WO2024036902A1 - Carbonaceous material and preparation method therefor, and sodium-ion battery - Google Patents

Carbonaceous material and preparation method therefor, and sodium-ion battery Download PDF

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Publication number
WO2024036902A1
WO2024036902A1 PCT/CN2023/077075 CN2023077075W WO2024036902A1 WO 2024036902 A1 WO2024036902 A1 WO 2024036902A1 CN 2023077075 W CN2023077075 W CN 2023077075W WO 2024036902 A1 WO2024036902 A1 WO 2024036902A1
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Prior art keywords
temperature
optionally
sintering
carbonaceous material
carbon
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PCT/CN2023/077075
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French (fr)
Chinese (zh)
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张苗
阮丁山
李长东
毛林林
郑爽
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024036902A1 publication Critical patent/WO2024036902A1/en

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    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—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 present application relates to the technical field of sodium-ion batteries, to a carbonaceous material, its preparation method and sodium-ion batteries.
  • the precursors for preparing hard carbon materials at this stage mainly include biomass materials, such as corn starch, coconut shell, wood, etc.; organic polymer materials, such as phenolic resin, polyethylene, polyaniline, etc.; mineral materials, such as humic acid, lignite , lignite, etc.
  • biomass materials such as corn starch, coconut shell, wood, etc.
  • organic polymer materials such as phenolic resin, polyethylene, polyaniline, etc.
  • mineral materials such as humic acid, lignite , lignite, etc.
  • Adding a thermal conductive medium with excellent thermal conductivity during the heat treatment of the hard carbon precursor can effectively improve the heating uniformity of the hard carbon precursor, but there is a risk of introducing impurity phases.
  • most hard carbon precursors are organic polymer powders. Due to the risk of dust explosion, the rotary kiln that improves heating uniformity is not suitable for preparing hard carbon materials.
  • the purpose of this application is to provide a carbonaceous material, its preparation method and a sodium-ion battery.
  • the method of the present application can improve the sintering uniformity of carbonaceous materials, has very wide applicability, and has practical significance for the improvement of carbonaceous material processes.
  • this application provides a method for preparing carbonaceous materials, which method includes the following steps:
  • This application utilizes the characteristic that the thermal conductivity of the carbonaceous material precursor is significantly improved after high-temperature carbonization treatment.
  • a part of the carbonaceous material precursor is pre-sintered to obtain the carbon material, and is evenly mixed with the carbonaceous material precursor, and sintering to prepare the final Finished carbon material.
  • the uniformity of performance of the carbonaceous material prepared by the above method is significantly improved, and the performance difference at different positions of the sagger is small.
  • the carbonaceous material may be a hard carbon material.
  • Using the hard carbon material prepared by this method as an anode material for a sodium ion battery can significantly improve the discharge specific capacity and first Coulombic efficiency.
  • the carbonaceous material precursor includes at least one of corn starch, coconut shell, phenolic resin, polyethylene, humic acid and lignite.
  • the mesh number of the carbonaceous material precursor is 300 to 500 mesh, such as 300 mesh, 325 mesh, 400 mesh or 500 mesh.
  • the carbonaceous material precursor is pre-treated before use, and the pre-treatment is: pickling with a mixed acid solution of hydrochloric acid and hydrofluoric acid.
  • the concentrations of the hydrochloric acid and hydrofluoric acid are independently 0.5-1 mol/L, and the concentrations are, for example, 0.5 mol/L, 0.6 mol/L, 0.8 mol/L, 0.9 mol/L or 1 mol/L, etc.
  • concentrations of hydrochloric acid and hydrofluoric acid can be the same or different.
  • the volume ratio of hydrochloric acid and hydrofluoric acid is (1-2):(1-2), such as 1:1, 1.5:1, 2:1, 1:1.5 or 1:2, etc.
  • the pretreatment is followed by steps of washing, separation and drying.
  • This application does not limit the specific operations of washing and separation.
  • it may be suction filtration and washing until the pH value of the filtered water becomes neutral.
  • the application does not limit the drying method.
  • it can be oven drying.
  • the drying temperature is preferably 60-80°C, such as 60°C, 65°C, 70°C, 72°C, 75°C, 78°C or 80°C.
  • the drying time is preferably 12 to 24h, such as 12h, 14h, 15h, 18h, 20h, 21h, 23h or 24h, etc.
  • Impurities in the carbonaceous material precursor containing impurities can be removed through pretreatment, and those skilled in the art can choose whether to pretreat the carbonaceous material precursor as needed.
  • the carbonization treatment in step (1) is performed under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium.
  • the carbonization treatment includes low-temperature sintering and high-temperature carbonization.
  • Low-temperature sintering before high-temperature carbonization is mainly to allow some volatile components to fully react and form micropores inside for sodium ion storage. If high-temperature carbonization is carried out directly, the number of micropores obtained will be relatively small, which will lead to The capacity is relatively low.
  • the insulation temperature for low-temperature sintering is 200-600°C, such as 200°C, 240°C, 280°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 550°C °C or 600 °C, etc.; the holding time is 3 to 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc.
  • the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min, such as 3°C/min, 4°C/min, or 5°C/min.
  • the insulation temperature for high-temperature carbonization is 1200-1600°C, such as 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C or 1600°C, etc.;
  • the holding time is 1 to 3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc.
  • the heating rate is 5 to 10°C/min, such as 5°C/min, 6°C/min. min, 7°C/min, 8°C/min, 9°C/min or 10°C/min, etc.
  • the oxygen concentration is lower than 200 ppm, such as 180 ppm, 160 ppm, 150 ppm, 120 ppm, 100 ppm, 80 ppm or 50 ppm, etc.
  • step (1) also includes the step of cooling after heat preservation, generally cooling to room temperature.
  • step (1) when the carbon material obtained by the carbonization treatment in step (1) is agglomerated, a crushing step is performed before the refinement in step (1').
  • step (1′) the particle size of the powder is refined to meet: Dv50 is 3 to 6 ⁇ m, such as 3 ⁇ m, 3.5 ⁇ m, 3.8 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m or 6 ⁇ m, etc.; Dv10 is 1 ⁇ 4 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 3.8 ⁇ m or 4 ⁇ m, etc.; Dv99 is 10 ⁇ 15 ⁇ m, For example, 10 ⁇ m, 11 ⁇ m, 11.5 ⁇ m, 12 ⁇ m, 13 ⁇ m, 13.5 ⁇ m, 14 ⁇ m or 15 ⁇ m, etc. Refining the powder is beneficial to the subsequent preparation of battery pole pieces, so that the battery slurry has appropriate viscosity and fineness.
  • step (1') crush the powder until the particle size is less than 2mm, such as 1.8mm, 1.7mm, 1.5mm, 1.4mm, 1.3mm, 1.2mm, 1.1mm, 1mm, 0.9mm, 0.8mm, 0.5mm, 0.4mm, 0.3mm or 0.2mm, etc.
  • the equipment used for crushing and refining is not limited.
  • the equipment used for crushing can be, for example, one or both of a jaw crusher and a roller machine used in combination.
  • the equipment used for refinement may be, for example, a jet mill.
  • the crushing step in step (1') is performed in two steps.
  • a jaw crusher is used to crush the particles to a size less than 10mm (for example, 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm). , 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm, etc.), and then use a pair of rollers to continue crushing until the particle size is less than 2mm.
  • the mass ratio of the carbon material to the remaining carbonaceous material precursor is 1:1 to 1:3.5, such as 1:1, 1 :1.5, 1:2, 1:2.5 or 1:3, etc., preferably 1:2.5 to 1:3.5. If the amount of carbon material added is too small, the temperature uniformity will be poor and the effect of improving sintering uniformity will be reduced; if there is too much carbon material, the processing cost will increase.
  • step (2) a gravity-free mixer is used for mixing, and the mixing time is 1 to 5 minutes, such as 1 minute, 2 minutes, 3 minutes, 4 minutes or 5 minutes, etc.
  • the sintering in step (2) is performed under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium.
  • the sintering includes low-temperature sintering and high-temperature sintering.
  • Low-temperature sintering before high-temperature sintering is mainly to allow some volatile components to fully react and form micropores inside for sodium ion storage. Direct high-temperature sintering will result in a relatively small number of micropores, which will lead to The quantity is relatively low.
  • the insulation temperature for low-temperature sintering is 200-600°C, such as 200°C, 240°C, 280°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 550°C °C or 600 °C, etc.; the holding time is 3 to 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc.
  • the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min, such as 3°C/min, 4°C/min, or 5°C/min.
  • the heat preservation temperature for high-temperature sintering is 1200-1600°C, such as 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C or 1600°C, etc.;
  • the holding time is 1 to 3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc.
  • the heating rate is 5 to 10°C/min, such as 5°C/min, 6°C/min. min, 7°C/min, 8°C/min, 9°C/min or 10°C/min, etc.
  • the oxygen concentration is lower than 200 ppm, such as 180 ppm, 160 ppm, 150 ppm, 120 ppm, 100 ppm, 80 ppm or 50 ppm, etc.
  • the sintering system of step (2) is the same as the sintering system of carbonization treatment of step (1).
  • the sintering system includes the temperature of heat preservation in each stage, the heating rate, the time of heat preservation, etc.
  • step (2) also includes the step of cooling after heat preservation, generally cooling to room temperature.
  • step (2) when the carbonaceous material obtained by sintering in step (2) agglomerates, a crushing step is performed before the refining in step (2').
  • step (2') refine the powder until the particle size satisfies:
  • Dv50 is 3-6 ⁇ m, for example, 3 ⁇ m, 3.5 ⁇ m, 3.8 ⁇ m, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m or 6 ⁇ m, etc.
  • Dv10 is 1 ⁇ 4 ⁇ m, such as 1 ⁇ m, 1.5 ⁇ m, 2 ⁇ m, 2.5 ⁇ m, 3 ⁇ m, 3.5 ⁇ m, 3.8 ⁇ m or 4 ⁇ m, etc.
  • Dv99 is 10 ⁇ 15 ⁇ m, such as 10 ⁇ m, 11 ⁇ m, 11.5 ⁇ m, 12 ⁇ m, 13 ⁇ m, 13.5 ⁇ m, 14 ⁇ m or 15 ⁇ m, etc.
  • step (2') crush the powder until the particle size is less than 2mm, such as 1.8mm, 1.7mm, 1.5mm, 1.4mm, 1.3mm, 1.2mm, 1.1mm, 1mm, 0.9mm, 0.8mm, 0.5mm, 0.4mm, 0.3mm or 0.2mm, etc.
  • the equipment used for crushing and refining is not limited.
  • the equipment used for crushing can be, for example, one or both of a jaw crusher and a roller machine used in combination.
  • the equipment used for refinement may be, for example, a jet mill.
  • the crushing step in step (2') is performed in two steps.
  • a jaw crusher is used to crush the particles to a size less than 10mm (for example, 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm). , 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm, etc.), and then use a pair of rollers to continue crushing until the particle size is less than 2mm.
  • the method includes the following steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and the hard carbon precursor of 300 to 500 mesh in a gravity-free mixer for 3 minutes at a mass ratio of 1:1 to 1:3.5;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger and place it in a nitrogen-protected sintering furnace. Raise the temperature to 200-600°C at 3-5°C/min and keep it for 3-6 hours, then raise the temperature to 1200-1600°C at 5-10°C/min and keep it for 1-3 hours, then cool to room temperature to obtain the finished hard carbon product;
  • the present application provides a carbonaceous material prepared by the method described in the first aspect.
  • the present application provides a sodium-ion battery, in which the negative electrode of the sodium-ion battery includes the carbonaceous material described in the second aspect.
  • This application utilizes the characteristic that the thermal conductivity of the carbonaceous material precursor is significantly improved after high-temperature carbonization treatment.
  • a part of the carbonaceous material precursor is pre-sintered to obtain the carbon material, and is evenly mixed with the carbonaceous material precursor, and sintering to prepare the final Finished carbon material.
  • the uniformity of performance of the carbonaceous material prepared by the above method is significantly improved, and the performance difference at different positions of the sagger is small.
  • Figure 1 is a schematic diagram of step (4) sintering in Example 1.
  • Figure 2 is a schematic diagram of the internal position of the sagger in one embodiment of the present application, where H represents the height, W represents the width, and L represents the length.
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh hard carbon precursor corn starch in a gravity-free mixer at a mass ratio of 1:1 for 3 minutes;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer for 3 minutes at a mass ratio of 1:2;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch at a mass ratio of 1:3. Mix in a gravity-free mixer for 3 minutes;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (2) Place the coconut shell powder obtained in step (1) into a graphite sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, and then raise the temperature to 1500°C at 5°C/min. And keep it warm for 2 hours, then cool to room temperature to obtain monoburned carbon;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, Cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh phenolic resin powder in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 400°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps: Steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh polyethylene powder in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 400°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (2) Place the humic acid powder obtained in step (1) into a graphite sagger, heat it to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, and then heat it up to 1500°C at 5°C/min. and keep warm 2h, cool to room temperature to obtain monoburned carbon;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (2) Place the lignite powder obtained in step (1) into a graphite sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, then raise the temperature to 1500°C at 5°C/min and Keep it warm for 2 hours, then cool to room temperature to obtain monoburned carbon;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
  • This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 350°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 5 hours, then raise the temperature to 1450°C at 10°C/min and keep it warm. 2.5h, cool to room temperature to obtain the finished hard carbon product;
  • This comparative example provides a method for preparing hard carbon negative electrode materials for sodium ion batteries, including the following specific steps:
  • step (3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer at a mass ratio of 1:4 for 3 minutes;
  • step (3) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at 5°C/min and keep it for 2 hours. , cool to room temperature to obtain the finished hard carbon product;
  • step (3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer at a mass ratio of 1:5 for 3 minutes;
  • step (3) The homogeneous mixture obtained in step (3) is heated to 230°C at 3°C/min in a nitrogen-protected sintering furnace and kept for 4 hours, then heated to 1500°C at 5°C/min and kept for 2 hours, and then cooled to room temperature to obtain Hard carbon finished product;
  • step (3) the monocarbonate powder and 300 mesh corn starch are mixed in a mass ratio of 1:10.
  • This comparative example provides a method for preparing hard carbon negative electrode materials for sodium ion batteries, including the following specific steps:
  • Example 1 The difference between this comparative example and Example 1 is that the steps (1) and (2) are not performed, and graphite with the same particle size distribution as in Example 1 is directly used.
  • Table 1 shows the specific surface area of the finished hard carbon products prepared in Examples 1 to 11 and Comparative Examples 1 to 2.
  • the specific data were obtained by testing with a specific surface area meter, where the comprehensive specific surface area is the sagger (referring to the steps of Examples 1 to 11 ( The sagger in 4), the specific surface area measured after the materials in each area of the sagger in step (1) of Comparative Examples 1 and 2 are evenly mixed (the position in the sagger in Table 1 is shown in Figure 2).
  • Electrochemical performance testing uses button cells.
  • the working electrode is to mix the active material (specifically, the carbon materials prepared in Examples 1 to 12 and Comparative Examples 1 to 2), conductive carbon, and sodium carboxymethyl cellulose in deionized water in a mass ratio of 95:2:3. It is then coated on copper foil, and sodium foil is used as the counter electrode.
  • the electrolyte is 1 mol/L NaClO 4 dissolved in an EC/PC (volume ratio of 1:1) mixed solvent and 5wt% FEC is added, and the separator is made of glass fiber. Assembling the button cells takes place in a glove box with oxygen and water levels below 1 ppm. Battery The electrochemical performance test was performed on an electrochemical workstation.
  • Table 2 shows the electrochemical properties of the hard carbon products prepared in Examples 1 to 11 and Comparative Examples 1 to 2.
  • the comprehensive first charge specific capacity is the charge specific capacity measured after the materials in each zone in the sagger are evenly mixed.
  • Examples 1, 2, 3, 4, 5, and 6 show that the two-step sintering process has a positive effect in improving the uniformity of electrochemical properties of biomass-based hard carbon, organic polymer-based hard carbon, and mineral-based hard carbon. .

Abstract

The present application discloses a carbonaceous material and a preparation method therefor, and a sodium-ion battery. The method comprises the following steps: (1) carbonizing a part of a carbonaceous material precursor to obtain a carbon material; and (2) mixing the carbon material with the remaining carbonaceous material precursor, and sintering the mixture to obtain the carbonaceous material. According to the present application, by using the characteristic that the thermal conductivity of the carbonaceous material precursor is remarkably improved after the carbonaceous material precursor is subjected to high-temperature carbonization treatment, a part of the carbonaceous material precursor is sintered in advance to obtain a carbon material, and the carbon material and the carbonaceous material precursor are uniformly mixed and sintered to prepare a final carbonaceous material finished product. The uniformity of the performance of the carbonaceous material prepared by means of the method is remarkably improved, and the performance difference at different positions of a saggar is small.

Description

一种碳质材料、其制备方法和钠离子电池A kind of carbonaceous material, its preparation method and sodium-ion battery 技术领域Technical field
本申请涉及钠离子电池技术领域，涉及一种碳质材料、其制备方法和钠离子电池。The present application relates to the technical field of sodium-ion batteries, to a carbonaceous material, its preparation method and sodium-ion batteries.
背景技术Background technique
钠离子电池与锂离子电池的概念均在1970年至1980年之间提出，然而随着锂离子电池在1990年商业化，钠离子电池的相关研究几乎处于停滞状态，这种情况一直持续到20世纪末。阻碍钠离子电池发展的原因之一是缺乏合适的负极材料。近期由于锂价格的持续攀升，钠离子电池的研究重新引起了人们的关注，多种负极材料被认为在钠离子电池中具有应用潜力，包括合金、有机材料、碳质材料等。其中硬碳材料因具有高的储钠容量、合适的工作电位、优异的循环稳定性以及储量丰富等优势，被认为是最具应用前景的钠离子电池负极材料。The concepts of sodium-ion batteries and lithium-ion batteries were both proposed between 1970 and 1980. However, with the commercialization of lithium-ion batteries in 1990, related research on sodium-ion batteries was almost at a standstill. This situation lasted until the 20th century. end of the century. One of the reasons hindering the development of sodium-ion batteries is the lack of suitable anode materials. Recently, due to the continued rise in lithium prices, the research on sodium-ion batteries has attracted renewed attention. A variety of negative electrode materials are considered to have application potential in sodium-ion batteries, including alloys, organic materials, carbonaceous materials, etc. Among them, hard carbon materials are considered to be the most promising anode materials for sodium-ion batteries due to their high sodium storage capacity, suitable working potential, excellent cycle stability, and abundant reserves.
现阶段制备硬碳材料的前驱体主要包括生物质材料，如玉米淀粉、椰壳、木材等；有机高分子材料，如酚醛树脂、聚乙烯、聚苯胺等；矿物质材料，如腐植酸、褐煤、褐煤等。为得到储钠性能优异的硬碳材料，需根据不同硬碳前驱体的分子结构采用不同的烧结工艺对其进行烧结处理。然而，绝大多数硬碳前驱体的导热能力较差，导致同一匣钵中不同位置烧结出样品性能差异性较大。在硬碳前驱体热处理过程中加入导热性能优异的导热介质可有效提升硬碳前驱体的受热均匀性，但存在引入杂质相的风险。同时，硬碳前驱体多数为有机高分子粉料，因其具有扬尘***的风险导致提升加热均匀性的回转窑并不适用于制备硬碳材料。The precursors for preparing hard carbon materials at this stage mainly include biomass materials, such as corn starch, coconut shell, wood, etc.; organic polymer materials, such as phenolic resin, polyethylene, polyaniline, etc.; mineral materials, such as humic acid, lignite , lignite, etc. In order to obtain hard carbon materials with excellent sodium storage properties, different sintering processes need to be used to sinter different hard carbon precursors according to their molecular structures. However, most hard carbon precursors have poor thermal conductivity, resulting in large differences in the performance of samples sintered at different locations in the same sagger. Adding a thermal conductive medium with excellent thermal conductivity during the heat treatment of the hard carbon precursor can effectively improve the heating uniformity of the hard carbon precursor, but there is a risk of introducing impurity phases. At the same time, most hard carbon precursors are organic polymer powders. Due to the risk of dust explosion, the rotary kiln that improves heating uniformity is not suitable for preparing hard carbon materials.
因此，有必要一种提升烧结均匀性的烧结方法，以提升碳质材料的质量。 Therefore, a sintering method that improves sintering uniformity is necessary to improve the quality of carbonaceous materials.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
针对现有技术中存在的上述问题，本申请的目的在于提供一种碳质材料、其制备方法和钠离子电池。本申请的方法能够提升碳质材料的烧结均匀性，适用性十分广泛，对碳质材料工艺的改进具有现实意义。In view of the above-mentioned problems existing in the prior art, the purpose of this application is to provide a carbonaceous material, its preparation method and a sodium-ion battery. The method of the present application can improve the sintering uniformity of carbonaceous materials, has very wide applicability, and has practical significance for the improvement of carbonaceous material processes.
为达上述目的，本申请采用以下技术方案：In order to achieve the above purpose, this application adopts the following technical solutions:
第一方面，本申请提供一种碳质材料的制备方法，所述方法包括以下步骤：In a first aspect, this application provides a method for preparing carbonaceous materials, which method includes the following steps:
(1)将一部分碳质材料前驱体进行碳化处理，得到碳材料；(1) Carbonize a part of the carbonaceous material precursor to obtain a carbon material;
(2)将所述的碳材料与剩余的碳质材料前驱体混合，烧结，得到所述的碳质材料。(2) Mix the carbon material with the remaining carbonaceous material precursor and sinter to obtain the carbonaceous material.
本申请中，步骤(2)所述碳化处理和步骤(4)烧结过程中，需要将物料放入匣钵中，本申请对匣钵的具体种类不作限定，包括但不限于石墨匣钵或刚玉匣钵。In this application, during the carbonization treatment in step (2) and the sintering process in step (4), the materials need to be put into a sagger. This application does not limit the specific type of sagger, including but not limited to graphite saggers or corundum. Sagger.
本申请利用碳质材料前驱体经高温碳化处理后其导热性能有显著地提升的特性，预先烧结一部分碳质材料前驱体得到碳材料并将其与碳质材料前驱体混合均匀，烧结制备最终的碳质材料成品。通过上述方法制备的碳质材料性能的均一性显著提升，在匣钵不同位置处性能差异性较小。This application utilizes the characteristic that the thermal conductivity of the carbonaceous material precursor is significantly improved after high-temperature carbonization treatment. A part of the carbonaceous material precursor is pre-sintered to obtain the carbon material, and is evenly mixed with the carbonaceous material precursor, and sintering to prepare the final Finished carbon material. The uniformity of performance of the carbonaceous material prepared by the above method is significantly improved, and the performance difference at different positions of the sagger is small.
本申请中，碳质材料可以是硬碳材料，将该方法制备得到的硬碳材料作为钠离子电池负极材料，可以显著提升放电比容量和首次库伦效率。In this application, the carbonaceous material may be a hard carbon material. Using the hard carbon material prepared by this method as an anode material for a sodium ion battery can significantly improve the discharge specific capacity and first Coulombic efficiency.
以下作为本申请优选的技术方案，但不作为对本申请提供的技术方案的限制，通过以下优选的技术方案，可以更好的达到和实现本申请的技术目的和有益效果。 The following are preferred technical solutions for this application, but are not intended to limit the technical solutions provided by this application. Through the following preferred technical solutions, the technical objectives and beneficial effects of this application can be better achieved and realized.
可选地，所述碳质材料前驱体包括玉米淀粉、椰壳、酚醛树脂、聚乙烯、腐植酸和褐煤中的至少一种。Optionally, the carbonaceous material precursor includes at least one of corn starch, coconut shell, phenolic resin, polyethylene, humic acid and lignite.
可选地，所述碳质材料前驱体的目数为300～500目，例如300目、325目、400目或500目等。Optionally, the mesh number of the carbonaceous material precursor is 300 to 500 mesh, such as 300 mesh, 325 mesh, 400 mesh or 500 mesh.
可选地，所述碳质材料前驱体在使用前经预处理，所述预处理为：采用盐酸和氢氟酸的混合酸液进行酸洗。Optionally, the carbonaceous material precursor is pre-treated before use, and the pre-treatment is: pickling with a mixed acid solution of hydrochloric acid and hydrofluoric acid.
可选地，所述盐酸和氢氟酸的浓度独立地为0.5～1mol/L，浓度例如0.5mol/L、0.6mol/L、0.8mol/L、0.9mol/L或1mol/L等。其中，“独立地”指盐酸和氢氟酸的浓度可以相同也可以不同。Optionally, the concentrations of the hydrochloric acid and hydrofluoric acid are independently 0.5-1 mol/L, and the concentrations are, for example, 0.5 mol/L, 0.6 mol/L, 0.8 mol/L, 0.9 mol/L or 1 mol/L, etc. Among them, "independently" means that the concentrations of hydrochloric acid and hydrofluoric acid can be the same or different.
可选地，所述盐酸和氢氟酸的体积比为(1～2):(1～2)，例如1:1、1.5:1、2:1、1:1.5或1:2等。Optionally, the volume ratio of hydrochloric acid and hydrofluoric acid is (1-2):(1-2), such as 1:1, 1.5:1, 2:1, 1:1.5 or 1:2, etc.
可选地，所述预处理后进行洗涤、分离和干燥的步骤。本申请对洗涤和分离的具体操作不作限定，例如可以是抽滤并洗涤至滤水的pH值呈中性。Optionally, the pretreatment is followed by steps of washing, separation and drying. This application does not limit the specific operations of washing and separation. For example, it may be suction filtration and washing until the pH value of the filtered water becomes neutral.
本申请对干燥的方式不作限定，例如可以是烘干，烘干的温度优选为60～80℃，例如60℃、65℃、70℃、72℃、75℃、78℃或80℃等，烘干的时间优选为12～24h，例如12h、14h、15h、18h、20h、21h、23h或24h等。The application does not limit the drying method. For example, it can be oven drying. The drying temperature is preferably 60-80°C, such as 60°C, 65°C, 70°C, 72°C, 75°C, 78°C or 80°C. The drying time is preferably 12 to 24h, such as 12h, 14h, 15h, 18h, 20h, 21h, 23h or 24h, etc.
通过预处理可以去除含有杂质的碳质材料前驱体中的杂质，本领域技术人员可根据需要选择是否对碳质材料前驱体进行预处理。Impurities in the carbonaceous material precursor containing impurities can be removed through pretreatment, and those skilled in the art can choose whether to pretreat the carbonaceous material precursor as needed.
作为本申请所述方法的一个优选技术方案，步骤(1)所述碳化处理在保护气体的保护下进行，所述保护气体选自氮气、氩气或氦气中的至少一种。As a preferred technical solution of the method described in this application, the carbonization treatment in step (1) is performed under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium.
可选地，步骤(1)中，所述碳化处理包括低温烧结和高温碳化。在高温碳化之前进行低温烧结主要是为了让一些挥发性成分充分反应，在内部形成微孔供钠离子存储。若直接进行高温碳化会导致得到的微孔数量相对较少，进而导 致容量相对偏低。Optionally, in step (1), the carbonization treatment includes low-temperature sintering and high-temperature carbonization. Low-temperature sintering before high-temperature carbonization is mainly to allow some volatile components to fully react and form micropores inside for sodium ion storage. If high-temperature carbonization is carried out directly, the number of micropores obtained will be relatively small, which will lead to The capacity is relatively low.
可选地，步骤(1)中，低温烧结的保温温度为200～600℃，例如200℃、240℃、280℃、300℃、325℃、350℃、400℃、450℃、500℃、550℃或600℃等；保温时间为3～6h，例如3h、3.5h、4h、4.5h、5h、5.5h或6h等。Optionally, in step (1), the insulation temperature for low-temperature sintering is 200-600°C, such as 200°C, 240°C, 280°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 550°C ℃ or 600 ℃, etc.; the holding time is 3 to 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc.
可选地，步骤(1)中，升温至低温烧结的保温温度的升温速率为3～5℃/min，例如3℃/min、4℃/min或5℃/min等。Optionally, in step (1), the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min, such as 3°C/min, 4°C/min, or 5°C/min.
可选地，步骤(1)中，高温碳化的保温温度为1200～1600℃，例如1200℃、1250℃、1300℃、1350℃、1400℃、1450℃、1500℃、1550℃或1600℃等；保温时间为1～3h，例如1h、1.5h、2h、2.5h或3h等。Optionally, in step (1), the insulation temperature for high-temperature carbonization is 1200-1600°C, such as 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C or 1600°C, etc.; The holding time is 1 to 3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc.
可选地，步骤(1)中，从所述低温烧结的保温温度升温至所述高温碳化的保温温度的过程中，升温速率为5～10℃/min，例如5℃/min、6℃/min、7℃/min、8℃/min、9℃/min或10℃/min等。Optionally, in step (1), during the process of rising from the low-temperature sintering insulation temperature to the high-temperature carbonization insulation temperature, the heating rate is 5 to 10°C/min, such as 5°C/min, 6°C/min. min, 7℃/min, 8℃/min, 9℃/min or 10℃/min, etc.
可选地，步骤(1)所述碳化处理的保温过程中，氧浓度低于200ppm，例如180ppm、160ppm、150ppm、120ppm、100ppm、80ppm或50ppm等。Optionally, during the heat preservation process of the carbonization treatment in step (1), the oxygen concentration is lower than 200 ppm, such as 180 ppm, 160 ppm, 150 ppm, 120 ppm, 100 ppm, 80 ppm or 50 ppm, etc.
本领域技术人员应该理解，步骤(1)所述碳化处理还包括在保温后进行冷却的步骤，一般冷却至室温。Those skilled in the art should understand that the carbonization treatment in step (1) also includes the step of cooling after heat preservation, generally cooling to room temperature.
作为本申请所述方法的又一优选技术方案，步骤(1)所述碳化处理后进行步骤(1＇)：细化。As another preferred technical solution of the method described in this application, step (1'): refinement is performed after the carbonization treatment in step (1).
可选地，当步骤(1)所述碳化处理得到的碳材料结块时，步骤(1＇)所述细化前还进行破碎的步骤。Optionally, when the carbon material obtained by the carbonization treatment in step (1) is agglomerated, a crushing step is performed before the refinement in step (1').
可选地，步骤(1＇)中，细化至粉末的粒径满足：Dv50为3～6μm，例如3μm、3.5μm、3.8μm、4μm、4.5μm、5μm、5.5μm或6μm等；Dv10为1～4μm，例如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、3.8μm或4μm等；Dv99为10～15μm， 例如10μm、11μm、11.5μm、12μm、13μm、13.5μm、14μm或15μm等。将粉体细化有利于后续电池极片的制备，使电池浆料具有合适的粘度和细度。Optionally, in step (1′), the particle size of the powder is refined to meet: Dv50 is 3 to 6 μm, such as 3 μm, 3.5 μm, 3.8 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm or 6 μm, etc.; Dv10 is 1～4μm, such as 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 3.8μm or 4μm, etc.; Dv99 is 10～15μm, For example, 10 μm, 11 μm, 11.5 μm, 12 μm, 13 μm, 13.5 μm, 14 μm or 15 μm, etc. Refining the powder is beneficial to the subsequent preparation of battery pole pieces, so that the battery slurry has appropriate viscosity and fineness.
可选地，步骤(1＇)中，破碎至粉末的粒径小于2mm，例如1.8mm、1.7mm、1.5mm、1.4mm、1.3mm、1.2mm、1.1mm、1mm、0.9mm、0.8mm、0.5mm、0.4mm、0.3mm或0.2mm等。Optionally, in step (1'), crush the powder until the particle size is less than 2mm, such as 1.8mm, 1.7mm, 1.5mm, 1.4mm, 1.3mm, 1.2mm, 1.1mm, 1mm, 0.9mm, 0.8mm, 0.5mm, 0.4mm, 0.3mm or 0.2mm, etc.
本申请步骤(1＇)中，对破碎和细化采用的设备不作限定，破碎采用的设备例如可以是鄂破机和对辊机中的一种或两种配合使用。细化采用的设备例如可以是气流磨。In step (1') of the present application, the equipment used for crushing and refining is not limited. The equipment used for crushing can be, for example, one or both of a jaw crusher and a roller machine used in combination. The equipment used for refinement may be, for example, a jet mill.
在一个实施例中，步骤(1＇)中破碎的步骤分两步进行，先使用鄂破机破碎至颗粒尺寸为小于10mm(例如9.5mm、9mm、8.5mm、8mm、7mm、6.5mm、6mm、5.5mm、5mm、4mm、3.5mm、3mm或2.5mm等)，再使用对辊机继续破碎至颗粒尺寸为粒径小于2mm。In one embodiment, the crushing step in step (1') is performed in two steps. First, a jaw crusher is used to crush the particles to a size less than 10mm (for example, 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm). , 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm, etc.), and then use a pair of rollers to continue crushing until the particle size is less than 2mm.
作为本申请所述方法的再一优选技术方案，步骤(2)中，所述的碳材料与剩余的碳质材料前驱体的质量比为1:1～1:3.5，例如1:1、1:1.5、1:2、1:2.5或1:3等，优选为1:2.5～1:3.5。若碳材料加入量过少，温度均匀性较差，改善烧结均匀性的效果下降；若碳材料过多，则加工成本上升。As another preferred technical solution of the method described in the present application, in step (2), the mass ratio of the carbon material to the remaining carbonaceous material precursor is 1:1 to 1:3.5, such as 1:1, 1 :1.5, 1:2, 1:2.5 or 1:3, etc., preferably 1:2.5 to 1:3.5. If the amount of carbon material added is too small, the temperature uniformity will be poor and the effect of improving sintering uniformity will be reduced; if there is too much carbon material, the processing cost will increase.
可选地，步骤(2)中，采用无重力混合机进行混合，混合的时间为1～5min，例如1min、2min、3min、4min或5min等。Optionally, in step (2), a gravity-free mixer is used for mixing, and the mixing time is 1 to 5 minutes, such as 1 minute, 2 minutes, 3 minutes, 4 minutes or 5 minutes, etc.
可选地，步骤(2)所述烧结在保护气体的保护下进行，所述保护气体选自氮气、氩气或氦气中的至少一种。Optionally, the sintering in step (2) is performed under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium.
可选地，步骤(2)中，所述烧结包括低温烧结和高温烧结。在高温烧结之前进行低温烧结主要是为了让一些挥发性成分充分反应，在内部形成微孔供钠离子存储。若直接进行高温烧结会导致得到的微孔数量相对较少，进而导致容 量相对偏低。Optionally, in step (2), the sintering includes low-temperature sintering and high-temperature sintering. Low-temperature sintering before high-temperature sintering is mainly to allow some volatile components to fully react and form micropores inside for sodium ion storage. Direct high-temperature sintering will result in a relatively small number of micropores, which will lead to The quantity is relatively low.
可选地，步骤(2)中，低温烧结的保温温度为200～600℃，例如200℃、240℃、280℃、300℃、325℃、350℃、400℃、450℃、500℃、550℃或600℃等；保温时间为3～6h，例如3h、3.5h、4h、4.5h、5h、5.5h或6h等。Optionally, in step (2), the insulation temperature for low-temperature sintering is 200-600°C, such as 200°C, 240°C, 280°C, 300°C, 325°C, 350°C, 400°C, 450°C, 500°C, 550°C ℃ or 600 ℃, etc.; the holding time is 3 to 6h, such as 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, etc.
可选地，步骤(2)中，升温至低温烧结的保温温度的升温速率为3～5℃/min，例如3℃/min、4℃/min或5℃/min等。Optionally, in step (2), the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min, such as 3°C/min, 4°C/min, or 5°C/min.
可选地，步骤(2)中，高温烧结的保温温度为1200～1600℃，例如1200℃、1250℃、1300℃、1350℃、1400℃、1450℃、1500℃、1550℃或1600℃等；保温时间为1～3h，例如1h、1.5h、2h、2.5h或3h等。Optionally, in step (2), the heat preservation temperature for high-temperature sintering is 1200-1600°C, such as 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C or 1600°C, etc.; The holding time is 1 to 3h, such as 1h, 1.5h, 2h, 2.5h or 3h, etc.
可选地，步骤(2)中，从所述低温烧结的保温温度升温至所述高温烧结的保温温度的过程中，升温速率为5～10℃/min，例如5℃/min、6℃/min、7℃/min、8℃/min、9℃/min或10℃/min等。Optionally, in step (2), during the process of heating from the low-temperature sintering holding temperature to the high-temperature sintering holding temperature, the heating rate is 5 to 10°C/min, such as 5°C/min, 6°C/min. min, 7℃/min, 8℃/min, 9℃/min or 10℃/min, etc.
可选地，步骤(2)所述烧结的保温过程中，氧浓度低于200ppm，例如180ppm、160ppm、150ppm、120ppm、100ppm、80ppm或50ppm等。Optionally, during the heat preservation process of sintering in step (2), the oxygen concentration is lower than 200 ppm, such as 180 ppm, 160 ppm, 150 ppm, 120 ppm, 100 ppm, 80 ppm or 50 ppm, etc.
可选地，步骤(2)烧结的制度和步骤(1)碳化处理的烧结制度相同，烧结制度包括各阶段保温的温度、升温速率和保温的时间等。Optionally, the sintering system of step (2) is the same as the sintering system of carbonization treatment of step (1). The sintering system includes the temperature of heat preservation in each stage, the heating rate, the time of heat preservation, etc.
本领域技术人员应该理解，步骤(2)所述烧结还包括在保温后进行冷却的步骤，一般冷却至室温。Those skilled in the art should understand that the sintering in step (2) also includes the step of cooling after heat preservation, generally cooling to room temperature.
作为本申请所述方法的再一优选技术方案，步骤(2)所述烧结后进行步骤(2＇)：细化。As another preferred technical solution of the method described in this application, step (2'): refinement is performed after the sintering in step (2).
可选地，当步骤(2)所述烧结得到的碳质材料结块时，步骤(2＇)所述细化前还进行破碎的步骤。Optionally, when the carbonaceous material obtained by sintering in step (2) agglomerates, a crushing step is performed before the refining in step (2').
可选地，步骤(2＇)中，细化至粉末的粒径满足：Dv50为3～6μm，例如3μm、 3.5μm、3.8μm、4μm、4.5μm、5μm、5.5μm或6μm等；Dv10为1～4μm，例如1μm、1.5μm、2μm、2.5μm、3μm、3.5μm、3.8μm或4μm等；Dv99为10～15μm，例如10μm、11μm、11.5μm、12μm、13μm、13.5μm、14μm或15μm等。Optionally, in step (2'), refine the powder until the particle size satisfies: Dv50 is 3-6 μm, for example, 3 μm, 3.5μm, 3.8μm, 4μm, 4.5μm, 5μm, 5.5μm or 6μm, etc.; Dv10 is 1~4μm, such as 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 3.8μm or 4μm, etc.; Dv99 is 10 ~15 μm, such as 10 μm, 11 μm, 11.5 μm, 12 μm, 13 μm, 13.5 μm, 14 μm or 15 μm, etc.
可选地，步骤(2＇)中，破碎至粉末的粒径小于2mm，例如1.8mm、1.7mm、1.5mm、1.4mm、1.3mm、1.2mm、1.1mm、1mm、0.9mm、0.8mm、0.5mm、0.4mm、0.3mm或0.2mm等。Optionally, in step (2'), crush the powder until the particle size is less than 2mm, such as 1.8mm, 1.7mm, 1.5mm, 1.4mm, 1.3mm, 1.2mm, 1.1mm, 1mm, 0.9mm, 0.8mm, 0.5mm, 0.4mm, 0.3mm or 0.2mm, etc.
本申请步骤(2＇)中，对破碎和细化采用的设备不作限定，破碎采用的设备例如可以是鄂破机和对辊机中的一种或两种配合使用。细化采用的设备例如可以是气流磨。In step (2') of this application, the equipment used for crushing and refining is not limited. The equipment used for crushing can be, for example, one or both of a jaw crusher and a roller machine used in combination. The equipment used for refinement may be, for example, a jet mill.
在一个实施例中，步骤(2＇)中破碎的步骤分两步进行，先使用鄂破机破碎至颗粒尺寸为小于10mm(例如9.5mm、9mm、8.5mm、8mm、7mm、6.5mm、6mm、5.5mm、5mm、4mm、3.5mm、3mm或2.5mm等)，再使用对辊机继续破碎至颗粒尺寸为粒径小于2mm。In one embodiment, the crushing step in step (2') is performed in two steps. First, a jaw crusher is used to crush the particles to a size less than 10mm (for example, 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm). , 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm, etc.), and then use a pair of rollers to continue crushing until the particle size is less than 2mm.
作为本申请所述方法的进一步优选技术方案，所述方法包括以下步骤：As a further preferred technical solution of the method described in this application, the method includes the following steps:
(1)将300～500目的硬碳前驱体置于石墨匣钵中，在氮气保护的烧结炉中以3～5℃/min升温至200～600℃并保温3～6h，随后以5～10℃/min升温至1200～1600℃并保温1～3h，冷却至室温得到一烧碳；(1) Place the hard carbon precursor of 300 to 500 mesh in a graphite sagger, raise the temperature to 200 to 600°C at 3 to 5°C/min in a nitrogen-protected sintering furnace and keep it warm for 3 to 6 hours, and then heat it to 5 to 10 °C/min. Raise the temperature to 1200~1600°C and keep it for 1~3h. Cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于10mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将一烧碳处理至Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size of less than 10mm, then use a pair of rollers to crush the particle size to less than 2mm, and finally use an airflow mill to process the burnt carbon to a Dv50 of 3 to 6 μm. Dv10 is 1~4μm, Dv99 is 10~15μm;
(3)将步骤(2)得到的一烧碳粉末与300～500目的硬碳前驱体按质量比为1:1～1:3.5在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the hard carbon precursor of 300 to 500 mesh in a gravity-free mixer for 3 minutes at a mass ratio of 1:1 to 1:3.5;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中 以3～5℃/min升温至200～600℃并保温3～6h，随后以5～10℃/min升温至1200～1600℃并保温1～3h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger and place it in a nitrogen-protected sintering furnace. Raise the temperature to 200-600°C at 3-5°C/min and keep it for 3-6 hours, then raise the temperature to 1200-1600°C at 5-10°C/min and keep it for 1-3 hours, then cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于10mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将硬碳成品处理至Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products until the particle size is less than 10mm, then use a pair of rollers to crush the particle size to less than 2mm, and finally use an airflow mill to process the hard carbon products until the Dv50 is 3~6μm. Dv10 is 1~4μm, Dv99 is 10~15μm.
第二方面，本申请提供一种如第一方面所述的方法制备得到的碳质材料。In a second aspect, the present application provides a carbonaceous material prepared by the method described in the first aspect.
第三方面，本申请提供一种钠离子电池，所述钠离子电池的负极中包括第二方面所述的碳质材料。In a third aspect, the present application provides a sodium-ion battery, in which the negative electrode of the sodium-ion battery includes the carbonaceous material described in the second aspect.
与已有技术相比，本申请具有如下有益效果：Compared with the existing technology, this application has the following beneficial effects:
本申请利用碳质材料前驱体经高温碳化处理后其导热性能有显著地提升的特性，预先烧结一部分碳质材料前驱体得到碳材料并将其与碳质材料前驱体混合均匀，烧结制备最终的碳质材料成品。通过上述方法制备的碳质材料性能的均一性显著提升，在匣钵不同位置处性能差异性较小。This application utilizes the characteristic that the thermal conductivity of the carbonaceous material precursor is significantly improved after high-temperature carbonization treatment. A part of the carbonaceous material precursor is pre-sintered to obtain the carbon material, and is evenly mixed with the carbonaceous material precursor, and sintering to prepare the final Finished carbon material. The uniformity of performance of the carbonaceous material prepared by the above method is significantly improved, and the performance difference at different positions of the sagger is small.
采用本申请的方法制备硬碳材料并将其作为钠离子电池负极材料，可以显著提升放电比容量和首次库伦效率。Using the method of this application to prepare hard carbon materials and using them as negative electrode materials for sodium-ion batteries can significantly improve the discharge specific capacity and first Coulombic efficiency.
在阅读并理解了附图和详细描述后，可以明白其他方面。Other aspects will be apparent after reading and understanding the drawings and detailed description.
附图说明Description of drawings
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solutions herein, and do not constitute a limitation of the technical solutions herein.
图1实施例1步骤(4)烧结的示意图。Figure 1 is a schematic diagram of step (4) sintering in Example 1.
图2本申请一个实施例中匣钵内位置示意图，其中，H表示高度，W表示宽度，L表示长度。 Figure 2 is a schematic diagram of the internal position of the sagger in one embodiment of the present application, where H represents the height, W represents the width, and L represents the length.
具体实施方式Detailed ways
下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。The technical solution of the present application will be further described below with reference to the accompanying drawings and through specific implementation methods.
实施例1Example 1
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目硬碳前驱体玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place the 300-mesh hard carbon precursor corn starch in a graphite sagger, heat it to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, and then heat it up to 1500°C at 5°C/min. Keep it warm for 2 hours, then cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目硬碳前驱体玉米淀粉按质量比为1:1在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh hard carbon precursor corn starch in a gravity-free mixer at a mass ratio of 1:1 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例2Example 2
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min 升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place 300 mesh corn starch in a graphite sagger and bake it in a nitrogen-protected sintering furnace at 3°C/min. Raise the temperature to 230°C and keep it for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it for 2 hours, then cool to room temperature to obtain monocarbonate;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目玉米淀粉按质量比为1:2在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer for 3 minutes at a mass ratio of 1:2;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例3Example 3
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place 300 mesh corn starch in a graphite sagger, raise the temperature to 230°C at a rate of 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at a rate of 5°C/min and keep it for 2 hours, then cool. to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目玉米淀粉按质量比为1:3在 无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch at a mass ratio of 1:3. Mix in a gravity-free mixer for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例4Example 4
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目椰壳粉置于盐酸和氢氟酸混合液中进行酸洗，盐酸和氢氟酸的浓度均为1mol/L，盐酸和氢氟酸的体积比为1:1，酸洗后产物通过抽滤洗涤至滤水pH值呈中性，随后在80℃烘箱中干燥12h；(1) Place 300 mesh coconut shell powder in a mixture of hydrochloric acid and hydrofluoric acid for pickling. The concentrations of hydrochloric acid and hydrofluoric acid are both 1mol/L. The volume ratio of hydrochloric acid and hydrofluoric acid is 1:1. After washing, the product is washed by suction filtration until the pH value of the filtered water is neutral, and then dried in an oven at 80°C for 12 hours;
(2)将步骤(1)得到的椰壳粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(2) Place the coconut shell powder obtained in step (1) into a graphite sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, and then raise the temperature to 1500°C at 5°C/min. And keep it warm for 2 hours, then cool to room temperature to obtain monoburned carbon;
(3)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(3) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(4)将步骤(2)得到的一烧碳粉末与步骤(1)得到的椰壳粉按质量比为1:3在无重力混合机中混合3min；(4) Mix the calcined carbon powder obtained in step (2) and the coconut shell powder obtained in step (1) in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
(5)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温2h， 冷却至室温得到硬碳成品；(5) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, Cool to room temperature to obtain the finished hard carbon product;
(6)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(6) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5mm, then use a pair of rollers to crush the particle size to less than 1mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例5Example 5
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目酚醛树脂粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至400℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place 300 mesh phenolic resin powder in a graphite sagger, raise the temperature to 400°C at 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at 5°C/min and keep it for 2 hours. Cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目酚醛树脂粉按质量比为1:3在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh phenolic resin powder in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至400℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 400°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例6Example 6
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步 骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps: Steps:
(1)将300目聚乙烯粉末置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至400℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place 300 mesh polyethylene powder in a graphite sagger, raise the temperature to 400°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it for 2 hours. Cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目聚乙烯粉末按质量比为1:3在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the 300-mesh polyethylene powder in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至400℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 400°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例7Example 7
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目腐植酸粉置于盐酸和氢氟酸混合液中进行酸洗，盐酸和氢氟酸的浓度均为1mol/L，盐酸和氢氟酸的体积比为1:1，酸洗后产物通过抽滤洗涤至滤水pH值呈中性，随后在80℃烘箱中干燥12h；(1) Place 300 mesh humic acid powder in a mixture of hydrochloric acid and hydrofluoric acid for pickling. The concentrations of hydrochloric acid and hydrofluoric acid are both 1mol/L. The volume ratio of hydrochloric acid and hydrofluoric acid is 1:1. After washing, the product is washed by suction filtration until the pH value of the filtered water is neutral, and then dried in an oven at 80°C for 12 hours;
(2)将步骤(1)得到的腐植酸粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温 2h，冷却至室温得到一烧碳；(2) Place the humic acid powder obtained in step (1) into a graphite sagger, heat it to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, and then heat it up to 1500°C at 5°C/min. and keep warm 2h, cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与步骤(1)得到的腐植酸粉按质量比为1:3在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the humic acid powder obtained in step (1) in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例8Example 8
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将300目褐煤粉置于盐酸和氢氟酸混合液中进行酸洗，盐酸和氢氟酸的浓度均为1mol/L，酸洗后产物通过抽滤洗涤至滤水pH值呈中性，随后在80℃烘箱中干燥12h；(1) Place 300 mesh lignite powder in a mixture of hydrochloric acid and hydrofluoric acid for pickling. The concentrations of hydrochloric acid and hydrofluoric acid are both 1 mol/L. After pickling, the product is washed by suction filtration until the pH value of the filtered water is neutral. properties, and then dried in an oven at 80°C for 12 hours;
(2)将步骤(1)得到的褐煤粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(2) Place the lignite powder obtained in step (1) into a graphite sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it for 4 hours, then raise the temperature to 1500°C at 5°C/min and Keep it warm for 2 hours, then cool to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm， Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5mm, then use a pair of rollers to crush the particle size to less than 1mm, and finally use an airflow mill to process the burnt carbon to a Dv50 of 5μm. Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与步骤(1)得到的褐煤粉按质量比为1:3在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the lignite powder obtained in step (1) in a gravity-free mixer at a mass ratio of 1:3 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至300℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 300°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 4 hours, then raise the temperature to 1500°C at 5°C/min and keep it warm. 2h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例9Example 9
本实施例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This embodiment provides a method for preparing a hard carbon negative electrode material for a sodium ion battery, including the following specific steps:
(1)将400目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以4℃/min升温至260℃并保温6h，随后以8℃/min升温至1400℃并保温3h，冷却至室温得到一烧碳；(1) Place 400 mesh corn starch in a graphite sagger, raise the temperature to 260°C at 4°C/min in a nitrogen-protected sintering furnace and keep it warm for 6 hours, then raise the temperature to 1400°C at 8°C/min and keep it warm for 3 hours, then cool. to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将一烧碳处理至Dv50为6μm，Dv10为3μm，Dv99为12.5μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 2 mm, and finally use an airflow mill to process the burnt carbon to a Dv50 of 6 μm and a Dv10 of 3μm, Dv99 is 12.5μm;
(3)将步骤(2)得到的一烧碳粉末与步骤(1)得到的褐煤粉按质量比为1:3在无重力混合机中混合5min；(3) Mix the calcined carbon powder obtained in step (2) and the lignite powder obtained in step (1) in a gravity-free mixer at a mass ratio of 1:3 for 5 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3℃/min升温至350℃并保温5h，随后以10℃/min升温至1450℃并保温2.5h，冷却至室温得到硬碳成品； (4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 350°C at 3°C/min in a nitrogen-protected sintering furnace and keep it warm for 5 hours, then raise the temperature to 1450°C at 10°C/min and keep it warm. 2.5h, cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将硬碳成品处理至Dv50为6μm，Dv10为3μm，Dv99为12.5μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 2 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 6 μm and a Dv10 of 3μm, Dv99 is 12.5μm.
实施例10Example 10
本对比例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This comparative example provides a method for preparing hard carbon negative electrode materials for sodium ion batteries, including the following specific steps:
(1)将300目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到一烧碳；(1) Place 300 mesh corn starch in a graphite sagger, raise the temperature to 230°C at a rate of 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at a rate of 5°C/min and keep it for 2 hours, then cool. to room temperature to obtain monoburned carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目玉米淀粉按质量比为1:4在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer at a mass ratio of 1:4 for 3 minutes;
(4)将步骤(3)得到的均匀混合物放入匣钵，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 230°C at 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at 5°C/min and keep it for 2 hours. , cool to room temperature to obtain the finished hard carbon product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例11Example 11
(1)将300目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室 温得到一烧碳；(1) Place 300 mesh corn starch in a graphite sagger, raise the temperature to 230°C at a rate of 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at a rate of 5°C/min and keep it for 2 hours, then cool. To the room Warm to obtain burnt carbon;
(2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为5μm，Dv10为2μm，Dv99为12μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the burnt carbon until Dv50 is 5 μm and Dv10 is 2μm, Dv99 is 12μm;
(3)将步骤(2)得到的一烧碳粉末与300目玉米淀粉按质量比为1:5在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and 300 mesh corn starch in a gravity-free mixer at a mass ratio of 1:5 for 3 minutes;
(4)将步骤(3)得到的均匀混合物在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(4) The homogeneous mixture obtained in step (3) is heated to 230°C at 3°C/min in a nitrogen-protected sintering furnace and kept for 4 hours, then heated to 1500°C at 5°C/min and kept for 2 hours, and then cooled to room temperature to obtain Hard carbon finished product;
(5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将硬碳成品处理至Dv50为5μm，Dv10为2μm，Dv99为12μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products to a particle size of less than 5 mm, then use a pair of rollers to crush the particle size to less than 1 mm, and finally use an airflow mill to process the hard carbon products to a Dv50 of 5 μm and a Dv10 of 2μm, Dv99 is 12μm.
实施例12Example 12
与实施例1的区别在于，步骤(3)中，一烧碳粉末与300目玉米淀粉按质量比为1:10混合。The difference from Example 1 is that in step (3), the monocarbonate powder and 300 mesh corn starch are mixed in a mass ratio of 1:10.
对比例1Comparative example 1
本对比例提供一种钠离子电池硬碳负极材料的制备方法，包括以下具体步骤：This comparative example provides a method for preparing hard carbon negative electrode materials for sodium ion batteries, including the following specific steps:
(1)将300目玉米淀粉置于石墨匣钵中，在氮气保护的烧结炉中以3℃/min升温至230℃并保温4h，随后以5℃/min升温至1500℃并保温2h，冷却至室温得到硬碳成品；(1) Place 300 mesh corn starch in a graphite sagger, raise the temperature to 230°C at a rate of 3°C/min and keep it for 4 hours in a nitrogen-protected sintering furnace, then raise the temperature to 1500°C at a rate of 5°C/min and keep it for 2 hours, then cool. to room temperature to obtain the finished hard carbon product;
(2)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于5mm，随后使用对辊机将颗粒尺寸破碎至小于1mm，最后使用气流磨将一烧碳处理至Dv50为 5μm，Dv10为2μm，Dv99为12μm。(2) Use a jaw crusher to crush the agglomerated hard carbon products until the particle size is less than 5mm, then use a pair of rollers to crush the particle size to less than 1mm, and finally use an airflow mill to process the burnt carbon to Dv50. 5μm, Dv10 is 2μm, Dv99 is 12μm.
对比例2Comparative example 2
本对比例与实施例1的区别在于，不进行步骤(1)和步骤(2)，而直接采用与实施例1具有相同粒径分布的石墨。The difference between this comparative example and Example 1 is that the steps (1) and (2) are not performed, and graphite with the same particle size distribution as in Example 1 is directly used.
成品质量：Finished product quality:
表1为实施例1～11与对比例1～2制备的硬碳成品的比表面积，具体数据由比表面积测定仪测试得到，其中综合比表面积为匣钵(指的是实施例1～11步骤(4)中的匣钵，对比例1和2步骤(1)的匣钵)中各区材料混合均匀后测得的比表面积(表1中匣钵内位置如图2所示)。Table 1 shows the specific surface area of the finished hard carbon products prepared in Examples 1 to 11 and Comparative Examples 1 to 2. The specific data were obtained by testing with a specific surface area meter, where the comprehensive specific surface area is the sagger (referring to the steps of Examples 1 to 11 ( The sagger in 4), the specific surface area measured after the materials in each area of the sagger in step (1) of Comparative Examples 1 and 2 are evenly mixed (the position in the sagger in Table 1 is shown in Figure 2).
表1 硬碳产品的比表面积

Table 1 Specific surface area of hard carbon products

由表1可知，实施例1各区比表面积值相接近，而对比例1各区比表面积值相差较大，且实施例1的综合比表面积值低于对比例1，表明相较于一步烧结，本申请通过两步烧结工艺可以保证样品的烧结质量，有效提升硬碳成品的均一性。同时，实施例1～12的结果表明两步烧结工艺在提升生物质类硬碳、有机高分子类硬碳、矿物质类硬碳的均一性方面均有积极的效果。It can be seen from Table 1 that the specific surface area values of each area in Example 1 are close, while the specific surface area values in each area in Comparative Example 1 are quite different, and the comprehensive specific surface area value of Example 1 is lower than Comparative Example 1, indicating that compared with one-step sintering, this method has Applying for a two-step sintering process can ensure the sintering quality of the sample and effectively improve the uniformity of the hard carbon finished product. At the same time, the results of Examples 1 to 12 show that the two-step sintering process has a positive effect in improving the uniformity of biomass-based hard carbon, organic polymer-based hard carbon, and mineral-based hard carbon.
实施例1、2、3各区比表面积值差异性明显小于实施例12，表明一烧碳的质量占比相对较小时不能保证样品的受热均匀性。The difference in specific surface area values of each zone in Examples 1, 2, and 3 is significantly smaller than that in Example 12, indicating that the heating uniformity of the sample cannot be guaranteed when the mass proportion of burnt carbon is relatively small.
电化学性能：Electrochemical properties:
电化学性能测试使用纽扣电池。工作电极是将活性物质(具体为实施例1～12和对比例1～2制备的碳材料)、导电碳、羧甲基纤维素钠按质量比为95:2:3在去离子水中混合均匀后涂覆于铜箔上制得，对电极使用钠箔。电解液为1mol/L的NaClO4溶于EC/PC(体积比为1:1)混合溶剂中并添加5wt％FEC，隔膜采用玻璃纤维。扣式电池的组装在氧气和水含量均低于1ppm的手套箱中进行。电池 的电化学性能测试在电化学工作站上进行。Electrochemical performance testing uses button cells. The working electrode is to mix the active material (specifically, the carbon materials prepared in Examples 1 to 12 and Comparative Examples 1 to 2), conductive carbon, and sodium carboxymethyl cellulose in deionized water in a mass ratio of 95:2:3. It is then coated on copper foil, and sodium foil is used as the counter electrode. The electrolyte is 1 mol/L NaClO 4 dissolved in an EC/PC (volume ratio of 1:1) mixed solvent and 5wt% FEC is added, and the separator is made of glass fiber. Assembling the button cells takes place in a glove box with oxygen and water levels below 1 ppm. Battery The electrochemical performance test was performed on an electrochemical workstation.
表2为实施例1～11与对比例1～2制得的硬碳成品的电化学性能，其中综合首次充电比容量为匣钵中各区材料混合均匀后测得的充电比容量。Table 2 shows the electrochemical properties of the hard carbon products prepared in Examples 1 to 11 and Comparative Examples 1 to 2. The comprehensive first charge specific capacity is the charge specific capacity measured after the materials in each zone in the sagger are evenly mixed.
表2 硬碳产品的首次充电比容量对比

Table 2 Comparison of first charge specific capacity of hard carbon products

由表2可知，实施例1各区首次充电比容量相接近，而对比例1各区首次充电比容量相差较大，且实施例1的综合首次充电比容量高于对比例1，表明相较于一步烧结，两步烧结工艺既可以提升硬碳成品的均一性，也可以提升所制备硬碳成品的电化学性能。It can be seen from Table 2 that the first charge specific capacity of each area in Example 1 is close, while the first charge specific capacity of each area in Comparative Example 1 is quite different, and the comprehensive first charge specific capacity of Example 1 is higher than that of Comparative Example 1, indicating that compared with the one-step Sintering, the two-step sintering process can not only improve the uniformity of the hard carbon finished product, but also improve the electrochemical performance of the prepared hard carbon finished product.
实施例1、2、3各区首次充电比容量差异性明显小于实施例12，表明一烧碳的质量占比相对较小时不能保证样品电化学性能的均一性。The difference in first charge specific capacity in each zone of Examples 1, 2, and 3 is significantly smaller than that of Example 12, indicating that the uniformity of the electrochemical performance of the sample cannot be guaranteed when the mass proportion of burnt carbon is relatively small.
实施例1、2、3、4、5、6表明两步烧结工艺在提升生物质类硬碳、有机高分子类硬碳、矿物质类硬碳电化学性能的均一性方面均有积极的效果。Examples 1, 2, 3, 4, 5, and 6 show that the two-step sintering process has a positive effect in improving the uniformity of electrochemical properties of biomass-based hard carbon, organic polymer-based hard carbon, and mineral-based hard carbon. .
申请人声明，本申请通过上述实施例来说明本申请的详细方法，但本申请并不局限于上述详细方法，即不意味着本申请必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。 The applicant declares that this application illustrates the detailed methods of the present application through the above embodiments, but the present application is not limited to the above detailed methods, that is, it does not mean that the present application must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvements to the present application, equivalent replacement of raw materials of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.

Claims (14)

  1. 一种碳质材料的制备方法，其中，所述方法包括以下步骤：A method for preparing carbonaceous materials, wherein the method includes the following steps:
    (1)将一部分碳质材料前驱体进行碳化处理，得到碳材料；(1) Carbonize a part of the carbonaceous material precursor to obtain a carbon material;
    (2)将所述的碳材料与剩余的碳质材料前驱体混合，烧结，得到所述的碳质材料。(2) Mix the carbon material with the remaining carbonaceous material precursor and sinter to obtain the carbonaceous material.
  2. 根据权利要求1所述的方法，其中，所述碳质材料前驱体包括玉米淀粉、椰壳、酚醛树脂、聚乙烯、腐植酸和褐煤中的至少一种。The method according to claim 1, wherein the carbonaceous material precursor includes at least one of corn starch, coconut shell, phenolic resin, polyethylene, humic acid and lignite.
  3. 根据权利要求2所述的方法，其中，所述碳质材料前驱体的目数为300～500目。The method according to claim 2, wherein the mesh number of the carbonaceous material precursor is 300 to 500 mesh.
  4. 根据权利要求2所述的方法，其特征在于其中，所述碳质材料前驱体在使用前经预处理，所述预处理为：采用盐酸和氢氟酸的混合酸液进行酸洗；The method according to claim 2, wherein the carbonaceous material precursor is pretreated before use, and the pretreatment is: pickling with a mixed acid solution of hydrochloric acid and hydrofluoric acid;
    可选地，所述盐酸和氢氟酸的浓度独立地为0.5～1mol/L；Optionally, the concentrations of hydrochloric acid and hydrofluoric acid are independently 0.5 to 1 mol/L;
    可选地，所述盐酸和氢氟酸的体积比为(1～2):(1～2)；Optionally, the volume ratio of hydrochloric acid and hydrofluoric acid is (1～2): (1～2);
    可选地，所述预处理后进行洗涤、分离和干燥的步骤。Optionally, the pretreatment is followed by steps of washing, separation and drying.
  5. 根据权利要求1或2或3或4所述的方法，其中，步骤(1)所述碳化处理在保护气体的保护下进行，所述保护气体选自氮气、氩气或氦气中的至少一种。The method according to claim 1 or 2 or 3 or 4, wherein the carbonization treatment in step (1) is carried out under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium. kind.
  6. 根据权利要求5所述的方法，其中，步骤(1)中，所述碳化处理包括低温烧结和高温碳化；The method according to claim 5, wherein in step (1), the carbonization treatment includes low-temperature sintering and high-temperature carbonization;
    可选地，步骤(1)中，低温烧结的保温温度为200～600℃，保温时间为3～6h；Optionally, in step (1), the insulation temperature for low-temperature sintering is 200-600°C, and the insulation time is 3-6 hours;
    可选地，步骤(1)中，升温至低温烧结的保温温度的升温速率为3～5℃/min；Optionally, in step (1), the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min;
    可选地，步骤(1)中，高温碳化的保温温度为1200～1600℃，保温时间为1～3h；Optionally, in step (1), the insulation temperature for high-temperature carbonization is 1200-1600°C, and the insulation time is 1-3 hours;
    可选地，步骤(1)中，从所述低温烧结的保温温度升温至所述高温碳化的 保温温度的过程中，升温速率为5～10℃/min；Optionally, in step (1), the temperature is raised from the low-temperature sintering insulation temperature to the high-temperature carbonization temperature. During the heat preservation process, the heating rate is 5 to 10°C/min;
    可选地，步骤(1)所述碳化处理的保温过程中，氧浓度低于200ppm。Optionally, during the heat preservation process of the carbonization treatment in step (1), the oxygen concentration is lower than 200 ppm.
  7. 根据权利要求1-6任一项所述的方法，其中，步骤(1)所述碳化处理后进行步骤(1＇)：细化；The method according to any one of claims 1 to 6, wherein step (1'): refinement is performed after the carbonization treatment in step (1);
    可选地，当步骤(1)所述碳化处理得到的碳材料结块时，步骤(1＇)所述细化前还进行破碎的步骤；Optionally, when the carbon material obtained by the carbonization treatment in step (1) is agglomerated, a crushing step is performed before the refinement in step (1');
    可选地，步骤(1＇)中，细化至粉末的粒径满足：Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm；Optionally, in step (1'), refine the powder until the particle size meets: Dv50 is 3-6 μm, Dv10 is 1-4 μm, and Dv99 is 10-15 μm;
    可选地，步骤(1＇)中，破碎至粉末的粒径小于2mm。Optionally, in step (1'), crush the powder until the particle size is less than 2 mm.
  8. 根据权利要求1-7任一项所述的方法，其中，步骤(2)中，所述的碳材料与剩余的碳质材料前驱体的质量比为1:1～1:3.5，优选为1:2.5～1:3.5；The method according to any one of claims 1 to 7, wherein in step (2), the mass ratio of the carbon material to the remaining carbonaceous material precursor is 1:1 to 1:3.5, preferably 1 :2.5～1:3.5;
  9. 根据权利要求8任一项所述的方法，其中，步骤(2)中，采用无重力混合机进行混合，混合的时间为1～5min。The method according to any one of claims 8, wherein in step (2), a gravity-free mixer is used for mixing, and the mixing time is 1 to 5 minutes.
  10. 根据权利要求1-9任一项所述的方法，其中，步骤(2)所述烧结在保护气体的保护下进行，所述保护气体选自氮气、氩气或氦气中的至少一种；The method according to any one of claims 1 to 9, wherein the sintering in step (2) is performed under the protection of a protective gas, and the protective gas is selected from at least one of nitrogen, argon or helium;
    可选地，步骤(2)中，所述烧结包括低温烧结和高温烧结；Optionally, in step (2), the sintering includes low-temperature sintering and high-temperature sintering;
    可选地，步骤(2)中，低温烧结的保温温度为200～600℃，保温时间为3～6h；Optionally, in step (2), the insulation temperature for low-temperature sintering is 200-600°C, and the insulation time is 3-6 hours;
    可选地，步骤(2)中，升温至低温烧结的保温温度的升温速率为3～5℃/min；Optionally, in step (2), the heating rate to the holding temperature for low-temperature sintering is 3 to 5°C/min;
    可选地，步骤(2)中，高温烧结的保温温度为1200～1600℃，保温时间为1～3h；Optionally, in step (2), the insulation temperature for high-temperature sintering is 1200-1600°C, and the insulation time is 1-3 hours;
    可选地，步骤(2)中，从所述低温烧结的保温温度升温至所述高温烧结的保温温度的过程中，升温速率为5～10℃/min；Optionally, in step (2), in the process of rising from the insulation temperature of low-temperature sintering to the insulation temperature of high-temperature sintering, the temperature rise rate is 5-10°C/min;
    可选地，步骤(2)所述烧结的保温过程中，氧浓度低于200ppm。 Optionally, during the heat preservation process of sintering in step (2), the oxygen concentration is lower than 200 ppm.
  11. 根据权利要求1-10任一项所述的方法，其中，步骤(2)所述烧结后进行步骤(2＇)：细化；The method according to any one of claims 1 to 10, wherein step (2'): refinement is performed after the sintering in step (2);
    可选地，当步骤(2)所述烧结得到的碳质材料结块时，步骤(2＇)所述细化前还进行破碎的步骤；Optionally, when the carbonaceous material obtained by sintering in step (2) agglomerates, a crushing step is performed before the refining in step (2');
    可选地，步骤(2＇)中，细化至粉末的粒径满足：Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm；Optionally, in step (2'), refine the powder until the particle size meets: Dv50 is 3-6 μm, Dv10 is 1-4 μm, and Dv99 is 10-15 μm;
    可选地，步骤(2＇)中，破碎至粉末的粒径小于2mm。Optionally, in step (2'), the powder is crushed until the particle size is less than 2 mm.
  12. 根据权利要求1-11任一项所述的方法，其中，所述方法包括以下步骤：The method according to any one of claims 1-11, wherein the method includes the following steps:
    (1)将300～500目的硬碳前驱体置于石墨匣钵中，在氮气保护的烧结炉中以3～5℃/min升温至200～600℃并保温3～6h，随后以5～10℃/min升温至1200～1600℃并保温1～3h，冷却至室温得到一烧碳；(1) Place the hard carbon precursor of 300 to 500 mesh in a graphite sagger, raise the temperature to 200 to 600°C at 3 to 5°C/min in a nitrogen-protected sintering furnace and keep it warm for 3 to 6 hours, and then heat it to 5 to 10 °C/min. Raise the temperature to 1200~1600°C and keep it for 1~3h. Cool to room temperature to obtain monoburned carbon;
    (2)将结块的一烧碳使用鄂破机破碎至颗粒尺寸小于10mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将一烧碳处理至Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm；(2) Use a jaw crusher to crush the agglomerated burnt carbon to a particle size of less than 10mm, then use a pair of rollers to crush the particle size to less than 2mm, and finally use an airflow mill to process the burnt carbon to a Dv50 of 3 to 6 μm. Dv10 is 1~4μm, Dv99 is 10~15μm;
    (3)将步骤(2)得到的一烧碳粉末与300～500目的硬碳前驱体按质量比为1:1～1:3.5在无重力混合机中混合3min；(3) Mix the calcined carbon powder obtained in step (2) and the hard carbon precursor of 300 to 500 mesh in a gravity-free mixer for 3 minutes at a mass ratio of 1:1 to 1:3.5;
    (4)将步骤(3)得到的均匀混合物放入匣钵中，在氮气保护的烧结炉中以3～5℃/min升温至200～600℃并保温3～6h，随后以5～10℃/min升温至1200～1600℃并保温1～3h，冷却至室温得到硬碳成品；(4) Put the homogeneous mixture obtained in step (3) into a sagger, raise the temperature to 200-600°C at 3-5°C/min in a nitrogen-protected sintering furnace and keep it for 3-6 hours, and then heat it at 5-10°C /min, heat up to 1200~1600℃ and keep it for 1~3h, then cool to room temperature to obtain the finished hard carbon product;
    (5)将结块的硬碳成品使用鄂破机破碎至颗粒尺寸小于10mm，随后使用对辊机将颗粒尺寸破碎至小于2mm，最后使用气流磨将硬碳成品处理至Dv50为3～6μm，Dv10为1～4μm，Dv99为10～15μm。(5) Use a jaw crusher to crush the agglomerated hard carbon products until the particle size is less than 10mm, then use a pair of rollers to crush the particle size to less than 2mm, and finally use an airflow mill to process the hard carbon products until the Dv50 is 3~6μm. Dv10 is 1~4μm, Dv99 is 10~15μm.
  13. 一种如权利要求1-12任一项所述的方法制备得到的碳质材料。 A carbonaceous material prepared by the method according to any one of claims 1-12.
  14. 一种钠离子电池，其中，所述钠离子电池的负极中包括权利要求13所述的碳质材料。 A sodium-ion battery, wherein the negative electrode of the sodium-ion battery includes the carbonaceous material of claim 13.
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US20210242462A1 (en) * 2020-02-04 2021-08-05 Cpc Corporation, Taiwan Method of Manufacturing Biomass Hard Carbon for Negative Electrode of Sodium-ion Batteries and Sodium-ion Batteries Containing Biomass Hard Carbon Thereof
CN112397715A (en) * 2020-10-10 2021-02-23 北京化工大学 Hard carbon material, preparation method thereof and sodium ion battery
CN112661133A (en) * 2020-12-23 2021-04-16 浙江阿佩克斯能源科技有限公司 Preparation method of hard carbon material
CN113206246A (en) * 2021-04-27 2021-08-03 天津理工大学 Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof
CN113800496A (en) * 2021-08-06 2021-12-17 深圳市德方纳米科技股份有限公司 Hard carbon material and preparation method and application thereof
CN115159502A (en) * 2022-08-18 2022-10-11 广东邦普循环科技有限公司 Carbonaceous material, preparation method thereof and sodium ion battery

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