Graded porous carbon material and preparation method thereof

Abstract

The invention relates to the field of energy, in particular to a graded porous carbon material and a preparation method thereof.The method comprises the steps that thermoplastic phenolic resin is prepared, and the thermoplastic phenolic resin is low-molecular-weight resole; curing the thermoplastic phenolic resin to obtain thermosetting phenolic resin; carbonizing the thermosetting phenolic resin to obtain a carbide; and activating the carbide to obtain the graded porous carbon. According to the method, the micro-mesoporous graded carbon is formed, conveying holes matched with the deposition pore volume are provided, the pore channel resistance is reduced, and the silicon loading efficiency is improved; the graphitization degree is obviously improved, so that the conductivity of pyrolytic carbon is improved.

Description

Technical Field

[0001] The present invention relates to the field of energy, and more specifically, to a hierarchical porous carbon material and a preparation method thereof. Background Art

[0002] The rapid development of industries like lithium-ion vehicles and electronics is driving an increasingly urgent demand for high-energy-density lithium-ion batteries. Silicon-based anode materials, with their high theoretical specific capacity, are considered the preferred anode material for next-generation high-capacity lithium-ion batteries. However, they also present challenges such as volume expansion after lithium insertion, material shattering, performance degradation over multiple cycles, and capacity loss due to SEI formation.

[0003] With continuous technological iterations and breakthroughs, the fourth generation of vapor-deposited silicon-carbon (VDS) has gradually gained market acceptance and begun to be used in consumer and power battery applications. Porous carbon, the carbon skeleton of VDS silicon-carbon materials, is crucial for its performance, with its specific surface area, pore size distribution, and electrical conductivity being key factors.

[0004] Porous carbon, a carbon material with a highly developed pore structure and large specific surface area, is primarily obtained by carbonizing and activating various precursors. Phenolic resin, with its controllable chemical structure, high carbonization yield, low impurity content, strong cross-linked structure, and abundant porosity, is an ideal precursor for preparing porous carbon by pyrolysis. However, its low degree of graphitization and poor electrical conductivity after direct carbonization are currently being explored. Currently, the addition of transition metals such as iron, cobalt, and nickel, either as single elements or as compounds, is often used to increase the graphitization of carbon produced by pyrolysis of phenolic resin, yielding highly graphitized carbon materials. However, inorganic catalysts suffer from poor compatibility with the resin, leading to catalyst aggregation and reduced catalytic performance during the catalytic process. Furthermore, the porous carbon obtained by activating phenolic resin often results in a highly disordered state with a uniform pore size distribution. This lack of transport pores matches the deposited pore volume, resulting in high pore resistance, low silicon loading efficiency, and poor electrical conductivity. These issues severely impact the electrochemical performance of silicon-carbon anodes and limit their application in other fields. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a method for preparing a hierarchical porous carbon material, comprising:

[0006] Preparation of thermoplastic phenolic resin, wherein the thermoplastic phenolic resin is a low molecular weight resol phenolic resin;

[0007] curing the thermoplastic phenolic resin to obtain a thermosetting phenolic resin;

[0008] carbonizing the thermosetting phenolic resin to obtain a carbide;

[0009] The carbide is activated to obtain the hierarchical porous carbon.

[0010] Furthermore, the thermoplastic phenolic resin is a thermoplastic phenolic resin modified by an organic iron source;

[0011] Preferably, the preparation of the thermoplastic phenolic resin comprises:

[0012] reacting a phenolic compound, an aldehyde compound, and an organic iron salt under acidic conditions to obtain the thermoplastic phenolic resin;

[0013] Further preferably, the mass ratio of the phenolic compound, the aldehyde compound and the organic iron salt is 1:0.6-0.9:0.01-0.15;

[0014] More preferably, the reaction conditions are: temperature 50-100° C., time 1-3 h.

[0015] Furthermore, the organic iron salt is at least one of ferrous acetate, ferric gluconate, ferrous lactate or ferrous oxalate;

[0016] Furthermore, the phenolic compound is at least one of phenol, resorcinol, p-aminophenol or phloroglucinol;

[0017] Furthermore, the aldehyde compound is at least one of formaldehyde, furfural, acetaldehyde, malondialdehyde or succinaldehyde.

[0018] Furthermore, the curing comprises: adding a curing agent to the thermoplastic phenolic resin and first curing it under an inert atmosphere;

[0019] Furthermore, the curing conditions are: heating rate 1-5°C / min, heating to 100-200°C, holding time 1-3h;

[0020] Further preferably, the curing agent is at least one of hexamethylenetetramine, paraformaldehyde or benzenesulfonic acid;

[0021] Further preferably, the mass of the curing agent is 5%-15% of the mass of the thermoplastic phenolic resin.

[0022] Furthermore, the carbonization conditions are: heating rate 1-5°C / min, heating to 400-600°C, and holding time 1-3h.

[0023] Furthermore, the obtaining of the hierarchical porous carbon comprises: mixing an activator with the carbide, and then activating the carbide under an inert atmosphere;

[0024] Preferably, the activation conditions include: heating to 700-1200°C at 1-5°C / min and keeping warm for 1-6h;

[0025] Further preferably, the activator is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, phosphoric acid, zinc chloride or potassium chloride;

[0026] Further preferably, the mass ratio of the activator to the carbide is 1-5:1.

[0027] Furthermore, the activation further includes hydrochloric acid treatment;

[0028] Preferably, the hydrochloric acid treatment is to soak the activated product in hydrochloric acid;

[0029] Further preferably, the soaking conditions are: time 1-12 hours, hydrochloric acid concentration 0.5-6 mol / L.

[0030] Also provided is a hierarchical porous carbon material prepared by any of the above methods.

[0031] A graded porous carbon material is also provided, with a specific surface area of ​​1230-2660 m2 / g, an average pore diameter of 1.4-2.6 nm, and a pore volume of 0.5-1.3 cm 3 / g;

[0032] Furthermore, the size of 0.3-0.7nm accounts for 30%-39%, the size of 0.7-2nm accounts for 25%-59%, the size of 2-50nm accounts for 4%-28%, and the size greater than 50nm accounts for 1%-16%.

[0033] Furthermore, the electrical conductivity is greater than 38 S / cm.

[0034] Beneficial effects of this patent:

[0035] 1. The formation of micro-mesoporous graded carbon provides transport pores that match the deposition pore volume, reduces the pore resistance, and improves the silicon loading efficiency.

[0036] 2. Significantly improve its graphitization degree, thereby increasing the conductivity of pyrolytic carbon.

[0037] Other features and advantages of the present invention will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present invention. The purposes and other advantages of the present invention can be realized and obtained by the structures particularly pointed out in the description, claims, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The accompanying drawings are used to provide a further understanding of the technical solution of the present invention and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solution of the present invention and do not constitute a limitation on the technical solution of the present invention.

[0039] Figure 1This is an electron microscope image of Example 1 of the present invention;

[0040] Figure 2 This is a specific surface area distribution diagram of Example 1 of the present invention;

[0041] Figure 3 is the conductivity of Example 1 of the present invention. DETAILED DESCRIPTION

[0042] To make the purpose, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the appendix of the specific embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] An embodiment of the present invention provides a preparation method for a hierarchical porous carbon material, comprising: preparing a thermoplastic phenolic resin, wherein the thermoplastic phenolic resin is a low molecular weight resol phenolic resin; curing the thermoplastic phenolic resin to obtain a thermosetting phenolic resin; carbonizing the thermosetting phenolic resin to obtain a carbide; and activating the carbide to obtain the hierarchical porous carbon.

[0044] In another embodiment of the present invention, the thermoplastic phenolic resin is a thermoplastic phenolic resin modified with an organic iron source.

[0045] In another embodiment of the present invention, the thermosetting phenolic resin has a spatial network structure.

[0046] In another embodiment of the present invention, the preparation of the thermoplastic phenolic resin includes: mixing a phenolic compound, an aldehyde compound, and an organic iron salt, and reacting the mixture under acidic conditions to generate the thermoplastic phenolic resin.

[0047] This method uses phenolic compounds, aldehyde compounds, and organic iron salts as raw materials. First, a resol-type linear phenolic resin is synthesized under acidic conditions to avoid precipitation of the organic iron salt under alkaline conditions. Then, a thermosetting phenolic resin with a spatial network structure is synthesized in the presence of a curing agent, thereby obtaining an organic iron salt-modified thermosetting phenolic resin. This method utilizes the in-situ anchoring of the organic iron salt by the functional groups of the phenolic resin during the polymerization process, resulting in a uniform distribution within the phenolic resin. This method avoids the problem of poor compatibility between the inorganic catalyst and the resin, which can lead to catalyst aggregation and reduced catalytic performance during the catalytic process.

[0048] In another embodiment of the present invention, the mass ratio of the phenolic compound, the aldehyde compound and the organic iron salt is 1:0.6-0.9:0.01-0.15.

[0049] In another embodiment of the present invention, the reaction conditions are: temperature 50-100° C., time 1-3 h.

[0050] In another embodiment of the present invention, the organic iron salt is at least one of ferric acetate, ferric gluconate, ferrous lactate, or ferrous oxalate. Such iron salts can react with phenols or aldehydes to bind to the phenolic resin.

[0051] In another embodiment of the present invention, the phenolic compound is at least one of phenol, resorcinol, p-aminophenol or phloroglucinol.

[0052] In another embodiment of the present invention, the aldehyde compound is at least one of formaldehyde, furfural, acetaldehyde, malondialdehyde or succinaldehyde.

[0053] In another embodiment of the present invention, the acidic condition is achieved by adding hydrochloric acid, sulfuric acid or oxalic acid.

[0054] In another embodiment of the present invention, the amount of hydrochloric acid, sulfuric acid or oxalic acid added is sufficient to ensure that the pH is less than 7.

[0055] In another embodiment of the present invention, the curing comprises adding a curing agent to the thermoplastic phenolic resin and first curing under an inert atmosphere.

[0056] In another embodiment of the present invention, the curing conditions are: heating rate of 1-5°C / min, heating to 100-200°C, and holding time of 1-3h.

[0057] In another embodiment of the present invention, the curing agent is at least one of hexamethylenetetramine, paraformaldehyde or benzenesulfonic acid.

[0058] In another embodiment of the present invention, the mass of the curing agent is 5%-15% of the mass of the thermoplastic phenolic resin.

[0059] In another embodiment of the present invention, the carbonization conditions are: heating rate of 1-5°C / min, heating to 400-600°C, and holding time of 1-3h.

[0060] The carbonization is also carried out under an inert atmosphere.

[0061] In another embodiment of the present invention, the step of obtaining the hierarchical porous carbon includes: mixing an activator with the carbide, and then activating the mixture under an inert atmosphere.

[0062] In this method, during the pyrolysis process, iron salts are oxidized into iron oxides, which act as catalysts to effectively convert the phenolic resin pyrolytic carbon from an amorphous carbon structure to a graphite structure, significantly improving its graphitization degree and thereby increasing the conductivity of the pyrolytic carbon.

[0063] In this method, the iron oxide generated during the pyrolysis of phenolic resin not only serves as a graphitization catalyst, but also serves as a template in the porous carbon activation process, producing a large number of mesoporous structures in the carbon skeleton, thereby forming micro-mesoporous graded carbon, providing transport pores that match the deposition pore volume, reducing the pore resistance and improving the silicon loading efficiency.

[0064] In another embodiment of the present invention, the activation conditions include: heating to 700-950° C. at a rate of 1-5° C. / min and keeping the temperature for 1-6 hours.

[0065] In another embodiment of the present invention, the activator is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, phosphoric acid, zinc chloride or potassium chloride.

[0066] In another embodiment of the present invention, the mass ratio of the activator to the carbide is 1-5:1.

[0067] In another embodiment of the present invention, the inert atmosphere is at least one of nitrogen and argon.

[0068] In another embodiment of the present invention, the activation further includes hydrochloric acid treatment.

[0069] The hydrochloric acid treatment is used to remove any excess activator and generated salts, and to remove iron oxides to form additional pores.

[0070] Specifically, the hydrochloric acid treatment is to soak the activated product in hydrochloric acid.

[0071] In another embodiment of the present invention, the soaking conditions are: time of 1-12 hours, hydrochloric acid concentration of 0.5-6 mol / L. Under these conditions, excess activator and impurities can be effectively removed, and effective pores can be formed.

[0072] In another embodiment of the present invention, after the hydrochloric acid treatment, the step further includes washing with deionized water until neutral, filtering, and drying to obtain graded porous carbon.

[0073] Another embodiment of the present invention further provides a hierarchical porous carbon material prepared by any of the above methods.

[0074] In another embodiment of the present invention, a hierarchical porous carbon material is provided, which has a specific surface area of ​​1230-2660 m2 / g, an average pore diameter of 1.4-2.6 nm, and a pore volume of 0.5-1.3 cm 3 / g.

[0075] In another embodiment of the present invention, the hierarchical porous carbon material has a rich multi-level pore structure, with pores of 0.3-0.7 nm accounting for 30%-39%, pores of 0.7-2 nm accounting for 25%-59%, pores of 2-50 nm accounting for 4%-28%, and pores larger than 50 nm accounting for 1%-16%.

[0076] In another embodiment of the present invention, the electrical conductivity of the hierarchical porous carbon material is greater than 38 S / cm.

[0077] The present invention will be further described below by way of examples, but is not limited to the following examples.

[0078] Example 1

[0079] (1) 10 g of resorcinol, 0.8 g of ferric acetate, and 0.01 ml of hydrochloric acid were mixed uniformly, and 8 ml of formaldehyde was added to the mixture, stirred, and reacted at 85° C. for 2 h to obtain a thermoplastic phenolic resin;

[0080] (2) Weigh 1 g of hexamethylenetetramine and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, put them into a rotary kiln, heat them to 150° C. at 3° C. / min under an inert gas atmosphere, and keep them at this temperature for 2 h for curing.

[0081] (3) subsequently heating to 600°C at 3°C / min, holding for 2 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0082] (3) Take 6g of potassium hydroxide and 3g of carbide and mix them evenly. Then transfer them to a rotary kiln and activate them for 2h at a temperature of 3℃ / min under nitrogen atmosphere. After cooling to room temperature, soak the material in (3mol / l) hydrochloric acid for 12h to remove excess activator and other impurities. Then, wash with deionized water until neutral, filter and dry to obtain hierarchical porous carbon PC-1. See the electron microscope image for details. Figure 1 , see specific surface area Figure 2 , conductivity see Figure 3 .

[0083] Example 2

[0084] (1) 10 g of resorcinol, 0.5 g of ferric gluconate, and 0.04 ml of sulfuric acid were mixed uniformly, and 9 ml of acetaldehyde was added to the mixture, stirred, and reacted at 75°C for 2 h to obtain a thermoplastic phenolic resin;

[0085] (2) Weigh 1 g of paraformaldehyde and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them to 150° C. at 3° C. / min under an inert gas atmosphere, and keep them at this temperature for 2 h to cure;

[0086] (3) subsequently heating to 600°C at 3°C / min, holding for 2 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0087] (4) 3 g of zinc chloride and 3 g of carbide were uniformly mixed and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 800 °C at 3 °C / min for activation for 3 h. After cooling to room temperature, the material was immersed in (3 mol / l) hydrochloric acid for 6 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-2.

[0088] Example 3

[0089] (1) 12 g of p-aminophenol, 1.2 g of ferrous oxalate, and 0.6 ml of oxalic acid were mixed uniformly, and 10 ml of furfural was added to the mixture, stirred, and reacted at 75°C for 2 h to obtain a thermoplastic phenolic resin;

[0090] (2) Weigh 1 g of paraformaldehyde and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them at 5°C / min to 150°C under an inert gas atmosphere, and keep them at this temperature for 2 h to cure;

[0091] (3) subsequently heating to 600°C at 5°C / min, holding for 2 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0092] (4) 6 g of sodium carbonate and 3 g of carbide were mixed uniformly and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 850 °C at 5 °C / min for activation for 1 h. After cooling to room temperature, the material was immersed in (6 mol / l) hydrochloric acid for 1 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-3.

[0093] Example 4

[0094] (1) 10 g of resorcinol, 0.05 g of ferric acetate, and 0.01 ml of hydrochloric acid were mixed uniformly, and 6 ml of formaldehyde was added to the mixture, stirred, and reacted at 50° C. for 1 h to obtain a thermoplastic phenolic resin;

[0095] (2) Weigh 1 g of hexamethylenetetramine and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them to 100° C. at 5° C. / min under an inert gas atmosphere, and keep them at this temperature for 2 h to cure;

[0096] (3) subsequently heating to 500°C at 5°C / min, maintaining the temperature for 2 h for carbonization, cooling to room temperature, and then pulverizing to obtain carbide;

[0097] (4) 6 g of sodium hydroxide and 3 g of carbide were mixed uniformly and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 950°C at 1°C / min for activation for 6 h. After cooling to room temperature, the material was immersed in (3 mol / l) hydrochloric acid for 12 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-4.

[0098] Example 5

[0099] (1) Take 10g of resorcinol, 0.8g of ferric acetate, and 0.01ml of hydrochloric acid, mix them evenly, then take 8ml of malondialdehyde and add it to the mixture, stir, and react at 100°C for 3h to prepare thermoplastic phenolic resin;

[0100] (2) Weigh 1 g of hexamethylenetetramine and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them to 200° C. at 5° C. / min under an inert gas atmosphere, and keep them at this temperature for 3 h for curing;

[0101] (3) subsequently heating to 400°C at 5°C / min, maintaining the temperature for 3 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0102] (4) 15 g of potassium hydroxide and 3 g of carbide were mixed uniformly and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 900 °C at 5 °C / min for 4 h for activation. After cooling to room temperature, the material was immersed in (1 mol / l) hydrochloric acid for 12 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-5.

[0103] Example 6

[0104] (1) 10 g of phloroglucinol, 0.8 g of ferrous lactate, and 0.01 ml of hydrochloric acid were mixed uniformly, and 9 ml of succinaldehyde was added to the mixture, stirred, and reacted at 75°C for 3 h to obtain a thermoplastic phenolic resin;

[0105] (2) Weigh 1 g of benzenesulfonic acid and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them to 180° C. at 1° C. / min under an inert gas atmosphere, and keep them at this temperature for 1 h to cure;

[0106] (3) subsequently heating to 600°C at 1°C / min, holding for 1 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0107] (4) 15 g of potassium carbonate and 3 g of carbide were mixed uniformly and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 800 °C at 5 °C / min for 4 h for activation. After cooling to room temperature, the material was immersed in (0.5 mol / l) hydrochloric acid for 12 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-6.

[0108] Comparative Example 1

[0109] (1) 10 g of resorcinol, 0.01 g of ferric gluconate, and 0.01 ml of hydrochloric acid were mixed uniformly, and 8 ml of formaldehyde was added to the mixture, stirred, and reacted at 85° C. for 2 h to obtain a thermoplastic phenolic resin;

[0110] (2) Weigh 1 g of hexamethylenetetramine and 15 g of the above-mentioned thermoplastic phenolic resin, dissolve them in 20 ml of anhydrous ethanol, mix them evenly, place them in a rotary kiln, heat them to 150° C. at 3° C. / min under an inert gas atmosphere, and keep them at this temperature for 2 h to cure;

[0111] (3) subsequently heating to 600°C at 3°C / min, holding for 2 h for carbonization, cooling to room temperature, and pulverizing to obtain carbide;

[0112] (4) 6 g of potassium hydroxide and 3 g of carbide were mixed uniformly and then transferred to a rotary kiln. Under a nitrogen atmosphere, the temperature was raised to 800 °C at 3 °C / min for activation. After cooling to room temperature, the material was immersed in (3 mol / l) hydrochloric acid for 12 h to remove excess activator and other impurities. Subsequently, the mixture was washed with deionized water until neutral, filtered, and dried to obtain hierarchical porous carbon PC-7.

[0113] Table 1 is the test results of the embodiments and comparative examples

[0114]

[0115] Although the embodiments disclosed herein are as described above, the contents described herein are merely embodiments for facilitating understanding of the present invention and are not intended to limit the present invention. Any person skilled in the art may make any modifications and variations in the form and details of the embodiments without departing from the spirit and scope of the present invention. However, the scope of patent protection of the present invention shall remain subject to the scope defined by the appended claims.

Claims

1. A preparation method of a hierarchical porous carbon material, characterized in that: include: Preparation of thermoplastic phenolic resin, wherein the thermoplastic phenolic resin is a low molecular weight resol phenolic resin; curing the thermoplastic phenolic resin to obtain a thermosetting phenolic resin; carbonizing the thermosetting phenolic resin to obtain a carbide; The carbide is activated to obtain the hierarchical porous carbon.

2. The preparation method according to claim 1, characterized in that The thermoplastic phenolic resin is a thermoplastic phenolic resin modified by an organic iron source; Preferably, the preparation of the thermoplastic phenolic resin comprises: reacting a phenolic compound, an aldehyde compound, and an organic iron salt under acidic conditions to obtain the thermoplastic phenolic resin; Further preferably, the mass ratio of the phenolic compound, the aldehyde compound and the organic iron salt is 1:0.6-0.9:0.01-0.15; More preferably, the reaction conditions are: temperature 50-100° C., time 1-3 h.

3. The preparation method according to claim 2, characterized in that The organic iron salt is at least one of ferrous acetate, ferrous gluconate, ferrous lactate or ferrous oxalate; and / or the phenolic compound is at least one of phenol, resorcinol, p-aminophenol or phloroglucinol; And / or the aldehyde compound is at least one of formaldehyde, furfural, acetaldehyde, malondialdehyde or succinaldehyde.

4. The preparation method according to claim 1, characterized in that The curing comprises: adding a curing agent to the thermoplastic phenolic resin and curing it under an inert atmosphere; Preferably, the curing conditions are: heating rate 1-5°C / min, heating to 100-200°C, holding time 1-3h; Further preferably, the curing agent is at least one of hexamethylenetetramine, paraformaldehyde or benzenesulfonic acid; Further preferably, the mass of the curing agent is 5%-15% of the mass of the thermoplastic phenolic resin.

5. The preparation method according to claim 1, characterized in that The carbonization conditions are: heating rate 1-5°C / min, heating to 400-600°C, and holding time 1-3h.

6. The preparation method according to claim 1, characterized in that The step of obtaining the hierarchical porous carbon comprises: mixing an activator with the carbide, and then activating the carbide under an inert atmosphere; Preferably, the activation conditions include: heating to 700-1200°C at 1-5°C / min and keeping warm for 1-6h; Further preferably, the activator is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium carbonate, phosphoric acid, zinc chloride or potassium chloride; Further preferably, the mass ratio of the activator to the carbide is 1-5:

1.

7. The preparation method according to claim 1, characterized in that Activation also includes hydrochloric acid treatment; Preferably, the hydrochloric acid treatment is to soak the activated product in hydrochloric acid; Further preferably, the soaking conditions are: time 1-12 hours, hydrochloric acid concentration 0.5-6 mol / L.

8. A hierarchical porous carbon material, characterized in that: Prepared by the method according to any one of claims 1 to 6.

9. A hierarchical porous carbon material, characterized in that: The specific surface area is 1230-2660㎡ / g, the average pore diameter is 1.4-2.6nm, and the pore volume is 0.5-1.3cm 3 / g; And / or the size of 0.3-0.7nm accounts for 30%-39%, the size of 0.7-2nm accounts for 25%-59%, the size of 2-50nm accounts for 4%-28%, and the size greater than 50nm accounts for 1%-16%.

10. The hierarchical porous carbon material according to claim 9, characterized in that The conductivity is greater than 38S / cm.

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