CN115159502A - Carbonaceous material, preparation method thereof and sodium ion battery - Google Patents

Carbonaceous material, preparation method thereof and sodium ion battery Download PDF

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Publication number
CN115159502A
CN115159502A CN202210993705.2A CN202210993705A CN115159502A CN 115159502 A CN115159502 A CN 115159502A CN 202210993705 A CN202210993705 A CN 202210993705A CN 115159502 A CN115159502 A CN 115159502A
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temperature
carbonaceous material
sintering
carbon
heating
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Inventor
张苗
阮丁山
李长东
毛林林
郑爽
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202210993705.2A priority Critical patent/CN115159502A/en
Publication of CN115159502A publication Critical patent/CN115159502A/en
Priority to PCT/CN2023/077075 priority patent/WO2024036902A1/en
Priority to FR2308765A priority patent/FR3138970A1/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

Abstract

The invention discloses a carbonaceous material, a preparation method thereof and a sodium ion battery. The method comprises the following steps: (1) Carbonizing a part of carbonaceous material precursor to obtain a carbon material; (2) And mixing the carbon material with the rest of the carbonaceous material precursor, and sintering to obtain the carbonaceous material. According to the invention, by utilizing the characteristic that the heat-conducting property 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 pre-sintered to obtain the carbon material, and the carbon material is uniformly mixed with the carbonaceous material precursor and sintered to prepare the final carbonaceous material finished product. The carbonaceous material prepared by the method has the advantages of obviously improved uniformity of performance and smaller performance difference at different positions of the saggar.

Description

Carbonaceous material, preparation method thereof and sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion batteries, and relates to a carbonaceous material, a preparation method thereof and a sodium ion battery.
Background
The concepts of sodium ion batteries and lithium ion batteries were both introduced in 1970 to 1980, however, with the commercialization of lithium ion batteries in 1990, the research on sodium ion batteries has almost stagnated, which has continued until the end of the 20 th century. One of the reasons impeding the development of sodium ion batteries is the lack of suitable anode materials. Recently, due to the continuous rise of lithium price, research on sodium ion batteries has attracted renewed attention, and various negative electrode materials are considered to have application potential in sodium ion batteries, including alloys, organic materials, carbonaceous materials, and the like. The hard carbon material has the advantages of high sodium storage capacity, proper working potential, excellent cycling stability, rich storage capacity and the like, and is considered to be the sodium ion battery cathode material with the most application prospect.
The precursor for preparing the hard carbon material at the present stage mainly comprises biomass materials, such as corn starch, coconut shells, wood and the like; organic high molecular materials such as phenol resin, polyethylene, polyaniline, and the like; mineral materials such as humic acid, lignite, etc. In order to obtain the hard carbon material with excellent sodium storage performance, different sintering processes are adopted to sinter the hard carbon material according to the molecular structures of different hard carbon precursors. However, most hard carbon precursors have poor thermal conductivity, resulting in greater variability in properties of sintered samples from different locations in the same sagger. The heat-conducting medium with excellent heat-conducting property is added in the heat treatment process of the hard carbon precursor, so that the heating uniformity of the hard carbon precursor can be effectively improved, but the risk of introducing an impurity phase exists. Meanwhile, most of hard carbon precursors are organic polymer powder, and the rotary kiln with the risk of dust explosion to improve the heating uniformity is not suitable for preparing hard carbon materials.
Therefore, there is a need for a sintering method that improves the uniformity of sintering to improve the quality of carbonaceous materials.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a carbonaceous material, a method for preparing the same, and a sodium ion battery. The method can improve the sintering uniformity of the carbonaceous material, has wide applicability and has practical significance for improving the process of the carbonaceous material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of a carbonaceous material, the process comprising the steps of:
(1) Carbonizing a part of carbonaceous material precursor to obtain a carbon material;
(2) And mixing the carbon material with the rest carbonaceous material precursor, and sintering to obtain the carbonaceous material.
In the present invention, during the carbonization treatment in step (2) and the sintering in step (4), the material needs to be put into the sagger, and the present invention does not limit the kind of the sagger, including but not limited to graphite sagger or corundum sagger.
According to the invention, by utilizing the characteristic that the heat-conducting property 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 pre-sintered to obtain the carbon material, and the carbon material is uniformly mixed with the carbonaceous material precursor and sintered to prepare the final carbonaceous material finished product. The carbonaceous material prepared by the method has the advantages of obviously improved uniformity of performance and smaller performance difference at different positions of the saggar.
According to the invention, the carbonaceous material can be a hard carbon material, and the hard carbon material prepared by the method can be used as a sodium ion battery cathode material, so that the discharge specific capacity and the first coulombic efficiency can be remarkably improved.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the carbonaceous material precursor includes at least one of corn starch, coconut shell, phenolic resin, polyethylene, humic acid, and lignite.
Preferably, the mesh number of the carbonaceous material precursor is 300 to 500 meshes, for example, 300 meshes, 325 meshes, 400 meshes, 500 meshes, or the like.
Preferably, the carbonaceous material precursor is pre-treated prior to use, the pre-treatment being: acid cleaning is carried out by adopting mixed acid liquid of hydrochloric acid and hydrofluoric acid.
Preferably, the concentration of the hydrochloric acid and the hydrofluoric acid is independently 0.5 to 1mol/L, such as 0.5mol/L, 0.6mol/L, 0.8mol/L, 0.9mol/L, or 1 mol/L. Wherein "independently" means that the concentrations of hydrochloric acid and hydrofluoric acid may be the same or different.
Preferably, the volume ratio of the hydrochloric acid to the hydrofluoric acid is (1-2) to (1-2), such as 1:1, 1.5.
Preferably, the pretreatment is followed by washing, separation and drying steps. The specific operation of washing and separation in the present invention is not limited, and may be, for example, suction filtration and washing until the pH of the filtrate becomes neutral.
The drying method is not limited in the present invention, and for example, the drying may be performed at a temperature of 60 to 80 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃, and the drying time is preferably 12 to 24 hours, for example, 12 hours, 14 hours, 15 hours, 18 hours, 20 hours, 21 hours, 23 hours or 24 hours.
Impurities in the carbonaceous material precursor containing the impurities can be removed by pretreatment, and a person skilled in the art can select whether to pretreat the carbonaceous material precursor according to needs.
As a preferable embodiment of the method of the present invention, the carbonization treatment in step (1) is performed under the protection of a protective gas, and the protective gas is at least one selected from nitrogen, argon, and helium.
Preferably, in the step (1), the carbonization treatment includes low-temperature sintering and high-temperature carbonization. The low-temperature sintering before high-temperature carbonization is mainly used for fully reacting some volatile components and forming micropores in the material for storing sodium ions. If the carbonization is directly carried out at a high temperature, the obtained micropores are relatively small in number, and the capacity is relatively low.
Preferably, in the step (1), the low-temperature sintering is performed at a holding temperature of 200 to 600 ℃, for example, 200 ℃, 240 ℃, 280 ℃, 300 ℃, 325 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, etc.; the heat preservation time is 3 to 6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours.
Preferably, in the step (1), the temperature rise rate of the temperature rise to the holding temperature of the low-temperature sintering is 3 to 5 ℃/min, for example, 3 ℃/min, 4 ℃/min, or 5 ℃/min.
Preferably, in the step (1), the high-temperature carbonization is performed at a holding temperature of 1200 to 1600 ℃, for example, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃ or the like; the heat preservation time is 1 to 3 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.
Preferably, in the step (1), in the process of raising the temperature from the holding temperature of the low-temperature sintering to the holding temperature of the high-temperature carbonization, the temperature raising rate is 5 to 10 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min.
Preferably, the oxygen concentration during the incubation of the carbonization treatment in step (1) is less than 200ppm, such as 180ppm, 160ppm, 150ppm, 120ppm, 100ppm, 80ppm or 50 ppm.
It will be understood by those skilled in the art that the carbonization treatment in step (1) may further include a cooling step after the temperature is maintained, typically to room temperature.
As another preferable embodiment of the method of the present invention, the carbonization treatment in the step (1) is followed by the step (1'): and (5) thinning.
Preferably, when the carbon material obtained by the carbonization treatment in the step (1) is agglomerated, the step (1') of crushing is further performed before the refining.
Preferably, in step (1'), the size of the powder is reduced to a size that satisfies: dv50 is 3 to 6 μm, for example 3 μm, 3.5 μm, 3.8 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm or 6 μm; dv10 is 1 to 4 μm, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 3.8 μm, or 4 μm; dv99 is 10 to 15 μm, for example, 10 μm, 11 μm, 11.5 μm, 12 μm, 13 μm, 13.5 μm, 14 μm or 15 μm. The powder is refined, so that the subsequent preparation of the battery pole piece is facilitated, and the battery slurry has proper viscosity and fineness.
Preferably, in step (1'), the powder is crushed to a particle size of less than 2mm, e.g. 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.
In the step (1') of the present invention, the equipment used for crushing and refining is not limited, and the equipment used for crushing may be, for example, one or both of a jaw crusher and a twin roll crusher. The equipment used for refining may be, for example, an air jet mill.
In one embodiment, the step of crushing in step (1') is carried out in two steps, first crushing to a particle size of less than 10mm (e.g. 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm, 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm etc.) using a jaw crusher and then continuing crushing to a particle size of less than 2mm using a twin roll crusher.
As a further preferable technical solution of the method of the present invention, in the step (2), the mass ratio of the carbonaceous material to the remaining carbonaceous material precursor is 1:1-1.5, for example, 1:1, 1.5, 1:2, 1. If the addition amount of the carbon material is too small, the temperature uniformity is poor, and the effect of improving the sintering uniformity is reduced; if the carbon material is too much, the processing cost increases.
Preferably, in step (2), the mixing is performed by a gravity-free mixer, and the mixing time is 1-5 min, such as 1min, 2min, 3min, 4min or 5min.
Preferably, the sintering in step (2) is performed under the protection of a protective gas, and the protective gas is at least one selected from nitrogen, argon or helium.
Preferably, in the step (2), the sintering includes low-temperature sintering and high-temperature sintering. The low-temperature sintering is carried out before the high-temperature sintering, which mainly aims to ensure that some volatile components are fully reacted and micropores are formed in the low-temperature sintering for storing sodium ions. If the sintering is directly carried out at a high temperature, the obtained micropores are relatively small in number, and the capacity is relatively low.
Preferably, in the step (2), the low-temperature sintering is performed at a temperature of 200 to 600 ℃, for example, 200 ℃, 240 ℃, 280 ℃, 300 ℃, 325 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃; the heat preservation time is 3 to 6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours.
Preferably, in the step (2), the temperature rise rate of the temperature rise to the holding temperature of the low-temperature sintering is 3 to 5 ℃/min, for example, 3 ℃/min, 4 ℃/min, or 5 ℃/min.
Preferably, in the step (2), the high-temperature sintering is performed at a holding temperature of 1200 to 1600 ℃, such as 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃ or 1600 ℃ and the like; the holding time is 1-3 h, such as 1h, 1.5h, 2h, 2.5h or 3 h.
Preferably, in the step (2), in the process of raising the temperature from the low-temperature sintering holding temperature to the high-temperature sintering holding temperature, the temperature raising rate is 5 to 10 ℃/min, such as 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min.
Preferably, the oxygen concentration during the heat preservation of the sintering in step (2) is less than 200ppm, such as 180ppm, 160ppm, 150ppm, 120ppm, 100ppm, 80ppm or 50 ppm.
Preferably, the sintering schedule in the step (2) is the same as that in the carbonization treatment in the step (1), and the sintering schedule comprises the temperature for heat preservation, the temperature rise rate, the heat preservation time and the like in each stage.
It will be understood by those skilled in the art that the sintering in step (2) may further include a cooling step after the heat preservation, typically to room temperature.
As a further preferable technical scheme of the method of the invention, the sintering in the step (2) is followed by the step (2'): and (5) thinning.
Preferably, when the sintered carbonaceous material obtained in step (2) is agglomerated, the step of crushing is further performed before the step of refining (2').
Preferably, in step (2'), the particle size of the powder is refined to satisfy: dv50 is 3 to 6 μm, for example 3 μm, 3.5 μm, 3.8 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm or 6 μm; dv10 is 1 to 4 μm, for example, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 3.8 μm, or 4 μm; dv99 is 10 to 15 μm, for example, 10 μm, 11 μm, 11.5 μm, 12 μm, 13 μm, 13.5 μm, 14 μm or 15 μm.
Preferably, in step (2'), the powder is crushed to a particle size of less than 2mm, e.g. 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.
In the step (2') of the present invention, the equipment used for crushing and refining is not limited, and the equipment used for crushing may be, for example, one or both of a jaw crusher and a twin roll crusher. The equipment used for refining may be, for example, an air jet mill.
In one embodiment, the step of crushing in step (2') is carried out in two steps, first crushing to a particle size of less than 10mm (e.g. 9.5mm, 9mm, 8.5mm, 8mm, 7mm, 6.5mm, 6mm, 5.5mm, 5mm, 4mm, 3.5mm, 3mm or 2.5mm etc.) using a jaw crusher and then continuing crushing to a particle size of less than 2mm using a twin roll mill.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) Placing a 300-500-mesh hard carbon precursor into a graphite sagger, heating to 200-600 ℃ at a speed of 3-5 ℃/min in a nitrogen-protected sintering furnace, preserving heat for 3-6 h, then heating to 1200-1600 ℃ at a speed of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated calcined carbon by using a jaw crusher until the particle size is smaller than 10mm, then crushing the particle size by using a double-roller crusher until the particle size is smaller than 2mm, and finally treating the calcined carbon by using an airflow mill until the Dv50 is 3-6 mu m, the Dv10 is 1-4 mu m and the Dv99 is 10-15 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) with a hard carbon precursor of 300-500 meshes in a gravity-free mixer for 3min according to the mass ratio of 1:1-1;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 200-600 ℃ at a speed of 3-5 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 3-6 h, then heating to 1200-1600 ℃ at a speed of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain a hard carbon finished product;
(5) Crushing the agglomerated hard carbon finished product to a particle size of less than 10mm by using a jaw crusher, then crushing the particle size of less than 2mm by using a double-roller crusher, and finally processing the hard carbon finished product by using an air flow mill until the Dv50 is 3-6 mu m, the Dv10 is 1-4 mu m and the Dv99 is 10-15 mu m.
In a second aspect, the present invention provides a carbonaceous material produced by the method of the first aspect.
In a third aspect, the present invention provides a sodium ion battery comprising a negative electrode comprising the carbonaceous material of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by utilizing the characteristic that the heat-conducting property 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 pre-sintered to obtain the carbon material, and the carbon material is uniformly mixed with the carbonaceous material precursor and sintered to prepare the final carbonaceous material finished product. The carbonaceous material prepared by the method has the advantages of obviously improved uniformity of performance and smaller performance difference at different positions of the saggar.
The hard carbon material prepared by the method is used as the negative electrode material of the sodium ion battery, so that the specific discharge capacity and the first coulombic efficiency can be remarkably improved.
Drawings
FIG. 1 schematic diagram of step (4) sintering of example 1.
FIG. 2 is a schematic diagram of the position in the saggar according to one embodiment of the present invention, wherein H represents the height, W represents the width, and L represents the length.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh hard carbon precursor corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh hard carbon precursor corn starch in a gravity-free mixer for 3min according to the mass ratio of 1:1;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 2
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a nitrogen-protected sintering furnace, preserving heat for 4 hours, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh corn starch in a non-gravity mixer for 3min according to the mass ratio of 1:2;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 3
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon char to a particle size of less than 5mm using a jaw crusher, subsequently crushing the particle size to a particle size of less than 1mm using a twin roll mill, and finally treating the primary carbon char using a jet mill to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh corn starch in a non-gravity mixer for 3min according to the mass ratio of 1:3;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 4
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh coconut shell powder into a mixed solution of hydrochloric acid and hydrofluoric acid for acid washing, wherein the concentrations of the hydrochloric acid and the hydrofluoric acid are both 1mol/L, the volume ratio of the hydrochloric acid to the hydrofluoric acid is 1:1, washing a product after acid washing by suction filtration until the pH value of filtered water is neutral, and then drying in an oven at 80 ℃ for 12 hours;
(2) Placing the coconut shell powder obtained in the step (1) in a graphite sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-fired carbon;
(3) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(4) Mixing the calcined carbon powder obtained in the step (2) and the coconut shell powder obtained in the step (1) in a gravity-free mixer for 3min according to the mass ratio of 1:3;
(5) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(6) Crushing the agglomerated hard carbon finished product to a particle size of less than 5mm by using a jaw crusher, then crushing the particle size of less than 1mm by using a double-roll crusher, and finally processing the hard carbon finished product to a Dv50 of 5 micrometers, a Dv10 of 2 micrometers and a Dv99 of 12 micrometers by using an air flow mill.
Example 5
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh phenolic resin powder in a graphite sagger, heating to 400 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh phenolic resin powder in a non-gravity mixer for 3min according to the mass ratio of 1:3;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 400 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 6
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh polyethylene powder in a graphite sagger, heating to 400 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh polyethylene powder according to the mass ratio of 1:3 in a gravity-free mixer for 3min;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 400 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 7
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing the humic acid powder of 300 meshes in a mixed solution of hydrochloric acid and hydrofluoric acid for acid cleaning, wherein the concentrations of the hydrochloric acid and the hydrofluoric acid are both 1mol/L, the volume ratio of the hydrochloric acid to the hydrofluoric acid is 1:1, washing a product after acid cleaning by suction filtration until the pH value of filtered water is neutral, and then drying in an oven at 80 ℃ for 12 hours;
(2) Placing the humic acid powder obtained in the step (1) in a graphite sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated primary carbon char to a particle size of less than 5mm using a jaw crusher, subsequently crushing the particle size to a particle size of less than 1mm using a twin roll mill, and finally treating the primary carbon char using a jet mill to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm;
(3) Mixing the calcined carbon powder obtained in the step (2) and the humic acid powder obtained in the step (1) in a gravity-free mixer for 3min according to the mass ratio of 1:3;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 8
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh brown coal powder into a mixed solution of hydrochloric acid and hydrofluoric acid for acid cleaning, wherein the concentrations of the hydrochloric acid and the hydrofluoric acid are both 1mol/L, washing a product after the acid cleaning by suction filtration until the pH value of filtered water is neutral, and then drying the product in an oven at 80 ℃ for 12 hours;
(2) Placing the brown coal powder obtained in the step (1) in a graphite sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and the brown coal powder obtained in the step (1) in a gravity-free mixer for 3min according to the mass ratio of 1:3;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 300 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 9
The embodiment provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 400-mesh corn starch in a graphite sagger, heating to 260 ℃ at a speed of 4 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 6h, then heating to 1400 ℃ at a speed of 8 ℃/min, preserving heat for 3h, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 2mm by using a double-roller crusher, and finally treating the primary carbon by using an airflow mill until the Dv50 is 6 mu m, the Dv10 is 3 mu m and the Dv99 is 12.5 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and the brown coal powder obtained in the step (1) in a gravity-free mixer for 5min according to the mass ratio of 1:3;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 350 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 5 hours, then heating to 1450 ℃ at a speed of 10 ℃/min, preserving heat for 2.5 hours, and cooling to room temperature to obtain a hard carbon finished product;
(5) Crushing the agglomerated hard carbon finished product to a particle size of less than 5mm by using a jaw crusher, then crushing the particle size of less than 2mm by using a double-roll crusher, and finally processing the hard carbon finished product to a Dv50 of 6 μm, a Dv10 of 3 μm and a Dv99 of 12.5 μm by using an air jet mill.
Example 10
The comparative example provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a nitrogen-protected sintering furnace, preserving heat for 4 hours, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh corn starch in a non-gravity mixer for 3min according to the mass ratio of 1:4;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 11
(1) Placing 300-mesh corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain primary-burned carbon;
(2) Crushing the agglomerated primary carbon into particles with the size of less than 5mm by using a jaw crusher, then crushing the particles with the size of less than 1mm by using a double-roller crusher, and finally treating the primary carbon by using an air flow mill until the Dv50 is 5 mu m, the Dv10 is 2 mu m and the Dv99 is 12 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) and 300-mesh corn starch in a non-gravity mixer for 3min according to the mass ratio of 1:5;
(4) Heating the uniform mixture obtained in the step (3) to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(5) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, subsequently crushed to a particle size of less than 1mm using a roll crusher, and finally treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Example 12
The difference from example 1 is that in step (3), the calcined carbon powder is mixed with 300-mesh corn starch in a mass ratio of 1.
Comparative example 1
The comparative example provides a preparation method of a hard carbon negative electrode material of a sodium ion battery, which comprises the following specific steps:
(1) Placing 300-mesh corn starch in a graphite sagger, heating to 230 ℃ at a speed of 3 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 4h, then heating to 1500 ℃ at a speed of 5 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain a hard carbon finished product;
(2) The agglomerated hard carbon finished product was crushed to a particle size of less than 5mm using a jaw crusher, followed by crushing to a particle size of less than 1mm using a roll crusher, and finally, the monocarbon was treated to a Dv50 of 5 μm, a Dv10 of 2 μm, and a Dv99 of 12 μm using a jet mill.
Comparative example 2
This comparative example differs from example 1 in that step (1) and step (2) are not performed, and graphite having the same particle size distribution as that of example 1 is directly used.
And (3) quality of a finished product:
table 1 shows specific surface areas of the hard carbon products prepared in examples 1 to 11 and comparative examples 1 to 2, and specific data are obtained by a specific surface area meter test, wherein the comprehensive specific surface area is the specific surface area measured after materials in each region are uniformly mixed in a sagger (referring to the sagger in step (4) of examples 1 to 11 and the sagger in step (1) of comparative examples 1 and 2) (the position in the sagger in table 1 is shown in fig. 2).
TABLE 1 specific surface area of hard carbon products
Figure BDA0003804787780000181
Figure BDA0003804787780000191
As can be seen from table 1, the specific surface area values of the regions in example 1 are close to each other, the specific surface area values of the regions in comparative example 1 are greatly different, and the comprehensive specific surface area value of example 1 is lower than that of comparative example 1, which indicates that compared with one-step sintering, the sintering quality of the sample can be ensured by the two-step sintering process, and the uniformity of the hard carbon finished product is effectively improved. Meanwhile, the results of examples 1 to 12 show that the two-step sintering process has a positive effect on improving the uniformity of biomass hard carbon, organic polymer hard carbon and mineral hard carbon.
The differences in specific surface area values among the regions of examples 1, 2 and 3 are significantly smaller than those of example 12, indicating that the uniformity of heating of the sample cannot be ensured when the mass ratio of the carbon monoxide is relatively small.
Electrochemical performance:
the electrochemical performance test used coin cells. The working electrode is prepared by uniformly mixing an active material (specifically, the carbon material prepared in examples 1 to 12 and comparative examples 1 to 2), conductive carbon and sodium carboxymethyl cellulose in deionized water according to a mass ratio of 95. Electrolyte is 1mol/L NaClO 4 Dissolving in EC/PC (volume ratio of 1:1) mixed solvent, and adding 5wt% FEC, glass fiber was used as separator. The assembly of the button cells was carried out in a glove box with oxygen and water contents below 1 ppm. Electrochemical performance testing of the cells was performed on an electrochemical workstation.
Table 2 shows the electrochemical properties of the hard carbon products obtained in examples 1 to 11 and comparative examples 1 to 2, wherein the integrated first charge specific capacity is the charge specific capacity measured after the materials in each region of the sagger were uniformly mixed.
TABLE 2 comparison of first Charge specific Capacity of hard carbon products
Figure BDA0003804787780000192
Figure BDA0003804787780000201
As can be seen from table 2, the first charge specific capacities of the regions in example 1 are close to each other, the first charge specific capacities of the regions in comparative example 1 are different from each other, and the comprehensive first charge specific capacity of example 1 is higher than that of comparative example 1, which indicates that compared with one-step sintering, the two-step sintering process can improve the uniformity of the hard carbon product and the electrochemical performance of the prepared hard carbon product.
The difference of the first charging specific capacities of the regions of examples 1, 2 and 3 is obviously smaller than that of example 12, which shows that the uniformity of the electrochemical performance of the sample cannot be ensured when the mass ratio of the one-time carbon is relatively small.
Examples 1, 2, 3, 4, 5 and 6 show that the two-step sintering process has a positive effect on improving the uniformity of electrochemical properties of biomass hard carbon, organic polymer hard carbon and mineral hard carbon.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A method of preparing a carbonaceous material, the method comprising the steps of:
(1) Carbonizing a part of carbonaceous material precursor to obtain a carbon material;
(2) And mixing the carbon material with the rest of the carbonaceous material precursor, and sintering to obtain the carbonaceous material.
2. The method of claim 1, wherein the carbonaceous material precursor comprises at least one of corn starch, coconut shell, phenolic resin, polyethylene, humic acid, and lignite;
preferably, the mesh number of the carbonaceous material precursor is 300-500 meshes;
preferably, the carbonaceous material precursor is pre-treated prior to use, the pre-treatment being: acid cleaning is carried out by adopting mixed acid liquid of hydrochloric acid and hydrofluoric acid;
preferably, the concentration of the hydrochloric acid and the hydrofluoric acid is 0.5-1 mol/L independently;
preferably, the volume ratio of the hydrochloric acid to the hydrofluoric acid is (1-2) to (1-2);
preferably, the pretreatment is followed by washing, separation and drying steps.
3. The method according to claim 1 or 2, wherein the carbonization treatment of step (1) is performed under the protection of a protective gas selected from at least one of nitrogen, argon or helium;
preferably, in the step (1), the carbonization treatment comprises low-temperature sintering and high-temperature carbonization;
preferably, in the step (1), the heat preservation temperature of the low-temperature sintering is 200-600 ℃, and the heat preservation time is 3-6 h;
preferably, in the step (1), the heating rate of the heating to the holding temperature of the low-temperature sintering is 3-5 ℃/min;
preferably, in the step (1), the heat preservation temperature of the high-temperature carbonization is 1200-1600 ℃, and the heat preservation time is 1-3 h;
preferably, in the step (1), in the process of raising the temperature from the heat preservation temperature of the low-temperature sintering to the heat preservation temperature of the high-temperature carbonization, the temperature raising rate is 5-10 ℃/min;
preferably, the oxygen concentration during the heat preservation of the carbonization treatment in the step (1) is less than 200ppm.
4. The method according to any one of claims 1 to 3, wherein the carbonization treatment of step (1) is followed by step (1'): thinning;
preferably, when the carbon material obtained by the carbonization treatment in the step (1) is agglomerated, the step (1') of crushing is further performed before the refining;
preferably, in step (1'), the particle size of the powder is refined to satisfy: dv50 is 3 to 6 μm, dv10 is 1 to 4 μm, dv99 is 10 to 15 μm;
preferably, in step (1'), the powder is crushed to a particle size of less than 2mm.
5. The method according to any one of claims 1 to 4, 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;
preferably, in the step (2), a gravity-free mixer is adopted for mixing, and the mixing time is 1-5 min.
6. The method according to any one of claims 1 to 5, wherein the sintering of step (2) is performed under the protection of a protective gas selected from at least one of nitrogen, argon or helium;
preferably, in the step (2), the sintering includes low-temperature sintering and high-temperature sintering;
preferably, in the step (2), the heat preservation temperature of the low-temperature sintering is 200-600 ℃, and the heat preservation time is 3-6 h;
preferably, in the step (2), the heating rate of heating to the holding temperature of the low-temperature sintering is 3-5 ℃/min;
preferably, in the step (2), the heat preservation temperature of the high-temperature sintering is 1200-1600 ℃, and the heat preservation time is 1-3 h;
preferably, in the step (2), in the process of heating from the heat preservation temperature of the low-temperature sintering to the heat preservation temperature of the high-temperature sintering, the heating rate is 5-10 ℃/min;
preferably, during the heat preservation of the sintering in the step (2), the oxygen concentration is lower than 200ppm.
7. The method according to any one of claims 1 to 6, wherein step (2) is followed by step (2'): thinning;
preferably, when the sintered carbonaceous material obtained in step (2) is agglomerated, the step (2') of pulverizing is further performed before the refining;
preferably, in step (2'), the size of the powder is reduced to a size that satisfies: dv50 is 3 to 6 μm, dv10 is 1 to 4 μm, dv99 is 10 to 15 μm;
preferably, in step (2'), the powder is crushed to a particle size of less than 2mm.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
(1) Placing a 300-500-mesh hard carbon precursor into a graphite sagger, heating to 200-600 ℃ at a rate of 3-5 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 3-6 h, then heating to 1200-1600 ℃ at a rate of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain primary-fired carbon;
(2) Crushing the agglomerated calcined carbon by using a jaw crusher until the particle size is smaller than 10mm, then crushing the particle size by using a double-roller crusher until the particle size is smaller than 2mm, and finally treating the calcined carbon by using an airflow mill until the Dv50 is 3-6 mu m, the Dv10 is 1-4 mu m and the Dv99 is 10-15 mu m;
(3) Mixing the calcined carbon powder obtained in the step (2) with a hard carbon precursor of 300-500 meshes in a gravity-free mixer for 3min according to the mass ratio of 1:1-1;
(4) Putting the uniform mixture obtained in the step (3) into a sagger, heating to 200-600 ℃ at a speed of 3-5 ℃/min in a sintering furnace protected by nitrogen, preserving heat for 3-6 h, then heating to 1200-1600 ℃ at a speed of 5-10 ℃/min, preserving heat for 1-3 h, and cooling to room temperature to obtain a hard carbon finished product;
(5) Crushing the agglomerated hard carbon finished product by using a jaw crusher until the particle size is less than 10mm, then crushing the particle size by using a double-roller crusher until the particle size is less than 2mm, and finally processing the hard carbon finished product by using an air flow mill until the Dv50 is 3-6 mu m, the Dv10 is 1-4 mu m and the Dv99 is 10-15 mu m.
9. A carbonaceous material produced by the process of any one of claims 1 to 8.
10. A sodium ion battery, characterized in that the carbonaceous material according to claim 9 is included in a negative electrode of the sodium ion battery.
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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
CN112968169A (en) * 2021-02-02 2021-06-15 常德速碳新能源科技有限公司 Composite negative electrode material for lithium ion battery and preparation method thereof
CN114702022A (en) * 2022-03-15 2022-07-05 广东邦普循环科技有限公司 Preparation method and application of hard carbon negative electrode material

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WO2024036902A1 (en) * 2022-08-18 2024-02-22 广东邦普循环科技有限公司 Carbonaceous material and preparation method therefor, and sodium-ion battery
CN115636405A (en) * 2022-10-31 2023-01-24 湖州强大分子筛科技有限公司 Preparation method of high-capacity hard carbon negative electrode material
CN115650699A (en) * 2022-12-08 2023-01-31 长沙中瓷新材料科技有限公司 Molded graphite sagger and preparation method and application thereof
CN115650699B (en) * 2022-12-08 2023-06-02 长沙中瓷新材料科技有限公司 Molded graphite sagger and preparation method and application thereof

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