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

Abstract

The present application belongs to the field of composite materials and lithium batteries, and particularly relates to a preparation method of isotropic porous carbon material, a porous carbon reinforced nonmetal or metal composite material and a preparation method and application thereof. Liquid polyacrylonitrile oligomers are subjected to heat treatment technology under a protective atmosphere to obtain a porous carbon precursor material; the porous carbon precursor material is subjected to high-temperature graphitization enhancement technology under a protective atmosphere to obtain a porous carbon material; and quantitative pore making is performed by controlling oxygen flow under an oxygen atmosphere to obtain an isotropic porous carbon material with uniform pore structure distribution. The above-prepared isotropic porous carbon material is used as a reinforcing phase to be combined with metal or nonmetal to prepare composite materials with different properties, so as to improve the performance of the composite materials, which can be applied to lightweight high-strength structural parts in the fields of aerospace and automobile industry, and can also be used as negative electrode materials in the field of lithium batteries.

Description

TECHNICAL FIELD

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

[0002] The porous carbon material can be used in the field of material science as a reinforcing phase in a composite material to improve the mechanical properties, electrical conductivity and heat resistance of the material; due to the uniform distribution of micropores, the porous carbon can also be used as a carrier for nano-silicon in the field of lithium batteries to make negative electrode materials. The porous carbon reinforced metallic composite material has high specific strength, excellent thermal conductivity, electrical conductivity, ductility and wear resistance. The addition of the porous carbon reinforcing phase in a non-metallic matrix can significantly improve the mechanical properties, electrical conductivity, thermal conductivity and thermal stability of the material. The porous carbon reinforced composite material has a wide application prospect in the fields of automobiles, aerospace, electronics and optical instruments.

[0003] However, the performance of the current porous carbon composite material is greatly affected due to the non-uniform pore structure of the porous carbon. SUMMARY

[0004] The present application provides a preparation method of isotropic porous carbon material, a porous carbon reinforced non-metallic or metallic composite material and a preparation method and application thereof. The preparation method provided by the present application can obtain isotropic porous carbon material with uniform pore structure distribution, which is beneficial to improve the performance of the porous carbon composite material.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] The present application provides a preparation method of isotropic porous carbon material, which comprises the following steps:

[0007] The liquid polyacrylonitrile oligomer is heat treated in a protective gas atmosphere to prepare a porous carbon precursor material, and the temperature of the heat treatment is < 240 DEG C.

[0008] The porous carbon precursor material is graphitized in a protective gas atmosphere to obtain a porous carbon material.

[0009] The porous carbon material is quantitatively pore-formed in an oxygen atmosphere to obtain isotropic porous carbon material with uniform pore structure distribution, and the flow rate of the oxygen is 30-150 mL / min, and the temperature of the quantitative pore formation is < 500 DEG C.

[0010] Preferably, the temperature of the heat treatment is 180-230 DEG C, the time is 1-6h; the temperature rising rate from room temperature to the temperature of the heat treatment is 3-10 DEG C / min; the protective gas of the heat treatment comprises one or more of nitrogen, helium and argon;

[0011] The temperature of the graphitization treatment is 1000-3000 DEG C, the time is 1-10h, the temperature rising rate from room temperature to the temperature of the graphitization treatment is 3-10 DEG C / min, and the protective gas of the graphitization treatment comprises one or more of nitrogen, helium and argon.

[0012] The temperature of the quantitative pore forming is 300-450 DEG C, and the time is 1-6h.

[0013] The present application provides a porous carbon reinforced resin composite material, comprising 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 described in the above technical solution.

[0014] The present application provides a preparation method of the porous carbon reinforced resin composite material described in the above technical solution, comprising the following steps:

[0015] The isotropic porous carbon material is immersed in a resin solution for compounding to obtain the porous carbon reinforced resin composite material.

[0016] The present application provides a porous carbon reinforced metal composite material, comprising a porous carbon skeleton and a metal material compounded 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.

[0017] The present application provides a preparation method of the porous carbon reinforced metal composite material described in the above technical solution, comprising the following steps:

[0018] The metal material is heated and melted to obtain a metal material melt;

[0019] The isotropic porous carbon material is placed in the metal material melt for compounding to obtain the porous carbon reinforced metal composite material.

[0020] The present application provides a porous carbon material vapor deposition 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.

[0021] The present application provides a preparation method of the porous carbon material vapor deposition silicon composite material described in the above technical solution, comprising the following steps:

[0022] The isotropic porous carbon material is ground into powder, and then gas phase deposition is carried out under the condition of inert gas by introducing a reaction gas, the reaction gas comprising hydrogen and silane gas, to obtain the porous carbon material gas phase deposition silicon composite material.

[0023] The application provides application of the porous carbon reinforced resin composite material or the porous carbon reinforced metal composite material in aerospace structural parts or automobile structural parts.

[0024] The application provides application of the porous carbon material gas phase deposition silicon composite material as a negative electrode material in the field of lithium batteries.

[0025] The application provides a preparation method of an isotropic porous carbon material, comprising the following steps: heat treatment of liquid polyacrylonitrile oligomers in a protective gas atmosphere to prepare a porous carbon precursor material, wherein the heat treatment temperature is less than 240 DEG C; graphitization treatment of the porous carbon precursor material in a protective gas atmosphere to obtain a porous carbon material; and quantitative pore forming of the porous carbon material in an oxygen atmosphere to obtain an isotropic porous carbon material with uniform pore structure distribution, wherein the oxygen flow rate is 30-150 mL / min, and the quantitative pore forming temperature is less than 500 DEG C. The isotropic porous carbon material is prepared by using liquid polyacrylonitrile oligomers as raw materials, heat treatment and graphitization treatment, and reasonable optimization of the heat treatment temperature range, and then the porous carbon material is subjected to quantitative pore forming in an oxygen atmosphere, so that the isotropic porous carbon material with uniform pore structure distribution can be prepared by optimizing the oxygen flow rate and the quantitative pore forming temperature. The isotropic porous carbon material prepared by the method can be used as a reinforcing phase to prepare a composite material, so that the uniformity of the composite material can be improved, and the performance of the composite material can be improved.

[0026] In conclusion, the isotropic porous carbon material prepared by the method has a three-dimensional structure and high strength and strong adsorption and shaping capacity. Meanwhile, the preparation method is low in preparation cost, simple in preparation method and easy for industrial production.

[0027] The application provides a porous carbon reinforced resin composite material, comprising a porous carbon framework and resin material filled in the porous carbon framework; the porous carbon framework is an isotropic porous carbon material prepared by the preparation method in the above technical solution.

[0028] The application provides a porous carbon reinforced metal composite material, comprising a porous carbon framework and metal material filled in the porous carbon framework, the porous carbon framework is an isotropic porous carbon material prepared by the preparation method in the above technical solution, and the metal material comprises a metal element and / or metal alloy.

[0029] The application provides a porous carbon material vapor deposition silicon composite material, comprising a porous carbon framework and silicon deposited in the porous carbon framework; the porous carbon framework is an isotropic porous carbon material prepared by the preparation method in the above technical solution.

[0030] In summary, the porous carbon reinforced resin composite material, the porous carbon reinforced metal composite material and the porous carbon material vapor deposition silicon composite material provided by the application have the following advantages: the isotropic porous carbon material is used as the carbon framework, the isotropic porous carbon material is combined with resin material, metal material or silicon material, and the uniformity of the composite material is significantly improved.

[0031] The application provides a preparation method of the porous carbon reinforced resin composite material, the porous carbon reinforced metal composite material and the porous carbon material vapor deposition silicon composite material. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 A photograph of the isotropic porous carbon material product with uniform pore structure distribution prepared in Example 1 of the present application;

[0033] Figure 2 A photograph of the isotropic porous carbon material product with 94% porosity prepared in Example 2 of the present application;

[0034] Figure 3 A photograph of the isotropic porous carbon material product with 94% porosity prepared in Example 3 of the present application;

[0035] Figure 4 A photograph of the isotropic porous carbon material product with 94% porosity prepared in Example 4 of the present application. DETAILED DESCRIPTION

[0036] The present application provides a preparation method of isotropic porous carbon material, comprising the following steps:

[0037] The liquid polyacrylonitrile oligomer is heat treated in a protective gas atmosphere to prepare a porous carbon precursor material, and the temperature of the heat treatment is < 240℃.

[0038] The porous carbon precursor material is graphitized in a protective gas atmosphere to obtain a porous carbon material.

[0039] The porous carbon material is quantitatively pore-formed in an oxygen atmosphere to obtain an isotropic porous carbon material with uniform pore structure distribution, and the flow rate of the oxygen is 30-150 mL / min, and the temperature of the quantitative pore-formation is < 500℃.

[0040] In the present application, all the raw materials / components are commercially available products well known to those skilled in the art, unless otherwise specified.

[0041] The liquid polyacrylonitrile oligomer is heat treated in a protective gas atmosphere to prepare a porous carbon precursor material, and the temperature of the heat treatment is < 240℃.

[0042] In the present application, the liquid polyacrylonitrile oligomer (LPAN) is in a liquid state, and the molecular weight of the liquid polyacrylonitrile oligomer is 100-100000, and the chemical structural formula is as follows:

[0043] .

[0044] In the present application, the heat-treated preparation raw material preferably further comprises a pore-forming material and / or a filling material. The pore-forming material preferably comprises one or more of inorganic oxide, salt and organic material. In the present application, the inorganic oxide is preferably copper oxide. The salt is preferably copper acetate. The organic material is preferably polyacrylonitrile powder. The filling material preferably comprises one or more of polyacrylonitrile powder and carbon nanotube.

[0045] In the present application, when the heat-treated preparation raw material further comprises a pore-forming material and / or a filling material, the mass ratio of the pore-forming material and / or the filling material to the liquid polyacrylonitrile oligomer is preferably 0.5:1. In the present application, when the heat-treated preparation method further comprises a pore-forming material and / or a filling material, before the heat treatment, the present application preferably further comprises mixing the liquid polyacrylonitrile oligomer, the pore-forming material and the filling material to obtain a mixture, and subjecting the mixture to the heat treatment. When the heat-treated preparation method further comprises a pore-forming material and a filling material, the present application does not have special requirements for the mass ratio of the pore-forming material to the filling material.

[0046] In the present application, the heat treatment is preferably carried out in a container, which can be a sagger. The heat treatment is preferably carried out in a sintering furnace. The temperature of the heat treatment is preferably 180-230℃, and in the embodiments can be 220℃. The time of the heat treatment is preferably 1-6h, and in the embodiments can be 4h. The heating rate from room temperature to the temperature of the heat treatment is preferably 3-10℃ / min, and more preferably 5-8℃ / min. The protective gas of the heat treatment preferably comprises one or more of nitrogen, helium and argon, and in the embodiments can be nitrogen or argon. By optimizing the temperature, time and heating rate of the heat treatment, the present application can effectively control the generation rate of the porous carbon precursor material, and obtain a porous carbon precursor material with optimized pore structure, and a porous carbon material with optimized pore structure after graphitization treatment.

[0047] After obtaining the porous carbon precursor material, the porous carbon precursor material is subjected to graphitization treatment in a protective gas atmosphere to obtain the porous carbon material. In the present application, the graphitization treatment is preferably performed in a sintering furnace. The temperature of the graphitization treatment is preferably 900-3000°C, more preferably 1000-2000°C, and can be 1400°C in the examples. The time of the graphitization treatment is preferably 1-10h, more preferably 2-8h, and further preferably 2.5-6h, and can be 3h in the examples. The temperature rising rate from room temperature to the temperature of the graphitization treatment is preferably 3-10°C / min, and more preferably 5-8°C / min. The protective gas of the graphitization treatment preferably includes one or more of nitrogen, helium, and argon, and can be nitrogen or argon in the examples. The present application enhances the strength of the material by controlling the degree of graphitization of the material by adjusting the graphitization temperature.

[0048] After obtaining the porous carbon material, the porous carbon material is subjected to quantitative pore formation in an oxygen atmosphere to obtain an isotropic porous carbon material with uniform pore structure distribution, and the flow rate of the oxygen is 30-150mL / min, and the temperature of the quantitative pore formation is <500°C.

[0049] The present application controls the quantitative pore formation in an oxygen atmosphere by controlling the flow rate of the oxygen.

[0050] In the present application, the temperature of the quantitative pore formation is preferably 300-450°C, and can be 400°C in the examples. The time of the quantitative pore formation is preferably 1-6h, and more preferably 2-5h, and can be 3h in the examples. The present application controls the degree of oxidation and the number of micropores of the material by adjusting the temperature and time of the quantitative pore formation, thereby obtaining an isotropic porous carbon material with uniform pore structure distribution, strong hydrophilicity, and high specific surface area.

[0051] The isotropic porous carbon material with uniform pore structure distribution prepared in the present application has an expansion rate of <400%, and preferably 30-200%. The isotropic porous carbon material with uniform pore structure distribution has a porosity of <97%, and preferably 47-94%.

[0052] In the examples of the present application, when the raw material is a liquid polyacrylonitrile oligomer, the isotropic porous carbon material with uniform pore structure distribution can have an expansion rate of 200% and a porosity of 94%. When the raw material further includes the pore-forming material and / or the filler material described above, the porous carbon material can have an expansion rate of 50% and a porosity of 47%.

[0053] The application provides the isotropic porous carbon material with uniform pore structure distribution prepared by the preparation method.

[0054] The isotropic porous carbon material with uniform pore structure distribution provided by the application has a three-dimensional structure, can shape metal or non-metal in a carbon skeleton composite material, and has high wettability and strong adsorption.

[0055] The application provides a porous carbon reinforced resin composite material, which comprises a porous carbon skeleton and a resin material compounded in the porous carbon skeleton.

[0056] In the application, the resin material is preferably epoxy resin.

[0057] The application provides a preparation method of the porous carbon reinforced resin composite material, which comprises the following steps:

[0058] The isotropic porous carbon material is impregnated in a resin solution for compounding to obtain the porous carbon reinforced resin composite material.

[0059] In the application, the resin solution is preferably an epoxy resin solution.

[0060] In the present application, the compounding is preferably carried out under vacuum. The compounding is preferably carried out in a protective gas atmosphere, and the protective gas preferably comprises nitrogen and / or argon. In the present application, the compounding preferably comprises sequentially carrying out first-stage compounding and second-stage compounding. The pressure of the first-stage compounding is preferably -0.08~ -0.05 MPa, and can be -0.08 MPa in an embodiment; the time is preferably 1~10 min, and can be 2 min in an embodiment. The pressure of the second-stage compounding is preferably 0.05~0.08 MPa, and can be 0.08 MPa in an embodiment; the time is preferably 1~10 min, and can be 2 min in an embodiment. In the present application, the obtained material is subjected to heat curing after the compounding is completed, to obtain the porous carbon reinforced resin composite material. The temperature of the heat curing is preferably 80℃.

[0061] The present application provides a porous carbon reinforced metal composite material, comprising a porous carbon skeleton and a metal material compounded 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.

[0062] In the present application, the metal element preferably comprises aluminum element, copper element, iron element, cobalt element or nickel element, and can be aluminum element in an embodiment. The metal alloy preferably comprises aluminum alloy, copper alloy, iron alloy, cobalt alloy or nickel alloy, and can be aluminum alloy in an embodiment. The present application does not have special requirements for the composition of the metal alloy.

[0063] The present application provides a preparation method of the porous carbon reinforced metal composite material described in the above technical solution, comprising the following steps:

[0064] Melting the metal material by heating to obtain a metal material melt;

[0065] Compounding the isotropic porous carbon material in the metal material melt to obtain the porous carbon reinforced metal composite material.

[0066] In the present application, the temperature of the heating and melting is preferably 800~1600℃, and can be 1000℃ in an embodiment.

[0067] After obtaining the metal material melt, the present application compounds the isotropic porous carbon material in the metal material melt to obtain the porous carbon reinforced metal composite material.

[0068] In the present application, the compounding is preferably carried out under vacuum. The compounding is preferably carried out in a protective gas atmosphere, and the protective gas preferably comprises nitrogen and / or argon. In the present application, the placing is preferably soaking the isotropic porous carbon material in the metal material melt. The compounding preferably comprises sequentially carrying out first-stage compounding and second-stage compounding. The pressure of the first-stage compounding is preferably -0.08~ -0.05 MPa, and in an embodiment can be -0.08 MPa; the time is preferably 1~10 min, and in an embodiment can be 2 min. The pressure of the second-stage compounding is preferably 0.05~0.08 MPa, and in an embodiment can be 0.08 MPa; the time is preferably 1~10 min, and in an embodiment can be 2 min. In the present application, the obtained material is cooled after the compounding is completed, to obtain the porous carbon reinforced metal composite material.

[0069] The present application provides the application of the porous carbon reinforced resin composite material in the above technical solution or the porous carbon reinforced resin composite material prepared by the preparation method in the above technical solution or the application of the porous carbon reinforced metal composite material in the above technical solution or the porous carbon reinforced metal composite material prepared by the preparation method in the above technical solution in aerospace structural parts or automobile structural parts.

[0070] The present application provides a porous carbon material vapor deposition 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 in the above technical solution.

[0071] The present application provides a preparation method of the porous carbon material vapor deposition silicon composite material in the above technical solution, comprising the following steps:

[0072] The isotropic porous carbon material is ground into powder, then heated to the vapor deposition temperature under the condition of inert gas, and then the reaction gas comprising hydrogen and silane gas is introduced for vapor deposition, to obtain the porous carbon material vapor deposition silicon composite material.

[0073] In the present application, the inert gas is preferably argon. In the present application, the raw material for preparing the silane gas is preferably liquid silane, and the liquid silane is preferably dichlorodimethylsilane. In the present application, the silane gas is preferably prepared by heating the liquid silane to 80℃ by water bath.

[0074] In the present application, when the vapor deposition is carried out, the liquid silane water bath is heated and evaporated, the evaporated silane gas is transported into the vapor deposition reactor by inert gas, then the mixed gas of hydrogen and inert gas is introduced into the vapor deposition reactor, and then the vapor deposition is carried out. The volume content of hydrogen in the mixed gas of hydrogen and inert gas is preferably 5-8%, and in the examples, it can be 8%. The flow rate of the mixed gas of hydrogen and inert gas is preferably 50-60sccm. The flow rate of the inert gas for transporting the silane gas is preferably 80-100sccm.

[0075] In the present application, the temperature of the vapor deposition is preferably 750-900℃, and the holding time is preferably 0.5-2h. In the examples, the temperature of the vapor deposition can be 850℃, and the holding time can be 1h. In the present application, after the vapor deposition is completed, the material obtained by the vapor deposition is cooled under the protection of the gas to obtain the porous carbon composite nano-silicon negative electrode material.

[0076] The present application provides the application of the porous carbon material vapor deposition silicon composite material in the field of lithium batteries as a negative electrode material.

[0077] The porous carbon reinforced metal / non-metal composite material prepared by the simple method of the present application realizes the construction of the three-dimensional structure of the porous carbon. The isotropic porous carbon material with uniform pore structure distribution obtained by the pore forming of the porous carbon under the oxygen atmosphere and the increase of the oxidation groups on the surface of the porous carbon significantly improves the hydrophilicity, thereby improving the wettability of the isotropic porous carbon material to the molten metal material. The metal material or non-metal material uniformly penetrates into the interior of the isotropic porous carbon material. The adsorbability of the isotropic porous carbon material effectively limits the flow of the molten metal / non-metal, thereby shaping the porous carbon reinforced metal / non-metal composite material. Therefore, the porous carbon reinforced metal / non-metal composite material has the lightweight, high strength, wear resistance, electrical conductivity and thermal conductivity.

[0078] In order to further illustrate the present application, the technical solutions provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0079] Example 1: Preparation of isotropic porous carbon material with uniform pore structure distribution

[0080] The liquid polyacrylonitrile oligomer is placed in the crucible, and is heat treated at a temperature of 220℃ for 4 hours under the inert atmosphere (argon) of the sintering furnace.

[0081] Then, under the condition of argon, high-temperature graphitization treatment is carried out at a temperature of 1400 DEG C for 3 hours.

[0082] Finally, the oxygen flow is adjusted to 100 mL / min, and directional pore forming treatment is carried out under the condition of oxygen at a temperature of 400 DEG C for 3 hours, so that the isotropic porous carbon material with uniform pore structure distribution is obtained. Figure 1 A physical map of the isotropic porous carbon material product with uniform pore structure distribution prepared in Example 1 of the present application.

[0083] Example 2: Preparation of porous carbon reinforced aluminum metal composite material

[0084] The liquid polyacrylonitrile oligomer is placed in a sagger, and heat treatment is carried out under the inert atmosphere (argon) of a sintering furnace at a temperature of 220 DEG C for 4 hours, then high-temperature graphitization treatment is carried out under the condition of argon at a temperature of 1400 DEG C for 3 hours, and finally directional pore forming treatment is carried out under the condition of oxygen at a temperature of 400 DEG C for 3 hours with the oxygen flow being adjusted to 100 mL / min, so that the isotropic porous carbon material with uniform pore structure distribution is obtained.

[0085] The aluminum metal particles are placed in a melting furnace and melted at 1000 DEG C, then the isotropic porous carbon material with uniform pore structure distribution is immersed in the molten metal, the environmental pressure is adjusted to -0.08 MPa and kept for 2 min, then the environmental pressure is adjusted to 0.08 MPa and kept for 2 min, then the isotropic porous carbon material after aluminum alloy melting is taken out of the melting furnace and cooled, so that the porous carbon reinforced aluminum metal composite material is obtained.

[0086] Example 3: Preparation of porous carbon reinforced epoxy resin composite material

[0087] The liquid polyacrylonitrile oligomer is placed in a sagger, and heat treatment is carried out under the inert atmosphere (argon) of a sintering furnace at a temperature of 220 DEG C for 4 hours, then high-temperature graphitization treatment is carried out under the condition of argon at a temperature of 1400 DEG C for 3 hours, and finally directional pore forming treatment is carried out under the condition of oxygen at a temperature of 400 DEG C for 3 hours with the oxygen flow being adjusted to 100 mL / min, so that the isotropic porous carbon material with uniform pore structure distribution is obtained.

[0088] The A glue and B glue of the epoxy resin are mixed (the mass ratio of A glue to B glue is 2:1) to obtain an epoxy resin solution, then the isotropic porous carbon material with uniform pore structure distribution is immersed in the epoxy resin solution, and composite is carried out at 80 DEG C; the environmental pressure is adjusted to -0.08 MPa and kept for 2 min, then the environmental pressure is adjusted to 0.08 MPa and kept for 2 min, then the epoxy resin is gelled under the condition of constant temperature of 80 DEG C and normal pressure, then the porous carbon after epoxy resin composite is cooled, so that the porous carbon reinforced epoxy resin composite material is obtained. Figure 3A photograph of a resin composite material reinforced by the isotropic porous carbon material with 94% porosity prepared in Example 3.

[0089] Example 4: Preparation of a porous carbon material vapor deposition silicon composite material

[0090] The liquid polyacrylonitrile oligomer was placed in a sagger, and heat treated at a temperature of 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace, and then high-temperature graphitized at a temperature of 1400°C for 3 hours under an argon atmosphere, and finally subjected to directional pore forming treatment at a temperature of 400°C for 3 hours under an oxygen atmosphere with an oxygen flow rate of 100 mL / min, to obtain an isotropic porous carbon material with uniform pore structure distribution.

[0091] The isotropic porous carbon material with uniform pore structure distribution was ground into powder, and the ground isotropic porous carbon powder was placed in a vapor deposition reaction kettle and heated to 850°C under an inert atmosphere (argon); dichlorodimethylsilane was evaporated by heating in a water bath to 80°C, to obtain silane gas, which was then delivered into the vapor deposition reaction kettle by argon gas at a flow rate of 100 sccm; a mixed gas of hydrogen and argon (H2 / Ar mixed gas with an H2 content of 8 vol%) was introduced into the vapor deposition reaction kettle at a flow rate of 60 sccm, to perform vapor deposition at a temperature of 850°C for 1 h; a porous carbon material vapor deposition silicon composite material (400°C@8%H2-Si-CVD) was obtained.

[0092] Comparative Example 1: 97% porosity porous carbon prepared by heat treatment at 240°C

[0093] The liquid polyacrylonitrile oligomer was placed in a sagger, and heat treated at a temperature of 240°C for 4 hours under an inert atmosphere (argon) in a sintering furnace;

[0094] and then high-temperature graphitized at a temperature of 1400°C for 3 hours under an argon atmosphere;

[0095] and finally subjected to directional pore forming treatment at a temperature of 400°C for 3 hours under an oxygen atmosphere with an oxygen flow rate of 100 mL / min, to obtain an isotropic porous carbon material.

[0096] Comparative Example 2: preparation of a porous carbon reinforced aluminum metal composite material

[0097] The liquid polyacrylonitrile oligomer was placed in a sagger, and heat treated at a temperature of 220°C for 4 hours under an inert atmosphere (argon) in a sintering furnace, and then high-temperature graphitized at a temperature of 1400°C for 3 hours under an argon atmosphere, to obtain a porous carbon material.

[0098] The aluminum metal particles were placed in a melting furnace, and melted at 1000℃; then the prepared porous carbon material was immersed in the molten metal, the pressure of the molten environment was adjusted to -0.08 MPa, and was kept for 2 min, then the pressure of the molten environment was adjusted to 0.08 MPa, and was kept for 2 min; then the molten composite porous carbon was taken out of the melting furnace, thereby obtaining a porous carbon reinforced aluminum-based metal composite material.

[0099] Test Example 1: Porous carbon with different porosities

[0100] The isotropic porous carbon material prepared by pre-burning (i.e. heat treatment) the liquid polyacrylonitrile oligomer at 220℃ in Example 1 had an expansion rate of 200% and a porosity of 94%, and the pores were relatively uniform; while the isotropic porous carbon prepared by pre-burning the liquid polyacrylonitrile oligomer at 240℃ in Comparative Example 1 had an expansion rate of 400% and a porosity of 97%, and the pores were relatively large. As can be seen from Table 1, too high a pre-burning temperature (240℃) can result in an isotropic porous carbon material with too large an expansion rate and too large a porosity, and the isotropic porous carbon material has poor mechanical properties. The expansion rate in Table 1 = (thickness of porous carbon / thickness of initial slurry) x 100%. The porosity data in Table 1 was measured by the Archimedes principle, and the porosity = volume of water immersed in the porous carbon / (effective volume of porous carbon + volume of water immersed in the porous carbon) x 100%.

[0101] Table 1 Comparison of expansion rate and porosity of isotropic porous carbon materials prepared in Example 1 and Comparative Example 1

[0102]

[0103] Test Example 2: Oil-wettability and water-wettability of porous carbon material

[0104] The isotropic porous carbon material prepared in Example 1 has excellent oil-wettability, which is beneficial for the penetration of non-metallic polymers and the preparation of porous carbon reinforced non-metallic composite materials, but has poor water-wettability, and water droplets cannot spontaneously penetrate the material surface and will float on the water surface in water; the porous carbon material prepared in Example 2 has excellent oil-wettability and water-wettability, and water droplets can instantly penetrate into the material, and can sink to the bottom of the water.

[0105] Table 2 Oil-wettability and water-wettability of materials prepared in Example 1 and the blank group

[0106]

[0107] The preparation method of the blank group in Table 2: liquid polyacrylonitrile oligomer was put into a crucible, and heat treated at a temperature of 220°C for 4 hours in a sintering furnace inert atmosphere (argon); then high-temperature graphitized at a temperature of 1400°C for 3 hours under argon to obtain a porous carbon material.

[0108] Test Example 3: Effect of controlled quantitative pore forming on the material

[0109] The isotropic porous carbon material prepared from Example 1 has excellent lipophilicity, hydrophilicity, a specific surface area of 15.00 m 2 / g, which is conducive to the penetration and adsorption of non-metallic polymers and molten metals, and the strength is not much different from that of the blank group without quantitative pore forming; the total pore volume of the blank group (graphitized product) increases from 0.0018 cm 3 / g to 0.0050 cm 3 / g, which is 2.77 times that of the porous carbon prepared by the blank group, and the number of micropores increases significantly, thereby making the material have a large specific surface area and strong adsorption force on molten metal. The degree of oxidation in Table 3 = (weight before quantitative pore forming / weight after quantitative pore forming) x 100%.

[0110] Table 3: Comparison of properties of materials prepared by Example 1 and the blank group

[0111]

[0112] The preparation method of the blank group in Table 3: liquid polyacrylonitrile oligomer was put into a crucible, and heat treated at a temperature of 220°C for 4 hours in a sintering furnace inert atmosphere (argon); then high-temperature graphitized at a temperature of 1400°C for 3 hours under argon to obtain a porous carbon material.

[0113] Test Example 4: Effect of whether the porous carbon is quantitatively pore-formed on the composite aluminum metal material

[0114] Example 2, Comparative Example 2, Example 2 uses isotropic porous carbon material prepared by quantitative pore forming technology to prepare porous carbon reinforced aluminum metal composite material, and from the cross-sectional view of the sample Figure 2 , it can be seen that the aluminum metal in the composite material uniformly penetrates into the interior of the porous carbon; while Comparative Example 2 uses porous carbon material without pore forming to prepare the composite material, the surface of the sample is aluminum metal while the interior is still porous carbon. By comparison, it can be confirmed that the isotropic porous carbon material prepared by the quantitative pore forming technology has high wettability with aluminum metal, the polar groups in it are compatible with aluminum metal, and due to the increase in the number of micropores after pore forming, the material has strong adsorption, which can actively adsorb molten aluminum, thereby preparing the porous carbon reinforced aluminum composite material with high uniformity.

[0115] The tensile strength of the sample porous carbon reinforced aluminum-based metal composite (400℃ C@Al) of Example 2 is 1010 MPa, the tensile modulus is 112 GPa, the thermal conductivity is 410 W / (m·k), the electrical conductivity is 60 MS / m, and the wear rate (dry grinding) is 9.0 x 10 -5 mm 3 / (Nm).

[0116] The isotropic porous carbon material with uniform pore structure prepared by 400℃ pore forming is used to reinforce the aluminum-based metal, and the uniformity of the aluminum-based metal is high, and the strength, wear resistance, and thermal and electrical conductivity of the aluminum-based metal are significantly improved.

[0117] Table 4 Mechanical properties of products of Example 2, Comparative Example 2 and the blank group

[0118]

[0119] Table 5 Wear resistance and electrical and thermal conductivity of the product prepared in Example 2

[0120]

[0121] Test Example 5: Porous carbon reinforced epoxy resin composite

[0122] The tensile strength of the porous carbon reinforced resin composite prepared in Example 3 is 130 MPa, and the elastic modulus is 5.5 GPa, which is significantly improved.

[0123] Table 6 Mechanical properties of the porous carbon reinforced resin composite prepared in Example 3

[0124]

[0125] Test Example 6: Porous carbon vapor-deposited silicon composite

[0126] Figure 4 The charge-discharge curve of the 94% porosity isotropic porous carbon material vapor-deposited silicon composite prepared in Example 4 as a negative electrode is shown in the figure. The specific capacity of the porous carbon vapor-deposited silicon composite prepared in Example 4 as a silicon negative electrode material is 389.09 mAh / g, which is 136.68 mAh / g higher than that of the porous carbon oxidized at 400℃. The capacity is significantly improved, and at the same time, after high-temperature sintering, the initial efficiency is also improved to 80.50%.

[0127] Table 7 Performance of the porous carbon vapor-deposited silicon composite button cell

[0128]

[0129] The blank group in Table 7 is the isotropic porous carbon material with uniform pores prepared in Example 4.

[0130] The porous carbon reinforced non-metallic composite material and the porous carbon reinforced metallic composite material provided by the application have light weight, high strength, excellent wear resistance and electric and thermal conductivity, and can be applied to the preparation of light-weight high-strength structural parts in the fields of aerospace, automobile industry and the like.

[0131] Although the above embodiments have made a detailed description of the application, it is only a part of the embodiments of the application, not all the embodiments, and other embodiments can be obtained under the premise of no creativity according to the embodiments, and these embodiments all belong to the protection scope of the application.

Claims

1. A method for producing an isotropic porous carbon material, characterized by, The method comprises the following steps: The liquid polyacrylonitrile oligomer is heat-treated in a protective gas atmosphere to obtain a porous carbon precursor material, wherein the heat treatment temperature is 180-230℃; The porous carbon precursor material is graphitized in a protective gas atmosphere to obtain a porous carbon material, wherein the graphitization temperature is 1000-2000℃; The porous carbon material is quantitatively pore-formed in an oxygen atmosphere to obtain an isotropic porous carbon material with uniform pore structure, wherein the oxygen flow rate is 30-150mL / min, and the quantitative pore-forming temperature is 300-450℃.

2. The production method according to claim 1, characterized by, The heat treatment time is 1-6h, the temperature rising rate from room temperature to the heat treatment temperature is 3-10℃ / min, and the protective gas for the heat treatment comprises one or more of nitrogen, helium and argon; The graphitization time is 1-10h, the temperature rising rate from room temperature to the graphitization temperature is 3-10℃ / min, and the protective gas for the graphitization comprises one or more of nitrogen, helium and argon; The quantitative pore-forming time is 1-6h.

3. A porous carbon-reinforced resin composite, characterized by, The porous carbon material comprises a porous carbon skeleton and a resin material compounded in the porous carbon skeleton, wherein the porous carbon skeleton is the isotropic porous carbon material prepared by the preparation method of claim 1 or 2.

4. The method of producing a porous carbon-reinforced resin composite material according to claim 3, characterized by, The method comprises the following steps: The isotropic porous carbon material is impregnated in a resin solution to obtain the porous carbon reinforced resin composite material.

5. A porous carbon reinforced metal composite, characterized by, The porous carbon material comprises a porous carbon skeleton and a metal material compounded in the porous carbon skeleton, wherein the porous carbon skeleton is the isotropic porous carbon material prepared by the preparation method of claim 1 or 2, and the metal material comprises a metal element and / or a metal alloy.

6. The method for producing a porous carbon reinforced metal composite according to claim 5, characterized by, The method comprises the following steps: The metal material is heated and melted to obtain a metal material melt; The isotropic porous carbon material is compounded in the metal material melt to obtain the porous carbon reinforced metal composite material.

7. A porous carbon material gas-phase deposited silicon composite material, characterized by, The porous carbon material comprises a porous carbon skeleton and silicon deposited in the porous carbon skeleton, wherein the porous carbon skeleton is the isotropic porous carbon material prepared by the preparation method of claim 1 or 2.

8. The method for producing a porous carbon material gas phase deposition silicon composite material according to claim 7, characterized by, The method comprises the following steps: The isotropic porous carbon material is ground into powder, and then a reaction gas comprising hydrogen and silane gas is introduced for gas phase deposition under the condition of inert gas to obtain the porous carbon material gas phase deposition silicon composite material.

9. The application of the porous carbon reinforced resin composite material of claim 3 or the porous carbon reinforced resin composite material prepared by the preparation method of claim 4 or the porous carbon reinforced metal composite material of claim 5 or the porous carbon reinforced metal composite material prepared by the preparation method of claim 6 in aerospace structural parts or automobile structural parts.

10. The application of the porous carbon material gas phase deposition silicon composite material of claim 7 or the porous carbon material gas phase deposition silicon composite material prepared by the preparation method of claim 8 as a negative electrode material in the field of lithium batteries.

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