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

Abstract

The present invention relates to the technical field of anode materials for lithium batteries, and specifically discloses a resin-based self-activated porous carbon material, a preparation method thereof and an application. The preparation method includes the following steps: carrying out a polycondensation reaction on hydroquinone monomers, hydroquinone monomers containing thioether bonds, formaldehyde or polyaldehydes, and catalyst A to obtain a phenolic resin; carbonizing the phenolic resin to obtain the resin-based self-activated porous carbon material. The present invention synthesizes a phenolic resin by using hydroquinone monomers containing thioether bonds, thereby introducing thioether alkane side chains into the phenolic resin. During the carbonization process of the phenolic resin, since thioether bonds are extremely easy to decompose to generate gas at high temperature, pores can be formed in the phenolic resin skeleton. The prepared resin-based self-activated porous carbon material has a high specific surface area and pore volume. By controlling the structure and modification ratio of the thioether alkane side chains, controllable design of the internal pore structure of the resin-based porous carbon can be achieved, and an ideal pore distribution can be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of anode materials for lithium batteries, and particularly relates to a resin-based self-activated porous carbon material, a preparation method thereof, and an application thereof. Background Art

[0002] As the main power battery in the fields of new energy vehicles, portable electronic devices, etc., the improvement of the energy density of lithium batteries has always been the focus of research. Silicon materials have a theoretical specific capacity of up to 4200 mAh / g and are considered the most potential candidates to replace traditional graphite anode materials. However, during the charge and discharge process, silicon materials will undergo a huge volume expansion, resulting in the pulverization and shedding of the electrode materials, seriously affecting the cycle life and safety performance of the battery.

[0003] At present, the preparation of porous silicon-carbon anode materials by chemical vapor deposition is considered an effective way to solve the volume expansion problem of silicon anode materials. This method uses porous carbon as the carrier of the silicon source, and introduces silane gas into the pores of the porous carbon under high-temperature conditions, so that the silicon source is deposited in the pores of the porous carbon to form a silicon-carbon composite material. The pore structure of the porous carbon provides a buffer space for the expansion of silicon, effectively inhibiting the pulverization of silicon particles. However, it is difficult to avoid the generation of ultramicropores (pore diameter < 0.7 nm) in the porous carbon materials prepared by existing physical activation, alkali activation and other methods. This ultramicropore structure will affect the insertion and extraction of lithium ions, reducing the initial Coulomb efficiency and rate performance of the battery. Therefore, developing a resin-based self-activated porous carbon material with a customizable pore structure size and avoiding the generation of ultramicropore structures 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 the present invention is to provide a resin-based self-activated porous carbon material, a preparation method thereof, and an application thereof. By controlling the structure and modification ratio of the thioether alkane side chain, the controllable design of the internal pore structure of the resin-based porous carbon can be realized, and an ideal pore distribution can be obtained to meet the specific requirements of the silicon-carbon anode material for the pore structure.

[0005] To achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention first provides a preparation method of a resin-based self-activated porous carbon material, which includes the following steps:

[0007] Carry out a polycondensation reaction on hydroquinone monomers, hydroquinone monomers containing a thioether bond, formaldehyde or polyaldehyde, and catalyst A to obtain a phenolic resin;

[0008] Carbonize the phenolic resin to obtain a resin-based self-activated porous carbon material.

[0009] As a further improvement of the above solution of the present invention, the preparation method of the hydroquinone monomer containing a thioether bond is as follows: 2,5-dihydroxybenzenethiol and a haloalkane are added to a solvent, a catalyst B is added and reacted, and aftertreatment is carried out to obtain the hydroquinone monomer containing a thioether bond.

[0010] As a further improvement of the above solution of the present invention, the molar ratio of 2,5-dihydroxybenzenethiol to the haloalkane is 1:1 - 1.5, and the mass of the catalyst B is 3% - 5% of the sum of the masses of 2,5-dihydroxybenzenethiol and the haloalkane; and / or, the haloalkane is 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 of the above solution of the present invention, the reaction between 2,5-dihydroxybenzenethiol, the haloalkane, and the catalyst B is carried out at 60 - 70 °C for 2 - 3 h. The aftertreatment includes filtration, washing, and drying in sequence. The washing is carried out by washing with deionized water several times, and the drying is carried out at 80 - 90 °C for 10 - 14 h.

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

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

[0014] As a further improvement of the above solution of the present invention, the carbonization is carried out under a protective atmosphere. First, the temperature is raised to 170 - 180 °C and held for 2 - 3 h, then the temperature is raised at a heating rate of 1 °C / min - 10 °C / min to 450 - 500 °C and held for 4 - 6 h, and then the temperature is raised at a heating rate of 1 °C / min - 10 °C / min to 800 - 900 °C and held for 4 - 6 h.

[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 described above, which is used for preparing a negative electrode material for a lithium battery.

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

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

[0019] The present invention uses a hydroquinone monomer containing a thioether bond to synthesize a phenolic resin, thereby introducing a thioether alkane side chain into the phenolic resin. During the carbonization process of the phenolic resin, since the thioether bond is extremely easy to decompose and generate gas at high temperature, it can create pores in the phenolic resin skeleton, promote the formation of micropores and mesopores, thereby increasing the specific surface area. Compared with the traditional physical activation or alkali activation methods, the method of the present invention effectively avoids the problem of the generation of inherent ultra-microporous structures during the preparation of porous carbon materials; at the same time, the flexible alkane molecular chain helps to relieve the structural stress during the carbonization process, reduce pore channel 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, and enhancing the application potential of the material in electrochemical energy storage or catalysis.

[0020] By controlling the structure and modification ratio of the thioether alkane side chain, the present invention can realize the controllable design of the internal pore structure of the resin-based porous carbon, obtain an ideal pore distribution, meet the specific requirements of the silicon-carbon anode material for the pore structure, and provide a solution for the customized design of porous structure carbon materials such as porous carbon and supercapacitor carbon.

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

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

[0023] Figure 2 It is the SEM image of the porous carbon material prepared in the comparative example;

[0024] Figure 3 The contrast diagram of pore size / pore integral volume of the porous carbon materials prepared in Example 1 and Comparative Example of the present invention;

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

[0026] Figure 5 The pore size distribution diagram of the porous carbon material prepared in the Comparative Example. Detailed implementation manners

[0027] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0029] Example 1

[0030] This example provides a resin-based self-activated porous carbon material, and its preparation method includes the following steps:

[0031] S1. Add 2,5-dihydroxybenzenethiol and bromohexane into an ethanol solvent at a molar ratio of 1:1, and stir to dissolve them fully; then slowly add sodium hydroxide as a catalyst, and the dosage of sodium hydroxide is 5% of the sum of the masses of 2,5-dihydroxybenzenethiol and bromohexane, and heat to 60 °C for reaction for 2 h; after the reaction is completed, wash with deionized water 3 times, filter, and dry at 80 °C for 12 h to obtain a hydroquinone monomer containing a thioether bond, and its structural formula is:

[0032]

[0033] The reaction mechanism of this step is: R-S-Na + R′Br ─→ R-S-R′ + NaBr, which is a nucleophilic substitution reaction, and the reaction equation is:

[0034]

[0035] S2. Add the benzene diol monomer containing a thioether bond prepared in step S1, resorcinol, and formaldehyde to an ethanol solvent at a molar ratio of 1:1:2. After stirring evenly, add oxalic acid as a catalyst (the dosage of oxalic acid is 5% of the sum of the masses of the benzene diol monomer containing a thioether bond, resorcinol, and formaldehyde), and heat up to 90 °C for reaction for 4 h to obtain a phenolic resin;

[0036] S3. Under a nitrogen atmosphere, first heat up the phenolic resin obtained in step S2 to 180 °C and keep it warm for 2 h for curing, then heat it up to 500 °C at a heating rate of 1 °C / min and keep it warm for 4 h for self-activation, and then heat it up to 900 °C at a heating rate of 5 °C / min for carbonization for 4 h to obtain a resin-based self-activated porous carbon material.

[0037] Example 2

[0038] This example proposes a resin-based self-activated porous carbon material, and its preparation method includes the following steps:

[0039] S1. Add 2,5-dihydroxybenzenethiol and bromobutane to an ethanol solvent at a molar mass ratio of 1:1.2, and stir to dissolve it fully; then slowly add sodium hydroxide as a catalyst, and the dosage of sodium hydroxide is 3% of the total mass of 2,5-dihydroxybenzenethiol and bromobutane, and heat up to 70 °C for reaction for 3 h; after the reaction ends, wash it with deionized water 3 times, filter, and dry it at 90 °C for 10 h to obtain a benzene diol monomer containing a thioether bond;

[0040] S2. Add the benzene diol monomer containing a thioether bond prepared in step S1, resorcinol, and malonaldehyde to an ethanol solvent at a molar ratio of 1:0.8:1.8. After stirring evenly, add hydrochloric acid as a catalyst (the dosage of hydrochloric acid is 3% of the sum of the masses of the benzene diol monomer containing a thioether bond, resorcinol, and formaldehyde), and heat up to 85 °C for reaction for 5 h to obtain a phenolic resin;

[0041] S3. Under a nitrogen atmosphere, first heat up the phenolic resin obtained in step S2 to 170 °C and keep it warm for 2 h for curing, then heat it up to 500 °C at a heating rate of 1 °C / min and keep it warm for 4 h for self-activation, and then heat it up to 850 °C at a heating rate of 5 °C / min for carbonization for 4 h to obtain a resin-based self-activated porous carbon material.

[0042] Example 3

[0043] This example proposes a resin-based self-activated porous carbon material, and its preparation method includes the following steps:

[0044] S1. Add 2,5-dihydroxybenzenethiol and 1-bromooctane into an ethanol solvent at a molar mass ratio of 1:1.5, and stir to dissolve them fully. Then slowly add sodium hydroxide as a catalyst, with the dosage of sodium hydroxide being 4% of the total mass of 2,5-dihydroxybenzenethiol and 1-bromooctane. Heat up to 65 °C and react for 2.5 h. After the reaction ends, wash it with deionized water three times, filter, and dry at 85 °C for 14 h to obtain a benzenediol monomer containing a thioether bond.

[0045] S2. Add the benzenediol monomer containing a thioether bond prepared in step S1, resorcinol, and formaldehyde into an ethanol solvent at a molar ratio of 1:0.5:1.5. After stirring evenly, add hydrochloric acid as a catalyst (the dosage of hydrochloric acid is 4% of the sum of the masses of the benzenediol monomer containing a thioether bond, resorcinol, and formaldehyde). Heat up to 80 °C and react for 6 h to obtain a phenolic resin.

[0046] S3. Under a nitrogen atmosphere, first heat up the phenolic resin obtained in step S2 to 180 °C and keep it warm for 2 h for curing, then heat it up to 500 °C at a heating rate of 1 °C / min and keep it warm for 4 h for self-activation, and then heat it up to 800 °C at a heating rate of 5 °C / min and carbonize for 4 h to obtain a resin-based self-activated porous carbon material.

[0047] Example 4

[0048] This example presents a resin-based self-activated porous carbon material, and its preparation method includes the following steps:

[0049] S1. Add 2,5-dihydroxybenzenethiol and 1-bromooctane into an ethanol solvent at a molar mass ratio of 1:1.5, and stir to dissolve them fully. Then slowly add sodium hydroxide as a catalyst, with the catalyst dosage being 4% of the total mass of 2,5-dihydroxybenzenethiol and 1-bromooctane. Heat up to 65 °C and react for 2.5 h. After the reaction ends, wash it with deionized water three times, filter, and dry at 85 °C for 14 h to obtain a benzenediol monomer containing a thioether bond.

[0050] S2. Add the benzenediol monomer containing a thioether bond prepared in step S1, resorcinol, and formaldehyde into an ethanol solvent at a molar ratio of 1:2:3. After stirring evenly, add hydrochloric acid as a catalyst (the dosage of hydrochloric acid is 4% of the sum of the masses of the benzenediol monomer containing a thioether bond, resorcinol, and formaldehyde). Heat up to 80 °C and react for 6 h to obtain a phenolic resin.

[0051] S3. Under a nitrogen atmosphere, first heat up the phenolic resin obtained in step S2 to 180 °C and keep it warm for 2 h for curing, then heat it up to 500 °C at a heating rate of 1 °C / min and keep it warm for 4 h for self-activation, and then heat it up to 800 °C at a heating rate of 5 °C / min and carbonize for 4 h to obtain a resin-based self-activated porous carbon material.

[0052] Example 5

[0053] This example presents a resin-based self-activated porous carbon material, and its preparation method includes the following steps:

[0054] S1. Add 2,5-dihydroxybenzenethiol and bromohexane into an ethanol solvent at a molar mass ratio of 1:1, and stir to dissolve them fully; then slowly add sodium hydroxide as a catalyst, with the dosage of sodium hydroxide being 5% of the total mass of 2,5-dihydroxybenzenethiol and bromohexane, heat up to 60 °C and react for 2 h; after the reaction ends, wash with deionized water 3 times, filter, and dry at 80 °C for 12 h to obtain a hydroquinone monomer containing a thioether bond;

[0055] S2. Add the hydroquinone monomer containing a thioether bond obtained in step S1, resorcinol, and formaldehyde into an ethanol solvent at a molar ratio of 1:1:2, stir evenly, then add oxalic acid as a catalyst (the dosage of oxalic acid is 5% of the sum of the masses of the hydroquinone monomer containing a thioether bond, resorcinol, and formaldehyde), heat up to 90 °C and react for 4 h to obtain a phenolic resin;

[0056] S3. Under a nitrogen atmosphere, first heat the phenolic resin obtained in step S2 to 180 °C and keep it warm for 2 h for curing, then heat it at a heating rate of 5 °C / min to 500 °C and keep it warm for 4 h for self-activation, and then heat it at a heating rate of 5 °C / min to 900 °C and carbonize for 4 h to obtain the resin-based self-activated porous carbon material.

[0057] Comparative Example

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

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

[0060] S2. Slowly dropwise add a 4 wt% aqueous potassium hydroxide solution to the prepolymer solution while stirring, with the stirring speed being 800 r / min, and finish dropping in 1 h. Then take a 37% aqueous formaldehyde solution and finish dropping in 30 min. The molar ratio of formaldehyde to the resorcinol in step S1 is 0.5:1; heat to 70 °C and keep it warm for 8 h for a crosslinking reaction to obtain a gel; place the obtained gel in an oven at 100 °C for drying to obtain a dried material;

[0061] S3. Under a nitrogen atmosphere, keep the dried material at 700 °C for 3 h for carbonization; introduce carbon dioxide and nitrogen (the volume ratio of carbon dioxide to nitrogen is 1:5), heat up to 800 °C and keep it for 5 h for activation, then cool to room temperature, and carry out grinding, classification, shaping, and screening to obtain a porous carbon material with a D50 particle size of 5 - 8 μm.

[0062] Test Example

[0063] (1) Use a scanning electron microscope to characterize the porous carbon materials prepared in Example 1 and the comparative example, and obtain Figure 1 and Figure 2 . From Figure 1 , Figure 2 , it can be seen that there are no loose macropores on the surface of the porous carbon material prepared in Example 1, while there are obvious loose macropores on the surface of the porous carbon material prepared in the comparative example; this shows that the method of the present invention can avoid the formation of macropore structures on the surface of the porous carbon.

[0064] (2) Carry out pore volume, average pore diameter, and specific surface area tests on the porous carbon materials prepared in Examples 1 - 5 and the comparative example: The test instrument is a V-Sorb X800TP specific surface area and pore size analyzer, and the test method: The test gas is nitrogen, and degassing is carried out at 300 °C for 6 h. The results are shown in Table 1, Figures 3 - 5 .

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

[0066]

[0067] It can be seen from the results in Table 1 that:

[0068] Comparing Examples 1 - 3 with the comparative example, it can be seen that by controlling the molar ratio of the hydroquinone monomer containing a thioether bond, the pore volume, specific surface area, and pore diameter of the porous carbon material can be regulated, and the ultramicropore ratio of the porous carbon materials in Examples 1 - 3 is much lower than that of the comparative example; this shows that the present invention can realize the controllable design of the internal pore structure of the resin-based porous carbon by controlling the structure and modification ratio of the thioether alkane side chain, and obtain an ideal pore distribution;

[0069] Comparing with Example 3, it can be seen that in Example 4, by reducing the molar ratio of the hydroquinone monomer with a thioether bond, the pore diameter of the self-activated porous carbon can be controlled below 1 nm; at the same time, comparing with the comparative example, it can be found that in Example 4, when the average pore diameter of the porous carbon is reduced, the ultramicropore ratio can still be effectively controlled;

[0070] From the test results of Example 1 and Example 5, it can be seen that 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 become larger. This is because the C-O bond of the phenolic resin functional group and the C-S-C bond of the thioether group are broken concentratedly, and the gas escapes simultaneously during activation, resulting in an increase in the pore size of the porous carbon;

[0071] From Figure 3 it can be seen that the ultra-micropore volume ratio of the porous carbon prepared in Example 1 below 0.7 nm is significantly lower than that of the comparative example; From Figure 4 , Figure 5 it can be seen that by comparing the pore size distributions of Example 1 and the comparative example, the pore size distribution of the porous carbon prepared by the present invention is narrower and more uniform.

[0072] Application Example

[0073] The porous carbon materials prepared in Examples 1-5 and the comparative example were respectively used to prepare the anode materials for lithium batteries. The method was as follows: The porous carbon material was placed in a fluidized bed chemical vapor deposition device, and a mixed gas of silane (SiH4) and argon (the volume ratio of silane to argon was 1:4) was introduced, and chemical vapor deposition was carried out at 460 °C for 3 h; then the device was flushed with argon for 30 min, and a mixed gas of acetylene and argon (the volume ratio of acetylene to argon was 1:2) was introduced, and chemical vapor deposition was carried out at 570 °C for 3 h to obtain the anode materials for lithium batteries.

[0074] Then, the obtained anode materials for lithium batteries were respectively prepared into CR2025 type button cells: They were mixed according to the weight ratio of the anode material for lithium battery, conductive agent (Super-P), binder (sodium carboxymethyl cellulose CMC), and polyacrylonitrile binder (LA133) of 80:10:8:2, and an appropriate amount of ultrapure water was added to make a slurry, which was coated on a copper foil, and then vacuum dried and rolled to prepare a negative electrode sheet; The positive electrode used a lithium metal sheet, the electrolyte was a 1 mol / L LiPF6 solution (the solvent was a mixture of dimethyl carbonate DMC, diethyl carbonate DEC, and ethylene carbonate EC in a mass ratio of 1:1:1), and the separator used a polypropylene microporous membrane to assemble a CR2025 type button cell. The obtained CR2025 type button cells were subjected to electrochemical performance tests on a BlueTEC battery test system: Under normal temperature conditions, constant current charge and discharge at 0.1C, and the charge and discharge voltage was 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 the present invention have better capacity performance and first efficiency at 0.8V. It can be seen that the silicon-carbon composite material prepared by the present invention has more excellent electrochemical performance; it shows that the controllable design of the internal pore structure of the resin-based porous carbon and the doping of sulfur atoms in the present invention are beneficial to improving the electrochemical performance of the silicon-carbon composite material.

[0079] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0080] The above-described embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it cannot be understood as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the invention patent should be subject to the appended claims.

Claims

1. A preparation method of a resin-based self-activated porous carbon material, characterized in that, It includes the following steps: Carry out a polycondensation reaction on hydroquinone monomers, hydroquinone monomers containing sulfur ether bonds, formaldehyde or polyaldehydes, and catalyst A to obtain a phenolic resin containing sulfur ether alkane side chains; the molar ratio of the hydroquinone monomers containing sulfur ether bonds, hydroquinone monomers, formaldehyde or polyaldehydes is 1:0.5 - 2:1.5 - 3; Carbonize the phenolic resin, wherein the sulfur ether bonds in the phenolic resin decompose to generate gas during carbonization to achieve self-activation pore formation, thus obtaining a resin-based self-activated porous carbon material; the carbonization is carried out under a protective atmosphere. First, heat to 170 - 180 °C and keep warm for 2 - 3 h, then heat at a heating rate of 1 °C / min - 10 °C / min to 450 - 500 °C and keep warm for 4 - 6 h, and then heat at a heating rate of 1 °C / min - 10 °C / min to 800 - 900 °C and keep warm for 4 - 6 h.

2. The preparation method of the resin-based self-activated porous carbon material according to claim 1, characterized in that, The preparation method of the hydroquinone monomers containing sulfur ether bonds is as follows: Add 2,5-dihydroxybenzenethiol and haloalkanes to a solvent, add catalyst B and react, and then carry out post-treatment to obtain the hydroquinone monomers containing sulfur ether bonds.

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

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

5. The preparation method of the resin-based self-activated porous carbon material according to claim 1, wherein, The mass of catalyst A is 3% - 5% of the sum of the masses of the hydroquinone monomers containing sulfur ether bonds, hydroquinone monomers, formaldehyde or polyaldehydes; the polyaldehydes are at least one of malondialdehyde, succinaldehyde, glutaraldehyde, 2-hydroxypentanedial, malealdehyde; the catalyst A is at least one of hydrochloric acid and oxalic acid.

6. The preparation method of the resin-based self-activated porous carbon material according to claim 1, wherein, The polycondensation reaction is carried out at 80 - 90 °C for 4 - 6 h.

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

8. Use of the resin-based self-activating porous carbon material according to claim 7, characterized in that, It is used for preparing the anode material of a lithium battery.

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

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