Preparation method of isotropic porous carbon material, porous carbon reinforced nonmetal or metal composite material as well as preparation method and application of porous carbon reinforced nonmetal or metal composite material

Abstract

The invention belongs to the field of composite materials and lithium batteries, and particularly relates to a preparation method of an isotropic porous carbon material, a porous carbon reinforced nonmetal or metal composite material and a preparation method and application of the porous carbon reinforced nonmetal or metal composite material. The preparation method comprises the following steps: carrying out heat treatment on a liquid polyacrylonitrile oligomer in a protective atmosphere to obtain a porous carbon precursor material; performing a high-temperature graphitization enhancement technology on the porous carbon precursor material in a protective atmosphere to obtain a porous carbon material; and quantitative pore forming is carried out by controlling oxygen flow in an oxygen atmosphere, so that the isotropic porous carbon material with uniformly distributed pore structures is prepared. The prepared isotropic porous carbon material is used as a reinforcing phase and compounded with metal or nonmetal to prepare composite materials with different properties, so that various properties of the composite materials are improved, and the isotropic porous carbon material can be applied to light high-strength structural parts in the fields of aerospace and automobile industry and can also be used as a negative electrode material in the field of lithium batteries.

Description

Technical Field

[0001] The present invention belongs to the field of composite materials and lithium batteries, and specifically relates to a preparation method of an isotropic porous carbon material, a porous carbon reinforced non-metallic or metal composite material, and a preparation method and application thereof. Background Art

[0002] Porous carbon materials are used in materials science as reinforcements in composite materials, improving their mechanical properties, electrical conductivity, and thermal resistance. Due to their uniformly distributed micropores, porous carbon can also be used as a carrier for nanosilicon in lithium batteries as anode materials. Porous carbon-reinforced metal composites offer advantages such as high specific strength, excellent thermal and electrical conductivity, good ductility, and wear resistance. Adding a porous carbon reinforcement to a non-metallic matrix can significantly enhance the material's mechanical properties, electrical conductivity, thermal conductivity, and thermal stability. These materials hold broad application prospects in the automotive, aerospace, electronics, and optical instrumentation sectors.

[0003] However, the performance of current porous carbon composites will be greatly affected due to the uneven pore structure of porous carbon. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of isotropic porous carbon materials, porous carbon reinforced non-metallic or metal composite materials and their preparation methods and applications. The preparation method provided by the present invention can obtain an isotropic porous carbon material with uniform pore structure distribution, which is beneficial to improving the performance of the porous carbon composite material.

[0005] In order to achieve the above object, the present invention provides the following technical solutions: The present invention provides a method for preparing an isotropic porous carbon material, comprising the following steps: Heat-treating liquid polyacrylonitrile oligomer in a protective gas atmosphere to prepare a porous carbon precursor material, wherein the heat-treating temperature is less than 240° C.; In a protective gas atmosphere, graphitizing the porous carbon precursor material to obtain a porous carbon material; The porous carbon material is quantitatively pore-formed under oxygen atmosphere conditions to obtain an isotropic porous carbon material with uniform pore structure distribution, the flow rate of the oxygen is 30-150 mL / min, and the temperature of the quantitative pore-formation is less than 500°C.

[0006] Preferably, the heat treatment temperature is 180-230°C, the time is 1-6 hours; the heating rate from room temperature to the heat treatment temperature is 3-10°C / min; the protective gas for the heat treatment includes one or more of nitrogen, helium and argon; The temperature of the graphitization treatment is 1000-3000°C, the time is 1-10 hours, the heating rate from room temperature to the temperature of the graphitization treatment is 3-10°C / min, and the protective gas of the graphitization treatment includes one or more of nitrogen, helium and argon; The temperature of the quantitative pore formation is 300-450° C., and the time is 1-6 hours.

[0007] The present invention provides a porous carbon reinforced resin composite material, comprising a porous carbon skeleton and a resin material composited in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution.

[0008] The present invention provides a method for preparing the porous carbon reinforced resin composite material described in the above technical solution, comprising the following steps: The isotropic porous carbon material is immersed in a resin solution for compounding to obtain the porous carbon reinforced resin composite material.

[0009] The present invention provides a porous carbon reinforced metal composite material, comprising a porous carbon skeleton and a metal material composited in the porous carbon skeleton, wherein the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution, and the metal material comprises a metal element and / or a metal alloy.

[0010] The present invention provides a method for preparing the porous carbon reinforced metal composite material described in the above technical solution, comprising the following steps: Heating and melting the metal material to obtain a metal material melt; The isotropic porous carbon material is placed in the metal material melt for compounding to obtain the porous carbon reinforced metal composite material.

[0011] The present invention provides a porous carbon material vapor-deposited silicon composite material, comprising a porous carbon skeleton and silicon deposited in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution.

[0012] The present invention provides a method for preparing the porous carbon material vapor-deposited silicon composite material described in the above technical solution, comprising the following steps: The isotropic porous carbon material is ground into powder, and then a reaction gas is introduced under an inert gas condition to perform vapor deposition, wherein the reaction gas includes hydrogen and silane gas, to obtain the porous carbon material vapor-deposited silicon composite material.

[0013] The present invention provides the use of the porous carbon reinforced resin composite material described in the above technical solution or the porous carbon reinforced resin composite material prepared by the preparation method described in the above technical solution or the porous carbon reinforced metal composite material described in the above technical solution or the porous carbon reinforced metal composite material prepared by the preparation method described in the above technical solution in aerospace structural parts or automobile structural parts.

[0014] The present invention provides the use of the porous carbon material vapor-deposited silicon composite material described in the above technical solution or the porous carbon material vapor-deposited silicon composite material prepared by the preparation method described in the above technical solution as a negative electrode material in the field of lithium batteries.

[0015] The present invention provides a method for preparing an isotropic porous carbon material, comprising the following steps: heat-treating a liquid polyacrylonitrile oligomer in a protective gas atmosphere to obtain a porous carbon precursor material, wherein the heat treatment temperature is less than 240°C; graphitizing the porous carbon precursor material in the protective gas atmosphere to obtain a porous carbon material; and quantitatively forming pores in the porous carbon material under an oxygen atmosphere to obtain an isotropic porous carbon material having a uniform pore structure distribution, wherein the oxygen flow rate is 30 to 150 mL / min and the quantitative forming temperature is less than 500°C. The present invention uses liquid polyacrylonitrile oligomer as a raw material, adopts a two-step process of heat treatment and graphitization, and rationally optimizes the heat treatment temperature range to prepare the porous carbon material. The porous carbon material is then subjected to quantitative forming of pores under an oxygen atmosphere. By optimizing the oxygen flow rate and the quantitative forming temperature, an isotropic porous carbon material having a uniform pore structure distribution can be prepared. The use of the isotropic porous carbon material prepared by the present invention as a reinforcing phase to prepare a composite material can improve the uniformity of the composite material, which is beneficial to improving various properties of the composite material.

[0016] In summary, the isotropic porous carbon material prepared by the present invention has a three-dimensional structure, high strength, and strong adsorption and shaping ability. At the same time, the preparation method provided by the present invention is low in preparation cost, simple in preparation method, and easy to industrialize.

[0017] The present invention provides a porous carbon-reinforced resin composite material comprising a porous carbon skeleton and a resin material filled within the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution. The isotropic porous carbon material prepared by the present invention has extremely strong oleophilic properties and isotropy, which facilitates the penetration and adsorption of the resin material. In the resulting porous carbon-reinforced resin composite material, the resin material is evenly distributed within the pore structure of the carbon skeleton, resulting in a highly uniform overall composite structure and excellent mechanical properties and thermal stability.

[0018] The present invention provides a porous carbon-reinforced metal composite material, comprising a porous carbon skeleton and a metal material filled in the porous carbon skeleton. The porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution, and the metal material comprises a metal element and / or a metal alloy. The isotropic porous carbon material prepared by the present invention has extremely strong oleophilic and hydrophilic properties and isotropy. The pore structure contains microporous structures obtained by quantitative pore formation, resulting in a high specific surface area, which is conducive to the penetration and adsorption of molten metal materials. The resulting porous carbon-reinforced metal composite material has high overall structural uniformity and excellent mechanical properties, electrical conductivity, thermal conductivity, ductility, and wear resistance.

[0019] The present invention provides a porous carbon material vapor-deposited silicon composite material comprising a porous carbon skeleton and silicon deposited within the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared using the preparation method described in the above technical solution. The porous carbon material vapor-deposited silicon composite material provided by the present invention is used as a negative electrode material in lithium batteries and exhibits excellent mechanical properties, electrical conductivity, and thermal conductivity.

[0020] In summary, the porous carbon-reinforced resin composite material, porous carbon-reinforced metal composite material, and porous carbon-vapor-deposited silicon composite material provided by the present invention utilize an isotropic porous carbon material as a carbon skeleton to achieve a composite of the isotropic porous carbon material with a resin material, a metal material, or a silicon material, significantly improving the uniformity of the composite material. The resulting porous carbon-reinforced resin composite material, porous carbon-reinforced metal composite material, and porous carbon-vapor-deposited silicon composite material exhibit lightweight properties, high strength, excellent wear resistance, and electrical or thermal conductivity; they can be used to prepare lightweight, high-strength structural parts in fields such as aerospace and the automotive industry.

[0021] The present invention provides methods for preparing the porous carbon-reinforced resin composites, porous carbon-reinforced metal composites, and porous carbon-vapor-deposited silicon composites described in the above technical solutions. The composite materials provided herein are prepared using a combination of resin solution impregnation, metal melt impregnation, or vapor deposition, resulting in simple, easy-to-perform procedures suitable for industrial applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a physical picture of the isotropic porous carbon material product with uniform pore structure distribution prepared in Example 1 of the present invention; Figure 2 This is a physical picture of the isotropic porous carbon material reinforced aluminum-based metal composite material with a porosity of 94% prepared in Example 2 of the present invention; Figure 3 This is a photo of the isotropic porous carbon material reinforced resin composite material with a porosity of 94% prepared in Example 3 of the present invention; Figure 4 This is a charge and discharge curve diagram of a button cell using the isotropic porous carbon material vapor-deposited silicon composite material with a porosity of 94% prepared in Example 4 of the present invention as the negative electrode. DETAILED DESCRIPTION

[0023] The present invention provides a method for preparing an isotropic porous carbon material, comprising the following steps: Heat-treating liquid polyacrylonitrile oligomer in a protective gas atmosphere to prepare a porous carbon precursor material, wherein the heat-treating temperature is less than 240° C.; In a protective gas atmosphere, graphitizing the porous carbon precursor material to obtain a porous carbon material; The porous carbon material is quantitatively pore-formed under oxygen atmosphere conditions to obtain an isotropic porous carbon material with uniform pore structure distribution, the flow rate of the oxygen is 30-150 mL / min, and the temperature of the quantitative pore-formation is less than 500°C.

[0024] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0025] The present invention heat-treats liquid polyacrylonitrile oligomer in a protective gas atmosphere to prepare a porous carbon precursor material, wherein the heat-treating temperature is less than 240°C.

[0026] In the present invention, the liquid polyacrylonitrile oligomer (LPAN) is in liquid form, has a molecular weight of 100 to 100,000, and has the chemical structural formula: .

[0027] In the present invention, the raw materials for the heat treatment preferably further include a pore-forming material and / or a filler. The pore-forming material preferably includes one or more of an inorganic oxide, a salt, and an organic material. In the present invention, the inorganic oxide is preferably copper oxide. The salt is preferably copper acetate. The organic material is preferably polyacrylonitrile powder. The filler preferably includes one or more of polyacrylonitrile powder and carbon nanotubes.

[0028] In the present invention, when the raw materials for the heat treatment further include a pore-forming material and / or a filler, the ratio of the mass of the pore-forming material and / or filler to the mass of the liquid polyacrylonitrile oligomer is preferably 0.5:1. In the present invention, when the heat treatment preparation method further includes a pore-forming material and / or a filler, prior to the heat treatment, the present invention preferably further includes mixing the liquid polyacrylonitrile oligomer, the pore-forming material, and the filler to obtain a mixed material, and subjecting the mixed material to the heat treatment. When the heat treatment preparation method further includes a pore-forming material and a filler, the present invention has no particular requirements for the mass ratio of the pore-forming material to the filler.

[0029] In the present invention, the heat treatment is preferably carried out in a container, and the container may be a sagger. The heat treatment is preferably carried out in a sintering furnace. The temperature of the heat treatment is preferably 180-230°C, and in the embodiment it may be 220°C. The time of the heat treatment is preferably 1-6h, and in the embodiment it may be 4h. The heating rate from room temperature to the temperature of the heat treatment is preferably 3-10°C / min, and more preferably 5-8°C / min. The protective gas for the heat treatment preferably includes one or more of nitrogen, helium and argon, and in the embodiment it may be nitrogen or argon. The present invention can effectively control the generation rate of the porous carbon precursor material by optimizing the temperature, time and heating rate of the heat treatment, and can obtain a porous carbon precursor material with optimized pore structure, and obtain a porous carbon material with optimized pore structure after graphitization treatment.

[0030] After obtaining the porous carbon precursor material, the present invention graphitizes the porous carbon precursor material in a protective gas atmosphere to obtain the porous carbon material. In the present invention, the graphitization treatment is preferably carried out in a sintering furnace. The temperature of the graphitization treatment is preferably 900~3000℃, more preferably 1000~2000℃, and can be 1400℃ in the embodiment. The time of the graphitization treatment is preferably 1~10h, more preferably 2~8h, further preferably 2.5~6h, and can be 3h in the embodiment. The heating rate from room temperature to the temperature of the graphitization treatment is preferably 3~10℃ / min, more preferably 5~8℃ / min. The protective gas for the graphitization treatment preferably includes one or more of nitrogen, helium and argon, and can be nitrogen or argon in the embodiment. The present invention enhances the strength of the material by controlling the degree of graphitization of the material by regulating the graphitization temperature.

[0031] After obtaining the porous carbon material, the present invention performs quantitative pore formation on the porous carbon material under oxygen atmosphere conditions to obtain an isotropic porous carbon material with uniform pore structure distribution. The oxygen flow rate is 30-150 mL / min, and the temperature of the quantitative pore formation is less than 500°C.

[0032] The invention performs quantitative pore formation by controlling the oxygen flow rate under an oxygen atmosphere.

[0033] In the present invention, the temperature for quantitative pore formation is preferably 300-450°C, and in the embodiment, it can be 400°C. The time for quantitative pore formation is preferably 1-6 hours, more preferably 2-5 hours, and in the embodiment, it can be 3 hours. The present invention controls the degree of oxidation of the material and the number of micropores by regulating the temperature and time of quantitative pore formation, thereby obtaining an isotropic porous carbon material with strong hydrophilicity and a high specific surface area and a uniformly distributed pore structure.

[0034] The expansion rate of the isotropic porous carbon material with uniform pore structure distribution prepared by the present invention is less than 400%, preferably 30-200%. The porosity of the isotropic porous carbon material with uniform pore structure distribution is less than 97%, preferably 47-94%.

[0035] In an embodiment of the present invention, when the raw material is liquid polyacrylonitrile oligomer, the expansion ratio of the isotropic porous carbon material with a uniform pore structure distribution can be 200%, and the porosity can be 94%. When the raw material also includes the above-mentioned pore-forming material and / or filler material, the expansion ratio of the porous carbon material can be 50%, and the porosity can be 47%.

[0036] The present invention provides an isotropic porous carbon material having a uniformly distributed pore structure, prepared by the preparation method described in the above technical solution. The isotropic porous carbon material having a uniformly distributed pore structure prepared by the present invention has oxygen-containing groups on its carbon skeleton surface. The isotropic porous carbon material having a uniformly distributed pore structure has excellent hydrophilic and oleophilic properties. The isotropic porous carbon material having a uniformly distributed pore structure has an isotropic characteristic.

[0037] The isotropic porous carbon material with a uniform pore structure provided by the present invention serves as a reinforcing phase of a carbon skeleton composite material, has a three-dimensional structure, and can shape the metal or non-metal in the carbon skeleton composite material. In addition, the isotropic porous carbon material with a uniform pore structure provided by the present invention serves as a reinforcing phase, has high wettability and strong adsorption capacity, and is easy to penetrate into molten metal / non-metal.

[0038] The present invention provides a porous carbon reinforced resin composite material, comprising a porous carbon skeleton and a resin material composited in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution.

[0039] In the present invention, the resin material is preferably epoxy resin.

[0040] The present invention provides a method for preparing the porous carbon reinforced resin composite material described in the above technical solution, comprising the following steps: The isotropic porous carbon material is immersed in a resin solution for compounding to obtain the porous carbon reinforced resin composite material.

[0041] In the present invention, the resin solution is preferably an epoxy resin solution. In the present invention, the epoxy resin solution is preferably a mixed adhesive obtained by mixing epoxy resins A and B. The isotropic porous carbon material is impregnated in the mixed adhesive for compounding. The temperature of the epoxy resin solution is preferably 60-100°C, and in the embodiment, it can be 80°C.

[0042] In the present invention, the composite is preferably carried out under vacuum conditions. The composite is preferably carried out in a protective gas atmosphere, and the protective gas preferably includes nitrogen and / or argon. In the present invention, the composite preferably includes sequentially carrying out a first-stage composite and a second-stage composite. The pressure of the first-stage composite is preferably -0.08~-0.05MPa, and in the embodiment it can be -0.08MPa; the time is preferably 1~10min, and in the embodiment it can be 2min. The pressure of the second-stage composite is preferably 0.05~0.08MPa, and in the embodiment it can be 0.08MPa; the time is preferably 1~10min, and in the embodiment it can be 2min. In the present invention, after the composite is completed, the obtained material is thermally cured to obtain the porous carbon reinforced resin composite material. The temperature of the thermal curing is preferably 80°C.

[0043] The present invention provides a porous carbon reinforced metal composite material, comprising a porous carbon skeleton and a metal material composited in the porous carbon skeleton, wherein the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution, and the metal material comprises a metal element and / or a metal alloy.

[0044] In the present invention, the metal element preferably includes aluminum, copper, iron, cobalt, or nickel, and in embodiments, may be aluminum. The metal alloy preferably includes an aluminum alloy, a copper alloy, an iron alloy, a cobalt alloy, or a nickel alloy, and in embodiments, may be an aluminum alloy. The present invention has no particular requirements for the composition of the metal alloy.

[0045] The present invention provides a method for preparing the porous carbon reinforced metal composite material described in the above technical solution, comprising the following steps: Heating and melting the metal material to obtain a metal material melt; The isotropic porous carbon material is placed in the metal material melt for compounding to obtain the porous carbon reinforced metal composite material.

[0046] The present invention heats and melts the metal material to obtain a metal melt. In the present invention, the temperature of the heating and melting is preferably 800-1600°C, and in an embodiment, it can be 1000°C.

[0047] After obtaining the metal material melt, the present invention places the isotropic porous carbon material in the metal material melt for compounding to obtain the porous carbon reinforced metal composite material.

[0048] In the present invention, the composite is preferably carried out under vacuum conditions. The composite is preferably carried out in a protective gas atmosphere, and the protective gas preferably includes nitrogen and / or argon. In the present invention, the placing is preferably to immerse the isotropic porous carbon material in the metal material melt. The composite preferably includes sequentially performing a first-stage composite and a second-stage composite. The pressure of the first-stage composite is preferably -0.08~-0.05MPa, and in the embodiment it can be -0.08MPa; the time is preferably 1~10min, and in the embodiment it can be 2min. The pressure of the second-stage composite is preferably 0.05~0.08MPa, and in the embodiment it can be 0.08MPa; the time is preferably 1~10min, and in the embodiment it can be 2min. In the present invention, after the composite is completed, the obtained material is cooled to obtain the porous carbon reinforced metal composite material.

[0049] The present invention provides the use of the porous carbon reinforced resin composite material described in the above technical solution or the porous carbon reinforced resin composite material prepared by the preparation method described in the above technical solution or the porous carbon reinforced metal composite material described in the above technical solution or the porous carbon reinforced metal composite material prepared by the preparation method described in the above technical solution in aerospace structural parts or automobile structural parts.

[0050] The present invention provides a porous carbon material vapor-deposited silicon composite material, comprising a porous carbon skeleton and silicon deposited in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method described in the above technical solution.

[0051] The present invention provides a method for preparing the porous carbon material vapor-deposited silicon composite material described in the above technical solution, comprising the following steps: The isotropic porous carbon material is ground into powder, then heated to a vapor deposition temperature under inert gas conditions, and then a reaction gas is introduced for vapor deposition, wherein the reaction gas includes hydrogen and silane gas to obtain the porous carbon material vapor-deposited silicon composite material.

[0052] In the present invention, the inert gas is preferably argon. In the present invention, the raw material for preparing the silane gas is preferably liquid silane, and the liquid silane is preferably dichlorodimethylsilane. In the present invention, the silane gas is preferably prepared by heating the liquid silane to 80°C in a water bath.

[0053] In the present invention, during the vapor deposition, the present invention preferably evaporates the liquid silane by heating it in a water bath, and transports the evaporated silane gas to a vapor deposition reactor by introducing an inert gas, and then introduces a mixture of hydrogen and inert gas into the vapor deposition reactor, and then performs the vapor deposition. The volume content of hydrogen in the mixture of hydrogen and inert gas is preferably 5-8%, and in the embodiment, it can be 8%. The flow rate of the mixture of hydrogen and inert gas is preferably 50-60 sccm. The flow rate of the inert gas for transporting silane gas is preferably 80-100 sccm.

[0054] In the present invention, the temperature of the vapor deposition is preferably 750-900°C; the holding time is preferably 0.5-2 hours. In an embodiment, the temperature of the vapor deposition can be 850°C, and the holding time can be 1 hour. In the present invention, after the vapor deposition is completed, the material obtained by the vapor deposition is cooled under protective gas conditions to obtain the porous carbon composite nano-silicon negative electrode material.

[0055] The present invention provides the use of the porous carbon material vapor-deposited silicon composite material described in the above technical solution or the porous carbon material vapor-deposited silicon composite material prepared by the preparation method described in the above technical solution as a negative electrode material in the field of lithium batteries.

[0056] The porous carbon reinforced metal / non-metal composite material prepared by the present invention through a simple method realizes the construction of a porous carbon three-dimensional structure. The present invention forms pores in the porous carbon under oxygen atmosphere conditions and adds oxidizing groups on the surface of the porous carbon. The isotropic porous carbon material with uniform pore structure distribution obtained by the present invention significantly improves the hydrophilicity, thereby improving the wettability of the isotropic porous carbon material to the molten metal material. The metal material or non-metallic material uniformly penetrates into the interior of the isotropic porous carbon material. The adsorption property of the isotropic porous carbon material effectively restricts the flow of the molten metal / non-metal and thereby shapes it to form a porous carbon reinforced metal / non-metal composite material. Therefore, the porous carbon reinforced metal / non-metal composite material has light weight and high strength, wear resistance, electrical conductivity and thermal conductivity.

[0057] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0058] Example 1: Preparation of isotropic porous carbon material with uniform pore structure distribution The liquid polyacrylonitrile oligomer was placed in a sagger and heat treated at 220°C for 4 hours in an inert atmosphere (argon) of a sintering furnace. Then, the product was graphitized at 1400°C for 3 hours under argon gas. Finally, the oxygen flow rate was adjusted to 100 mL / min, and a directional pore-forming treatment was performed under oxygen conditions at a temperature of 400°C for 3 hours to obtain an isotropic porous carbon material with uniform pore structure distribution. Figure 1 This is a physical picture of the isotropic porous carbon material product with uniform pore structure distribution prepared in Example 1 of the present invention.

[0059] Example 2: Preparation of porous carbon reinforced aluminum metal composite material Liquid polyacrylonitrile oligomer was placed in a sagger and heat treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace. It was then subjected to high-temperature graphitization treatment at 1400°C for 3 hours under argon conditions. Finally, the oxygen flow rate was adjusted to 100 mL / min, and a directional pore-forming treatment was carried out under oxygen conditions at 400°C for 3 hours to obtain an isotropic porous carbon material with uniform pore structure distribution.

[0060] Aluminum metal particles are placed in a melting furnace and melted at 1000°C; then, an isotropic porous carbon material with a uniformly distributed pore structure is immersed in the molten metal, the ambient pressure is adjusted to -0.08 MPa, and the pressure is maintained for 2 minutes, and then the ambient pressure is adjusted to 0.08 MPa and the pressure is maintained for 2 minutes; then, the isotropic porous carbon material after the aluminum alloy melt composite is removed from the melting furnace and cooled to obtain a porous carbon reinforced aluminum metal composite material.

[0061] Example 3: Preparation of porous carbon reinforced epoxy resin composite material Liquid polyacrylonitrile oligomer was placed in a sagger and heat treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace. It was then subjected to high-temperature graphitization treatment at 1400°C for 3 hours under argon conditions. Finally, the oxygen flow rate was adjusted to 100 mL / min, and a directional pore-forming treatment was carried out under oxygen conditions at 400°C for 3 hours to obtain an isotropic porous carbon material with uniform pore structure distribution.

[0062] Epoxy resin glue A and glue B are mixed (the mass ratio of glue A to glue B is 2:1) to obtain an epoxy resin solution, and then the isotropic porous carbon material with uniform pore structure distribution is immersed in the epoxy resin solution and compounded at 80°C; the ambient pressure is adjusted to -0.08MPa, and the pressure is maintained for 2 minutes, and then the ambient pressure is adjusted to 0.08MPa, and the pressure is maintained for 2 minutes; then the epoxy resin glue is solidified at a constant temperature of 80°C under normal pressure, and then the porous carbon compounded with epoxy resin is cooled to obtain a porous carbon reinforced epoxy resin composite material. Figure 3 This is a physical picture of the isotropic porous carbon material reinforced resin composite material with a porosity of 94% prepared in Example 3 of the present invention.

[0063] Example 4: Preparation of porous carbon material vapor-deposited silicon composite material Liquid polyacrylonitrile oligomer was placed in a sagger and heat treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace. It was then subjected to high-temperature graphitization treatment at 1400°C for 3 hours under argon conditions. Finally, the oxygen flow rate was adjusted to 100 mL / min, and a directional pore-forming treatment was carried out under oxygen conditions at 400°C for 3 hours to obtain an isotropic porous carbon material with uniform pore structure distribution.

[0064] An isotropic porous carbon material with uniform pore structure distribution is ground into powder, and the ground isotropic porous carbon powder is placed in a vapor deposition reactor and heated to 850°C under an inert atmosphere (argon); dichlorodimethylsilane is heated to 80°C in a water bath to evaporate to obtain silane gas, and then the silane gas is transported to the vapor deposition reactor by argon, and the flow rate of the argon gas transporting the silane gas is 100sccm; a mixed gas of hydrogen and argon (H2 / Ar mixed gas with an H2 content of 8vol%) is introduced into the vapor deposition reactor, and the flow rate of the mixed gas of hydrogen and argon is 60sccm, and vapor deposition is carried out. The vapor deposition temperature is 850°C, and the holding time is 1h; a porous carbon material vapor deposition silicon composite material (400°C@8%H2-Si-CVD) is obtained.

[0065] Comparative Example 1: Preparation of 97% porosity porous carbon by heat treatment at 240°C The liquid polyacrylonitrile oligomer was placed in a sagger and heat treated at 240°C for 4 hours in an inert atmosphere (argon) of a sintering furnace. Then, graphitization was performed at 1400 °C for 3 h under argon conditions; Finally, the oxygen flow rate was adjusted to 100 mL / min, and a directional pore-forming treatment was performed under oxygen conditions at a temperature of 400° C. for 3 hours to obtain an isotropic porous carbon material.

[0066] Comparative Example 2: Preparation of porous carbon reinforced aluminum metal composite material Liquid polyacrylonitrile oligomer is placed in a sagger and heat-treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace. It is then graphitized at 1400°C for 3 hours under argon to produce a porous carbon material.

[0067] Aluminum metal particles are placed in a melting furnace and melted at 1000°C; the prepared porous carbon material is then immersed in the molten metal, the melting environment pressure is adjusted to -0.08 MPa, and the pressure is maintained for 2 minutes, and then the melting environment pressure is adjusted to 0.08 MPa, and the pressure is maintained for 2 minutes; the molten composite porous carbon is then removed from the melting furnace to obtain a porous carbon reinforced aluminum-based metal composite material.

[0068] Test Example 1: Porous carbon with different porosities The isotropic porous carbon material prepared by pre-calcining (i.e., heat-treating) the liquid polyacrylonitrile oligomer at 220°C in Example 1 exhibited an expansion rate of 200% and a porosity of 94%, indicating relatively uniform pores. In contrast, the isotropic porous carbon material prepared by pre-calcining the liquid polyacrylonitrile oligomer at 240°C in Comparative Example 1 exhibited an expansion rate of 400%, a porosity of 97%, and relatively large pores. Table 1 shows that a pre-calcining temperature that is too high (240°C) results in excessive expansion and porosity in the prepared isotropic porous carbon material, resulting in poor mechanical properties. The expansion rate in Table 1 is calculated as (porous carbon thickness / initial slurry thickness) × 100%. The porosity data in Table 1 was measured using the Archimedean principle: porosity = volume of water immersed in the porous carbon / (effective volume of the porous carbon + volume of water immersed in the porous carbon) × 100%.

[0069] Table 1 Comparison of expansion rate and porosity of isotropic porous carbon materials prepared in Example 1 and Comparative Example 1

[0070] Test Example 2: Oleophilicity and Hydrophilicity of Porous Carbon Materials The isotropic porous carbon material prepared in Example 1 has excellent lipophilicity, which is beneficial to the penetration of non-metallic polymers and the preparation of porous carbon reinforced non-metallic composite materials, but has poor hydrophilicity. Water droplets cannot spontaneously penetrate the specific surface of the material and will float on the water surface. The porous carbon material prepared in Example 2 has excellent lipophilicity and hydrophilicity. Water droplets can instantly penetrate into the interior of the material and sink to the bottom of the water when placed in water.

[0071] Table 2 Hydrophilic and lipophilic properties of the materials prepared in Example 1 and the blank group

[0072] Preparation method of the blank group in Table 2: liquid polyacrylonitrile oligomer is placed in a sagger and heat-treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace; then, high-temperature graphitization is performed at 1400°C for 3 hours under argon to obtain a porous carbon material.

[0073] Test Example 3: Controlling the Effect of Quantitative Pore Formation on Materials The isotropic porous carbon material prepared in Example 1 has excellent oleophilicity and hydrophilicity, and the specific surface area is 15.00 m 2 / g, which is conducive to the penetration and adsorption of non-metallic polymers and molten metals, and its strength is not much different from that of the blank group without quantitative pore creation; when quantitative pore creation is performed at 400℃, the total pore volume is 0.0018cm3 of the blank group (graphitized product). 3 / g increased to 0.0050cm 3 / g, which is 2.77 times that of the porous carbon prepared in the blank group. This significantly increases the number of micropores, giving the material a larger specific surface area and strong adsorption capacity for molten metal. The degree of oxidation in Table 3 = (weight before quantitative pore creation / weight after quantitative pore creation) × 100%.

[0074] Table 3 Performance comparison of materials prepared in Example 1 and the blank group

[0075] Preparation method of the blank group in Table 3: liquid polyacrylonitrile oligomer was placed in a sagger and heat-treated at 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace; then, high-temperature graphitization was performed at 1400°C for 3 hours under argon to obtain a porous carbon material.

[0076] Test Example 4: The impact of quantitative pore formation on composite aluminum materials Example 2 and Comparative Example 2 are compared. In Example 2, the isotropic porous carbon material prepared by quantitative pore-forming technology is used to composite aluminum metal to prepare a porous carbon reinforced aluminum metal composite material. From the cross-sectional view of the sample ( Figure 2 ) shows that the aluminum in the composite material uniformly penetrates the porous carbon. Comparative Example 2, in which a composite material was prepared using unporated porous carbon, shows aluminum on the surface while the interior remains porous carbon. This comparison confirms that the isotropic porous carbon material prepared using quantitative pore-forming technology exhibits high wettability with aluminum. The polar groups within the carbon material are compatible with aluminum, and the increased number of micropores after pore-forming enhances the material's strong adsorption properties, allowing it to actively absorb molten aluminum. The resulting porous carbon-reinforced aluminum composite exhibits high uniformity.

[0077] The tensile properties of the porous carbon reinforced aluminum-based metal composite material (400℃C@Al) of Example 2 are excellent, reaching 1010MPa, the tensile modulus is 112GPa, and the thermal conductivity is 410W / (m·k), the thermal conductivity is 60MS / m, and the wear rate (dry grinding) is 9.0×10 -5 mm 3 / (Nm).

[0078] The aluminum-based metal reinforced with an isotropic porous carbon material with uniform pore structure distribution prepared by pore formation at 400°C has high uniformity and significantly improves its strength, wear resistance, thermal conductivity and electrical conductivity.

[0079] Table 4 Mechanical properties of the products of Example 2, Comparative Example 2 and Blank group

[0080] Table 5 Wear resistance and electrical and thermal conductivity of the product prepared in Example 2

[0081] Test Example 5: Porous carbon reinforced epoxy resin composite material The porous carbon reinforced resin composite material prepared in Example 3 has a tensile strength of 130 MPa and an elastic modulus of 5.5 GPa, which are significantly improved.

[0082] Table 6 Mechanical properties of porous carbon reinforced resin composites prepared in Example 3

[0083] Test Example 6: Porous Carbon Vapor Deposition Silicon Composite Material Figure 4 This is a charge-discharge curve for a coin cell battery using a 94% porosity, isotropic porous carbon vapor-deposited silicon composite material, prepared in Example 4 of the present invention, as the negative electrode. The porous carbon vapor-deposited silicon composite material prepared in Example 4, as the silicon negative electrode material, achieved a specific capacity of 389.09 mAh / g, 136.68 mAh / g higher than that of porous carbon oxidized at 400°C. This significant improvement also significantly increased the initial efficiency to 80.50% after high-temperature sintering.

[0084] Table 7 Performance of porous carbon vapor-deposited silicon composite button cells

[0085] The blank group in Table 7 is the isotropic porous carbon material with uniform pores prepared in Example 4.

[0086] From the above examples, it can be seen that the porous carbon reinforced non-metallic composite material and porous carbon reinforced metal composite material provided by the present invention, by using an isotropic porous carbon material with a uniform pore structure distribution as a carbon skeleton, realizes the composite of the isotropic porous carbon material with a uniform pore structure distribution and a metal material or a non-metallic polymer, which significantly improves the uniformity of the composite material. The obtained porous carbon reinforced non-metallic composite material and porous carbon reinforced metal composite material have lightweight, high strength, excellent wear resistance and electrical and thermal conductivity; they can be used in the preparation of lightweight and high-strength structural parts in the fields of aerospace, automotive industry, etc. The silicon negative electrode material prepared by porous carbon vapor deposition has better performance in button batteries and can be used as a negative electrode material in the field of lithium batteries.

[0087] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an isotropic porous carbon material, characterized in that: The following steps are involved: Heat-treating liquid polyacrylonitrile oligomer in a protective gas atmosphere to prepare a porous carbon precursor material, wherein the heat-treating temperature is less than 240° C.; In a protective gas atmosphere, graphitizing the porous carbon precursor material to obtain a porous carbon material; The porous carbon material is quantitatively pore-formed under oxygen atmosphere conditions to obtain an isotropic porous carbon material with uniform pore structure distribution, the flow rate of the oxygen is 30-150 mL / min, and the temperature of the quantitative pore-formation is less than 500°C.

2. The preparation method according to claim 1, characterized in that The heat treatment temperature is 180-230°C, and the time is 1-6 hours; the heating rate from room temperature to the heat treatment temperature is 3-10°C / min; the protective gas for the heat treatment includes one or more of nitrogen, helium and argon; The temperature of the graphitization treatment is 1000-3000°C, the time is 1-10 hours, the heating rate from room temperature to the temperature of the graphitization treatment is 3-10°C / min, and the protective gas of the graphitization treatment includes one or more of nitrogen, helium and argon; The temperature of the quantitative pore formation is 300-450° C., and the time is 1-6 hours.

3. A porous carbon reinforced resin composite material, characterized in that: It comprises a porous carbon skeleton and a resin material compounded in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method according to claim 1 or 2.

4. The method for preparing the porous carbon reinforced resin composite material according to claim 3, characterized in that: The following steps are involved: The isotropic porous carbon material is immersed in a resin solution for compounding to obtain the porous carbon reinforced resin composite material.

5. A porous carbon reinforced metal composite material, characterized in that: It comprises a porous carbon skeleton and a metal material composited in the porous carbon skeleton, wherein the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method according to claim 1 or 2, and the metal material comprises a metal element and / or a metal alloy.

6. The method for preparing the porous carbon reinforced metal composite material according to claim 5, characterized in that: The following steps are involved: Heating and melting the metal material to obtain a metal material melt; The isotropic porous carbon material is placed in the metal material melt for compounding to obtain the porous carbon reinforced metal composite material.

7. A porous carbon material vapor-deposited silicon composite material, characterized in that: It comprises a porous carbon skeleton and silicon deposited in the porous carbon skeleton; the porous carbon skeleton is an isotropic porous carbon material prepared by the preparation method according to claim 1 or 2.

8. The method for preparing the porous carbon material vapor-deposited silicon composite material according to claim 7, characterized in that: The following steps are involved: The isotropic porous carbon material is ground into powder, and then a reaction gas is introduced under an inert gas condition to perform vapor deposition, wherein the reaction gas includes hydrogen and silane gas, to obtain the porous carbon material vapor-deposited silicon composite material.

9. Use of the porous carbon-reinforced resin composite material according to claim 3, the porous carbon-reinforced resin composite material prepared by the preparation method according to claim 4, the porous carbon-reinforced metal composite material according to claim 5, or the porous carbon-reinforced metal composite material prepared by the preparation method according to claim 6 in aerospace structural parts or automotive structural parts.

10. Use of the porous carbon material vapor-deposited silicon composite material according to claim 7 or the porous carbon material vapor-deposited silicon composite material prepared by the preparation method according to claim 8 as a negative electrode material in the field of lithium batteries.

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