A method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon

Abstract

This invention provides a method for preparing a three-dimensional textured macroporous carbon composite with adjustable carbon shell morphology, comprising the following steps: S1, dispersing a phenolic prepolymer in a solvent to prepare a phenolic prepolymer slurry; S2, adding graphene oxide to the prepared phenolic prepolymer slurry, mixing well, and preparing a carbon precursor spraying liquid; S3, spraying the prepared carbon precursor spraying liquid onto a planar fiber carrier to obtain a carbon precursor carrier composite; S4, heat-treating the carbon precursor carrier composite to obtain three-dimensional hollow porous carbon. This invention uses planar fiber materials as the reaction site, eliminating the need for other templates, and uses graphene oxide as the key component of the carbon precursor. Combining the advantages of continuous operation technology such as ultrasonic dispersion and atomized spraying, the carbon precursor is composited on the surface and interior of the carrier. After heat treatment, three-dimensional hollow porous carbon is prepared. The morphology of the carbon shell composited on the three-dimensional textured macroporous carbon framework can be controlled simply by adjusting the content of the key components in the carbon precursor.

Description

Technical Field

[0001] This invention relates to the field of three-dimensional hollow porous carbon technology, and more particularly to a method for preparing a composite three-dimensional textured macroporous carbon with adjustable carbon shell morphology. Background Technology

[0002] The development of carbon nanomaterials, from zero-dimensional fullerenes and one-dimensional carbon nanotubes to two-dimensional graphene, demonstrates the expansion and deepening of carbon materials in terms of dimensions. Rapid technological iteration demands efficient, stable, and functionally diverse materials to support fields such as energy, catalysis, and biomedicine. Three-dimensional porous carbon, which combines the stability of zero-dimensional carbon, the electrical and thermal conductivity of one-dimensional carbon, and the high specific surface area of ​​two-dimensional carbon, exhibits diverse structures, strong controllability, and good stability. It can provide high energy density, high catalytic efficiency, and biocompatibility, making it of greater research significance and application prospects. The construction of three-dimensional hollow porous carbon, with its internal cavities supporting diverse application needs, and the coexistence of various pore levels resulting in abundant active sites and easy doping modification, significantly enhances the rate of mass exchange and transport, effectively mitigating strain relaxation during energy storage, thus becoming an ideal platform for advanced energy conversion and storage.

[0003] The most common synthetic routes for preparing three-dimensional hollow porous carbon are template-based hard template, soft template, and self-templating routes. Commonly used templates include spherical particle templates such as SiO2, PS, and PMMA; cubic crystal templates such as KCl, MnO, and MgO; metal particle templates such as Ni and Co; and MOF polyhedral templates. Different types of carbon precursors are used to grow and pyrolyze carbon on the template surface in situ, and after removing the template, three-dimensional hollow porous carbon is formed. Patent CN111793208B coats graphene oxide onto the surface of spherical SiO2 particles, reduces them at temperatures above 1000℃, and then etches the template with a hot strong alkaline solution to prepare three-dimensional hollow graphene spheres. Patent CN111533112B coats a template containing Fe, Co, or Ni metal salts with a carbon precursor, catalytically grows graphene in situ at 600~1200℃, and then etches the template with a strong acid solution to prepare graphene nanospheres. The above methods involve complex synthesis processes, low yields due to intermittent operation, and the need for strong acid and alkali solvents to etch the nano-carbon materials or carbon precursors onto the template surface after growth, which causes environmental pollution and severely limits the industrial application of such methods. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a composite three-dimensional textured macroporous carbon with adjustable carbon shell morphology, so as to achieve a simple, rapid and efficient synthesis of three-dimensional hollow porous carbon.

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

[0006] A method for preparing a composite three-dimensional textured macroporous carbon with adjustable carbon shell morphology includes the following steps:

[0007] S1. Prepare a phenolic prepolymer slurry by dispersing the phenolic prepolymer in a solvent;

[0008] S2. Add graphene oxide to the prepared phenolic prepolymer slurry, mix well, and prepare carbon precursor spraying liquid.

[0009] S3. Spray the prepared carbon precursor coating liquid onto the planar fiber carrier to obtain the carbon precursor carrier composite.

[0010] S4. Heat-treat the carbon precursor support composite to obtain three-dimensional hollow porous carbon.

[0011] Preferably, the phenolic prepolymer is a thermosetting phenolic resin precursor with a molecular weight of 400-600, the solvent is one or a mixture of two of ethanol and water, and the mass concentration of the phenolic prepolymer slurry is 5-30 wt%.

[0012] Preferably, the graphene oxide sheets used have a sheet diameter of 10~50μm, and the solid content of the graphene oxide in the phenolic prepolymer slurry is 0.1~10.0mg / mL.

[0013] Preferably, in step S2, after adding graphene oxide to the phenolic prepolymer slurry, an ultrasonic treatment step is further included, wherein the ultrasonic treatment parameters are an ultrasonic emission frequency of 20~25kHz, an ultrasonic power of 300~500W, and an ultrasonic time of 5~15min.

[0014] Preferably, the planar fiber carrier is a nonwoven dry cloth with a microscopic three-dimensional morphology and an adsorption capacity of 3 to 9 times its own weight.

[0015] Furthermore, the nonwoven dry fabric is made of one or more of polypropylene, polyester fiber, and wood pulp.

[0016] Preferably, the spraying is atomized spraying.

[0017] Furthermore, the atomization spraying adopts a pneumatic spray gun, wherein the spraying flow rate of the carbon precursor spraying liquid is 10~30mL / min, the spraying distance is 10~20cm, the air pressure is 0.15~0.3MPa, and the spraying time is 1~3min.

[0018] Preferably, the heat treatment includes: placing the carbon precursor carrier composite in a heating device and heating it in two stages; the first stage heating temperature is 120~140℃ for 12h, the atmosphere is air, and the heating rate is 5~20℃ / min; the second stage heating temperature is 600~900℃ for 2±0.5h, the atmosphere is inert gas, and the heating rate is 1~10℃ / min.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] This invention uses readily available planar fiber materials, such as commercially available dry wipes, as the base framework for constructing a three-dimensional hollow porous structure, and selects industrial-grade graphene oxide as the key component of the carbon precursor. The raw materials used in the preparation method are all commercially available industrial products, which are inexpensive and conducive to large-scale production.

[0021] This invention utilizes an ultrasonic disruptor to prepare a low-concentration dispersed graphene oxide phenolic prepolymer as a carbon precursor in 5-15 minutes; it employs a pneumatic spray gun to rapidly atomize the carbon precursor and spray it, and utilizes the strong adsorption capacity of a wiping cloth to efficiently obtain the composite material in just 1-3 minutes. The process is fast and simple; the heat treatment temperature is below 1000℃ to prepare three-dimensional hollow porous carbon, resulting in low energy consumption; the synthesis process does not require the addition of other template supports, eliminating the step of solvent etching of the template, simplifying the synthesis path and being environmentally friendly.

[0022] This invention efficiently controls the transformation of the microstructure of the product by adjusting the solid content of key components in the carbon precursor, and is easy to operate. The three-dimensional hollow porous carbon prepared by the preparation method described in this invention, after SEM characterization, has the structural feature of a hollow carbon shell composite on the surface of a three-dimensional textured macroporous carbon skeleton. The morphology of these carbon shells is controllable and can achieve a structural transformation from spherical to cypress fruit shape. Attached Figure Description

[0023] Figure 1 The microstructure of the spherical carbon shell composite three-dimensional textured macroporous carbon synthesized in Example 1 is shown in the SEM images from top to bottom at magnifications of 200', 5000', and 80000'.

[0024] Figure 2 The microstructure of the cypress fruit-shaped carbon shell composite three-dimensional textured macroporous carbon synthesized in Example 3 is shown in the SEM images from top to bottom at magnifications of 200', 20000', and 80000'. The small image in the upper right corner of the 80000' SEM image is a comparison image of the cypress fruit.

[0025] Figure 3The microstructure of the spherical carbon shell composite three-dimensional textured macroporous carbon synthesized in Comparative Example 1 is shown in the SEM images from top to bottom at magnifications of 100', 200', and 10000'.

[0026] Figure 4 The images show the microstructure of the irregularly shaped carbon shell composite three-dimensional textured macroporous carbon synthesized in Comparative Example 2. From top to bottom, they are SEM images magnified at 200', 20000', and 80000' respectively. Detailed Implementation

[0027] The purpose of this invention is to provide a simple, rapid, and efficient method for synthesizing three-dimensional hollow porous carbon, particularly a method for preparing three-dimensional textured macroporous carbon with adjustable carbon shell morphology. This invention cleverly selects readily available planar fiber materials, such as commercially available dry wipes, as the reaction site, eliminating the need for other templates. Using graphene oxide as the key component of the carbon precursor, and combining the advantages of continuous operation techniques such as ultrasonic dispersion and atomized spraying, the carbon precursor is composited on the surface and interior of the wipe. After heat treatment, three-dimensional hollow porous carbon is prepared. The morphology of the carbon shell composited on the three-dimensional textured macroporous carbon framework can be controlled simply by adjusting the content of the key components in the carbon precursor.

[0028] In an exemplary embodiment, the method for preparing the tunable carbon shell morphology composite three-dimensional textured macroporous carbon of the present invention includes the following steps:

[0029] A phenolic prepolymer slurry containing graphene oxide as a key component was prepared by using ultrasonic technology as a carbon precursor. The carbon precursor was rapidly compounded with a wiping cloth using atomization technology. After heat treatment, a three-dimensional hollow porous carbon was prepared. By adjusting the content of key components in the carbon precursor, a three-dimensional textured macroporous carbon with adjustable carbon shell morphology was efficiently obtained.

[0030] The solid content of graphene oxide in the phenolic prepolymer slurry is 0.1~10.0 mg / mL. As the content of key components in the carbon precursor increases, the microstructure of the prepared three-dimensional hollow porous carbon shows that the carbon shell composited on the three-dimensional textured macroporous carbon skeleton changes from a spherical shape to a cypress fruit shape.

[0031] In the method of the present invention, the wiping cloth is preferably a commercially available nonwoven dry cloth with a three-dimensional morphology, more preferably a three-dimensional network morphology with alternating protrusions, and has a strong adsorption capacity of 3 to 9 times its own weight. The material is one or a mixture of two or more of polypropylene, polyester fiber, and wood pulp, more preferably a mixture of polypropylene and wood pulp.

[0032] In another preferred embodiment, the phenolic prepolymer is a thermosetting phenolic resin precursor with a molecular weight of 400-600, exhibiting a yellow-orange viscous state; the phenolic prepolymer is mixed uniformly with a solvent at a temperature of 10-40°C to form a phenolic prepolymer slurry with a mass concentration of 5-30 wt%, and the solvent is one or a mixture of two or more of ethanol and water.

[0033] In a preferred embodiment, the graphene oxide is industrial-grade graphene oxide with a sheet diameter of 10~50μm and exhibits a dark brown powder morphology.

[0034] In a preferred embodiment, the ultrasonic technology uses an ultrasonic disruptor with an ultrasonic emission frequency of 20-25 kHz, an ultrasonic power of 300-500 W, and an ultrasonic duration of 5-15 min.

[0035] In another preferred embodiment, the atomization technology uses a pneumatic spray gun, with a carbon precursor spraying flow rate of 10~30mL / min, a spraying distance of 10~20cm, an air pressure of 0.15~0.3MPa, and a spraying time of 1~3min.

[0036] In another preferred embodiment, the heat treatment operation is carried out in two stages. The composite material constructed from the carbon precursor and the wiping cloth is placed in a heating device. The temperature of the first heating stage is 120~140℃, the time is 12h, the atmosphere is air, and the heating rate is 5~20℃ / min, more preferably 10℃ / min. The temperature of the second heating stage is 600~900℃, more preferably 800℃, the time is 2±0.5h, the atmosphere is inert gas, and the heating rate is 1~10℃ / min, more preferably 5℃ / min.

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] In the description of this invention, it should be noted that the terms "upper," "lower," "inner," "outer," "front end," "rear end," "both ends," "one end," and "the other end," etc., indicating orientation or positional relationships, are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0039] In the following examples, the phenolic prepolymer used is obtained by polymerizing phenol and formaldehyde in an alkaline environment and removing moisture at a temperature below 40°C to obtain a yellow-orange viscous state. Alternatively, commercially available low molecular weight phenolic resin can be used. The wiping wipes used are Kimberly-Clark's general-purpose wiping paper series (L series, X series, Jinte series). The graphene oxide used is industrial-grade graphene oxide (item number SE2430, sold by Changzhou Sixth Element Co., Ltd.). Example 1

[0040] (1) 5g of phenolic prepolymer (molecular weight about 500) and 50g of ethanol were mixed evenly in an environment of 25°C to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 10wt%).

[0041] (2) Graphene oxide powder with a sheet diameter of about 10 μm was added to the phenolic prepolymer slurry and ultrasonicated in an ultrasonic crusher for 10 min (frequency 20 kHz, power 400 W) to obtain a carbon precursor of black brown uniformly dispersed graphene oxide (solid content of 0.1 mg / mL).

[0042] (3) 30 mL of carbon precursor was placed in a pneumatic spray gun and sprayed onto the wiping cloth for 3 min (spraying flow rate 10 mL / min, spraying distance 15 cm, air pressure 0.2 MPa) to quickly obtain a composite material with uniform adsorption of carbon precursor. The size of the selected wiping cloth was 10 cm × 10 cm. The material of the selected wiping cloth was a mixture of polypropylene and wood pulp.

[0043] (4) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 120°C for 12 hours in flowing air (heating rate 10°C / min). Then it undergoes thermal decomposition treatment at 800°C for 2 hours in flowing nitrogen (heating rate 5°C / min). Natural cooling is then used to obtain black three-dimensional hollow porous carbon.

[0044] In this embodiment, a three-dimensional hollow porous carbon microstructure was prepared as follows: Figure 1As shown, the SEM images, from top to bottom, are magnified at 200x, 5000x, and 80000x. At 200x low magnification, it can be seen that the original three-dimensional network structure of the wiping cloth has been completely transformed into a three-dimensional textured macroporous structure of carbon material. The narrower-spacing fiber network is completely filled by carbon components, while the wider-spacing fiber network forms macroporous channels. The textured structure is formed after the original fiber network is removed by pyrolysis. At 5000x magnification, it can be seen that the carbon skeleton surface is covered with a spherical carbon shell, which is formed by the alternating protrusions inside the original wiping cloth serving as a support, completely replicated by the carbon precursor and removed by pyrolysis. At 80000x high magnification, the structural features of the spherical hollow carbon shell are more clearly visible. In this embodiment, the graphene content in the carbon precursor is low, and the carbon shell component is mainly formed by the replication of the original wiping cloth structure by the phenolic prepolymer in the carbon precursor. Example 2

[0045] (1) 15g of phenolic prepolymer (molecular weight about 600) and 50g of water were mixed evenly in an environment of 40℃ to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 30wt%).

[0046] (2) Graphene oxide powder with a sheet diameter of about 50 μm was added to the phenolic prepolymer slurry and ultrasonicated in an ultrasonic crusher for 15 min (frequency 20 kHz, power 300 W) to obtain a carbon precursor of black brown uniformly dispersed graphene oxide (solid content of 0.3 mg / mL).

[0047] (3) 30 mL of carbon precursor was placed in a pneumatic spray gun and sprayed onto the wiping cloth for 2 min (spraying flow rate 15 mL / min, spraying distance 20 cm, air pressure 0.3 MPa) to quickly obtain a composite material with uniform adsorption of carbon precursor. The size of the selected wiping cloth was 10 cm × 10 cm. The material of the selected wiping cloth was a mixture of polyester fiber and wood pulp.

[0048] (4) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 140°C for 12 hours in flowing air (heating rate 10°C / min). Then it undergoes thermal decomposition treatment at 700°C for 2.5 hours in flowing nitrogen (heating rate 5°C / min). Natural cooling is then used to obtain black three-dimensional hollow porous carbon. Example 3

[0049] (1) 5g of phenolic prepolymer (molecular weight about 500) and 50g of ethanol were mixed evenly in an environment of 25°C to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 10wt%).

[0050] (2) Graphene oxide powder with a sheet diameter of about 10 μm was added to the phenolic prepolymer slurry and ultrasonicated in an ultrasonic crusher for 10 min (frequency 20 kHz, power 400 W) to obtain a carbon precursor of black brown uniformly dispersed graphene oxide (solid content of 0.5 mg / mL).

[0051] (3) 30 mL of carbon precursor was placed in a pneumatic spray gun and sprayed onto the wiping cloth for 3 min (spraying flow rate 10 mL / min, spraying distance 15 cm, air pressure 0.2 MPa) to quickly obtain a composite material with uniform adsorption of carbon precursor. The size of the selected wiping cloth was 10 cm × 10 cm. The material of the selected wiping cloth was a mixture of polypropylene and wood pulp.

[0052] (4) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 120°C for 12 hours in flowing air (heating rate 10°C / min). Then it undergoes thermal decomposition treatment at 800°C for 2 hours in flowing nitrogen (heating rate 5°C / min). Natural cooling is then used to obtain black three-dimensional hollow porous carbon.

[0053] In this embodiment, a three-dimensional hollow porous carbon microstructure was prepared as follows: Figure 2 As shown, the SEM images, from top to bottom, are magnified at 200x, 20000x, and 80000x. At the low magnification of 200x, the same three-dimensional textured macroporous carbon structure as in Example 2 can be observed; at the high magnifications of 20000x and 80000x, the carbon skeleton surface is covered with a cypress-fruit-shaped carbon shell. Compared to Example 1, the main reason for the change in carbon shell morphology is the increased graphene oxide content in the carbon precursor, which allows it to participate more in replicating the internal structure of the original wiping cloth. Example 4

[0054] (1) 2.5g of phenolic prepolymer (molecular weight about 400), 5g of water and 45g of ethanol were mixed evenly at 10°C to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 5wt%).

[0055] (2) Graphene oxide powder with a sheet diameter of about 30 μm was added to the phenolic prepolymer slurry and ultrasonicated in an ultrasonic crusher for 15 min (frequency 25 kHz, power 500 W) to obtain a carbon precursor of black brown uniformly dispersed graphene oxide (solid content of 5 mg / mL).

[0056] (3) 30 mL of carbon precursor was placed in a pneumatic spray gun and sprayed onto the wiping cloth for 1 min (spraying flow rate 30 mL / min, spraying distance 10 cm, air pressure 0.15 MPa) to quickly obtain a composite material with uniform adsorption of carbon precursor. The size of the selected wiping cloth was 10 cm × 10 cm, and the material of the selected wiping cloth was polypropylene.

[0057] (4) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 140°C for 12 hours in flowing air (heating rate 10°C / min). Then it undergoes thermal decomposition treatment at 900°C for 1.5 hours in flowing nitrogen (heating rate 5°C / min). Natural cooling is then used to obtain black three-dimensional hollow porous carbon.

[0058] Comparative Example 1

[0059] (1) 5g of phenolic prepolymer (molecular weight about 500) and 50g of ethanol were mixed evenly in an environment of 25°C to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 10wt%).

[0060] (2) 30 mL of phenolic prepolymer slurry was placed in a pneumatic spray gun and sprayed onto the wiping cloth for 3 min (spraying flow rate 10 mL / min, spraying distance 15 cm, air pressure 0.2 MPa) to quickly obtain a composite material that uniformly adsorbs the phenolic prepolymer slurry. The size of the selected wiping cloth was 10 cm × 10 cm, and the material of the selected wiping cloth was a mixture of polypropylene and wood pulp.

[0061] (3) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 120°C for 12 hours in flowing air (heating rate 10°C / min). The surface of the composite material changes from light yellow phenolic prepolymer to reddish-brown phenolic resin. Then, it undergoes thermal decomposition treatment at 800°C for 2 hours in flowing nitrogen (heating rate 5°C / min). After natural cooling, black three-dimensional hollow porous carbon is obtained.

[0062] In this comparative example, a three-dimensional hollow porous carbon microstructure was prepared as follows: Figure 3 As shown, from top to bottom, the SEM images are magnified at 100x, 200x, and 10000x. Unlike the carbon precursors used in Examples 1-4, the carbon precursor in Comparative Example 1 is a phenolic prepolymer slurry without graphene oxide components. At low magnifications of 100x and 200x, the three-dimensional textured macroporous carbon structure of the carbon material is clearly visible; at high magnification of 10000x, the morphology of the spherical carbon shell, similar to that of Example 1, is visible. However, due to the absence of graphene oxide components in the carbon precursor, compared to Examples 1-4, the prepared carbon skeleton exhibits a more compact state; that is, the spherical carbon shells penetrate into the carbon skeleton and are layered and covered by the carbon skeleton formed by multiple spraying operations.

[0063] Comparative Example 2

[0064] (1) 5g of phenolic prepolymer (molecular weight about 500) and 50g of ethanol were mixed evenly in an environment of 25°C to obtain a light yellow, clear and transparent phenolic prepolymer slurry (mass concentration of 10wt%).

[0065] (2) Graphene oxide powder with a sheet diameter of about 10 μm was added to the phenolic prepolymer slurry and ultrasonicated in an ultrasonic crusher for 10 min (frequency 20 kHz, power 400 W) to obtain a carbon precursor of black brown uniformly dispersed graphene oxide (solid content of 0.5 mg / mL).

[0066] (3) The wiping cloth is completely immersed in 30mL of carbon precursor for 3min to obtain a composite material saturated with carbon precursor. The size of the selected wiping cloth is 10cm × 10cm. The material of the selected wiping cloth is a mixture of polypropylene and wood pulp.

[0067] (4) The composite material is placed in a heating device and first undergoes thermal polymerization treatment at 120°C for 12 hours in flowing air (heating rate 10°C / min). Then it undergoes thermal decomposition treatment at 800°C for 2 hours in flowing nitrogen (heating rate 5°C / min). Natural cooling is then used to obtain black three-dimensional hollow porous carbon.

[0068] In this comparative example, a three-dimensional hollow porous carbon microstructure was prepared as follows: Figure 4 As shown, from top to bottom, the SEM images are magnified at 200x, 20000x, and 80000x, respectively. Unlike the spraying technique used in Examples 1-4, Comparative Example 2 uses an impregnation technique to composite the carbon precursor onto a wiping cloth. At a low magnification of 200x, the same three-dimensional textured macroporous carbon structure as in Examples 1-4 can be seen; at high magnifications of 20000x and 80000x, an irregularly shaped carbon shell can be seen covering the surface of the carbon skeleton. Compared to Example 3, although the solid content of graphene oxide in the carbon precursor is 0.5 mg / mL, the impregnation operation causes the wiping cloth to become supersaturated with adsorption, resulting in excessive coating of the original wiping cloth's internal structure and the construction of an irregular carbon shell morphology.

[0069] Any aspects of this invention not described in detail are well-known to those skilled in the art.

[0070] Finally, it should be noted that the above specific embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications and substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing a composite three-dimensional textured macroporous carbon with adjustable carbon shell morphology, characterized in that, The method includes the following steps: S1. Prepare a phenolic prepolymer slurry by dispersing the phenolic prepolymer in a solvent; S2. Add graphene oxide to the prepared phenolic prepolymer slurry, mix well, and prepare a carbon precursor spraying liquid. The solid content of graphene oxide in the phenolic prepolymer slurry is 0.1~10.0 mg / mL. S3. Spray the prepared carbon precursor spraying liquid onto a planar fiber carrier to obtain a carbon precursor carrier composite. The planar fiber carrier is a nonwoven dry cloth with a microscopic three-dimensional morphology and an adsorption capacity of 3 to 9 times its own weight. S4. Heat-treat the carbon precursor support composite to obtain three-dimensional hollow porous carbon.

2. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, The phenolic prepolymer is a thermosetting phenolic resin precursor with a molecular weight of 400-600, and the solvent is one or a mixture of two of ethanol and water. The mass concentration of the phenolic prepolymer slurry is 5-30 wt%.

3. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, The diameter of the graphene oxide sheets used is 10~50μm.

4. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, In step S2, after adding graphene oxide to the phenolic prepolymer slurry, an ultrasonic treatment step is also included, wherein the ultrasonic treatment parameters are an ultrasonic emission frequency of 20~25kHz, an ultrasonic power of 300~500W, and an ultrasonic time of 5~15min.

5. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, The nonwoven dry fabric is made of one or more of polypropylene, polyester fiber, and wood pulp.

6. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, The spraying is atomized spraying.

7. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 6, characterized in that, The atomized spraying uses a pneumatic spray gun, wherein the spraying flow rate of the carbon precursor spraying liquid is 10~30mL / min, the spraying distance is 10~20cm, the air pressure is 0.15~0.3MPa, and the spraying time is 1~3min.

8. The method for preparing tunable carbon shell morphology composite three-dimensional textured macroporous carbon as described in claim 1, characterized in that, The heat treatment includes: placing the carbon precursor carrier composite in a heating device and heating it in two stages. The heating temperature of the first stage is 120~140℃, the time is 12h, the atmosphere is air, and the heating rate is 5~20℃ / min. The heating temperature of the second stage is 600~900℃, the time is 2±0.5h, the atmosphere is inert gas, and the heating rate is 1~10℃ / min.

Images