CN113800496A - Hard carbon material and preparation method and application thereof - Google Patents
Hard carbon material and preparation method and application thereof Download PDFInfo
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- CN113800496A CN113800496A CN202110903683.1A CN202110903683A CN113800496A CN 113800496 A CN113800496 A CN 113800496A CN 202110903683 A CN202110903683 A CN 202110903683A CN 113800496 A CN113800496 A CN 113800496A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- 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
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- 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 belongs to the technical field of battery materials, and particularly discloses a hard carbon material, and a preparation method and application thereof. The hard carbon material provided by the invention is an irregular blocky honeycomb porous material, and a mesoporous and microporous secondary porous structure is arranged in the hard carbon material. The hard carbon material is prepared into a solid reactant by mixing a carbon source and a template agent; then placing the solid reactant in an inert gas atmosphere for pre-carbonization treatment; then crushing the material subjected to the pre-carbonization treatment into powder, removing the template agent, performing pore-forming, and drying to obtain a precursor material; and carrying out heat treatment on the precursor material in inert gas to obtain the hard carbon material. The hard carbon material prepared by the method has large interlayer spacing and rich nano porous structure, provides more channels for the transmission of lithium ions or sodium ions, and simultaneously provides more active sites and lithium or sodium storage spaces for the insertion and extraction of ions, and the prepared secondary battery has high capacity and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a negative electrode material for a secondary battery, and specifically relates to a hard carbon material, and a preparation method and application thereof.
Background
Currently, the negative electrode material of Lithium Ion Batteries (LIBs) in commercial use is mainly graphite material, and graphite stores electric quantity by means of intercalation/deintercalation of lithium ions in a long-range ordered carbon layer. With the gradual maturity of lithium ion battery technology and the explosive increase of demand, the consumption of lithium materials is continuously increased, which leads to the sharp rise of lithium price, and it is very important to find an economic and efficient alternative solution for lithium ion batteries. Na (Na)+With Li+Similar physicochemical properties, abundant reserves and low cost, so that Sodium Ion Batteries (SIB) are receiving wide attention. However, the interlayer spacing of graphite is not sufficient to make the radius of Na larger+Free intercalation between the layers, and therefore, researchers have been very challenging in finding suitable anode materials.
In addition, the capacity of the secondary battery using the graphite material as the negative electrode material is insufficient, the requirement of the power battery is not met, the stability of the layered structure needs to be improved, and the rate capability is not good enough.
Therefore, there is a need to provide a novel material as a material of a negative electrode for a secondary battery instead of a graphite material.
Compared with graphite, the hard carbon has the structural characteristics of short-range order and isotropy, has larger interlayer spacing, can meet the requirement of free deintercalation of sodium ions between layers, and can also accelerate the diffusion of lithium ions; meanwhile, the hard carbon material also has the characteristics of good cycle performance and rate capability, low cost and the like. Therefore, the hard carbon negative electrode material has high capacity and high application potential in secondary batteries including lithium ion batteries and sodium ion batteries.
Related documents are reported on the preparation of hard carbon materials. The present invention is directed to provide a novel hard carbon material and a method for preparing the same to reduce production costs and improve the properties of the hard carbon material.
Disclosure of Invention
The invention mainly solves the technical problem of providing a novel hard carbon material which can be used as a negative electrode material of a secondary battery comprising a lithium ion battery and a sodium ion battery, in particular to a negative electrode material of the sodium ion battery.
The invention also provides a preparation method of the novel hard carbon material.
The invention also provides application of the novel hard carbon material as a negative electrode material of a secondary battery.
In order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing a hard carbon material, comprising the following steps:
(1) mixing a carbon source and a template agent to prepare a solid reactant:
the carbon source is at least one of high molecular polymer, petrochemical products and biomass materials;
preferably, the high molecular polymer is at least one selected from polyacrylonitrile, phenolic resin, epoxy resin, polyethylene terephthalate and polyfurfuryl alcohol;
the petrochemical product is at least one selected from natural asphalt, coal-based asphalt, petroleum-based asphalt and oxidized asphalt;
the biomass material is any one or more selected from glucose, starch, sucrose, cellulose, lignin and plant residues, for example, the biomass material can also be any one or more selected from pinecone, coconut, walnut shell, wheat straw, rice hull, blue algae, bean dregs, banana peel, cotton, peat, seaweed and cotton shell;
the template agent is high-melting-point water-soluble salt; preferably, the template agent is at least one selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, copper chloride, manganese chloride, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate;
(2) putting the solid reactant obtained in the step (1) in an inert gas atmosphere for pre-carbonization treatment;
preferably, the pre-carbonization treatment in step (2) can be performed by a tube furnace;
preferably, introducing inert gas into the tubular furnace for protection, and carrying out pre-carbonization treatment at 500-900 ℃, so as to realize pre-carbonization of the carbon source, but not melt the template agent;
preferably, the inert gas used can be at least one of nitrogen, argon and nitrogen-argon mixed gas;
(3) crushing the material treated in the step (2) into powder, removing the water-soluble template agent to perform pore-forming, and then drying to obtain a precursor material;
(4) and carrying out heat treatment on the precursor material in an inert gas atmosphere to ensure that the material is thoroughly cracked and carbonized to obtain the hard carbon material.
Preferably, the high-temperature heat treatment in the step (4) can be performed by using a tubular furnace; introducing inert gas into the tube furnace for protection, then heating up for high-temperature heat treatment to ensure that the material is thoroughly cracked and carbonized to obtain the hard carbon material.
Preferably, the inert gas used may be at least one of nitrogen, argon, and a nitrogen-argon mixture.
In a preferred embodiment of the present invention, when the solid reactant is prepared in step (1), the carbon source may be heated to be softened, and then mixed with the template agent uniformly, and cooled to harden to prepare the solid reactant.
As a preferred embodiment of the present invention, when the solid reactant is prepared in step (1), a solvent for dissolving the carbon source may be further added.
Preferably, the carbon source, the template and the solvent are mixed, stirred uniformly and then dried to prepare the solid reactant.
Preferably, the solvent for dissolving the carbon source may be water or DMF, etc.
As a preferred embodiment of the present invention, when preparing the solid reactant, the mass ratio of the carbon source to the template is 100: (1-30). More preferably 100: (10-30).
In a preferred embodiment of the present invention, the temperature of the pre-carbonization treatment in the step (2) is 500 to 900 ℃.
Preferably, the temperature rise rate of the pre-carbonization treatment in the step (2) is 0.5-10 ℃/min, preferably 1-6 ℃/min, and more preferably 2-5 ℃/min.
Preferably, the treatment time of the pre-carbonization treatment in the step (2) is 1-10 h, preferably 2-8 h, and more preferably 2-5 h.
As a preferred embodiment of the invention, the water-soluble template agent is removed by washing in the step (3), the template agent solution obtained by washing can be recycled, the template agent is recrystallized for recycling, and the template agent is recycled after water purification.
In a preferred embodiment of the present invention, the heat treatment temperature used in the heat treatment in step (4) is 1000 to 1800 ℃, preferably 1100 to 1700 ℃, and more preferably 1200 to 1500 ℃.
Preferably, the heating rate adopted in the step (4) is 0.5-10 ℃/min, preferably 1-6 ℃/min, and more preferably 2-5 ℃/min.
Preferably, the heat treatment time adopted in the step (4) is 1-10 h, preferably 2-8 h, and more preferably 2-5 h.
In a second aspect, the present invention provides a hard carbon material, which is a honeycomb-shaped porous hard carbon material having a secondary porous structure including mesopores and micropores therein.
The particle size of the hard carbon material is 1-200 mu m, the diameter of the mesopores is 2-50 nm, and the diameter of the micropores is less than or equal to 2 nm.
The macroscopic morphology of the hard carbon material is in an irregular honeycomb block-shaped porous structure.
In a preferred embodiment of the present invention, the hard carbon material has a particle size of 1 to 50 μm, preferably 1 to 10 μm.
As a preferred embodiment of the present invention, the hard carbon material contains a doping element including one or more of N, B, P and S. The doping elements are mainly introduced from different carbon sources.
The invention also provides the hard carbon material prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a method of preparing a negative electrode sheet for a secondary battery, the method comprising the steps of:
(1) preparing a hard carbon material by using the hard carbon material of the second aspect or the method of the first aspect; and
(2) and (2) mixing the hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
Preferably, in the step (2), after the hard carbon material, the conductive agent and the binder are mixed in proportion in the presence of the solvent, the mixture is subjected to homogenization, coating, drying and cutting to prepare the negative electrode sheet of the secondary battery.
Preferably, the negative plate is baked in a vacuum oven at 100 ℃ to remove trace water.
Preferably, the conductive agent is at least one of carbon black, acetylene black, ketjen black, vapor-deposited carbon fiber, conductive graphite, carbon nanotube, graphene, and the like.
In a fourth aspect, the present invention provides a negative electrode sheet for a secondary battery produced by the production method of the third aspect.
In a fifth aspect, the present invention provides a method of manufacturing a secondary battery, the method comprising the steps of:
(1) preparing a hard carbon material by using the hard carbon material of the second aspect or the method of the first aspect; and
(2) and (2) mixing the hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
Preferably, there is provided a method of manufacturing a lithium ion battery, the method comprising the steps of:
(1) preparing a hard carbon material by using the hard carbon material of the second aspect or the method of the first aspect; and
(2) mixing the hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare a negative plate of a lithium ion battery;
wherein the binder is at least one of polyacrylic acid, lithium polyacrylate, CMC/SBR and the like;
LiPF with electrolyte of 1mol/L6A solution;
the solvent consists of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1: 1.
Preferably, there is provided a method of making a sodium ion battery, the method comprising the steps of:
(1) preparing a hard carbon material by using the hard carbon material of the second aspect or the method of the first aspect; and
(2) mixing the hard carbon material prepared in the step (1), a conductive agent and a binder in proportion in the presence of a solvent to prepare a negative plate of the sodium-ion battery;
wherein the binder is at least one of sodium alginate, sodium polyacrylate, CMC/SBR and the like;
electrolyte is 1mol/L NaPF6A solution;
the solvent consisted of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1: 1.
In a sixth aspect, the present invention provides a secondary battery having the negative electrode sheet produced by the production method of the fourth aspect, or a secondary battery produced by the method of the fifth aspect.
The secondary battery is a lithium ion battery or a sodium ion battery.
In some embodiments, the battery is a CR2032 type coin cell battery.
In a seventh aspect, the present invention provides the use of the hard carbon material of the second aspect or the hard carbon material prepared by the method of the first aspect as a negative electrode material of a secondary battery, or in the preparation of a secondary battery.
According to the method, water-soluble salt is used as a template agent, the template agent is dissolved by washing, and pore forming is carried out, so that the template agent solution can be recycled after washing, the template agent is recrystallized and recycled, and the template agent is recycled after water purification, and the process is green and environment-friendly, and has no pollution and no discharge; meanwhile, dangerous chemicals such as acid, alkali and the like are not used in the production and preparation process, no waste liquid is generated, and the operation is simple.
According to the invention, the hard carbon material has large interlayer spacing and rich nano-porous structure through pore forming, so that the infiltration of electrolyte is facilitated, more channels are provided for the transmission of lithium ions or sodium ions, more active sites and lithium or sodium storage spaces are provided for the insertion and extraction of ions, and the prepared secondary battery has high capacity and stable cycle performance.
Meanwhile, the method can also controllably adjust the size and the amount of the pore structure of the prepared hard carbon material by adjusting the size and the dosage of the adopted template agent, thereby regulating and controlling the gram volume and the first effect of the hard carbon material.
Drawings
FIG. 1 is a schematic structural view of a hard carbon material provided by the present invention;
fig. 2 is an SEM image of a hard carbon material provided in example 2 of the present invention;
FIG. 3 is a graph of the charge and discharge performance of a lithium ion battery assembled using hard carbon materials prepared in examples 2-5 of the present invention;
fig. 4 is a graph showing the charge and discharge performance of a sodium ion battery assembled using hard carbon materials prepared in examples 2 to 5 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Example 1
The embodiment provides a hard carbon material, a schematic structural diagram of which is shown in fig. 1, and an SEM image of which is shown in fig. 2, and it can be seen that the hard carbon material is a honeycomb-shaped porous material with an irregular block-shaped macro morphology, and the hard carbon material has a secondary porous structure of mesopores and micropores inside.
Wherein the particle size of the hard carbon material is 1-50 μm, the diameter of the mesoporous structure is 2-50 nm, and the diameter of the microporous structure is less than or equal to 2 nm.
Example 2
This example provides a hard carbon material, prepared by the following steps: dissolving 100g of starch in sufficient hot water, adding 10g of potassium chloride, uniformly stirring, and drying in a forced air drying oven at 100 ℃ to obtain a solid reactant;
putting the solid reactant into a tubular furnace, introducing nitrogen for protection, heating to 700 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, and carrying out pre-carbonization treatment;
after natural cooling, mechanically crushing the pre-carbonized material into powder, adding enough water, stirring for 2 hours, washing and filtering for multiple times until no residual template agent exists, and drying to obtain a precursor;
placing the precursor in a tube furnace, introducing nitrogen for protection, heating to 1400 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and carrying out high-temperature heat treatment; and naturally cooling to obtain the hard carbon material which is marked as PHC-1.
The SEM image of the hard carbon material is shown in FIG. 2, and the porous structures on the surfaces of the material particles and at the fracture interface can be observed from the SEM image, which illustrates that the pore-forming effect of the method is remarkable and the porous hard carbon material is prepared.
Example 3
This example provides a hard carbon material, prepared by the following steps: dissolving 100g of polyacrylonitrile in sufficient DMF solvent, adding 1g of sodium chloride, uniformly stirring, and drying in a 150 ℃ forced air drying oven to obtain a solid reactant;
putting the solid reactant in a tubular furnace, introducing argon for protection, heating to 750 ℃ at the speed of 3 ℃/min, keeping the temperature for 3 hours, and carrying out pre-carbonization treatment;
after natural cooling, mechanically crushing the pre-carbonized material into powder, adding enough water, stirring for 2 hours, washing and filtering for multiple times until no residual template agent exists, and drying to obtain a precursor;
placing the precursor in a tube furnace, introducing argon for protection, heating to 1300 ℃ at the speed of 3 ℃/min, keeping the temperature for 3h, and carrying out high-temperature heat treatment; and naturally cooling to obtain the hard carbon material which is marked as PHC-2.
Example 4
This example provides a hard carbon material, prepared by the following steps: dissolving 100g of sucrose in sufficient water, adding 20g of sodium chloride, uniformly stirring, and drying in a forced air drying oven at 100 ℃ to obtain a solid reactant;
putting the solid reactant in a tubular furnace, introducing nitrogen for protection, heating to 750 ℃ at the speed of 2 ℃/min, keeping the temperature for 4 hours, and carrying out pre-carbonization treatment;
mechanically crushing the pre-carbonized material into powder, adding enough water, stirring for 2 hours, washing and filtering for multiple times until no template agent remains, and drying to obtain a precursor;
placing the precursor in a tube furnace, introducing nitrogen for protection, heating to 1500 ℃ at the speed of 2 ℃/min, keeping the temperature for 4 hours, and carrying out high-temperature heat treatment; and naturally cooling to obtain the hard carbon material which is marked as PHC-3.
Example 5
This example provides a hard carbon material, prepared by the following steps: heating 100g of oxidized asphalt until the oxidized asphalt is completely softened, adding 15g of magnesium chloride, stirring and mixing uniformly, and cooling and hardening to obtain a solid reactant;
putting the solid reactant in a tubular furnace, introducing argon for protection, heating to 680 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, and carrying out pre-carbonization treatment;
after natural cooling, mechanically crushing the pre-carbonized material into powder, adding enough water, stirring for 2 hours, washing and filtering for multiple times until no residual template agent exists, and drying to obtain a precursor;
placing the precursor in a tube furnace, introducing argon for protection, heating to 1400 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, and carrying out high-temperature heat treatment; and naturally cooling to obtain the hard carbon material which is marked as PHC-4.
Example 6
In this example, the hard carbon materials prepared in examples 2 to 5 were used as active materials, and were assembled into a button lithium ion battery and a sodium ion battery, respectively, and material performance tests were performed.
The method comprises the following specific steps:
(1) battery assembly
Respectively taking one of PHC-1, PHC-2, PHC-3 and PHC-4 as an active material, matching conductive carbon black and CMC/SBR according to the proportion of 8:1:1, and performing homogenate, coating, drying and cutting to prepare an electrode slice;
the lithium metal sheet is taken as a negative electrode, and 1mol/L LiPF is adopted as electrolyte6A solution is prepared by mixing EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1:1, and is assembled into a CR2032 button lithium ion battery;
sodium metal sheet is taken as a negative electrode, and 1mol/L NaPF is adopted as electrolyte6The solution and the solvent are a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1:1, and the CR2032 button sodium-ion battery is assembled.
(2) Performance testing
The assembled lithium ion battery and sodium ion battery are respectively tested by adopting the following test conditions;
the test conditions were: and (3) carrying out constant-current charge and discharge circulation at 0.1C multiplying power, wherein the voltage range is 0.005-2.0V, and standing for 5 min.
The charge and discharge performance test results of the lithium ion battery are shown in the following table 1, and the charge and discharge performance graph is shown in fig. 3.
TABLE 1
As can be seen from Table 1, the first discharge gram capacity of the lithium ion battery prepared by the invention can reach more than 350mAh/g, and especially the first discharge gram capacity of the lithium ion battery prepared by the invention can reach 499mAh/g by taking sucrose as a biomass material; the first charge gram capacity can reach more than 300mAh/g, and particularly, the first charge gram capacity of 384mAh/g can be reached by taking sucrose as a biomass material; the coulombic efficiency of the first circle can reach more than 77%, and the lithium ion battery prepared by the method has higher capacity and better energy density.
The charge and discharge performance test results of the sodium ion battery are shown in the following table 2, and the charge and discharge performance graph is shown in fig. 4.
TABLE 2
As can be seen from Table 2, the first discharge gram capacity of the sodium-ion battery prepared by the invention can reach more than 344mAh/g, and especially, the first discharge gram capacity of 476mAh/g can be reached by taking sucrose as a biomass material; the first charge gram capacity can reach more than 289mAh/g, and particularly, the first charge gram capacity of 343mAh/g can be reached by taking sucrose as a biomass material; the first-turn coulombic efficiency can reach more than 72%, and the sodium ion battery prepared by the method has higher capacity and better energy density.
As can be seen from tables 1 and 2, when the hard carbon material is prepared, the more the template agent is added, the richer the porous structure of the finally obtained hard carbon material is, the larger the electrolyte contact surface is, the more the lithium or sodium active sites are embedded, and the higher the gram capacity exerted by the hard carbon material is; meanwhile, the larger the contact surface is, the more active lithium or sodium is lost when an SEI film is formed in the process of first charge and discharge, so that the coulombic efficiency of the first circle is lower. Therefore, when the hard carbon material is prepared, the size and the amount of the pore structure of the prepared hard carbon material can be controllably adjusted by adjusting the using amount and/or the scale of the template agent, so that the gram volume and the first effect of the hard carbon material are regulated and controlled.
In addition, it should be noted that, since the radius of sodium ions is larger than that of lithium ions, the difficulty of sodium ion intercalation is greater than that of lithium ions, and therefore, the gram capacity exhibited by the same kind of hard carbon material in a sodium ion battery system is lower than that exhibited by a lithium ion battery system under the same conditions.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a hard carbon material is characterized by comprising the following steps:
(1) mixing a carbon source and a template agent to prepare a solid reactant:
the carbon source is at least one of high molecular polymer, petrochemical products and biomass materials;
preferably, the high molecular polymer is at least one selected from polyacrylonitrile, phenolic resin, epoxy resin, polyethylene terephthalate and polyfurfuryl alcohol;
the petrochemical product is at least one selected from natural asphalt, coal-based asphalt, petroleum-based asphalt and oxidized asphalt;
the biomass material is any one or more selected from glucose, starch, sucrose, cellulose, lignin and plant residues;
the template agent is high-melting-point water-soluble salt; preferably, the template agent is at least one selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, copper chloride, manganese chloride, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate;
(2) putting the solid reactant obtained in the step (1) in an inert gas atmosphere for pre-carbonization treatment;
(3) crushing the material treated in the step (2) into powder, removing the water-soluble template agent to perform pore-forming, and then drying to obtain a precursor material;
(4) and carrying out heat treatment on the precursor material in an inert gas atmosphere to obtain the hard carbon material.
2. The preparation method of claim 1, wherein the mass ratio of the carbon source to the template is 100: (1-30).
3. The method according to claim 1 or 2, wherein the pre-carbonization temperature is 500 to 900 ℃;
preferably, the temperature rise rate of the pre-carbonization treatment is 0.5-10 ℃/min, and/or the treatment time of the pre-carbonization treatment is 1-10 h.
4. The preparation method according to claim 3, wherein the water-soluble template is removed by washing in step (3); preferably, the template agent-containing solution obtained by washing is separated and purified to respectively obtain the template agent and the purified water, and the template agent and the purified water are recycled.
5. The method according to any one of claims 1 to 4, wherein the heat treatment is performed at a temperature of 1000 to 1800 ℃;
preferably, the heating rate of the heat treatment is 0.5-10 ℃/min, and/or the heat treatment time is 1-10 h.
6. The method according to any one of claims 1 to 5, wherein a solvent for dissolving a carbon source is added when the solid reactant is prepared in the step (1).
7. A hard carbon material is characterized in that the hard carbon material is a honeycomb-shaped porous hard carbon material, and a secondary porous structure is arranged in the hard carbon material and comprises mesopores and micropores;
wherein the particle size of the hard carbon material is 1-200 μm, the diameter of the mesopores is 2-50 nm, and the diameter of the micropores is less than or equal to 2 nm;
preferably, the hard carbon material is prepared by the preparation method of any one of claims 1 to 6.
8. Use of the hard carbon material prepared by the preparation method according to any one of claims 1 to 6 or the hard carbon material according to claim 7 in preparation of a secondary battery, preferably as a secondary battery negative electrode material.
9. A negative electrode sheet for a secondary battery, which is made of the hard carbon material produced by the production method according to any one of claims 1 to 6 or the hard carbon material according to claim 7;
preferably, the negative electrode sheet is prepared by a preparation method comprising the following steps:
(1) a hard carbon material produced by the production method according to any one of claims 1 to 6 or the hard carbon material according to claim 7; and
(2) and (2) mixing the hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
10. A secondary battery comprising the negative electrode sheet of claim 9; preferably, the secondary battery is a lithium ion battery or a sodium ion battery.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044508A (en) * | 2021-12-20 | 2022-02-15 | 张家港博威新能源材料研究所有限公司 | Hard carbon microsphere and preparation method and application thereof |
| CN114212770A (en) * | 2021-12-29 | 2022-03-22 | 上海杉杉科技有限公司 | Modified hard carbon material, preparation method thereof, electrode and application |
| CN114335523A (en) * | 2022-01-24 | 2022-04-12 | 天津大学 | Preparation method of hard carbon negative electrode for high-energy-density sodium ion battery |
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| CN114524425A (en) * | 2022-01-26 | 2022-05-24 | 广东海洋大学 | Hard carbon material, preparation method thereof and application thereof in sodium-ion battery |
| CN114524425B (en) * | 2022-01-26 | 2024-01-16 | 广东海洋大学 | Hard carbon material, preparation method thereof and application thereof in sodium ion battery |
| CN114709408A (en) * | 2022-04-18 | 2022-07-05 | 鸡西市唯大新材料科技有限公司 | Preparation method of sodium ion hard carbon negative electrode material |
| WO2024007461A1 (en) * | 2022-07-08 | 2024-01-11 | 广东邦普循环科技有限公司 | Hard carbon material, preparation method therefor and use thereof |
| CN115353090A (en) * | 2022-08-11 | 2022-11-18 | 华南理工大学 | Novel biomass hard carbon sodium ion battery material and preparation method thereof |
| 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 |
| CN115410834A (en) * | 2022-09-14 | 2022-11-29 | 常州大学 | Method for preparing lignin-based super-capacity carbon through catalytic activation |
| CN115676804A (en) * | 2022-12-23 | 2023-02-03 | 郑州中科新兴产业技术研究院 | Asphalt-based porous hard carbon negative electrode material and preparation method and application thereof |
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