High-performance graphite-based carbon composite material and preparation method thereof

Abstract

The invention discloses a high-performance graphite-based carbon composite material and a preparation method thereof, and relates to the technical field of carbon composite materials. Graphite, N, N-hexamethylene diacetamide and 3-hydroxyacetanilide are used as raw materials, a composite porous carbon material is formed through a high-temperature carbonization activation method, and the heat conduction performance and the electric conduction performance of the composite material are improved; then a three-dimensional ZIF-8 structure is formed after multiple times of alternate adsorption and solution and freeze drying, the specific surface area of the material is remarkably increased, the material is matched with a porous carbon material to form a multi-stage secondary pore structure, a large number of charge adsorption sites are provided, resistance between material interaction interfaces is reduced, and the conductivity of the composite material is improved; then a compact graphite-like carbon coating is formed on the surface of the composite porous carbon material through unbalanced magnetron sputtering, so that corrosive gas, liquid and the like are prevented from being in direct contact with the porous carbon material, the porous carbon material is effectively prevented from being eroded by the external environment, and the service life of the composite material is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of carbon composite materials, in particular to a high-performance graphite-based carbon composite material and a preparation method thereof. Background Art

[0002] As modern science and technology develop rapidly, various industries have increasingly stringent requirements on material performance. High-performance graphite-based carbon composite materials have broad application prospects in aerospace, electronics and other fields due to their low density and high specific strength. However, in reality, their thermal conductivity is not satisfactory. Ideally, composite materials should conduct heat quickly to ensure stable operation of the equipment, but in reality, factors such as internal microstructural defects, impurities, and interface thermal resistance make it inefficient in thermal conductivity and unable to meet the equipment's efficient heat dissipation needs, causing the equipment to easily have performance problems due to overheating.

[0003] At the same time, in scenarios with high conductivity requirements such as battery electrodes and power transmission, its resistance is large and its conductivity is poor. This causes excessive heat to be generated during current transmission, which not only reduces energy efficiency but also may cause safety risks. When in a complex operating environment, such as high temperature, high humidity, or chemical corrosion, and when subjected to mechanical stress, the material structure and performance will gradually deteriorate. For example, in the aerospace field, the performance of related components of aircraft has obviously deteriorated under long-term complex working conditions, affecting the safe and reliable operation of the aircraft. Summary of the invention

[0004] The purpose of the present invention is to provide a high-performance graphite-based carbon composite material and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: a high-performance graphite-based carbon composite material, wherein the high-performance graphite-based carbon composite material is prepared from graphite, N,N-hexamethylenebisacetamide, and 3-hydroxyacetanilide as raw materials, which are carbonized and activated at high temperature, and then adsorbed with zinc nitrate and imidazole solution for multiple times, and then freeze-dried, and then subjected to unbalanced magnetron sputtering to form a graphite-like carbon coating.

[0006] Furthermore, a method for preparing a high-performance graphite-based carbon composite material comprises the following preparation steps: (1) 14-22 parts of graphite, 5-7 parts of N,N-hexamethylenebisacetamide, and 6-10 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 18-36 hours, 32 parts of potassium hydroxide aqueous solution were added, mixed uniformly, and then placed in a calcining furnace for calcination for 2-3 hours. After naturally cooling to room temperature, 40 parts of dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 10-20 hours to obtain a composite porous carbon material; (2) soaking the composite porous carbon material in a zinc nitrate-methanol solution for 8 to 12 hours, taking it out and soaking it in methylimidazole-methanol for 8 to 12 hours, repeating 3 times, washing it with methanol 3 times, and drying it in a freeze dryer for 24 hours to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material is placed in a magnetic boat in a vacuum chamber, a graphite target is installed, a magnet is placed outside the vacuum chamber, the vacuum is evacuated to a degree of 0.1-0.5 Pa, and the deposition is performed for 3-5 hours to obtain a high-performance graphite-based carbon composite material.

[0007] Furthermore, the concentration of the potassium hydroxide aqueous solution in step (1) is 10 wt %.

[0008] Furthermore, the temperature of the calcining furnace in step (1) is 700-900°C.

[0009] Furthermore, the concentration of the dilute hydrochloric acid solution in step (1) is 1 mol / L.

[0010] Furthermore, the concentration of the zinc nitrate-methanol solution in step (2) is 15 mg / mL.

[0011] Furthermore, the concentration of N-methylimidazole-methanol in step (2) is 30 mg / mL.

[0012] Furthermore, the freeze dryer temperature in step (2) is -48°C.

[0013] Furthermore, in step (3), adjacent magnetic poles of the magnets are opposite.

[0014] Furthermore, the deposition parameters in step (3) are argon gas flow rate 15 sccm, substrate bias voltage -85 V, deposition pressure 3×10 -5 Pa, sputtering current 0.2~0.4A.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The present invention uses graphite, N,N-hexamethylenebisacetamide and 3-hydroxyacetanilide as raw materials, and forms a composite porous carbon material through a high-temperature carbonization activation method. The composite porous carbon material has a large specific surface area, so that heat can be quickly diffused in the material, thereby improving the thermal conductivity of the composite material, and introducing abundant active sites, providing more reaction sites for redox reactions, which is beneficial to the transfer and storage of electrons, thereby improving the electrical conductivity of the composite material; then, after multiple alternating adsorption solutions and freeze-drying, a three-dimensional ZIF-8 structure is formed, which significantly increases the specific surface area of ​​the material, cooperates with the porous carbon material to form a multi-level secondary pore structure, provides a large number of charge adsorption sites, and also provides a smooth channel for ion diffusion, thereby reducing the resistance between the material interaction interfaces and improving the electrical conductivity of the composite material; and then, through non-equilibrium magnetron sputtering, a dense graphite-like carbon coating is formed on the surface of the composite porous carbon material, thereby enhancing the overall performance and use performance of the material and extending the service life. At the same time, corrosive gases and liquids are prevented from directly contacting the porous carbon material, effectively preventing the porous carbon material from being eroded by the external environment, and further extending the service life of the composite material. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0017] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the high performance graphite-based carbon composite materials prepared in the following examples are as follows: Comprehensive thermal conductivity: Take the same mass of the embodiment and the comparative example, mix and solidify with a polymer with 10 times the mass to prepare a sample, and use a thermal resistance tester to test the comprehensive thermal conductivity of the sample.

[0018] Volume resistivity: Take the same mass of the embodiment and the comparative example, mix them with a high molecular polymer of 10 times the mass and solidify them to prepare a sample, use a low resistance tester to measure the resistance of the sample and calculate the volume resistivity.

[0019] Corrosion resistance test: Take the same mass of the embodiment and the comparative example, immerse them in hydrochloric acid solution and sodium hydroxide solution for 30 days, take them out and weigh them.

[0020] Example 1 (1) 14 parts of graphite, 5 parts of N,N-hexamethylenebisacetamide, and 6 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 18 hours, 32 parts of a 10wt% potassium hydroxide aqueous solution were added, mixed uniformly, and placed in a calcining furnace and calcined at 700°C for 2 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 10 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 8 h, and then immersed in a 30 mg / mL methylimidazole-methanol solution for 8 h, and the mixture was repeated 3 times. The mixture was washed with methanol 3 times, and then dried in a freeze dryer at -48 °C for 24 h to obtain a modified composite porous carbon material. (3) The modified composite porous carbon material was placed in a magnetic boat in a vacuum chamber, a graphite target was installed, and magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.1 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and a sputtering current of 0.2 A for 3 h to obtain a high-performance graphite-based carbon composite material.

[0021] Example 2 (1) 18 parts of graphite, 6 parts of N,N-hexamethylenebisacetamide, and 8 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed uniformly, and placed in a calcining furnace for calcination at 800°C for 2.5 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 10 h, and then immersed in a 30 mg / mL methylimidazole-methanol solution for 10 h, and the solution was repeated 3 times, and then washed with methanol 3 times, and then placed in a freeze dryer and dried at -48 °C for 24 h to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.3 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and sputtering current of 0.3A for 4 hours to obtain a high-performance graphite-based carbon composite material.

[0022] Example 3 (1) 22 parts of graphite, 7 parts of N,N-hexamethylenebisacetamide, and 10 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 36 hours, 50 parts of a 10wt% potassium hydroxide aqueous solution were added, mixed uniformly, and placed in a calcining furnace for calcination at 900°C for 3 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 20 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 12 h, and then immersed in a 30 mg / mL methylimidazole-methanol solution for 12 h, and the mixture was repeated 3 times, and then washed with methanol 3 times, and then placed in a freeze dryer and dried at -48 °C for 24 h to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.5 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and a sputtering current of 0.4 A for 5 h to obtain a high-performance graphite-based carbon composite material.

[0023] Comparative Example 1 (1) 18 parts of graphite and 8 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed uniformly, placed in a calcining furnace and calcined at 800°C for 2.5 hours, cooled naturally to room temperature, added with 40 parts of a 1 mol / L dilute hydrochloric acid solution, collected the solid, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 10 h, and then immersed in a 30 mg / mL methylimidazole-methanol solution for 10 h, and the solution was repeated 3 times, and then washed with methanol 3 times, and then placed in a freeze dryer and dried at -48 °C for 24 h to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.3 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and sputtering current of 0.3A for 4 hours to obtain a high-performance graphite-based carbon composite material.

[0024] Comparative Example 2 (1) 18 parts of graphite and 6 parts of N,N-hexamethylenebisacetamide were mixed evenly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed evenly, and placed in a calcining furnace for calcination at 800°C for 2.5 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 10 h, and then immersed in a 30 mg / mL methylimidazole-methanol solution for 10 h, and the solution was repeated 3 times, and then washed with methanol 3 times, and then placed in a freeze dryer and dried at -48 °C for 24 h to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.3 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and sputtering current of 0.3A for 4 hours to obtain a high-performance graphite-based carbon composite material.

[0025] Comparative Example 3 (1) 18 parts of graphite, 6 parts of N,N-hexamethylenebisacetamide, and 8 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed uniformly, and placed in a calcining furnace for calcination at 800°C for 2.5 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.3 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 -5 Pa and sputtering current of 0.3A for 4 hours to obtain a high-performance graphite-based carbon composite material.

[0026] Comparative Example 4 (1) 18 parts of graphite, 6 parts of N,N-hexamethylenebisacetamide, and 8 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed uniformly, and placed in a calcining furnace for calcination at 800°C for 2.5 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 10 h, taken out and immersed in a 30 mg / mL methylimidazole-methanol solution for 10 h, washed with methanol three times, and placed in a freeze dryer at -48 ° C. for 24 h to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material was placed in a vacuum chamber magnetic boat, a graphite target was installed, and adjacent magnets with opposite magnetic poles were placed outside the vacuum chamber. The vacuum was evacuated to 0.3 Pa. The argon gas flow rate was 15 sccm, the substrate bias voltage was -85 V, and the deposition pressure was 3×10 - 5 Pa and sputtering current of 0.3A for 4 hours to obtain a high-performance graphite-based carbon composite material.

[0027] Comparative Example 5 (1) 18 parts of graphite, 6 parts of N,N-hexamethylenebisacetamide, and 8 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 27 hours, added with 41 parts of a 10wt% potassium hydroxide aqueous solution, mixed uniformly, and placed in a calcining furnace for calcination at 800°C for 2.5 hours. After naturally cooling to room temperature, 40 parts of a 1 mol / L dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 15 hours to obtain a composite porous carbon material; (2) The composite porous carbon material was immersed in a 15 mg / mL zinc nitrate-methanol solution for 10 h, taken out and immersed in a 30 mg / mL methylimidazole-methanol solution for 10 h, repeated 3 times, washed with methanol 3 times, and placed in a freeze dryer at -48 °C for 24 h to obtain a high-performance graphite-based carbon composite material.

[0028] Effect example Table 1 below shows the performance analysis results of the high performance graphite-based carbon composite materials using Examples 1 to 3 of the present invention and Comparative Examples 1 to 5.

[0029] Table 1

[0030] From the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Examples 1 and 2, it can be found that the present invention uses graphite, N, N-hexamethylenebisacetamide, and 3-hydroxyacetanilide as raw materials, and forms a composite porous carbon material through a high-temperature carbonization activation method, which has a large specific surface area, so that heat can diffuse quickly in the material, thereby improving the thermal conductivity of the composite material, and at the same time introducing abundant active sites, providing more reaction sites for redox reactions, which is beneficial to the transfer and storage of electrons, thereby improving the electrical conductivity of the composite material; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Examples 3 and 4, it can be found that after multiple alternating adsorption solutions, a three-dimensional ZIF-8 structure is formed after freeze-drying. , significantly increasing the specific surface area of ​​the material, cooperating with the porous carbon material to form a multi-level secondary pore structure, providing a large number of charge adsorption sites, and also providing a smooth channel for ion diffusion, thereby reducing the resistance between the material interaction interfaces and improving the conductive properties of the composite material; from the comparison of the experimental data of Examples 1, 2, and 3 with Comparative Example 5, it can be found that through unbalanced magnetron sputtering, a dense graphite-like carbon coating is formed on the surface of the composite porous carbon material, which enhances the overall performance and use performance of the material and prolongs its service life. At the same time, it prevents corrosive gases and liquids from directly contacting the porous carbon material, effectively preventing the porous carbon material from being eroded by the external environment, and further prolonging the service life of the composite material.

[0031] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A high-performance graphite-based carbon composite material, characterized in that: The high-performance graphite-based carbon composite material is prepared by using graphite, N,N-hexamethylenebisacetamide and 3-hydroxyacetanilide as raw materials, and after high-temperature carbonization activation, repeatedly adsorbing zinc nitrate and imidazole solution respectively, and then freeze-drying, and then forming a graphite-like carbon coating through unbalanced magnetron sputtering.

2. A method for preparing a high-performance graphite-based carbon composite material, characterized in that: The method comprises the following preparation steps: (1) 14-22 parts of graphite, 5-7 parts of N,N-hexamethylenebisacetamide, and 6-10 parts of 3-hydroxyacetanilide were mixed uniformly, ground at room temperature for 20 minutes, then transferred to an autoclave, kept at 160°C for 18-36 hours, 32 parts of potassium hydroxide aqueous solution were added, mixed uniformly, and then placed in a calcining furnace for calcination for 2-3 hours. After naturally cooling to room temperature, 40 parts of dilute hydrochloric acid solution were added, the solid was collected, washed with deionized water 3 times, and dried at 40°C for 10-20 hours to obtain a composite porous carbon material; (2) soaking the composite porous carbon material in a zinc nitrate-methanol solution for 8 to 12 hours, taking it out and soaking it in methylimidazole-methanol for 8 to 12 hours, repeating 3 times, washing it with methanol 3 times, and drying it in a freeze dryer for 24 hours to obtain a modified composite porous carbon material; (3) The modified composite porous carbon material is placed in a magnetic boat in a vacuum chamber, a graphite target is installed, a magnet is placed outside the vacuum chamber, the vacuum is evacuated to a degree of 0.1-0.5 Pa, and the deposition is performed for 3-5 hours to obtain a high-performance graphite-based carbon composite material.

3. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The concentration of the potassium hydroxide aqueous solution in step (1) is 10 wt %.

4. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The temperature of the calcining furnace in step (1) is 700-900°C.

5. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The concentration of the dilute hydrochloric acid solution in step (1) is 1 mol / L.

6. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The concentration of the zinc nitrate-methanol solution in step (2) is 15 mg / mL.

7. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The concentration of N-methylimidazole-methanol in step (2) is 30 mg / mL.

8. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The freeze dryer temperature in step (2) is -48°C.

9. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: In step (3), the adjacent magnetic poles of the magnets are opposite.

10. The method for preparing a high-performance graphite-based carbon composite material according to claim 2, characterized in that: The deposition parameters in step (3) are argon gas flow rate 15 sccm, substrate bias voltage -85 V, deposition pressure 3×10 -5 Pa, sputtering current 0.2~0.4A.

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