CN116404128A - Porous hard carbon anode material and preparation method and application thereof - Google Patents
Porous hard carbon anode material and preparation method and application thereof Download PDFInfo
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- CN116404128A CN116404128A CN202310334853.8A CN202310334853A CN116404128A CN 116404128 A CN116404128 A CN 116404128A CN 202310334853 A CN202310334853 A CN 202310334853A CN 116404128 A CN116404128 A CN 116404128A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 47
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
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- 239000010416 ion conductor Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
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- 238000009826 distribution Methods 0.000 claims description 4
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 2
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
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- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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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- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/02—Fluorides
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- C01G53/00—Compounds of nickel
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- 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
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- 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
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Abstract
The invention relates to a porous hard carbon negative electrode material, a preparation method and application thereof, wherein the hard carbon negative electrode material is a high closed-cell hard carbon material which adopts a sodium ion conductor and metal or metal salt to modify the inner wall of a closed cell; the preparation method comprises the steps of obtaining a porous hard carbon precursor by using an organic matter or biomass as a raw material through a pyrolysis method, depositing a sodium ion conductor, metal or metal salt into open pores of the porous hard carbon precursor, then carrying out carbon coating on the composite material, and obtaining the porous hard carbon material with high closed pores through internal modification after heat treatment. The preparation method is simple and efficient, and the prepared internal modified closed-cell hard carbon negative electrode material reduces the deposition barrier of sodium ions in hard carbon and has good electrochemical dynamic performance.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a porous hard carbon anode material applicable to sodium ion batteries, and a preparation method and application thereof.
Background
Hard carbon is a common negative electrode material in sodium ion batteries, and has the advantages of proper working voltage, low cost, suitability for large-scale production and the like. However, in order to further increase the energy density of the sodium ion battery, the electrochemical performance of the hard carbon anode material needs to be further improved. From current research, the platform capacity of hard carbon below 0.1V is closely related to its closed cell structure. The literature (Energy Technology, 2022, 2200612;Energy Technology, 2019, 1900779) builds closed cell structures in porous hard carbon by carbon cladding methods, which greatly improves the platform capacity, but its kinetics is poor, probably due to the high deposition barrier of sodium ions in the closed cells. Modification of the closed cell inner wall is expected to improve its kinetic properties, since the deposition barrier of sodium ions in the closed cell inner wall is related to the inner wall structure.
A method for preparing a hard carbon material disclosed in patent application 202211247384.8, comprising: (i) Providing a phenolic resin and obtaining resin pyrolytic carbon by carbonizing and pyrolyzing the phenolic resin; (ii) Mixing the resin pyrolytic carbon from step (i) with hexamethylenetetramine to obtain a blend; (iii) Subjecting the blend from step (ii) to pyrolysis coating to obtain a hard carbon material; the phenolic resin in the step (i) is prepared by adding formaldehyde and glacial acetic acid into deionized water, then sequentially adding resorcinol, ammonium bicarbonate and a metal compound, stirring to obtain a solution, heating and drying to obtain the dry phenolic resin. The invention introduces a small amount of metal elements to facilitate the deposition of lithium and sodium in the pores, thereby improving the sodium storage capacity and lithium storage capacity of the hard carbon material; meanwhile, too high a content of metal elements can reduce the energy density of the hard carbon material, and too low a content of metal elements can reduce the effect of deposition of lithium and sodium in the pores; the hard carbon material with rich pores and communicated pore channels is synthesized by adopting the phenolic resin raw material, so that the utilization rate of the pores is improved and the closed pore lithium storage and sodium storage are increased while the rapid diffusion of lithium ions or sodium ions in the pore channels is ensured, thereby improving the energy density of the battery. The metal introduced by the method is inside the carbon matrix, and has randomness in the regulation and control of the components and the structure of the inner wall of the closed cell.
Patent 202210603931.5 discloses a method for preparing hard carbon based on biomass raw materials such as bamboo, bagasse, wheat straw, wood and derivatives thereof, which comprises the following steps: and (3) carrying out mechanical ball milling, vibration milling or swelling pretreatment on biomass, and carbonizing and cracking the pretreated biomass material in an inert atmosphere to obtain the biomass-derived hard carbon with high closed cell rate. The 202210603915.6 patent discloses a preparation method of biomass hard carbon based on low crystalline cellulose content, which comprises the following steps: biomass is subjected to acidolysis, alkaline hydrolysis and other pretreatment and then carbonized and pyrolyzed in inert atmosphere, so that high-closed-cell-rate biomass-derived hard carbon is obtained. The biomass with low crystalline cellulose content, such as birch cork, peanut shells, melon seed shells, rice husks, kraft paper, tapioca starch, sweet potato starch, tapioca residues, sweet potato residues, reed and the like, is used as a raw material, and the raw material of the biomass adopted by the invention is complex in component, and the formed hard carbon closed cell structure and component are unstable.
Therefore, research on a closed-cell inner wall modification technology of porous hard carbon to improve electrochemical dynamic performance of a hard carbon negative electrode is a technical problem to be solved.
Disclosure of Invention
The invention provides a porous hard carbon negative electrode material capable of reducing the deposition potential barrier of sodium ions in hard carbon and having good electrochemical dynamic performance, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the porous hard carbon negative electrode material is a high-closed-pore hard carbon material with a sodium ion conductor and a metal or metal salt for modifying the inner wall of a closed pore.
The preparation method of the porous hard carbon anode material comprises the steps of obtaining a porous hard carbon precursor by adopting an organic matter or biomass as a raw material through a pyrolysis method, depositing a sodium ion conductor, metal or metal salt into open pores of the porous hard carbon precursor, then carrying out carbon coating on the composite material, and obtaining the porous hard carbon material with high closed pores after heat treatment.
The preparation method of the porous hard carbon anode material comprises the following steps: the porous hard carbon precursor is further subjected to pore size distribution adjustment by a physical activation or chemical activation method.
The preparation method of the porous hard carbon anode material comprises the following specific steps:
s1: preparing a porous hard carbon precursor;
s2: depositing a sodium ion conductor, metal or metal salt into the open pores of the porous hard carbon;
s3: and (3) carrying out carbon coating on the composite material, and carrying out heat treatment to obtain the internal modified closed-cell hard carbon material.
The preparation method of the porous hard carbon anode material comprises the following steps: the sodium ion conductor in the step S2 is NaF or Na 3 SiO 4 。
The preparation method of the porous hard carbon anode material comprises the following steps: the metal in the step S2 is Cu, ni, au, ag, sb, and the metal salt is oxide, chloride, sulfate and nitrate of the corresponding metal.
The preparation method of the porous hard carbon anode material comprises the following steps: the mass ratio of the sodium ion conductor, the metal or the metal salt in the step S2 in the hard carbon precursor is 0.1-15%.
The preparation method of the porous hard carbon anode material comprises the following steps: the sodium ion conductor, metal or metal salt in the step S2 is deposited into the openings through heat treatment, the heat treatment temperature is 500-1300 ℃, and the heat treatment is carried out in an inert atmosphere for 0.5-1.5 hours.
The preparation method of the porous hard carbon anode material comprises the following steps: the carbon coating in the step S3 is a pyrolysis method or a chemical vapor deposition method, the heat treatment temperature is 700-1400 ℃, the time is 0.5-5 hours, and the atmosphere is inert atmosphere.
The application of the porous hard carbon anode material is used for preparing sodium ion batteries.
Advantageous effects
According to the porous hard carbon negative electrode material, the inner wall of the closed pore of the hard carbon is modified by adopting the sodium ion conductor, the metal or the metal salt, so that the deposition potential barrier of sodium atoms in the closed pore can be reduced, the deposition kinetics behavior of sodium ions is accelerated, and the capacity and the multiplying power performance of the hard carbon are improved. The preparation method is simple and efficient, and the prepared internal modified closed-cell hard carbon negative electrode material reduces the deposition barrier of sodium ions in hard carbon and has good electrochemical dynamic performance.
The porous hard carbon anode material is applied to sodium ion batteries and has the advantages of high platform capacity, good rate capability, stable cycle performance and the like.
Drawings
FIG. 1 is a process flow of the preparation of an internally modified closed-cell hard carbon material of the present invention;
FIG. 2 is an SEM image of a porous hard carbon material prepared according to example 1;
FIG. 3 is an SEM image of a porous hard carbon material of comparative example 1;
FIG. 4 shows Ni content in the X-ray photoelectron spectroscopy test of example 1;
FIG. 5 is the magnification data of the porous hard carbon negative electrode materials prepared in example 1 and comparative example 1;
FIG. 6 is electrochemical impedance data of porous hard carbon negative electrode materials prepared in example 1 and comparative example 1;
fig. 7 is a diffusion coefficient of the porous hard carbon anode material prepared in example 1 and comparative example 1 during discharge.
Description of the embodiments
The porous hard carbon negative electrode material is a high-closed-cell hard carbon material with a sodium ion conductor and a metal or metal salt for modifying the inner wall of a closed cell.
The preparation method of the porous hard carbon anode material comprises the steps of obtaining a porous hard carbon precursor by adopting an organic matter or biomass as a raw material through a pyrolysis method, depositing a sodium ion conductor, metal or metal salt into open pores of the porous hard carbon precursor, carrying out carbon coating on the composite material, and carrying out heat treatment to obtain the porous hard carbon material with high closed pores and internal modification.
Wherein, the porous hard carbon precursor can further adjust the pore size distribution by a physical activation or chemical activation method.
The preparation flow of the porous hard carbon anode is shown in figure 1, and comprises the following specific steps:
s1: preparing a porous hard carbon precursor;
s2: depositing a sodium ion conductor, metal or metal salt into the open pores of the porous hard carbon;
s3: and (3) carrying out carbon coating on the composite material, and carrying out heat treatment to obtain the internal modified closed-cell hard carbon material.
The porous hard carbon in the step S1 contains more open pores, and can be obtained by adopting organic matters (such as phenolic resin, asphalt and the like) or biomass (such as coconut shells, lotus leaf stems and the like) as raw materials through a conventional pyrolysis method; the hard carbon may be further modified in pore size distribution by physical or chemical activation methods.
The sodium ion conductor in the step S2 is NaF or Na 3 SiO 4 And the metal is Cu, ni, au, ag, sb, and the metal salt is oxide, chloride, sulfate, nitrate, and the like of the corresponding metal; the mass ratio of the sodium ion conductor, the metal or the metal salt in the hard carbon precursor is 0.1-15%; the sodium ion conductor, metal or metal salt is deposited into the openings by heat treatment at 500-1300 ℃ for 0.5-1.5 hours in an inert atmosphere.
The carbon coating in the step S3 is a pyrolysis method, a chemical vapor deposition method or the like, the heat treatment temperature is 700-1400 ℃, the time is 0.5-5 hours, the atmosphere is an inert atmosphere, and the inert atmosphere is argon, nitrogen, hydrogen-argon mixed gas, helium, vacuum atmosphere or the like.
The preparation method of the present invention is further described below with reference to specific examples.
Examples
The preparation method of the NiO closed-pore modified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
ni (NO) 3 ) 2 ·6H 2 O and porous hard carbon are uniformly mixed, ni (NO) 3 ) 2 ·6H 2 The mass of O is 15 percent of that of the hard carbon, and then the NiO/hard carbon composite material is obtained by heat treatment for 1 hour under the argon atmosphere at 500 ℃;
and mixing polypropylene with the NiO/hard carbon composite material, and performing heat treatment for 1 hour at 700 ℃ in an argon atmosphere to obtain the NiO closed-pore modified porous hard carbon anode material.
Examples
The preparation of the Cu closed-cell modified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
CuCl is added 2 Uniformly mixing with porous hard carbon, cuCl 2 The mass of the copper-carbon alloy is 5% of that of hard carbon, and then the copper-carbon alloy is subjected to heat treatment for 1 hour at 1000 ℃ in argon atmosphere to obtain a Cu/hard carbon composite material;
and mixing polypropylene with the Cu/hard carbon composite material, and performing heat treatment for 1 hour at 700 ℃ in an argon atmosphere to obtain the Cu closed-pore modified porous hard carbon anode material.
Examples
The preparation of the NaF closed-cell modified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
uniformly mixing NaF and porous hard carbon, wherein the mass of NaF is 0.1% of that of the hard carbon, and then carrying out heat treatment for 1 hour under the argon atmosphere at 1300 ℃ to obtain a NaF/hard carbon composite material;
and mixing polypropylene with the NaF/hard carbon composite material, and performing heat treatment for 3 hours at 700 ℃ in helium atmosphere to obtain the porous hard carbon anode material modified by NaF closed pores.
Examples
Na (Na) 3 SiO 4 The preparation of the closed-cell modified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
na is mixed with 3 SiO 4 Uniformly mixed with porous hard carbon, na 3 SiO 4 1% of hard carbon, and then heat-treating at 800 ℃ under nitrogen atmosphere for 0.5 hour to obtain Na 3 SiO 4 Hard carbon composite;
polypropylene and Na are adopted 3 SiO 4 Mixing the hard carbon composite material, and performing heat treatment at 1100 ℃ under vacuum atmosphere for 0.5 hour to obtain Na 3 SiO 4 A closed cell modified porous hard carbon anode material.
Examples
The preparation method of the Ag closed-cell modified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
AgNO is to be carried out 3 Uniformly mixing the solution with porous hard carbon, evaporating to dryness, wherein the mass of Ag is 10% of that of the hard carbon, and then carrying out heat treatment for 1.5 hours at 1100 ℃ under helium atmosphere to obtain an Ag/hard carbon composite material;
and mixing polypropylene with the Ag/hard carbon composite material, and performing heat treatment at 1400 ℃ under nitrogen atmosphere for 5 hours to obtain the Ag closed-pore modified porous hard carbon anode material.
Comparative example 1
The preparation of the unmodified porous hard carbon anode material comprises the following steps:
heat-treating asphalt at 250 ℃ in air for 3 hours, and then heat-treating the asphalt at 1400 ℃ in argon atmosphere for 0.5 hour to obtain porous hard carbon;
and mixing polypropylene with the hard carbon material, and carrying out heat treatment for 1 hour under the argon atmosphere at the temperature of 700 ℃ to obtain the porous hard carbon material (HC1400@0% NiO) without closed pore modification.
The following electrochemical test method was used: the hard carbon material, PVDF and conductive carbon black are uniformly mixed according to the mass ratio of 8:1:1, and then dispersed into NMP solution to form uniform slurry. Then coating the slurry on aluminum foil and vacuum drying at 80 ℃ to obtain a hard carbon electrode slice;
and (3) pairing the hard carbon electrode with a metal sodium negative electrode, assembling the CR2032 button cell in an inert atmosphere, and testing the electrochemical performance of the hard carbon electrode. The electrolyte was 1M NaPF6-EC/DEC (volume ratio 1:1) +5% FEC. The button cell structure includes a positive electrode case (stainless steel), a negative electrode case (stainless steel), a gasket (stainless steel), a hard carbon electrode, a sodium sheet, an electrolyte, and a separator (glass fiber).
SEM of the porous hard carbon material prepared in example 1 is shown in fig. 2 through electrochemical test; SEM of the porous hard carbon material prepared in comparative example 1 is shown in fig. 3; comparing fig. 2 and 3, it can be seen that the size and shape of the hard carbon particles after NiO compounding are not significantly changed from those of the uncomplexed pitch hard carbon, indicating that NiO compounding is uniformly distributed.
From the Ni content in the X-ray photoelectron spectroscopy test shown in FIG. 4, it was calculated that the NiO content in the product was about 3wt%.
As can be seen from the multiplying power data of the NiO/hard carbon composite material shown in fig. 5, the specific capacity of the hard carbon after NiO compounding at 2C current is still 102mAh/g, while the specific capacity of the hard carbon without NiO compounding is only 73mAh/g, which indicates that modification of the closed pore inner wall by NiO significantly improves the dynamics performance of the hard carbon.
As is evident from fig. 6, the slope of the hc1400@3% NiO curve in the low frequency region is larger, while the slope of the HC1400 curve is smaller, which indicates that modifying the closed pores with NiO can reduce the diffusion resistance of sodium ions during sodium storage, thereby improving the rate capability of hard carbon.
As can be seen from fig. 7, the diffusion coefficient (dna+) of hc1400@3% NiO is about two orders of magnitude higher than that of hc1400@0% NiO, which further proves that modification of the closed pores by NiO is favorable for diffusion of sodium ions in hard carbon, so that the hard carbon after compounding has better kinetic performance.
The porous hard carbon anode material can be applied to the preparation of anode materials of sodium ion batteries, and the prepared sodium ion batteries have the advantages of high capacity, good rate performance, stable electrochemical performance and the like.
Claims (10)
1. A porous hard carbon anode material, characterized in that: the hard carbon negative electrode material is a high-closed-cell hard carbon material with a sodium ion conductor and a metal or metal salt for modifying the inner wall of a closed cell.
2. The preparation method of the porous hard carbon anode material according to claim 1, wherein an organic matter or biomass is adopted as a raw material to obtain a porous hard carbon precursor through a pyrolysis method, then a sodium ion conductor, metal or metal salt is deposited into open pores of the porous hard carbon precursor, and then the composite material is subjected to carbon coating and heat treatment to obtain the porous hard carbon material with high closed pores and internal modification.
3. The method for preparing the porous hard carbon anode material according to claim 2, wherein: the porous hard carbon precursor is further subjected to pore size distribution adjustment by a physical activation or chemical activation method.
4. The method for preparing the porous hard carbon anode material according to claim 2, wherein: the preparation method of the porous hard carbon anode comprises the following specific steps:
s1: preparing a porous hard carbon precursor;
s2: depositing a sodium ion conductor, metal or metal salt into the open pores of the porous hard carbon;
s3: and (3) carrying out carbon coating on the composite material, and carrying out heat treatment to obtain the internal modified closed-cell hard carbon material.
5. The method for preparing the porous hard carbon anode material according to claim 4, wherein: the sodium ion conductor in the step S2 is NaF or Na 3 SiO 4 。
6. The method for preparing the porous hard carbon anode material according to claim 4, wherein: the metal in the step S2 is Cu, ni, au, ag, sb, and the metal salt is oxide, chloride, sulfate and nitrate of the corresponding metal.
7. The method for preparing the porous hard carbon anode material according to claim 4, wherein: the mass ratio of the sodium ion conductor, the metal or the metal salt in the step S2 in the hard carbon precursor is 0.1-15%.
8. The method for preparing the porous hard carbon anode material according to claim 4, wherein: the sodium ion conductor, metal or metal salt in the step S2 is deposited into the openings through heat treatment, the heat treatment temperature is 500-1300 ℃, and the heat treatment is carried out in an inert atmosphere for 0.5-1.5 hours.
9. The method for preparing the porous hard carbon anode material according to claim 4, wherein: the carbon coating in the step S3 is a pyrolysis method or a chemical vapor deposition method, the heat treatment temperature is 700-1400 ℃, the time is 0.5-5 hours, and the atmosphere is inert atmosphere.
10. The use of the porous hard carbon negative electrode material according to claim 1 for the preparation of sodium ion batteries.
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