CN109192985B - ZIF-9-based porous carbon/carbon fiber composite material and preparation method thereof - Google Patents
ZIF-9-based porous carbon/carbon fiber composite material and preparation method thereof Download PDFInfo
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Abstract
A ZIF-9-based porous carbon/carbon fiber composite material and a preparation method thereof belong to the technical field of preparation methods of metal nanoparticle doped porous carbon/carbon fiber conductive composite materials, and can solve the problems of poor conductivity and poor stability of the existing composite carbon materials.
Description
Technical Field
The invention belongs to the technical field of preparation methods of metal nanoparticle doped porous carbon/carbon fiber conductive composite materials, and particularly relates to a ZIF-9 based porous carbon/carbon fiber composite carbon material and a preparation method thereof, wherein ZIF-9 in high-density arrangement is grown on carbon fibers of a carbon fiber fabric, and then the ZIF-9 based porous carbon/carbon fiber composite material in high-density arrangement is generated through pyrolysis.
Background
The MOFs is constructed by organic ligand and inorganic metal or metal cluster-containing siteThe formed product has the characteristic of infinite extension of a uniform structure, has adjustability in structure and function, and becomes one of the research fields with the fastest chemical development speed; the structure of the MOFs can be constructed purposefully based on the geometrical mode of coordination of the organic ligand to the metal or metal cluster. The main structural characteristics of the porous material are that the porous material has ultrahigh porosity and internal specific surface area, which plays a crucial role in the fields of functional applications such as gas storage and separation, catalysis, sensing, proton conduction, drug sustained release and the like [ Jiano L, Wang Y, Jiang H L, et al]. Advanced Materials, 2017: 1703663.](ii) a MOFs as a kind of porous crystal materials with diversity and adjustability have unique advantages, can be used as a precursor to prepare a porous carbon or carbon nano composite material through one-step pyrolysis, and the pyrolyzed material has the advantages of high specific surface area, large porosity, unchanged morphology and higher stability; in recent years, MOFs are used as precursors to prepare carbon materials, and the MOFs are frequently used as electrode materials; wherein, CN200910048847.6 reports a method for preparing a porous carbon electrode material by a single-source compound one-step decomposition method, a metal organic framework material MOF-5 is adopted as a raw material, and N is2Pyrolyzing under the protection of atmosphere, obtaining porous carbon through one-step pyrolysis, and then preparing the porous carbon electrode material for the supercapacitor; the method has the advantages that the carbon source is single, the carbon content is low, and the conductivity of the material is poor; the material is powdery, and the long-term stability of the electrode is limited by the aid of a conductive adhesive when the three-dimensional porous electrode structure is formed; CN201510717297.8 reports a preparation method of an iron-based metal organic framework compound/graphene composite material, in which an iron-based metal organic framework compound is grown on a graphene lamellar structure in situ to form a graphene composite iron-based MOF material; in addition, CN201710888868.3 reports a multi-walled carbon nanotube/metal organic framework composite material and a preparation method thereof, in which modified multi-walled carbon nanotubes, terephthalic acid and ferric trichloride hexahydrate are dispersed in an organic solvent to perform a solvothermal reaction, so as to obtain the multi-walled carbon nanotube/metal organic framework composite material; although the two methods produce conductive carbon materials by different methods,the conductivity of the composite material is improved to a certain extent, but the MOF material has poor conductivity and is in a powder shape, so that the composite material still has the defects of poor conductivity, poor stability and the like when being used for preparing electrodes.
Disclosure of Invention
Aiming at the problems of poor conductivity and poor stability of the existing composite carbon material, the invention provides a ZIF-9-based porous carbon/carbon fiber composite material which is formed by growing ZIF-9 arranged in high density on carbon fibers of a carbon fiber fabric and then performing pyrolysis, and a preparation method of the ZIF-9-based porous carbon/carbon fiber composite material.
The invention adopts the following technical scheme:
the ZIF-9-based porous carbon/carbon fiber composite material is characterized in that carbon fibers of carbon fiber fabrics are used as a growth substrate, ZIF-9 arranged in a high density mode is grown on the growth substrate, and the carbon fibers are carbonized at high temperature in an inert gas atmosphere to generate the porous carbon/carbon fiber composite material, wherein the diameter range of the carbon fibers is 0.1-50 mu m, the growth thickness of the ZIF-9-based porous carbon is 20-180 mu m, and the growth density of the ZIF-9-based porous carbon per unit area is 5-25 mg/cm2And the skeleton size of the ZIF-9-based porous carbon particles is 5 x 5-55 x 55 mu m.
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite material comprises the following steps:
step one, carbon fiber surface pretreatment of carbon fiber fabric:
placing the carbon fiber fabric in isopropanol, ultrasonically cleaning for 5-60min, drying at 80 ℃ in the air atmosphere, and carrying out heat treatment at 800 ℃ for 1-12 h in the inert gas atmosphere; then, treating the mixture for 6 to 36 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the mixture in an organic amine solvent at 50 ℃ for 24 hours, and drying the mixture for later use;
step two, preparing a ZIF-9/carbon fiber three-dimensional composite material:
weighing cobalt salt according to a proportion, dissolving the cobalt salt in an organic solvent I to obtain a solution I, wherein the proportion of the cobalt salt to the organic solvent I is 0.015-0.03g:1mL, weighing benzimidazole according to a proportion, dissolving the benzimidazole in an organic solvent II to obtain a solution II, wherein the proportion of the benzimidazole to the organic solvent II is 0.026-0.052g:1mL, transferring the solution I into a high-pressure reaction kettle, soaking the carbon fiber fabric pretreated in the first step for 5-60min, transferring the solution II into the high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 80-100 ℃, keeping for 6-48 h, then heating to 100-150 ℃, keeping for 6-48 h, and naturally cooling to 25 ℃ after the reaction is finished; taking out the reacted material, washing the material with deionized water for 3-5 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber three-dimensional composite material;
thirdly, preparing a ZIF-9-based porous carbon/carbon fiber composite material:
and (3) putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the second step into a tube furnace, heating to 150 ℃ at the speed of 1-10 ℃/min in the inert gas atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the cooling speed of 1-5 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
In the first step, the organic amine solvent comprises one or any mixture of hydrazine, triethanolamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, ethanolamine, diethanolamine and tannic acid.
The inert gas in the first step includes any one of argon, nitrogen and helium.
The carbon fiber fabric in the first step includes any one of carbon fiber cloth, carbon fiber tape, carbon fiber paper, carbon fiber felt and carbon fiber sheet.
In the second step, the cobalt salt comprises one or any mixture of cobalt nitrate, cobalt acetate tetrahydrate, cobalt carbonate hexahydrate and cobalt sulfate heptahydrate.
In the second step, the organic solvent I comprises any one of N, N-dimethylformamide, N-methylpyrrolidone, ethanol, butanol, acetone, cyclohexane, cyclohexanone and methyl butanone.
The organic solvent II in the second step comprises any one of N, N-dimethylformamide, N-methylpyrrolidone, ethanol, butanol, acetone, cyclohexane, cyclohexanone and methyl butanone.
The invention has the following beneficial effects:
the method comprises the steps of directly growing a tightly combined high-density ZIF-9 on carbon fibers, and then obtaining a three-dimensional self-supporting porous carbon conductive material through a pyrolysis process; wherein, the multilayer carbon fibers are crossed and overlapped to form a stable conductive network, the appearance of the stable conductive network is not obviously changed in the pyrolysis process, and the stable conductive network is suitable for being used as an electrode three-dimensional current collector; the pyrolyzed ZIF-9 belongs to nitrogen-doped graphitized porous carbon and has the characteristics of high porosity, high specific surface area and high conductivity; the metal nano particles formed by in-situ doping metal particles and nitrogen-doped carbon substances are taken as cores, the nitrogen-doped carbon is taken as a shell structure M @ N-C mesoporous composite carbon material, and the composite carbon material is suitable for being used as a storage host and a catalytic and conductive material; the nanometer metal particle doped porous carbon/carbon fiber nanometer composite material formed by the direct growth of ZIF-9 and carbon fiber through the close combination of chemical bonds has the advantages of stable conductive frame structure, high conductivity, uniform pore structure, large pore volume, high specific surface area, catalysis and the like, and is suitable for preparing electrodes of lithium sulfur batteries, sodium sulfur batteries, lithium air batteries, fuel batteries and the like.
According to the invention, the carbon fibers on the carbon fiber fabric are used as carriers, so that the contact area between the surface of the carbon fibers and the ZIF-9 crystal is increased, the problems of low utilization rate of a carbon fiber substrate, unstable conductive network and the like are solved, and the ZIF-9-based porous carbon and conductive substrate integrated conductive network structure is realized.
The ZIF-9-based porous carbon/carbon fiber conductive composite material prepared by the method is formed into an M @ N-C structure mesoporous composite carbon material by in-situ doped metal particles and a nitrogen-doped carbon substance, has a catalytic effect on chemical reactions, and has the advantages of catalytic effect, large specific surface area and stable conductive network.
According to the invention, high-density ZIF-9 directly grows on carbon fibers of a carbon fiber fabric, and then a high-density porous carbon/carbon fiber conductive composite material is formed through a pyrolysis process, so that the high-density porous carbon/carbon fiber conductive composite material has a wide application prospect in the fields of fuel cells, sodium-sulfur batteries, lithium air batteries, super capacitors, lithium-sulfur batteries, catalysis and the like; for lithium-sulfur batteries, ZIF-9-based porous carbon/carbon fiber composites can provide high specific surface area, and a large number of hierarchical pores in the material can carry a large amount of active material; the uniformly distributed metal nano particles can bidirectionally catalyze the oxidation-reduction reaction of sulfur in the cathode; the carbon fibers on the carbon fiber fabric are used as a current collector, and the porous carbon is directly and tightly combined with the carbon fibers, so that a conductive network is stable, and a dense and smooth transmission channel is provided for electrons.
Drawings
FIG. 1 is a schematic structural view of ZIF-9 grown on carbon fibers of the present invention;
FIG. 2 is a schematic cross-sectional view of ZIF-9 grown on carbon fibers of the present invention;
FIG. 3 is a schematic structural view of ZIF-9 grown on a carbon fiber fabric of the present invention;
FIG. 4 is a side view of an SEM image of a ZIF-9/carbon fiber three-dimensional composite of the present invention;
FIG. 5 is a front view of an SEM image of a ZIF-9/carbon fiber three-dimensional composite of the present invention;
wherein: 1-carbon fibers; 2-ZIF-9 crystal.
Detailed Description
Example 1
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon fiber fabric:
placing the carbon fiber fabric in isopropanol, ultrasonically cleaning for 30 min, drying the carbon fiber fabric at 80 ℃ in the air atmosphere, and carrying out heat treatment for 6h at 600 ℃ in the Ar atmosphere; then, treating the mixture for 12 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the mixture in ethylenediamine at 50 ℃ for 24 hours, and drying the mixture for later use;
(2) preparing a ZIF-9/carbon fiber three-dimensional composite material:
0.6 g of Co (NO) is weighed3)2•6H2O (dissolved in 40 mL of N, N-Dimethylformamide (DMF) (solution I), 0.52 g of Benzimidazole (BIM) is weighed and dissolved in 20 mL of N, N-Dimethylformamide (DMF) (solution II), the solution I is poured into a high-pressure reaction kettle, the carbon fiber fabric pretreated in the step (1) is soaked in the solution I, and the solution I is preservedHolding for 30 min, transferring the solution II into a high-pressure reaction kettle, and sealing; heating the high-pressure reaction kettle to 80 ℃ for 48 h, then heating to 130 ℃ for 48 h, and cooling to room temperature after the reaction is finished; and taking out the reacted material, washing the material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material.
(3) Preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tubular furnace, heating to 150 ℃ at the speed of 3 ℃/min under the atmosphere of Ar, keeping the temperature for 2 h, then heating to 900 ℃ and keeping the temperature for 5 h, and finally cooling to room temperature at the cooling speed of 3 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
Example 2
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon paper:
placing carbon paper with carbon fiber diameter of 10 μm in isopropanol, ultrasonic cleaning for 60min, oven drying at 80 deg.C in air atmosphere, and drying with N2Heat treatment is carried out for 10 hours at 600 ℃ in the atmosphere; then, treating the mixture for 24 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the raw materials in hydrazine for 24 hours at 50 ℃, and drying the raw materials for later use;
(2) preparing a ZIF-9/carbon fiber three-dimensional composite material:
1.2 g CoCO was weighed3•6H2Dissolving O in 40 mL of nitrogen methyl pyrrolidone (solution I), weighing 1.04 g of Benzimidazole (BIM) and dissolving in 20 mL of nitrogen methyl pyrrolidone (solution II), pouring the solution I into a high-pressure reaction kettle, soaking the carbon paper pretreated in the step (1) in the solution I for 30 min, transferring the solution II into the high-pressure reaction kettle and sealing; heating the high-pressure reaction kettle to 100 ℃ for 12 h, then heating to 130 ℃ for 12 h, and cooling to room temperature after the reaction is finished; taking out the reacted material, washing the reacted material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material;
(3) preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tube furnace, and adding N2Heating to 150 ℃ at the speed of 5 ℃/min in the air atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the speed of 3 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
The performance parameters of the resulting ZIF-9-based porous carbon/carbon fiber composite are shown in the following table
Example 3
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite carbon material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon felt:
placing carbon felt with carbon fiber diameter of 1 μm in isopropanol, ultrasonic cleaning for 5 min, oven drying at 80 deg.C in air atmosphere, and drying with N2Heat treatment is carried out for 6 hours at 600 ℃ in the atmosphere; then, treating the mixture for 12 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the mixture in triethanolamine at 50 ℃ for 24 hours, and drying the mixture for later use;
(2) preparing a ZIF-9/carbon fiber three-dimensional composite material:
0.9 g CoSO was weighed out4•7H2Dissolving O in 40 mL of ethanol (solution I), weighing 0.78 g of Benzimidazole (BIM) and dissolving in 20 mL of ethanol (solution II), pouring the solution I into a high-pressure reaction kettle, soaking the carbon felt pretreated in the step (1) in the solution I for 20 min, transferring the solution II into the high-pressure reaction kettle, and sealing; heating the high-pressure reaction kettle to 80 ℃ and maintaining for 48 h, then heating to 110 ℃ and maintaining for 48 h, and cooling to room temperature after the reaction is finished; taking out the reacted material, washing the reacted material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material;
(3) preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, the methodPutting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tube furnace, and N2Heating to 150 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the speed of 3 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
Example 4
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite carbon material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon felt:
placing a carbon felt with the carbon fiber diameter of 50 microns in isopropanol, ultrasonically cleaning for 40 min, drying at 80 ℃ in the air atmosphere, and carrying out heat treatment for 6h at 600 ℃ in the Ar atmosphere; then, treating the mixture for 36 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the mixture in tannic acid for 24 hours at 50 ℃, and drying the mixture for later use;
(2) preparing a three-dimensional composite material ZIF-9/carbon fiber:
weighing 1.2 g of cobalt acetate tetrahydrate, dissolving in 40 mL of acetone (solution I), weighing 1.0 g of Benzimidazole (BIM), dissolving in 20 mL of acetone (solution II), pouring the solution I into a high-pressure reaction kettle, soaking the carbon felt pretreated in the step (1) in the solution I for 40 min, transferring the solution II into the high-pressure reaction kettle, and sealing; heating the high-pressure reaction kettle to 80 ℃ for 48 h, then heating to 100 ℃ for 48 h, and cooling to room temperature after the reaction is finished; taking out the reacted material, washing the reacted material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material;
(3) preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tube furnace, and adding N2Heating to 150 ℃ at the speed of 10 ℃/min in the air atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the speed of 3 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
Example 5
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite carbon material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon cloth:
placing carbon cloth with the diameter of 0.1 mu m in isopropanol, ultrasonically cleaning for 20 min, drying at 80 ℃ in air atmosphere, and carrying out heat treatment for 1 h at 800 ℃ under Ar atmosphere; then, treating the mixture for 6 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking in ethanolamine at 50 ℃ for 24 h, and drying for later use;
(2) preparing a ZIF-9/carbon fiber three-dimensional composite material:
weighing 1.2 g of cobalt acetate tetrahydrate, dissolving the cobalt acetate tetrahydrate in 40 mL of N, N-Dimethylformamide (DMF) (solution I), weighing 1.0 g of Benzimidazole (BIM), dissolving the benzimidazole in 20 mL of N, N-Dimethylformamide (DMF) (solution II), pouring the solution I into a high-pressure reaction kettle, soaking the carbon cloth pretreated in the step (1) in the solution I for 5 min, transferring the solution II into the high-pressure reaction kettle, and sealing; heating the high-pressure reaction kettle to 80 ℃ for 6h, then heating to 150 ℃ for 6h, and cooling to room temperature after the reaction is finished; taking out the reacted material, washing the reacted material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material;
(3) preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tube furnace, and adding N2Heating to 150 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the speed of 1 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
Example 6
A preparation method of a ZIF-9-based porous carbon/carbon fiber composite carbon material is implemented, and the preparation method is sequentially carried out according to the following steps:
(1) pretreatment of the fiber surface of the carbon cloth:
placing carbon cloth with the diameter of 5 mu m in isopropanol, ultrasonically cleaning for 50 min, drying at 80 ℃ in air atmosphere, and carrying out heat treatment for 12 h at 300 ℃ under Ar atmosphere; then, treating the mixture for 20 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking in diethanolamine for 24 h at 50 ℃, and drying for later use;
(2) preparing a ZIF-9/carbon fiber three-dimensional composite material:
0.8 g CoSO was weighed4•7H2Dissolving O in 40 mL of butanol (solution I), weighing 0.94 g of Benzimidazole (BIM) to be dissolved in 20 mL of butanol (solution II), pouring the solution I into a high-pressure reaction kettle, soaking the carbon cloth pretreated in the step (1) in the solution I for 60min, transferring the solution II into the high-pressure reaction kettle, and sealing; heating the high-pressure reaction kettle to 80 ℃ for 36h, then heating to 110 ℃ for 36h, and cooling to room temperature after the reaction is finished; taking out the reacted material, washing the reacted material with deionized water for 3 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber composite material;
(3) preparing a ZIF-9-based porous carbon/carbon fiber composite material:
firstly, putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the step (2) into a tube furnace, and adding N2Heating to 150 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the speed of 5 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
The above embodiments are preferred embodiments of the present invention, and the ZIF-9-based metal oxide porous carbon/carbon fiber composite carbon material can be prepared according to the above embodiments, and the morphology is shown in the figure; the technology controls the growth density and quality of ZIF-9-based porous carbon on carbon fibers by changing conditions such as a preparation method of ZIF-9, the type of carbon fiber fabric, the concentration ratio of reactants, the type of cobalt salt and the like.
Claims (7)
1. The ZIF-9-based porous carbon/carbon fiber composite material takes carbon fibers of carbon fiber fabrics as a growth substrate, ZIF-9 arranged in a high density manner grows on the growth substrate, and is carbonized at high temperature in an inert gas atmosphere to generate the porous carbon/carbon fiber composite material, wherein the diameter range of the carbon fibers is 0.1-50 μm, the growth thickness of the ZIF-9-based porous carbon is 20-180 μm, and the growth density per unit area of the ZIF-9-based porous carbon is 5-25 mg/cm2The ZIF-9-based porous carbon particle has a skeleton size of 5 x 5 to 55 x 55 μm, and is characterized in that: the preparation method comprises the following steps:
step one, carbon fiber surface pretreatment of carbon fiber fabric:
placing the carbon fiber fabric in isopropanol, ultrasonically cleaning for 5-60min, drying at 80 ℃ in the air atmosphere, and carrying out heat treatment at 800 ℃ for 1-12 h in the inert gas atmosphere; then, treating the mixture for 6 to 36 hours by using concentrated nitric acid in a high-pressure reaction kettle at the temperature of 150 ℃, washing the mixture to be neutral by using deionized water, and drying the mixture; finally, soaking the mixture in an organic amine solvent at 50 ℃ for 24 hours, and drying the mixture for later use;
step two, preparing a ZIF-9/carbon fiber three-dimensional composite material:
weighing cobalt salt according to a proportion, dissolving the cobalt salt in an organic solvent I to obtain a solution I, wherein the proportion of the cobalt salt to the organic solvent I is 0.015-0.03g:1mL, weighing benzimidazole according to a proportion, dissolving the benzimidazole in an organic solvent II to obtain a solution II, wherein the proportion of the benzimidazole to the organic solvent II is 0.026-0.052g:1mL, transferring the solution I into a high-pressure reaction kettle, soaking the carbon fiber fabric pretreated in the first step for 5-60min, transferring the solution II into the high-pressure reaction kettle, sealing, heating the high-pressure reaction kettle to 80-100 ℃, keeping for 6-48 h, then heating to 100-150 ℃, keeping for 6-48 h, and naturally cooling to 25 ℃ after the reaction is finished; taking out the reacted material, washing the material with deionized water for 3-5 times, and drying the material at 60 ℃ to obtain the ZIF-9/carbon fiber three-dimensional composite material;
thirdly, preparing a ZIF-9-based porous carbon/carbon fiber composite material:
and (3) putting the ZIF-9/carbon fiber three-dimensional composite material prepared in the second step into a tube furnace, heating to 150 ℃ at the speed of 1-10 ℃/min in the inert gas atmosphere, keeping for 2 h, heating to 900 ℃ again, keeping for 5 h, and finally cooling to room temperature at the cooling speed of 1-5 ℃/min to obtain the ZIF-9-based porous carbon/carbon fiber composite material.
2. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: in the first step, the organic amine solvent comprises one or any mixture of hydrazine, triethanolamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, ethanolamine, diethanolamine and tannic acid.
3. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: the inert gas atmosphere in the first step includes any one of argon, nitrogen and helium.
4. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: the carbon fiber fabric in the first step includes any one of carbon fiber cloth, carbon fiber tape, carbon fiber paper, and carbon fiber felt.
5. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: in the second step, the cobalt salt comprises one or any mixture of cobalt nitrate, cobalt acetate tetrahydrate, cobalt carbonate hexahydrate and cobalt sulfate heptahydrate.
6. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: in the second step, the organic solvent I comprises any one of N, N-dimethylformamide, N-methylpyrrolidone, ethanol, butanol, acetone, cyclohexane, cyclohexanone and methyl butanone.
7. The method of making a ZIF-9-based porous carbon/carbon fiber composite of claim 1, wherein: the organic solvent II in the second step comprises any one of N, N-dimethylformamide, N-methylpyrrolidone, ethanol, butanol, acetone, cyclohexane, cyclohexanone and methyl butanone.
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