Resin-based self-activated porous carbon material, and preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of negative electrode materials for lithium batteries, and particularly discloses a resin-based self-activated porous carbon material, and a preparation method therefor and the use thereof. The preparation method comprises the following steps: subjecting a benzenediol monomer, a benzenediol monomer containing a thioether bond, formaldehyde or polyaldehyde and a catalyst A to a condensation polymerization reaction, so as to obtain a phenolic resin; and carbonizing the phenolic resin, so as to obtain a resin-based self-activated porous carbon material. In the present invention, the phenolic resin is synthesized by using the benzenediol monomer containing a thioether bond, thereby introducing a thioether alkane side chain into the phenolic resin. During the carbonization process of the phenolic resin, the thioether bond readily decomposes at a high temperature to generate gas, which can form pores in a phenolic resin framework. The resulting resin-based self-activated porous carbon material has a relatively high specific surface area and pore volume. By controlling the structure and modification ratio of the thioether alkane side chain, the pore structure inside the resin-based porous carbon can be controllably designed to achieve an ideal pore size distribution.

Description

A resin-based self-activated porous carbon material, its preparation method and application Technical Field

[0001] This invention relates to the field of lithium battery anode material technology, and in particular to a resin-based self-activated porous carbon material, its preparation method, and its application. Background Technology

[0002] Lithium-ion batteries are the primary power batteries for new energy vehicles and portable electronic devices, and improving their energy density has always been a key research focus. Silicon materials, with a theoretical specific capacity as high as 4200 mAh / g, are considered the most promising candidate to replace traditional graphite anode materials. However, silicon materials undergo significant volume expansion during charge and discharge, leading to electrode material pulverization and detachment, which seriously affects the cycle life and safety performance of the battery.

[0003] Currently, vapor deposition (VCD) is considered an effective way to solve the volume expansion problem of silicon anode materials. This method utilizes porous carbon as a silicon source carrier, introducing silane gas into the pores of the porous carbon at high temperatures, causing the silicon source to deposit within the pores to form a silicon-carbon composite material. The porous structure of the carbon provides a buffer space for silicon expansion, effectively suppressing silicon particle pulverization. However, existing methods such as physical activation and alkaline activation inevitably result in the formation of ultra-micropores (pore size < 0.7 nm). This ultra-micropore structure affects lithium-ion insertion and extraction, reducing the initial coulombic efficiency and rate performance of the battery. Therefore, developing a resin-based self-activated porous carbon material with customizable pore size and avoiding the formation of ultra-micropores is of great significance for improving the electrochemical performance of porous silicon-carbon anode materials. Summary of the Invention

[0004] Based on this, the purpose of this invention is to provide a resin-based self-activated porous carbon material, its preparation method and application. By controlling the structure and modification ratio of the sulfide alkane side chains, the internal pore structure of the resin-based porous carbon can be designed in a controllable manner, obtaining an ideal pore distribution and meeting the specific requirements of silicon-carbon anode materials for pore structure.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] This invention first provides a method for preparing a resin-based self-activated porous carbon material, which includes the following steps:

[0007] A condensation reaction is carried out on hydroquinone monomer, hydroquinone monomer containing thioether bonds, formaldehyde or polyaldehyde, and catalyst A to obtain phenolic resin.

[0008] Carbonizing the phenolic resin yields a resin-based self-activated porous carbon material.

[0009] As a further improvement to the above-mentioned scheme of the present invention, the preparation method of the thioether-containing hydroquinone monomer is as follows: 2,5-dihydroxythiophenol and haloalkanes are added to a solvent, catalyst B is added to react, and then post-treatment is performed to obtain the thioether-containing hydroquinone monomer.

[0010] As a further improvement to the above-described scheme of the present invention, the molar ratio of 2,5-dihydroxythiophenol to haloalkanes is 1:1-1.5, the mass of catalyst B is 3%-5% of the sum of the masses of 2,5-dihydroxythiophenol and haloalkanes; and / or, the haloalkanes are at least one of bromohexane, bromobutane, and bromooctane; and / or, the catalyst B is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; and / or, the solvent is ethanol.

[0011] As a further improvement to the above-mentioned scheme of the present invention, the reaction between 2,5-dihydroxythiophenol, haloalkanes and catalyst B is carried out at 60-70°C for 2-3 hours. The post-treatment includes filtration, washing and drying in sequence. The washing is done by washing with deionized water several times, and the drying is done at 80-90°C for 10-14 hours.

[0012] As a further improvement to the above-described scheme of the present invention, the molar ratio of the hydroquinone monomer containing thioether bonds, the hydroquinone monomer, formaldehyde, or polyaldehyde is 1:0.5-2:1.5-3; the mass of catalyst A is 3%-5% of the sum of the masses of the hydroquinone monomer containing thioether bonds, the hydroquinone monomer, formaldehyde, or polyaldehyde; the polyaldehyde is at least one of malondialdehyde, succinal, glutaraldehyde, 2-hydroxyglutaraldehyde, and malealdehyde; and catalyst A is at least one of hydrochloric acid and oxalic acid.

[0013] As a further improvement to the above-mentioned scheme of the present invention, the polycondensation reaction is carried out at 80-90°C for 4-6 hours.

[0014] As a further improvement to the above-mentioned scheme of the present invention, the carbonization is carried out under a protective atmosphere by first heating to 170-180℃ and holding for 2-3 hours, then heating to 450-500℃ at a heating rate of 1℃ / min-10℃ / min and holding for 4-6 hours, and then heating to 800-900℃ at a heating rate of 1℃ / min-10℃ / min and holding for 4-6 hours.

[0015] The present invention also provides a resin-based self-activated porous carbon material, which is prepared by the preparation method described above.

[0016] The present invention also provides an application of the resin-based self-activated porous carbon material as described above, which is used to prepare lithium battery anode materials.

[0017] As a further improvement to the above-mentioned scheme of the present invention, the preparation of the lithium battery anode material includes the following steps: under a protective atmosphere, silicon is first deposited on the resin-based self-activated porous carbon material by chemical vapor deposition using a silicon source gas; then, carbon is coated on the resin-based self-activated porous carbon material by chemical vapor deposition using a carbon source gas, thereby obtaining the lithium battery anode material; the silicon source gas is at least one of silane, disilane, dichlorosilane, silicon tetrachloride, dichlorosilane, and trichlorosilane, and the silicon deposition temperature is 450-480℃ and the time is 2-4h; the carbon source gas is at least one of acetylene, methane, propane, and cyclohexane, and the carbon coating temperature is 560-580℃ and the time is 2-4h.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] This invention utilizes resorcinol monomers containing thioether bonds to synthesize phenolic resins, thereby introducing thioether alkane side chains into the phenolic resin. During the carbonization process of the phenolic resin, the thioether bonds readily decompose at high temperatures to generate gas, which can create pores in the phenolic resin framework, promoting the formation of micropores and mesopores, thus increasing the specific surface area. Compared with traditional physical activation or alkali activation methods, the method of this invention effectively avoids the inherent problem of ultra-microporous structure formation in the preparation of porous carbon materials. At the same time, the flexible alkane molecular chains help alleviate structural stress during the carbonization process, reduce pore collapse, and obtain a more uniform pore size distribution. The prepared resin-based self-activated porous carbon material has a high specific surface area and pore volume. The doping of sulfur atoms can form sulfur-carbon bonds or sulfur-oxygen bonds, providing additional adsorption sites and catalytic active sites, enhancing the material's application potential in electrochemical energy storage or catalysis.

[0020] This invention enables the controllable design of the internal pore structure of resin-based porous carbon by controlling the structure and modification ratio of thioether alkane side chains, thereby obtaining an ideal pore distribution and meeting the specific requirements of silicon-carbon anode materials for pore structure. It provides a solution for the customized design of porous carbon materials such as porous carbon and supercapacitor carbon.

[0021] The preparation method of this invention is simple and efficient, without the need for complex processes such as multiple carbon source composites or multi-step activation and doping. The preparation process is simple and low in cost. The prepared resin-based porous carbon material has a high specific surface area and pore volume, which can meet the higher requirements of high-energy-density lithium-ion batteries for anode materials. Attached Figure Description

[0022] Figure 1 is a SEM image of the resin-based self-activated porous carbon material prepared in Example 1 of the present invention;

[0023] Figure 2 shows the SEM image of the porous carbon material prepared in the comparative example.

[0024] Figure 3 is a comparison diagram of the pore size / pore volume of the porous carbon material prepared in Example 1 of the present invention and the comparative example.

[0025] Figure 4 is a pore size distribution diagram of the resin-based self-activated porous carbon material prepared in Example 1 of the present invention;

[0026] Figure 5 shows the pore size distribution of the porous carbon material prepared in the comparative example. Embodiments of the present invention

[0027] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0029] Example 1

[0030] This embodiment proposes a resin-based self-activated porous carbon material, the preparation method of which includes the following steps:

[0031] S1. Add 2,5-dihydroxythiophenol and bromohexane to ethanol solvent in a molar ratio of 1:1 and stir until fully dissolved. Then slowly add sodium hydroxide as a catalyst, the amount of sodium hydroxide being 5% of the sum of the mass of 2,5-dihydroxythiophenol and bromohexane. Heat to 60℃ and react for 2 hours. After the reaction is complete, wash three times with deionized water, filter, and dry at 80℃ for 12 hours to obtain the hydroquinone monomer containing a thioether bond, the structural formula of which is:

[0032]

[0033] The reaction mechanism in this step is: RS-Na + R′Br → RSR′ + NaBr, which is a nucleophilic substitution reaction. The reaction equation is:

[0034]

[0035] S2. The thioether-containing hydroquinone monomer, resorcinol and formaldehyde obtained in step S1 are added to ethanol solvent in a molar ratio of 1:1:2. After stirring evenly, oxalic acid is added as a catalyst (the amount of oxalic acid is 5% of the sum of the mass of the thioether-containing hydroquinone monomer, resorcinol and formaldehyde). The temperature is raised to 90℃ and reacted for 4 hours to obtain phenolic resin.

[0036] S3. The phenolic resin obtained in step S2 is first heated to 180℃ and held for 2 hours under a nitrogen atmosphere for curing. Then, it is heated to 500℃ at a heating rate of 1℃ / min and held for 4 hours for self-activation. Finally, it is heated to 900℃ at a heating rate of 5℃ / min for carbonization for 4 hours to obtain the resin-based self-activated porous carbon material.

[0037] Example 2

[0038] This embodiment proposes a resin-based self-activated porous carbon material, the preparation method of which includes the following steps:

[0039] S1. Add 2,5-dihydroxythiophenol and bromobutane to ethanol solvent at a molar mass ratio of 1:1.2 and stir until fully dissolved; then slowly add sodium hydroxide as a catalyst, the amount of sodium hydroxide being 3% of the total mass of 2,5-dihydroxythiophenol and bromobutane, and heat to 70℃ for 3 hours; after the reaction is complete, wash three times with deionized water, filter, and dry at 90℃ for 10 hours to obtain the hydroquinone monomer containing thioether bonds;

[0040] S2. The thioether-containing hydroquinone monomer, resorcinol and malondialdehyde obtained in step S1 are added to ethanol solvent in a molar ratio of 1:0.8:1.8. After stirring evenly, hydrochloric acid is added as a catalyst (the amount of hydrochloric acid is 3% of the sum of the mass of the thioether-containing hydroquinone monomer, resorcinol and formaldehyde). The temperature is raised to 85℃ and reacted for 5 hours to obtain phenolic resin.

[0041] S3. The phenolic resin obtained in step S2 is first heated to 170℃ and held for 2 hours under a nitrogen atmosphere for curing. Then, it is heated to 500℃ at a heating rate of 1℃ / min and held for 4 hours for self-activation. Finally, it is heated to 850℃ at a heating rate of 5℃ / min for carbonization for 4 hours to obtain the resin-based self-activated porous carbon material.

[0042] Example 3

[0043] This embodiment proposes a resin-based self-activated porous carbon material, the preparation method of which includes the following steps:

[0044] S1. Add 2,5-dihydroxythiophenol and bromooctane to ethanol solvent at a molar mass ratio of 1:1.5 and stir until fully dissolved; then slowly add sodium hydroxide as a catalyst, the amount of sodium hydroxide being 4% of the total mass of 2,5-dihydroxythiophenol and bromooctane, and heat to 65℃ for 2.5 h; after the reaction is complete, wash three times with deionized water, filter, and dry at 85℃ for 14 h to obtain the hydroquinone monomer containing thioether bonds;

[0045] S2. The thioether-containing hydroquinone monomer, resorcinol, and formaldehyde obtained in step S1 are added to ethanol solvent in a molar ratio of 1:0.5:1.5. After stirring evenly, hydrochloric acid is added as a catalyst (the amount of hydrochloric acid is 4% of the sum of the mass of the thioether-containing hydroquinone monomer, resorcinol, and formaldehyde). The temperature is raised to 80℃ and reacted for 6 hours to obtain phenolic resin.

[0046] S3. The phenolic resin obtained in step S2 is first heated to 180℃ and held for 2 hours under a nitrogen atmosphere for curing. Then, it is heated to 500℃ at a heating rate of 1℃ / min and held for 4 hours for self-activation. Finally, it is heated to 800℃ at a heating rate of 5℃ / min for carbonization for 4 hours to obtain the resin-based self-activated porous carbon material.

[0047] Example 4

[0048] This embodiment proposes a resin-based self-activated porous carbon material, the preparation method of which includes the following steps:

[0049] S1. Add 2,5-dihydroxythiophenol and bromooctane to ethanol solvent in a molar mass ratio of 1:1.5 and stir until fully dissolved; then slowly add sodium hydroxide as a catalyst, the amount of catalyst being 4% of the total mass of 2,5-dihydroxythiophenol and bromooctane, and heat to 65℃ for 2.5 h; after the reaction is completed, wash three times with deionized water, filter, and dry at 85℃ for 14 h to obtain the hydroquinone monomer containing thioether bonds;

[0050] S2. The thioether-containing hydroquinone monomer, resorcinol, and formaldehyde obtained in step S1 are added to ethanol solvent in a molar ratio of 1:2:3. After stirring evenly, hydrochloric acid is added as a catalyst (the amount of hydrochloric acid is 4% of the sum of the mass of the thioether-containing hydroquinone monomer, resorcinol, and formaldehyde). The temperature is raised to 80℃ and reacted for 6 hours to obtain phenolic resin.

[0051] S3. The phenolic resin obtained in step S2 is first heated to 180℃ and held for 2 hours under a nitrogen atmosphere for curing. Then, it is heated to 500℃ at a heating rate of 1℃ / min and held for 4 hours for self-activation. Finally, it is heated to 800℃ at a heating rate of 5℃ / min for carbonization for 4 hours to obtain the resin-based self-activated porous carbon material.

[0052] Example 5

[0053] This embodiment proposes a resin-based self-activated porous carbon material, the preparation method of which includes the following steps:

[0054] S1. Add 2,5-dihydroxythiophenol and bromohexane to ethanol solvent in a molar mass ratio of 1:1 and stir until fully dissolved; then slowly add sodium hydroxide as a catalyst, the amount of sodium hydroxide being 5% of the total mass of 2,5-dihydroxythiophenol and bromohexane, and heat to 60℃ for 2 hours; after the reaction is complete, wash three times with deionized water, filter, and dry at 80℃ for 12 hours to obtain the hydroquinone monomer containing thioether bonds;

[0055] S2. The thioether-containing hydroquinone monomer, resorcinol and formaldehyde obtained in step S1 are added to ethanol solvent in a molar ratio of 1:1:2. After stirring evenly, oxalic acid is added as a catalyst (the amount of oxalic acid is 5% of the sum of the mass of the thioether-containing hydroquinone monomer, resorcinol and formaldehyde). The temperature is raised to 90℃ and reacted for 4 hours to obtain phenolic resin.

[0056] S3. The phenolic resin obtained in step S2 is first heated to 180℃ and held for 2 hours under a nitrogen atmosphere for curing. Then, it is heated to 500℃ at a heating rate of 5℃ / min and held for 4 hours for self-activation. Finally, it is heated to 900℃ at a heating rate of 5℃ / min for carbonization for 4 hours to obtain the resin-based self-activated porous carbon material.

[0057] Comparative Example

[0058] This comparative example presents a resin-based porous carbon material, the preparation method of which includes the following steps:

[0059] S1. Add resorcinol and oxalic acid to deionized water at a molar ratio of 1:0.01, heat to 50°C, and then slowly add 37% formaldehyde aqueous solution dropwise while stirring at a stirring speed of 200 r / min. The addition is completed in 1 hour, and the molar ratio of formaldehyde to resorcinol is 1.5:1 to obtain the prepolymer solution.

[0060] S2. A 4 wt% potassium hydroxide aqueous solution is slowly added dropwise to the prepolymer solution while stirring at a speed of 800 r / min, and the addition is completed in 1 hour. Then, a 37% formaldehyde aqueous solution is added dropwise over 30 minutes. The molar ratio of formaldehyde to resorcinol in step S1 is 0.5:1. The mixture is heated to 70°C and kept at that temperature for 8 hours to carry out the crosslinking reaction, resulting in a gel. The resulting gel is then dried at 100°C to obtain the dried material.

[0061] S3. Under a nitrogen atmosphere, the dried material is carbonized at 700℃ for 3 hours; carbon dioxide and nitrogen (volume ratio of carbon dioxide and nitrogen is 1:5) are introduced, the temperature is raised to 800℃ and activated for 5 hours, then cooled to room temperature, and ground, graded, shaped and sieved to obtain porous carbon material with a particle size D50 of 5-8μm.

[0062] Test case

[0063] (1) The porous carbon materials prepared in Example 1 and the comparative example were characterized by scanning electron microscopy, and Figures 1 and 2 were obtained. As can be seen from Figures 1 and 2, the porous carbon material prepared in Example 1 has no loose macropores on its surface, while the porous carbon material prepared in the comparative example has obvious loose macropores on its surface; this shows that the method of the present invention can avoid the formation of macroporous structures on the surface of porous carbon.

[0064] (2) The porous carbon materials prepared in Examples 1-5 and the comparative examples were tested for pore volume, average pore size, and specific surface area. The testing instrument was a V-Sorb X800TP specific surface area and pore size analyzer. The testing method was to use nitrogen gas and degas at 300℃ for 6 hours. The results are shown in Table 1 and Figures 3-5.

[0065] Table 1. Test results of pore volume, pore size, and specific surface area.

[0066]

[0067] According to the results in Table 1:

[0068] Compared with the comparative example, Examples 1-3 show that by controlling the molar ratio of hydroquinone monomers containing thioether bonds, the pore volume, specific surface area, and pore size of porous carbon materials can be regulated. Furthermore, the microporosity of the porous carbon materials in Examples 1-3 is much lower than that in the comparative example. This demonstrates that by controlling the structure and modification ratio of the thioether alkane side chains, the present invention can achieve controllable design of the internal pore structure of resin-based porous carbon and obtain an ideal pore distribution.

[0069] Compared with Example 3, Example 4 can control the pore size of the self-activated porous carbon to below 1 nm by reducing the molar ratio of the hydroquinone monomer with thioether bond; at the same time, compared with the comparative example, it can be found that in Example 4, the ultra-microporosity can still be effectively controlled while reducing the average pore size of the porous carbon.

[0070] As can be seen from the test results of Examples 1 and 5, the heating rate can also be used as one of the means to control the pore volume and pore size. If the heating rate is too fast, the pore size of the self-activated porous carbon will increase. This is because the CO bond of the functional group of phenolic resin and the CSC bond of the thioether group are broken in a concentrated manner. During activation, the gas is released at the same time, which leads to the increase of the pore size of the porous carbon.

[0071] As shown in Figure 3, the porous carbon prepared in Example 1 has a significantly lower pore volume fraction below 0.7 nm than the comparative example. As shown in Figures 4 and 5, the pore size distribution of the porous carbon prepared in this invention is narrower and more uniform compared with that of the comparative example.

[0072] Application examples

[0073] The porous carbon materials obtained in Examples 1-5 and the comparative examples were used to prepare lithium battery anode materials. The method was as follows: the porous carbon material was placed in a fluidized bed vapor deposition equipment, and a mixture of silane (SiH4) and argon (the volume ratio of silane to argon was 1:4) was introduced, and vapor deposition was carried out at 460°C for 3 hours; then the equipment was flushed with argon for 30 minutes, and a mixture of acetylene and argon (the volume ratio of acetylene to argon was 1:2) was introduced, and vapor deposition was carried out at 570°C for 3 hours to obtain the lithium battery anode material.

[0074] The prepared lithium battery anode materials were then used to fabricate CR2025 coin cells: The lithium battery anode material, conductive agent (Super-P), binder (sodium carboxymethyl cellulose CMC), and polyacrylonitrile binder (LA133) were mixed in a weight ratio of 80:10:8:2, and an appropriate amount of ultrapure water was added to form a slurry. This slurry was coated onto copper foil and then vacuum dried and rolled to form the anode sheet. The positive electrode used a lithium metal sheet, and the electrolyte was a 1 mol / L LiPF6 solution (the solvent being a mixture of dimethyl carbonate DMC, diethyl carbonate DEC, and ethylene carbonate EC in a mass ratio of 1:1:1). The separator was a polypropylene microporous membrane. The resulting CR2025 coin cells were assembled. The electrochemical performance of the CR2025 coin cells was tested using a Blue Battery testing system: under room temperature conditions, constant current charge and discharge at 0.1C was performed, with the charge and discharge voltage limited to 0.005-1.5V. The results are shown in Table 2 below.

[0075] Table 2 Electrochemical performance results

[0076]

[0077] As can be seen from Table 2:

[0078] Compared with the comparative examples, the porous carbon materials provided in Examples 1-4 of this invention exhibit better capacity utilization and first-efficiency performance at 0.8V, demonstrating that the silicon-carbon composite material prepared by this invention has superior electrochemical performance. This illustrates that the controllable design of the internal pore structure of the resin-based porous carbon and the doping of sulfur atoms in this invention are beneficial to improving the electrochemical performance of the silicon-carbon composite material.

[0079] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0080] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a resin-based self-activated porous carbon material, characterized in that, It includes the following steps: A condensation reaction is carried out on hydroquinone monomer, hydroquinone monomer containing thioether bonds, formaldehyde or polyaldehyde, and catalyst A to obtain a phenolic resin containing thioether alkane side chains; the molar ratio of the hydroquinone monomer containing thioether bonds, hydroquinone monomer, formaldehyde or polyaldehyde is 1:0.5-2:1.5-3. The phenolic resin is carbonized, wherein the thioether bonds of the phenolic resin decompose during the carbonization process to generate gas and achieve self-activation and pore formation, thereby obtaining a resin-based self-activated porous carbon material; the carbonization is carried out under a protective atmosphere, first heating to 170-180℃ and holding for 2-3 hours, then heating to 450-500℃ at a heating rate of 1℃ / min-10℃ / min and holding for 4-6 hours, and then heating to 800-900℃ at a heating rate of 1℃ / min-10℃ / min and holding for 4-6 hours.

2. The method for preparing resin-based self-activated porous carbon material according to claim 1, characterized in that, The method for preparing the hydroquinone monomer containing thioether bonds is as follows: 2,5-dihydroxythiophenol and haloalkanes are added to a solvent, catalyst B is added to react, and then post-treatment is performed to obtain the hydroquinone monomer containing thioether bonds.

3. The method for preparing resin-based self-activated porous carbon material according to claim 2, characterized in that, The molar ratio of 2,5-dihydroxythiophenol to the haloalkane is 1:1-1.5; the mass of catalyst B is 3%-5% of the sum of the masses of 2,5-dihydroxythiophenol and the haloalkane; and / or, the haloalkane is at least one of bromohexane, bromobutane, and bromooctane; and / or, catalyst B is at least one of potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; and / or, the solvent is ethanol.

4. The method for preparing resin-based self-activated porous carbon material according to claim 2, characterized in that, The reaction between 2,5-dihydroxythiophenol, haloalkanes, and catalyst B is carried out at 60-70°C for 2-3 hours. The post-treatment includes filtration, washing, and drying. The washing is performed several times with deionized water, and the drying is carried out at 80-90°C for 10-14 hours.

5. The method for preparing resin-based self-activated porous carbon material according to claim 1, characterized in that, The mass of catalyst A is 3%-5% of the sum of the masses of the hydroquinone monomer containing the thioether bond, the hydroquinone monomer, formaldehyde, or polyaldehyde; the polyaldehyde is at least one of malondialdehyde, succinal, glutaraldehyde, 2-hydroxyglutaraldehyde, and malealdehyde; and catalyst A is at least one of hydrochloric acid and oxalic acid.

6. The method for preparing resin-based self-activated porous carbon material according to claim 1, characterized in that, The polycondensation reaction is carried out at 80-90℃ for 4-6 hours.

7. A resin-based self-activated porous carbon material, characterized in that, It is prepared by the preparation method described in any one of claims 1-6.

8. An application of the resin-based self-activated porous carbon material as described in claim 7, characterized in that, It is used to prepare lithium battery anode materials.

9. The application according to claim 8, characterized in that, The preparation of the lithium battery anode material includes the following steps: Under a protective atmosphere, silicon is first deposited on the resin-based self-activated porous carbon material via chemical vapor deposition using a silicon source gas; then, carbon is coated onto the resin-based self-activated porous carbon material via chemical vapor deposition using a carbon source gas, thus obtaining a lithium battery anode material. The silicon source gas is at least one of silane, disilane, dichlorosilane, silicon tetrachloride, dichlorosilane, and trichlorosilane. The silicon deposition temperature is 450-480℃ and the time is 2-4 hours. The carbon source gas is at least one of acetylene, methane, propane, and cyclohexane. The carbon coating temperature is 560-580℃ and the time is 2-4 hours.

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