出。在控制连续进料的下料速度不变的情况下，在石墨化设备中，每一时刻的物料会重复上一时刻的物料的轨迹，因此使得不同时刻进料的所有前驱体进行石墨化处理的温度及时间均相同。
本申请通过对粉体原料进行成型处理得到前驱体，再将前驱体进入石墨化设备进行石墨化处理并连续的排出得到负极材料，本申请的制备方法使得材料的形状能够进行粉-块状-粉的转变，本申请采用石墨化处理后可粉碎复原的方式使得负极材料的形态复原，解决了传统立式石墨炉无法对粉体原料进行连续石墨化生产的问题。此外，本申请采用前驱体连续进入及排出石墨化设备的方式，使得所有前驱体进行石墨化处理的温度及时间均相同，不存在温度梯度所造成的物料受热不均匀的问题，大大降低了负极材料的生产周期及成本。
以下结合实施例具体介绍本申请的制备方法：
步骤S100、将粉体原料进行成型处理得到前驱体。
在一些实施方式中，粉体原料包括焦类粉料和/或石墨，可以理解的，粉体原料可以是单一的焦类粉料或石墨，还可以是焦类粉料和石墨的混合。
在一些实施方式中，焦类粉料包括石油焦、沥青焦、针状焦、生焦、半煅焦和煅后焦中的至少一种。
在一些实施方式中，石墨包括鳞片石墨、微晶石墨和球形石墨中的至少一种。可以理解的，石墨可以是天然石墨，也可以是人造石墨，本申请对于石墨的类型不做限制。
在一些实施方式中，粉体原料的中值粒径为5μm～25μm，具体中值粒径可以为5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm和25μm等，当然也可以是上述范围内的其他值，在此不做限定。将粉体原料的中值粒径控制在上述范围内，有利于后续的加工成型处理，可选地，粉体原料的中值粒径为7μm～15μm。
中值粒径即为D50，表示粒径分布曲线上小于该粒径的颗粒质量占颗粒的总质量的50％对应的粒径。
在一些实施方式中，粉体原料的含碳量大于80％，具体地，粉体原料的含碳量可以是82％、85％、88％、90％、93％和95％等，当然也可以是上述范围内的其他值，在此不做限定。在本申请限定的范围内，含碳量越高的原料，有利于获得较高的嵌锂容量和循环稳定性，可选地，粉体原料的含碳量大于90％。
在一些实施方式中，粉体原料的挥发分小于15％，具体地，粉体原料的挥发分可以是5％、8％、10％和13％等，当然也可以是上述范围内的其他值，在此不做限定。挥发分指的是粉体原料在隔绝空气状态下加热逸出的挥发性气体量，挥发性气体一般为水、二氧化碳等，在制备负极材料的过程中，石墨中挥发分在受热时挥发，在石墨组织内留下孔洞，遇到剧烈的温度变化，疏松的结构难以耐受这样的热震，容易开裂，因此，需要将粉体原料的挥发分控制在本申请限定的范围内。
在一些实施方式中，成型处理的设备包括模压机、四柱液压机、螺旋挤压机、对辊挤压机、颗粒挤压机和压球机中的至少一种，可选地，成型设备为四柱液压机，四柱液压机的模具孔径尺寸为φ(10mm～500mm)×(200mm～1000mm)，具体孔径尺寸可以是φ10mm×200mm、φ50mm×500mm、φ100mm×200mm、φ300mm×600mm、φ500mm×200mm、φ500mm×1000mm，示例性地为φ10mm～300mm×200mm～600mm。
在一些实施方式中，成型处理的压力为5MPa～100MPa，成型处理的压力具体可以为5MPa、10MPa、20MPa、30MPa、40MPa、50MPa、60MPa、70MPa、80MPa、90MPa和100MPa等，当然也可以是上述范围内的其他值，在此不做限定。成型压力大于100MPa，则成型后的粒块的体积密度及强度过高，不利于后续成型物料的形态的复原；成型压力小于5MPa，则粒块的 强度过低，不利于连续石墨化的过程生产。可选地，成型处理的压力为5MPa～50MPa。
在一些实施方式中，成型处理的保压时间为10s～60s，成型处理的保压时间具体可以为10s、20s、30s、40s、50s和60s等，当然也可以是上述范围内的其他值，在此不做限定。
本申请对粉体原料进行成型处理的压力和保压时间控制在上述范围内，有利于进行连续石墨化的过程生产；同时，有利于后续成型物料的形态的复原，形成最终的粉体材料。
在一些实施方式中，前驱体的平均粒径为5mm～100mm，具体平均粒径可以是5mm、10mm、15mm、20mm、30mm、40mm、50mm、60mm、70mm、80mm、90mm和100mm等，当然也可以是上述范围内的其他值，在此不做限定。
平均粒径是指，对于一个由大小和形状不相同的粒子组成的实际粒子群，与一个由均一的球形粒子组成的假想粒子群相比，如果两者的粒径全长相同，则称此球形粒子的直径为实际粒子群的平均粒径。
在一些实施方式中，前驱体的体积密度为0.8g/cc～1.2g/cc，具体体积密度可以是0.8g/cc、0.85g/cc、0.9g/cc、0.95g/cc、1.0g/cc、1.05g/cc、1.1g/cc、1.15g/cc和1.2g/cc等，当然也可以是上述范围内的其他值，在此不做限定。
在一些实施方式中，粉体原料的粉体振实密度为T1，前驱体的粉体振实密度为T2，其中，T1-T2≤0.03g/cc，具体地，粉体原料的振实密度T1和前驱体材料的粉体振实密度T2差值可以是0.01g/cc、0.02g/cc和0.03g/cc等，当然也可以是上述范围内的其他值，在此不做限定。在上述范围内，前驱体材料与原料粉体的振实密度差距不大，说明成型处理后的前驱体具有可复原性，即成型处理后的前驱体经粉碎后可复原成粉体，成型处理对粉体原料的粉体形态不构成破坏。
在成型处理之前还包括将粉体原料与粘合剂和溶剂混合的步骤。
可以理解地，在成型处理之前加入粘合剂，使得成型后的颗粒之间通过粘合剂形成二次颗粒，成型处理后形成的二次颗粒之间粘结强度大、密度高。
在一些实施方式中，粘合剂在石墨化处理后转化为炭和石墨类物质中的至少一种。作为示例，粘合剂在石墨化处理后基本完全转化，例如90％以上、95％以上或者99％以上的粘合剂完成转化。可以理解的是，粘合剂可以在石墨化处理刚开始时就开始转化，也可以在石墨化处理中途开始转化。另外，粘合剂可以在石墨化处理中途就基本转化完全，也可以在石墨化处理结束时才基本转化完全。
示例性地，粘合剂包括重油、矿物质油、煤焦油、沥青、石油树脂、酚醛树脂、环氧树脂、古玛隆树脂、土豆淀粉、小麦淀粉、玉米淀粉、红薯淀粉、葛粉和木薯粉中的至少一种，本申请选择的粘合剂，在石墨化处理的高温下可以转化为炭或者石墨类物质，不会对最终产品造成污染。
在一些实施方式中，溶剂能够在石墨化处理后挥发完全。可以理解的是，溶剂可以在石墨化处理刚开始时就开始挥发，也可以在石墨化处理中途开始挥发。另外，溶剂可以在石墨化处理中途就挥发完全，也可以在石墨化处理结束时才挥发完全。
示例性地，溶剂包括水、乙醇、丙酮、苯、甲苯、喹啉、四氢呋喃和四氯化碳中的至少一种，溶剂的作用主要是将粘合剂和粉体原料混合，便于后续的成型处理，本申请所选择的溶剂，其在高温下可以挥发，不会对物料产生二次污染。
在一些实施方式中，粉体原料、粘合剂和溶剂的质量比为(10～100)：1：(5～60)，具体地，粉体原料、粘合剂和溶剂的质量比可以为10：1：5、20：1：5、30：1：60、50：1：50、80：1：10和100：1：5等，当然也可以是上述范围内的其他值，在此不做限定。可以理解地，本申请将粉体原料、粘合剂和溶剂的质量比控制在上述范围内，有利于后续的成型处理，可选地，粉体原料、粘合剂和溶剂的质量比为(10～50)：1：(5～30)。
在一些实施方式中，混合的方式包括机械混合和/或机械融合。
机械混合是指将物料相互分散但不相互融为一体，机械融合是指将物料相互融为一体。
在一些实施方式中，机械混合的设备可以是VC混合机、卧式螺带混合机、三维混合机、锥形混合机等，示例性地为卧式螺带混合机，机械融合的设备可以是机械融合机、加热融合机等。
在一些实施方式中，机械混合的转速为100r/min～500r/min，具体转速可以是100r/min、150r/min、200r/min、250r/min、300r/min、350r/min、400r/min、450r/min和500r/min等，当然也可以是上述范围内的其他值，在此不做限定。可选地，机械混合的转速为200r/min。
在一些实施方式中，机械混合的时间为10min～100min，具体混合时间可以是10min、20min、30min、40min、50min、60min、70min、80min、90min和100min等，当然也可以是上述范围内的其他值，在此不做限定。可选地，机械混合的时间为30min。
在一些实施方式中，机械融合的转速为200r/min～1000r/min，具体转速可以是200r/min、300r/min、400r/min、500r/min、600r/min、700r/min、800r/min、900r/min和1000r/min等，当然也可以是上述范围内的其他值，在此不做限定。可选地，机械混合的转速为500r/min。
在一些实施方式中，机械融合的时间为10min～80min，具体混合时间可以是10min、20min、30min、40min、50min、60min、70min和80min等，当然也可以是上述范围内的其他值，在此不做限定。可选地，机械融合的时间为20min。
焦类原料和/或石墨上包覆有粘合剂，采用机械混合和/或机械融合工艺，使粘合剂分散地更加均匀，从而达到理想的成型效果。
在一些实施方式中，在成型处理后且在将前驱体向石墨化设备连续加料前，还包括干燥处理的步骤。干燥的目的是为了使溶剂挥发，避免对物料产生污染。
在一些实施方式中，干燥处理采用的设备包括隧道式干燥机、滚筒式烘干机、网带式干燥机、箱式烘干机中的至少一种，示例性地为隧道式干燥机。
在一些实施方式中，干燥处理的温度为100℃～300℃，具体温度为100℃、120℃、170℃、200℃、230℃、250℃、280℃和300℃等，当然也可以是上述范围内的其他值，在此不做限定。可选地，干燥处理的温度为100℃～200℃。
在一些实施方式中，干燥处理的时间为4h～20h，具体干燥处理的时间可以是4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h和20h等，当然也可以是上述范围内的其他值，在此不做限定。可选地，干燥处理的时间为4h～10h。
本申请的制备方法，通过将粉体原料经过成型处理获得强度高、密度大的物料，经过粉体原料与粘合剂的混合成型处理实现粉料成型，通过添加溶剂液相包覆后的物料包覆均一性好，造粒后颗粒复合程度高，取向优。
步骤S200、将前驱体连续加料至石墨化设备的入口，前驱体自入口向靠近高温区的方向运动，依次经历预热处理和石墨化处理，之后从石墨化设备的出口连续排出，得到负极材料。
在一些实施方式中，将步骤S100得到的前驱体向石墨化设备的入口连续加料前，还包括对前驱体进行预炭化处理的步骤，该预炭化处理示例性地在对前驱体进行干燥处理之后。预炭化处理使得前驱体中的挥发分去除，能够减轻后续生产对石墨化设备的压力；在粉体原料与粘合剂混合的情况下，粘合剂经预炭化后可在前驱体颗粒之间形成架桥，达到对其进行二次造粒的作用，替代了传统石墨负极利用混合加热釜二次造粒的过程。
在一些实施方式中，预炭化处理采用的设备包括辊道窑、推板窑、网带窑、高砂窑、回转窑中的至少一种。
在一些实施方式中，预炭化处理的温度为700℃～1500℃，具体地，预炭化处理的温度可以是700℃、800℃、900℃、1000℃、1100℃、1200℃、1300℃、1400℃和1500℃等，当然也可以是上述范围内的其他值，在此不做限定。可选地，预炭化处理的时间为900℃～1300℃。
在一些实施方式中，预炭化处理的时间为10h～80h，具体时间为10h、20h、30h、40 h、50h、60h、70h和80h等，当然也可以是上述范围内的其他值，在此不做限定。可选地，预炭化处理的时间为20h～50h。
在一些实施方式中，预炭化处理经历的最高温度的保温时间大于1h，具体预炭化处理经历的最高温度保温时间可以为1.5h、2h、3h和4h等，当然也可以是上述范围内的其他值，在此不做限定。可选地，预炭化处理经历的最高温度的保温时间大于2h，可以理解地，预炭化处理经历的最高温度可以是预炭化处理温度中的任意值(即700℃～1500℃中的任意值)，预炭化处理过程中的温度可以波动也可以保持不变，温度保持不变的情况下预炭化处理经历的最高温度就是反应过程中保持的温度，预炭化处理时温度较多的维持在经历的最高炭化温度，有利于去除前驱体中的可挥发性杂质，从而有利于后续的石墨化，降低最终制备的负极材料的污染问题。
在一些实施方式中，预炭化处理在用于抗氧化的第一保护性氛围中进行，作为示例，该第一保护性氛围包括氮气、氩气、氖气和氙气中的至少一种。
在一些实施方式中，石墨化处理的保温温度为2800℃～3500℃，具体温度可以为2800℃、2900℃、3000℃、3100℃、3200℃、3300℃、3400℃、3500℃等，当然也可以是上述范围内的其他值，在此不做限定。将石墨化温度控制在上述范围内，有利于材料的石墨化，提高最终制备的负极材料的颗粒形态和振实密度，有利于后续的加工处理。连续石墨化处理的温度低于2800℃，则不利于杂质微量元素的排出，石墨化处理的温度高于3500℃，则导致炭/石墨材质的气化。可选地，石墨化处理的温度为3000℃～3500℃。
在一些实施方式中，石墨化设备为立式结构。
在一些实施方式中，前驱体在石墨化设备中的运动方式包括旋转、滚动、螺旋下降、垂直下落和水平移动中的至少一种。由于将前驱体为成型处理的块状或颗粒状物质，其在石墨化设备入口进行旋转、滚动、螺旋下降、垂直下落和水平移动中的至少一种运动状态达到炉内指定位置，本申请的前驱体在石墨化设备中下料畅快，效率高。
在一些实施方式中，前驱体在石墨化设备中的运动方式为自滚动且螺旋下降。
在一些实施方式中，石墨化设备的加热方式包括电弧加热、等离子体加热和电阻加热中的至少一种，可选地，采用电弧加热的方式进行加热，通过石墨炉内正极与负极之间产生电弧并形成高温热场，从而确保负极石墨化必需的温度条件。
在一些实施方式中，石墨化设备还包括抽风装置，抽风装置设置于所述石墨化设备的炉盖上并与石墨化设备的内部连通，或者抽风装置设置于炉盖周围并与石墨化设备内部连通，例如，通过抽风装置将石墨化设备内部的气体抽出并通过脱硫装置进行处理，较好的解决了传统敞开式石墨化设备气体排放所造成环境污染的问题。将抽风装置靠近炉盖配置，至少还具有以下好处：首先，使得抽风装置位于石墨化设备的高处，有利于抽气；同时，使得抽风装置远离高温区，避免抽风装置影响高温区的温度；此外，还使得抽风装置远离反应物料，避免抽走粉体物料而影响收率。
在一些实施方式中，前驱体的重力大于抽风装置产生的吸附力，单块前驱体的质量维持在5g～100g，抽风装置的风机频率为10Hz～20Hz，在上述风机频率范围内使得前驱体不会因风量过大而被抽走。
在一些实施方式中，石墨化设备的入口盖体的温度为500℃～1600℃，石墨化设备的入口盖体的温度例如可以是500℃、600℃、700℃、800℃、900℃、1000℃、1100℃、1200℃、1300℃、1400℃、1500℃和1600℃等，在上述温度范围内，有利于石墨设备内热平衡的控制。
在一些实施方式中，石墨化设备内的连续生产处理的时间为8h～50h，具体石墨化设备内的连续生产时间可以是8h、9h、10h、15h、20h、30h、40h和50h等，当然也可以是上述范围内的其他值，在此不做限定。可选地，石墨化设备内的连续生产处理的时间为8h～20h。
具体地，石墨化设备内的连续生产处理包括升温段、保温段和降温段；其中，升温段就是指预热处理，保温段就是指石墨化处理，降温段是指复原后的粉体离开高温区后经历的降温过程。以下做出示例：
升温段：将前驱体在3h～6h升温至2800℃～3500℃；
保温段：维持在2800℃～3500℃保温2h～4h；
降温段：保温结束后于3h～6h降温至100℃～200℃。
在一些实施方式中，石墨化处理的设备为连续石墨化炉。
在一些实施方式中，石墨化处理在用于抗氧化的第二保护性氛围中进行。
在一些实施方式中，第二保护性氛围包括氮气、氩气、氖气和氙气中的至少一种。
在一些实施方式中，石墨化处理的功率大于等于500KW，具体功率可以是500KW、600KW、700KW、800KW、900KW、1000KW和1100KW等，当然也可以是上述范围内的其他值，在此不做限定。可选地，石墨化处理的功率大于等于800KW。
在一些实施方式中，石墨化处理的出料速度为1kg/min～20kg/min，具体出料速度可以是1kg/min、2kg/min、3kg/min、4kg/min、5kg/min、6kg/min、7kg/min、8kg/min、9kg/min、10kg/min、12kg/min、15kg/min、18kg/min和20kg/min等，当然也可以是上述范围内的其他值，在此不做限定。可选地，石墨化处理的出料速度为1kg/min～10kg/min。将出料速度控制在上述范围内，有利于石墨化过程运行的稳定性。
在一些实施方式中，石墨化处理后还包括冷却处理，冷却处理采用多级水套循环水冷却，使物料在冷却过程中实现快速冷却至室温附近，确保炉子能够在高温条件下连续稳定运行。
可以理解地，将石墨化处理温度、功率和出料速度控制在上述范围内，本申请的石墨化处理的时间远远低于现有的石墨化处理时间，且所有物料通过石墨化处理的高温区的温度及时间均相同，不存在受热不均或温度梯度的问题。能够提高负极材料的容量和粉体压实密度，且物料一致性好。
在一些实施方式中，将石墨化处理后还包括对所得物料进行粉碎处理的步骤，粉碎处理的设备包括气流粉碎机、机械式粉碎机、研磨机中的至少一种，可选地，粉碎采用机械式粉碎机。具体地，机械式粉碎机包括齿式粉碎机、锤式粉碎机、涡轮式粉碎机、压磨式粉碎机、刀式粉碎机和铣削式粉碎机中的至少一种。
在一些实施方式中，粉体原料的中值粒径为5μm～25μm，石墨化处理后粉碎处理得到的负极材料的中值粒径为10μm～20μm，可以理解的，本申请的制备方法中，前驱体在石墨化处理并粉碎后粒径范围复原成粉体原料的粒径范围，作为示例，前驱体在石墨化处理并粉碎后可粉碎复原成粉体，并且粉碎复原后的粉体的中值粒径与粉体原料的中值粒径之比为1～4:1，具体比例可以是1:1、2:1、3:1和4:1等，当然也可以是上述范围内的其他值，在此不做限定。
本申请负极材料的制备方法，采用粉体原料进行成型处理得到前驱体，前驱体材料与原料粉体的振实密度差距不大，说明成型处理后的前驱体具有可复原性，即成型处理后的前驱体经石墨化处理并进行例如上述所列举方式的粉碎后可复原成粉体，成型处理对粉体原料的粉体形态不构成破坏。将上述前驱体进行连续的石墨化处理后得到的负极材料颗粒形貌好，振实密度高，成本低，可满足于高端动力或3C类产品的需求。
第二方面，本申请实施例提供一种负极材料，该负极材料包括石墨，能够由上述实施例提供的负极材料的制备方法制得。
在一些实施方式中，负极材料的I 004/I 110值为1.0～3.0。具体地，该负极材料的面积比通过XRD峰进行积分获得，I 004指的是负极材料(004)晶面衍射峰强度，I 110指的是负极材料(110)晶面衍射峰强度，I 004/I 110值即石墨负极材料的晶向指数OI值。负极材料的OI值具体可以是1.0、1.2、1.8、2.0、2.5、3.0等，当然也可以是上述范围内的其他值，在此不做限定。通过将粉体原料进行成型，在成型处理压力和粘合剂的共同作用下得到二次颗粒，使得制备的负极材料的OI值为1.0～3.0，在上述范围内表明材料的各项同性性能好，在快速充电时锂离子可以从各个方面嵌入到石墨层间，有利于锂离子的快速充电。
在一些实施方式中，负极材料主要包括二次颗粒，二次颗粒包括多个一次颗粒。可以理解的，本申请中“一次颗粒”是指单独存在而不形成凝聚体的粒子。“二次颗粒”是指上述一次粒子聚集或粘结而成的粒子。
在一些实施方式中，负极材料中值粒径为10μm～20μm，具体中值粒径可以是10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm和20μm等，当然也可以是上述范围内的其他值，在此不做限定。可选地，负极材料的中值粒径为12μm～18μm，将负极材料的中值粒径控制在上述范围内，有利于负极材料循环性能的提升。
在一些实施方式中，负极材料的D10为5μm～10μm，具体D10可以是5μm、6μm、7μm、8μm、9μm和10μm等，当然也可以是上述范围内的其他值，在此不做限定。
D10表示粒径分布曲线上小于该粒径的颗粒质量占颗粒的总质量的10％对应的粒径。
在一些实施方式中，负极材料的D90为15μm～35μm，具体D90可以是15μm、16μm、17μm、18μm、19μm、20μm、21μm、22μm、23μm、24μm、25μm、26μm、27μm、28μm、29μm、30μm、31μm、32μm、33μm、34μm和35μm等，当然也可以是上述范围内的其他值，在此不做限定。
D90表示粒径分布曲线上小于该粒径的颗粒质量占颗粒的总质量的90％对应的粒径。
在一些实施方式中，负极材料的振实密度为0.90g/cm 3～1.20g/cm 3，具体振实密度为0.90g/cm 3、0.95g/cm 3、1.00g/cm 3、1.05g/cm 3、1.10g/cm 3、1.15g/cm 3和1.20g/cm 3等，当然也可以是上述范围内的其他值，在此不做限定。可选地，负极材料的中值粒径为0.95g/cm 3～1.10g/cm 3。
在一些实施方式中，负极材料的比表面积为0.5m 2/g～5.0m 2/g，具体负极材料的比表面积为0.5m 2/g、0.8m 2/g、1.0m 2/g、1.5m 2/g、2.0m 2/g、2.5m 2/g、3.0m 2/g、4.0m 2/g和5.0m 2/g等，当然也可以是上述范围内的其他值，在此不做限定。将负极材料的比表面积控制在上述范围内，有利于提高负极材料的初始效率和输出特性。可选地，负极材料的比表面积为0.8m 2/g～3.0m 2/g。
在一些实施方式中，负极材料的比容量为330mAh/g～370mAh/g，具体负极材料的比容量可以是330mAh/g、340mAh/g、350mAh/g、360mAh/g和370mAh/g等，当然也可以是上述范围内的其他值，在此不做限定。可选地，负极材料的比容量为340mAh/g～360mAh/g。
在一些实施方式中，负极材料的粉体压实密度为1.50g/cm 3～2.10g/cm 3，负极材料的具体粉体压实密度可以是1.50g/cm 3、1.60g/cm 3、1.70g/cm 3、1.80g/cm 3、1.90g/cm 3、2.0g/cm 3和2.1g/cm 3等，当然也可以是上述范围内的其他值，在此不做限定。可选地，负极材料的粉体压实密度为1.70g/cm 3～2.05g/cm 3。
第三方面，本申请实施例提供一种负极极片，包括上述实施例提供的负极材料。
在一些实施方式中，负极极片包括集流体和负极活性物质层。负极活性物质层包括负极活性物质、导电剂和粘结剂。负极活性物质包括上述负极材料。
在一些实施方式中，负极极片的集流体可以包括铜箔、铝箔、镍箔或碳氟集流体中的至少一种。负极极片的粘结剂可以包括羧甲基纤维素(CMC)、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、聚丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种。负极极片的导电剂可以包括导电炭黑、科琴黑、乙炔黑、碳纳米管、VGCF(Vapor Grown Carbon Fiber，气相成长碳纤维)或石墨烯中的至少一种。
第四方面，本申请提供一种电池，包括上述实施例提供的负极材料。
从材料种类来说，电池可以是锂离子电池、钠离子电池等。从封装形式来说，电池可以是扣式电池、软包电池、方形电池等。
在一些实施方式中，电池为锂离子电池，锂离子电池包括正极极片、上述负极极片以及设置于正极极片和负极极片之间的隔离膜。
在一些实施方式中，正极活性物质层可以包括正极活性物质、导电剂和粘结剂。正极集流体可以采用Al箔，同样，也可以采用本领域常用的其他正极集流体。
正极极片的导电剂可以包括导电炭黑、片层石墨、石墨烯或碳纳米管中的至少一种。正极极片中的粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-丁二烯共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚醋酸乙烯酯、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。正极活性物质包括但不限于钴酸锂、镍酸锂、锰酸锂、镍锰酸锂、镍钴酸锂、磷酸铁锂、镍钴铝酸锂或镍钴锰酸锂中的至少一种，以上正极活性物质可以经过掺杂或包覆处理。
在一些实施方式中，隔离膜包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电池的稳定性。在一些实施例中，隔离膜的厚度在约5μm～500μm的范围内。
在一些实施方式中，锂离子电池还可以包括电解液。在一些实施例中，电解液包括但不限于碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、丙酸丙酯(PP)中的至少两种。此外，电解液还可以额外地包括作为电解液添加剂的碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)或二腈化合物中的至少一种。在一些实施例中，电解液还包括锂盐。
将正极极片、隔离膜、负极极片按顺序卷绕或堆叠成电极件，之后装入例如铝塑膜中进行封装，注入电解液，化成、封装，即制成锂离子电池。然后，对制备的锂离子电池进行性能测试及循环测试。
本领域的技术人员将理解，以上描述的锂离子电池的制备方法仅是实施例。在不背离本申请公开的内容的基础上，可以采用本领域常用的其他方法。
第五方面，本申请提供一种用电设备，包括上述实施例提供的负极材料。
在本申请中，用电设备可以为多种形式，例如，手机、便携式设备、笔记本电脑、电瓶车、电动汽车、轮船、航天器、电动玩具和电动工具等等。其中，航天器例如包括飞机、火箭、航天飞机和宇宙飞船等等；电动玩具例如包括固定式或移动式的电动玩具，例如，游戏机、电动汽车玩具、电动轮船玩具和电动飞机玩具等等；电动工具例如包括金属切削电动工具、研磨电动工具、装配电动工具和铁道用电动工具，例如，电钻、电动砂轮机、电动扳手、电动螺丝刀、电锤、冲击电钻、混凝土振动器和电刨。
下面分多个实施例对本申请实施例进行进一步的说明。其中，本申请实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
下述实施例与对比例中，预热处理、石墨化处理均在保护性氛围下进行；
下述实施例与对比例中，焦原料碳含量>99％，天然石墨的碳含量>95％；各类粘合剂的灰分＜0.1％；重油和焦油的结焦值为10％。
实施例1
(1)将D 50为8μm的石油焦原料与木薯粉、水在卧式螺带混合机中进行机械混合处理，石油焦原料、木薯粉和水的质量比为40:1:10，机械混合的转速控制为200r/min，混合的时间控制为30min。
(2)将步骤(1)混合处理后的所得料通过四柱液压机(压力为10MPa，模具孔径为φ250×500mm，保压时间为20s)成型处理得到前驱体，单块前驱体的质量为25g，体积密度为1.01g/cc。
(3)将前驱体在烘干机中180℃烘干处理8h。
(4)将步骤(3)所得料在辊道窑中经1000℃预炭化，预炭化时间为24h。
(5)将步骤(4)预炭化所得料连续加料至石墨化设备的入口，该预炭化所得料自入口向靠近高温区的方向运动并在高温区进行石墨化处理，将石墨化设备的送电功率控制在1000KW，下料速度控制为10kg/min，使得预炭化所得料在4h升温至3100℃，在3100℃保温3h，保温后经3h冷却至200℃左右，同时，通过抽风装置将石墨化炉内的气体抽出并通过脱硫装置进行处理，风机频率控制为14Hz，石墨化处理结束后将所得物料从石墨化设备的出口连续排出，再经涡轮式粉碎机粉碎，即得本申请的石墨负极材料。
实施例2
(1)将D 50为8μm的针状焦原料与玉米淀粉、水在卧式螺带混合机中进行机械混合处理，针状焦原料、玉米淀粉和水的质量比为40:1:10，机械混合的转速控制为200r/min，混合的时间控制为30min。
。
(2)将步骤(1)混合处理后的所得料通过压球机成型(模具孔径为φ50×40mm，保压时间为10s)处理得到前驱体，压力为10MPa，单块前驱体的质量为10g。体积密度为1.03g/cc。
(3)将前驱体在烘干机中180℃烘干处理8h。
(4)将步骤(3)所得料在辊道窑中经1000℃预炭化，预炭化时间为24h。
(5)将步骤(4)预炭化所得料连续加料至石墨化设备的入口，该预炭化所得料自入口向靠近高温区的方向运动并在高温区进行石墨化处理，将石墨化设备的送电功率控制在1000KW，下料速度控制为10kg/min，使得预炭化所得料在4h升温至3100℃，在3100℃保温3h，保温后经3h冷却至200℃左右，同时，通过抽风装置将石墨化炉内的气体抽出并通过脱硫装置进行处理，风机频率控制为14Hz，连续石墨化炉处理后经涡轮式粉碎机粉碎，即得本申请的石墨负极材料。
实施例3
(1)将D 50为8μm的石油焦原料与玉米淀粉、水在卧式螺带混合机中进行机械混合处理，石油焦原料、玉米淀粉和水的质量比为40:1:10，机械混合的转速控制为200r/min，混合的时间控制为30min。
(2)将步骤(1)混合处理后的所得料通过颗粒挤压机(模具孔径为φ20×45mm，保压时间为10s)，成型处理得到前驱体，压力为10MPa，单块前驱体的质量为8g。体积密度为1.05g/cc。
(3)将前驱体在烘干机中180℃烘干处理8h。
(4)将步骤(3)所得料在辊道窑中经1000℃预炭化，预炭化时间为24h。
(5)将步骤(4)预炭化所得料连续加料至石墨化设备的入口，该预炭化所得料自入口向靠近高温区的方向运动并在高温区进行石墨化处理，将石墨化设备的送电功率控制在1000KW，下料速度控制为10kg/min，使得预炭化所得料在4h升温至3100℃，在3100℃保温3h，保温后经3h冷却至200℃左右，同时，通过抽风装置将石墨化炉内的气体抽出并通过脱硫装置进行处理，风机频率控制为15Hz，连续石墨化炉处理后经涡轮式粉碎机粉碎，即得本申请的石墨负极材料。
实施例4
(1)将D 50为8μm的石油焦原料与木薯粉、水在卧式螺带混合机中进行机械混合处理，石油焦原料、木薯粉和水的质量比为40:1.2:10，机械混合的转速控制为200r/min，混合的时间控制为30min。
(2)将步骤(1)混合处理后的所得料通过对辊挤压机(模具孔径为φ20×40mm，保压时间为10s)成型处理得到前驱体，压力为10MPa，单块前驱体的质量为6g。体积密度为1.06g/cc。
(3)将前驱体在烘干机中180℃烘干处理8h。
(4)将步骤(3)所得料在辊道窑中经1000℃预炭化，预炭化时间为24h。
(5)将步骤(4)预炭化所得料连续加料至石墨化设备的入口，该预炭化所得料自入口向靠近高温区的方向运动并在高温区进行石墨化处理，将石墨化设备的送电功率控制在900KW，下料速度控制为8kg/min，使得预炭化所得料在4h升温至3100℃，在3100℃保温3h，保温后经3h冷却至200℃左右，同时，通过抽风装置将石墨化炉内的气体抽出并通过脱硫装置进行处理，风机频率控制为15Hz，连续石墨化炉处理后经涡轮式粉碎机粉碎，即得本申请的石墨负极材料。
实施例5
(1)将D 50为8μm的鳞片石墨与木薯粉、水在卧式螺带混合机中进行机械混合处理，鳞片石墨、木薯粉和水的质量比控制为40:1:10，机械混合的转速控制为200r/min，混合的时间控制为30min。
(2)将步骤(1)混合处理后的所得料通过螺旋挤压机(模具孔径为φ15×40mm，保压时间为10s)成型处理得到前驱体，压力为10MPa，单块前驱体的质量为6g。体积密度为1.14g/cc。
(3)将前驱体在烘干机中180℃烘干处理8h。
(4)将步骤(3)所得料在辊道窑中经1000℃预炭化，预炭化时间为24h。
(5)将步骤(4)预炭化所得料连续加料至石墨化设备的入口，该预炭化所得料自入口向靠近高温区的方向运动并在高温区进行石墨化处理，将石墨化设备的送电功率控制在1000KW，下料速度控制为10kg/min，使得预炭化所得料在4h升温至3100℃，在3100℃保温3h，保温后经3h冷却至200℃左右，同时，通过抽风装置将石墨化炉内的气体抽出并通过脱硫装置进行处理，风机频率控制为14Hz，连续石墨化炉处理后经涡轮式粉碎机粉碎，即得本申请的石墨负极材料。
实施例6
与实施例1不同的是，步骤(5)中保温温度为2600℃。
实施例7
与实施例1不同的是，步骤(5)中保温温度为2800℃。
实施例8
与实施例1不同的是，步骤(5)中保温温度为3300℃。
实施例9
与实施例1不同的是，步骤(5)中保温温度为3500℃。
实施例10
与实施例1不同的是，步骤(5)中保温时间为1.5h。
实施例11
与实施例1不同的是，步骤(5)中保温时间为2h。
实施例12
与实施例1不同的是，步骤(5)中保温时间为4h。
实施例13
与实施例1不同的是，步骤(5)中保温时间为4.5h。
实施例14
与实施例1不同的是，步骤(2)中成型压力为4MPa，所得前驱体的体积密度为0.72g/cc。
实施例15
与实施例1不同的是，步骤(2)中成型压力为5MPa，所得前驱体的体积密度为0.87g/cc。
实施例16
与实施例1不同的是，步骤(2)中成型压力为30MPa，所得前驱体的体积密度为1.02g/cc。
实施例17
与实施例1不同的是，步骤(2)中成型压力为50MPa，所得前驱体的体积密度为1.10g/cc。
实施例18
与实施例1不同的是，步骤(2)中成型压力为100MPa，所得前驱体的体积密度为1.12g/cc。
实施例19
与实施例1不同的是，步骤(2)中成型压力为110MPa，所得前驱体的体积密度为1.23g/cc。
实施例20
与实施例1不同的是，步骤(1)中粉体原料、粘合剂和溶剂的质量比为9：1：4。
实施例21
与实施例1不同的是，步骤(1)中粉体原料、粘合剂和溶剂的质量比为10：1：5。
实施例22
与实施例1不同的是，步骤(1)中粉体原料、粘合剂和溶剂的质量比为100：1：60。
实施例23
与实施例1不同的是，步骤(1)中粉体原料、粘合剂和溶剂的质量比为105：1：63。
实施例24
与实施例1不同的是，步骤(1)中直接采用D 50为8μm的石油焦原料通过四柱液压机进行成型处理。
实施例25
与实施例1不同的是，石油焦原料的中值粒径D50为3μm。
实施例26
与实施例1不同的是，石油焦原料的中值粒径D50为5μm。
实施例27
与实施例1不同的是，石油焦原料的中值粒径D50为15μm。
实施例28
与实施例1不同的是，石油焦原料的中值粒径D50为25μm。
实施例29
与实施例1不同的是，石油焦原料的中值粒径D50为28μm。
对比例1
直接将石油焦原料粉料先装入石墨坩埚内，然后再将石墨坩埚转移至艾奇逊炉内，经石墨化处理(最高温度3100℃，最高温度保温3h)得到负极材料。
对比例2
与实施例1不同的是，步骤(5)中将第四前驱体装入艾奇逊炉中(最高温度3100℃，最高温度保温3h)进行石墨化处理，回料经涡轮式粉碎机粉碎得到负极材料。
对比例3
与实施例5不同的是，步骤(5)中将第四前驱体装入艾奇逊炉中(最高温度3100℃，最高温度保温3h)进行石墨化处理，回料经涡轮式粉碎机粉碎得到负极材料。
性能测试：
将实施例1～29及对比例1～3制备出的负极材料样品、导电炭黑、PVDF按91.6:1.8:6.6的质量比在N-甲基吡咯烷酮溶液(NMP，AR)中磁力搅拌8h，使其混合均匀。将混合得到的浆料涂布在铜箔上，60℃真空干燥后作为工作电极。采用金属锂作为对电极和参比电极，隔膜为Celgard2325，电解液为1mol·L -1LiPF 6-EC(碳酸乙烯酯)/DMC(碳酸二甲酯)/EMC(碳酸甲乙酯)(体积比为1:1:1)，在充满高纯氩气的手套箱中完成CR2016型纽扣电池组装，每组样品制备4只电池。
(1)材料测试：
a.采用美国麦克仪器公司的Tristar3000全自动比表面积和孔隙度分析仪测试材料的比表面积。
b.采用马尔文激光粒度测试仪MS3000测试负极材料的粒度(D10、D50和D90)以及原料颗粒的粒度(D50)。
c.采用日本理学X射线衍射仪测试材料的结构，获得负极材料的石墨化度和晶向指数。
d.采用TESCAN公司的VEGA3扫描电子显微镜观察样品的表面微观组织形貌。
e.按照GB/T 24533-2019锂离子电池石墨类负极材料方法，采用康塔振实密度测试仪测试材料的振实密度。
f.采用CARVER压实密度仪测试材料5T压力下的粉体压实密度。
(2)电化学性能测试：
首次放电容量/首次放电效率测试在LAND电池测试仪上进行，充放电条件如下：
1)0.1C放电至5mV，0.09C，0.08C…0.02C放电至0.001V，0.1C充电到1.5V，循环2次；
2)根据活性物质重量，转换并输出4只电池各自首次放电容量及首次放电效率；3)计算4只电池均值，作为最终首次放电容量及首次放电效率的输出。
实施例1提供的负极材料的SEM图如图2所示。
根据图2可以看到，本申请实施例制备的负极材料的表面光滑，形貌较好。
实施例1提供的极材料制成扣式电池的首次充放电曲线图如图3所示。
图3中曲线1为放电曲线，图3中曲线2为充电曲线。根据图3可以看到，本申请实施例制备的负极材料制成的电池具有较高的充放电比容量和首次效率。
实施例1～29及对比例1～3的测试数据入下表1所示：
表1.实施例1～29及对比例1～3的测试数据
Figure PCTCN2022130296-appb-000001
Figure PCTCN2022130296-appb-000002
Figure PCTCN2022130296-appb-000003
通过表1可以看出，本申请实施例1～29制备的负极材料，粉体原料的粉体振实密度T1和前驱体粉体振实密度T2差异不大，说明本申请成型处理后的前驱体具有可复原性，且本申请的制备方法对材料的粉体形态不构成破坏。具体地，本申请通过对粉体原料进行液相包覆并进行成型处理，将粉料转化为颗粒或块状再进行预炭化处理，从而达到管道输送物料的目的，粘合剂经预炭化后可在颗粒之间形成架桥，达到对其进行二次造粒的作用，最后在2800℃～3500℃经连续石墨化处理后得到的物料颗粒形貌好，振实密度高，加工性能优异。由于本申请中石墨化加工过程为连续式作业，所有物料通过高温区的温度及时间均相同一致，不存在受热不均或温度梯度问题，使得制备的负极材料具备产品一致性好、容量高、纯度高和成本低的优点，可满足于高端动力或3C类锂电池产品需求。
在实施例6～9中，石墨化温度过低(实施例6)，导致负极材料的石墨化度和容量性能较差，晶向指数OI值较大，材料的各项同性性能差，且负极材料的振实密度和粉体压实密度也出现一定的下降。
在实施例10～13制备的负极材料中，石墨化处理的时间过短(实施例10)，导致材料的石墨化度和容量性能较差，晶向指数OI值较大，材料的各项同性性能较差，且负极材料的振实密度和粉体压实密度也出现一定的下降。石墨化处理的时间过长(实施例13)，材料的振实密度、粉体压实密度、石墨化度、容量性能和晶向指数等性能指标不再有效提升甚至出现下降。
在实施例14～19制备的负极材料中，成型处理压力太小(实施例14)，导致粒块的强度降低，导致负极材料的首次效率和石墨化度略差；成型压力太大(实施例19)，导致负极材料体积密度过高，比表面积较小，不利于负极材料粉末形态的复原，且负极材料的振实密度也出现一定的下降。
在实施例20～23制备的负极材料中，粉体原料和溶剂二者各自和粘合剂的质量比均太小(实施例20)，比表面积较小，不利于负极材料粉末形态的复原，且晶向指数较大；粉体原料和溶剂二者各自和粘合剂的质量比均太大(实施例23)，比表面积较小，不利于负极材料粉末形态的复原，且晶向指数较大。
在实施例24制备的负极材料中，不添加粘合剂和溶剂，直接采用石油焦原料进行成型处理，导致负极材料的比表面积较小，不利于负极材料粉末形态的复原；且晶向指数较大，材料的各项同性性能差。
在实施例25～28制备的负极材料中，粉体原料的D50太小(实施例25)，导致材料的容量性能较差，晶向指数较大，且负极材料的振实密度和粉体压实密度也出现一定的下降；粉体原料的D50太大(实施例28)，材料的容量性能和晶向指数等性能指标不再有效提升。
本申请所述方法制备的负极材料实施例1～5的振实密度、比表面积、首次可逆容量、石墨化度等指标与对比例1～3的均接近，而本申请实施例1～5的OI值(I 004/I 110)明显较对比例1～3的小，说明本申请的制备方法制备的负极材料取向更优。
对比例2和对比例3未经过石墨化设备内的连续进料、预热和石墨化处理，而是替换为在艾奇逊炉内石墨化后粉碎，其制备的负极材料的OI值(I 004/I 110)明显要高，粉末取向差，不利于锂离子的嵌入和迁移。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。
本申请虽然以较佳实施例公开如上，但并不是用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (12)

  1. 一种负极材料的制备方法，其特征在于，包括以下步骤：
    将粉体原料进行成型处理得到前驱体；及
    将所述前驱体连续加料至石墨化设备的入口，所述前驱体自所述入口向靠近高温区的方向运动，依次经历预热处理和石墨化处理，之后从所述石墨化设备的出口连续排出，得到负极材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述制备方法包括如下技术特征(1)～(8)中的至少一种：
    (1)所述前驱体在所述石墨化处理可粉碎复原成粉体，并且粉碎复原后的粉体的中值粒径与所述粉体原料的中值粒径之比为1～4:1；
    (2)所述前驱体在所述石墨化设备中的运动方式包括旋转、滚动、螺旋下降、垂直下落和水平移动中的至少一种；
    (3)所述前驱体在所述石墨化设备中的运动方式为自滚动且螺旋下降；
    (4)所述石墨化设备的加热方式包括电弧加热、等离子体加热和电阻加热中的至少一种；
    (5)所述石墨化设备为立式结构；
    (6)所述石墨化设备还包括抽风装置，所述抽风装置设置于所述石墨化设备的炉盖上并与所述石墨化设备的内部连通；
    (7)所述石墨化设备还包括抽风装置，所述前驱体的重力大于所述抽风装置产生的吸附力；
    (8)所述石墨化设备还包括抽风装置，所述抽风装置主风机的频率为10Hz～20Hz。
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述制备方法包括如下技术特征(1)～(6)中的至少一种：
    (1)所述粉体原料包括焦类粉料和/或石墨；
    (2)所述粉体原料包括焦类粉料，所述焦类粉料包括石油焦、沥青焦、针状焦、生焦、半煅焦和煅后焦中的至少一种；
    (3)所述粉体原料包括石墨，所述石墨包括鳞片石墨、微晶石墨和球形石墨中的至少一种；
    (4)所述粉体原料的中值粒径为5μm～25μm；
    (5)所述粉体原料的含碳量大于80％；
    (6)所述粉体原料的挥发分小于15％。
  4. 根据权利要求1～3任一项所述的制备方法，其特征在于，所述制备方法包括如下技术特征(1)～(8)中的至少一种：
    (1)所述成型处理的压力为5MPa～100MPa；
    (2)所述成型处理的保压时间为10s～60s；
    (3)所述前驱体的平均粒径为5mm～100mm；
    (4)所述前驱体的体积密度为0.8g/cc～1.2g/cc；
    (5)单块所述前驱体的质量为5g～100g；
    (6)所述粉体原料的粉体振实密度为T1，所述前驱体的粉体振实密度为T2，其中，T1-T2≤0.03g/cc；
    (7)所述成型处理的设备包括模压机、四柱液压机、螺旋挤压机、对辊挤压机、颗粒挤压机和压球机中的至少一种。
  5. 根据权利要求1～4任一项所述的制备方法，其特征在于，在所述成型处理之前还包括将所述粉体原料与粘合剂和溶剂混合的步骤。
  6. 根据权利要求5所述的制备方法，其特征在于，所述制备方法包括如下技术特征(1)～(14)中的至少一种：
    (1)所述粘合剂在所述石墨化处理后转化为炭和石墨类物质中的至少一种；
    (2)所述粘合剂包括重油、矿物质油、煤焦油、沥青、石油树脂、酚醛树脂、环氧树脂、古玛隆树脂、土豆淀粉、小麦淀粉、玉米淀粉、红薯淀粉、葛粉和木薯粉中的至少一种；
    (3)所述溶剂能够在所述石墨化处理后挥发完全；
    (4)所述溶剂包括水、乙醇、丙酮、苯、甲苯、喹啉、四氢呋喃和四氯化碳中的至少一种；
    (5)所述粉体原料、所述粘合剂和所述溶剂的质量比为(10～100)：1：(5～60)；
    (6)所述混合包括机械混合和/或机械融合；
    (7)所述混合包括机械混合，所述机械混合的转速为100r/min～500r/min；
    (8)所述混合包括机械混合，所述机械混合的时间为10min～100min；
    (9)所述混合包括机械融合，所述机械融合的转速为200r/min～1000r/min；
    (10)所述混合包括机械融合，所述机械融合的时间为10min～80min；
    (11)所述成型处理后且所述连续加料前还包括干燥处理的步骤；
    (12)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的设备包括隧道式干燥机、滚筒式烘干机、网带式干燥机和箱式烘干机中的至少一种；
    (13)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的温度为100℃～300℃；
    (14)所述成型处理后且所述连续加料前还包括干燥处理的步骤，所述干燥处理的时间为4h～20h。
  7. 根据权利要求1～6任一项所述的制备方法，其特征在于，所述连续加料前还包括对所述前驱体进行预炭化处理的步骤，所述制备方法包括如下技术特征(1)～(6)中的至少一种：
    (1)所述预炭化处理的设备包括辊道窑、推板窑、网带窑、高砂窑和回转窑中的至少一种；
    (2)所述预炭化处理的温度为700℃～1500℃；
    (3)所述预炭化处理的时间为10h～80h；
    (4)所述预炭化处理经历的最高温度的保温时间大于1h；
    (5)所述预炭化处理在用于抗氧化的第一保护性氛围中进行；
    (6)所述预炭化处理在用于抗氧化的第一保护性氛围中进行，所述第一保护性氛围包括氮气、氩气、氖气和氙气中的至少一种。
  8. 根据权利要求1～7任一项所述的制备方法，其特征在于，所述制备方法包括如下技术特征(1)～(5)中的至少一种：
    (1)所述石墨化处理在用于抗氧化的第二保护性氛围中进行；
    (2)所述石墨化处理在用于抗氧化的第二保护性氛围中进行，所述第二保护性氛围包括氮气、氩气、氖气和氙气中的至少一种；
    (3)所述石墨化处理的功率大于等于500KW；
    (4)所述石墨化处理的保温温度为2800℃～3500℃；
    (5)所述石墨化处理的保温时间为2h～4h。
  9. 一种负极材料，其特征在于，所述负极材料包括石墨，所述负极材料满足如下特征(1)～(8)中的至少一种：
    (1)所述负极材料的晶向指数OI值为1.0～3.0；
    (2)所述负极材料的中值粒径为10μm～20μm；
    (3)所述负极材料的振实密度为0.90g/cm 3～1.20g/cm 3；
    (4)所述负极材料的比表面积为0.5m 2/g～5.0m 2/g；
    (5)所述负极材料的比容量为330mAh/g～370mAh/g；
    (6)所述负极材料的粉体压实密度为1.50g/cm 3～2.10g/cm 3；
    (7)所述负极材料的D10为5μm～10μm；
    (8)所述负极材料的D90为15μm～35μm。
  10. 一种负极极片，其特征在于，包括：
    如权利要求1～8任一项所述的制备方法制得的负极材料；
    或者
    如权利要求9所述的负极材料。
  11. 一种电池，其特征在于，包括如权利要求1～8任一项所述的制备方法制得的负极材料或者如权利要求9所述的负极材料。
  12. 一种用电设备，其特征在于，包括如权利要求1～8任一项所述的制备方法制得的负极材料或者如权利要求9所述的负极材料。
PCT/CN2022/130296 2021-12-31 2022-11-07 负极材料及其制备方法、负极极片、电池及用电设备 WO2023124544A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22913807.8A EP4283724A1 (en) 2021-12-31 2022-11-07 Negative electrode material and preparation method therefor, negative electrode plate, battery, and electrical device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111662770.9 2021-12-31
CN202111662770.9A CN116417610A (zh) 2021-12-31 2021-12-31 负极材料的制备方法、锂离子电池

Publications (1)

Publication Number Publication Date
WO2023124544A1 true WO2023124544A1 (zh) 2023-07-06

Family

ID=86997578

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/130296 WO2023124544A1 (zh) 2021-12-31 2022-11-07 负极材料及其制备方法、负极极片、电池及用电设备

Country Status (3)

Country Link
EP (1) EP4283724A1 (zh)
CN (1) CN116417610A (zh)
WO (1) WO2023124544A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811718A (zh) * 2014-02-20 2014-05-21 深圳市贝特瑞新能源材料股份有限公司 一种石墨烯基复合负极材料的制备方法及制得的负极材料和锂离子电池
CN104085883A (zh) * 2014-07-09 2014-10-08 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用人造石墨负极材料及其制备方法
CN205933244U (zh) * 2016-07-27 2017-02-08 洛阳联创锂能科技有限公司 一种电池负极材料连续石墨化炉
CN107199008A (zh) * 2017-05-25 2017-09-26 广东东岛新能源股份有限公司 人造石墨前驱体二次造粒用高温反应装置及投料方法
CN112542587A (zh) * 2020-12-04 2021-03-23 宁德新能源科技有限公司 石墨材料、二次电池和电子装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811718A (zh) * 2014-02-20 2014-05-21 深圳市贝特瑞新能源材料股份有限公司 一种石墨烯基复合负极材料的制备方法及制得的负极材料和锂离子电池
CN104085883A (zh) * 2014-07-09 2014-10-08 深圳市贝特瑞新能源材料股份有限公司 一种锂离子电池用人造石墨负极材料及其制备方法
CN205933244U (zh) * 2016-07-27 2017-02-08 洛阳联创锂能科技有限公司 一种电池负极材料连续石墨化炉
CN107199008A (zh) * 2017-05-25 2017-09-26 广东东岛新能源股份有限公司 人造石墨前驱体二次造粒用高温反应装置及投料方法
CN112542587A (zh) * 2020-12-04 2021-03-23 宁德新能源科技有限公司 石墨材料、二次电池和电子装置

Also Published As

Publication number Publication date
CN116417610A (zh) 2023-07-11
EP4283724A1 (en) 2023-11-29

Similar Documents

Publication Publication Date Title
JP7185764B2 (ja) シリコン酸化物／炭素複合負極材料、その調製方法及びリチウムイオン電池
WO2021128603A1 (zh) 一种用于锂离子电池负极的改性一氧化硅材料及其制备方法
CN112366301B (zh) 一种锂离子电池用硅/硅氧化物/碳复合负极材料及其制备方法
CN111224078A (zh) 一种硅基复合负极材料及其制备方法、锂离子电池负极
CN104638252B (zh) 一种硅复合负极材料、制备方法及锂离子电池
US20170207457A1 (en) Multiple-Element Composite Material For Anodes, Preparation Method Therefor, And Lithium-Ion Battery Having Same
WO2016169149A1 (zh) 一种石墨细粉作为锂离子电池负极材料的循环利用方法
WO2021108982A1 (zh) 人造石墨、二次电池、制备方法及装置
CN110718685A (zh) 一种用于电极材料的硅氧颗粒及其制备方法和应用
CN111326715B (zh) 一种电池正极材料及其制备方法与应用
CN109167028B (zh) 一种磷酸铁锂/碳复合材料的再生制备方法
CN113206249B (zh) 一种具有良好电化学性能的锂电池硅氧复合负极材料及其制备方法
WO2023065909A1 (zh) 一种电化学装置和电子装置
CN108172791A (zh) 复合物负极材料及其制备方法、锂离子电池
CN108306002B (zh) 一种应用于锂离子电池负极的Li21Si5与石墨烯复合材料的制备
JP6739142B2 (ja) リチウムイオン２次電池用負極活物質およびその製造方法
CN110429272B (zh) 一种类火龙果结构的硅碳复合负极材料及其制备方法
CN113023724A (zh) 一种锂离子动力电池用高倍率石墨负极材料的制备方法
WO2023124544A1 (zh) 负极材料及其制备方法、负极极片、电池及用电设备
CN110723721A (zh) 一种制备锂电池硅碳负极材料的方法、负极材料和锂电池
CN116230895A (zh) 一种锂电池负极材料、锂电池及制备方法
CN114203979B (zh) 一种石墨负极材料及其制备方法和应用
TW201943131A (zh) 鋰離子二次電池用負極材料、鋰離子二次電池用負極材料的製造方法、鋰離子二次電池用負極材料漿料、鋰離子二次電池用負極及鋰離子二次電池
WO2021217620A1 (zh) 负极活性材料及其制备方法、二次电池和包含二次电池的装置
CN113422018A (zh) 一种高倍率多晶复合颗粒锂电负极活性材料的制备方法

Legal Events

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

Ref document number: 22913807

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022913807

Country of ref document: EP

Effective date: 20230824