CN103215693B - Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof - Google Patents
Graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to graphene-oxide-modified phenolic-resin-based ultrafine porous carbon fiber and a preparation method thereof. The diameter of the fiber is in a range of 0.3-1.7mum, and the specific surface area of the fiber is 500-900m<2>/g. The fiber has a porous structure which is formed by microporous mainly. Micro-pore volume is 0.20-0.50cm<3>/g, and surface oxygen atomic ratio is lower than 10%. The preparation method comprises the steps that: graphene oxide is added into an organic solvent and is subjected to ultrasonic dispersion, such that a graphene oxide solution is formed; termosetting phenolic resin and a high-molecular-weight linear polymer are added into the graphene oxide organic solution, and are completely dissolved by stirring; the mixed solution is spun into composite fiber, and solidification and carbonization are carried out, such that porous phenolic-resin-based carbon/graphite oxide composite ultrafine fiber is obtained. The sources of adopted raw materials are rich. The prepared composite fiber has the advantages of high structural stability, good flexibility, developed pore structure, controllable surface oxygen content, and suitability for practical application.
Description
Technical field
The invention belongs to porous carbon fiber technical field, relate to alkyd resin based ultra-fine porous carbon fiber and the preparation method of the modification of a kind of graphene oxide.
Background technology
The ultra-fine porous carbon fiber prepared by electrostatic spinning and subsequent heat treatment is paid close attention in Application Areass such as adsoption catalysis, biologic medical and energy energy storage widely because having the advantages such as high specific area, flourishing pore structure and self supporting structure.Up to the present the precursor for the preparation of ultra-fine porous carbon fiber is mainly polyacrylonitrile (PAN).But PAN fiber carbonization yield is low, very low without its specific area of activation, almost there is no pore structure.And alkyd resin based charcoal fine fibre charcoal productive rate is high, only namely obtain flourishing pore structure after charing, people are caused more and more to pay close attention to.
Graphene oxide becomes good nano-filled dose owing to having excellent character, and its abundant oxygen-containing functional group and pleated structure can impel and form stronger interface with macromolecule matrix.Therefore we propose a kind of employing in graphene oxide interpolation phenolic resins, are prepared the method for activated carbon composite fiber by method of electrostatic spinning.Electrostatic spinning is the effective ways preparing superfine fibre, and the good in a solvent dispersiveness of graphene oxide can not affect the spinnability of Polymer Solution.Pore structure and the Surface Oxygen functional group content of ultrafine carbon fiber can be regulated and controled by adding graphene oxide.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the alkyd resin based ultra-fine porous carbon fiber that the object of the present invention is to provide a kind of graphene oxide to modify and preparation method, commercially available thermosetting phenolic resin is mixed with graphene oxide and is dissolved in organic solvent and forms precursor solution, utilize method of electrostatic spinning to prepare the graphene oxide/phenolic resins composite fibre of uniformly continous.The advantage such as have that specific area is high, microcellular structure is flourishing, structural stability is strong through the ultrafine carbon fiber that solidification, charing are obtained and pliability is good.
To achieve these goals, the technical solution used in the present invention is:
The alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified, the diameter range of this fiber is 0.3 ~ 1.7 μm, and specific area is 500 ~ 900m
2/ g, has the loose structure based on micropore, and Micropore volume is 0.20 ~ 0.50cm
3/ g, surface oxygen atoms ratio is lower than 10%.
Based on the preparation method of the alkyd resin based ultra-fine porous carbon fiber that above-mentioned graphene oxide is modified, comprise the following steps:
Step one, adds graphene oxide in organic solvent, and it is 2.0 ~ 16.4mg/mL graphene oxide solution that ultrasonic disperse is made into concentration, and described organic solvent is ethanol, methyl alcohol, acetone, normal propyl alcohol or DMF;
Step 2, be the ratio of 1:0.010 ~ 0.024:0.01 ~ 0.10 in thermosetting phenolic resin, high molecular weight linear polymer and graphene oxide mass ratio, thermosetting phenolic resin and high molecular weight linear polymer are joined in graphene oxide solution, this mixed solution is stirred to and dissolves completely; Described high molecular weight linear polymer is the mixture of PVP, polyvinyl butyral resin, polyvinyl alcohol, polyacrylonitrile or above-mentioned arbitrary proportion several arbitrarily; Described thermosetting phenolic resin is commercially available prod, molecular weight 600<M
w<3000
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 20-30kV, and feed liquor speed is 1mL/h, operating distance 20-30cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 1 ~ 3 hour again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 800 DEG C ~ 1000 DEG C inert atmospheres or reducing atmosphere, obtain graphene oxide/alkyd resin based charcoal composite superfine porous fibre, inert atmosphere is nitrogen or argon gas; Reducing atmosphere is hydrogen, or the arbitrary proportion mist of hydrogen and nitrogen, or the arbitrary proportion mist of hydrogen and argon gas.
Thermosetting phenolic resin molecular weight in the present invention, the spinnability of solution is poor, therefore needs to mix high molecular weight linear polymer to improve spinnability.Its softening point of phenolic resins of molecular weight is low in addition, and directly when higher temperature, solidification can make fiber adhesion, destroys fibre structure.Therefore need staged to be heating and curing technique, heat the long period when low temperature, ensure phenolic resins molecule full cross-linked can not occur molten also, improve speed when high temperature and shorten hardening time.
The present invention has the following advantages: between graphene oxide oxygen-containing functional group and phenolic resins molecules hydroxyl groups the formation of hydrogen bond impel graphene oxide to be dispersed in macromolecule matrix and both promoting to be formed between strong interface interaction, thus define more stable network structure, heat endurance is improved, and gained charcoal/graphene oxide composite ultrafine fiber pliability improves; After graphene oxide adds, composite fibre has flourishing pore structure, and the specific area of charcoal/graphene oxide composite ultrafine fiber and pore structure can realize controllable variations by adjustment carbonization temperature; During by regulating graphene oxide addition or carbonizing, atmosphere used can prepare the composite ultrafine fiber with different surfaces oxygen content; Phenolic resins molecular weight used is low, and preparation cost is low, and graphene oxide raw material sources are extensive, and fiber has the slabbing structure and morphology of self-supporting, and these advantageous refinements all will be suitable for this composite fibre in the practical application better of the fields such as adsoption catalysis.
Accompanying drawing explanation
Fig. 1 is phenolic resins/graphene oxide composite fibre (a) of the embodiment of the present invention one and comparative example one preparation and the thermogravimetric curve of pure phenolic resin fiber (b).
Fig. 2 is the pattern photo of the alkyd resin based ultra-fine porous carbon fiber of graphene oxide modification prepared by the embodiment of the present invention one.
Fig. 3 is the pattern photo of the ultra-fine porous carbon fiber of alkyd resin based charcoal of comparative example one of the present invention preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment one
The present embodiment comprises the following steps:
Step one, adds graphene oxide in acetone, and it is 7.0mg/mL graphene oxide acetone soln that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.020:0.03 in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl butyral resin are joined in graphene oxide acetone soln, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 23kV, and feed liquor speed is 1mL/h, operating distance 24cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 800 DEG C of nitrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
As shown in Figure 1a, as shown in Figure 2, diameter range is 0.4 ~ 1.6 μm to the microscopic appearance of step 4 gained composite fibre to the thermogravimetric curve of phenolic resins/graphene oxide composite fibre that step 3 obtains, and specific area is 553m
2/ g, Micropore volume is 0.22cm
3/ g, surface oxygen atoms ratio is 4.95%.
Embodiment two
The present embodiment comprises the following steps:
Step one, adds graphene oxide in ethanol, and it is 12.1mg/mL graphene oxide ethanolic solution that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.024:0.05 in thermosetting phenolic resin, PVP and graphene oxide mass ratio, thermosetting phenolic resin and PVP are joined in graphene oxide ethanolic solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2300;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 22cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 1.5 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of argon gas atmosphere, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
This composite fibre diameter range is 0.5 ~ 1.7 μm, and specific area is 658m
2/ g, Micropore volume is 0.32cm
3/ g, surface oxygen atoms ratio is 8.32%.
Embodiment three
The present embodiment comprises the following steps:
Step one, adds graphene oxide in acetone, and it is 8.3mg/mL graphene oxide acetone soln that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.018:0.02 in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl butyral resin are joined in graphene oxide acetone soln, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 24cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of hydrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
The diameter range of gained composite fibre is 0.3 ~ 1.5 μm, and specific area is 628m
2/ g, Micropore volume is 0.28cm
3/ g, surface oxygen atoms ratio is 4.63%.
Embodiment four
The present embodiment comprises the following steps:
Step one, adds graphene oxide in methyl alcohol, and it is 13.2mg/mL graphene oxide methanol solution that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.024:0.05 in thermosetting phenolic resin, PVP and graphene oxide mass ratio, thermosetting phenolic resin and PVP are joined in graphene oxide methanol solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2300;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 25cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of hydrogen/argon gas atmosphere, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
This composite fibre diameter range is 0.4 ~ 1.6 μm, and specific area is 524m
2/ g, Micropore volume is 0.20cm
3/ g, surface oxygen atoms ratio is 6.70%.
Embodiment five
The present embodiment comprises the following steps:
Step one, adds graphene oxide in ethanol, and ultrasonic disperse is made into concentration 15.4mg/mL graphene oxide ethanolic solution;
Step 2, be the ratio of 1:0.020:0.06 in thermosetting phenolic resin, polyvinyl alcohol and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl alcohol are joined in graphene oxide ethanolic solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 23kV, and feed liquor speed is 1mL/h, operating distance 25cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 3 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 1000 DEG C of nitrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
This composite fibre diameter range is 0.4 ~ 1.7 μm, and specific area is 900m
2/ g, Micropore volume is 0.50cm
3/ g, surface oxygen atoms ratio is 3.08%.
Comparative example one
According to the method for embodiment one, do not add graphene oxide, direct electrospinning thermosetting phenolic resin fiber, obtain pure Thermosetting Phenolic charcoal superfine fibre through solidification, charing.As shown in Figure 1 b, the heat endurance of visible pure phenolic resin fiber is not as phenolic resins/graphene oxide composite fibre compared with embodiment one Fig. 1 a for the thermogravimetric curve of pure phenolic resin fiber.As shown in Figure 3, diameter range is 0.4 ~ 1.6 μm to pure charcoal superfine fibre microscopic appearance, and specific area is 615m
2/ g, Micropore volume is 0.26cm
3/ g, surface oxygen atoms ratio is 4.11%, and the pure fiber surface oxygen content of not adding graphene oxide is as can be seen here lower.The pliability of pure porous charcoal superfine fibre does not have the good of composite fibre yet in addition.
Claims (6)
1. the preparation method of the alkyd resin based ultra-fine porous carbon fiber of graphene oxide modification, it is characterized in that, the diameter range of this fiber is 0.3 ~ 1.7 μm, and specific area is 500 ~ 900m
2/ g, has the loose structure based on micropore, and Micropore volume is 0.20 ~ 0.50cm
3/ g, surface oxygen atoms ratio is lower than 10%; Preparation method comprises the following steps:
Step one, adds graphene oxide in organic solvent, and it is 2.0 ~ 16.4mg/mL graphene oxide solution that ultrasonic disperse is made into concentration, and described organic solvent is ethanol, methyl alcohol, acetone, normal propyl alcohol or DMF;
Step 2, be the ratio of 1:0.010 ~ 0.024:0.01 ~ 0.10 in thermosetting phenolic resin, high molecular weight linear polymer and graphene oxide mass ratio, thermosetting phenolic resin and high molecular weight linear polymer are joined in graphene oxide solution, this mixed solution is stirred to and dissolves completely; Described high molecular weight linear polymer is PVP, polyvinyl butyral resin, polyvinyl alcohol, polyacrylonitrile or above-mentioned mixture several arbitrarily; Described thermosetting phenolic resin is commercially available prod, molecular weight 600<M
w<3000
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 20-30kV, and feed liquor speed is 1mL/h, operating distance 20-30cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 1 ~ 3 hour again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 800 DEG C ~ 1000 DEG C inert atmospheres or reducing atmosphere, obtain graphene oxide/alkyd resin based charcoal composite superfine porous fibre, inert atmosphere is nitrogen or argon gas; Reducing atmosphere is hydrogen, or the arbitrary proportion mist of hydrogen and nitrogen, or the arbitrary proportion mist of hydrogen and argon gas.
2. preparation method according to claim 1, is characterized in that, comprises the following steps:
Step one, adds graphene oxide in acetone, and it is 7.0mg/mL graphene oxide acetone soln that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.020:0.03 in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl butyral resin are joined in graphene oxide acetone soln, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 23kV, and feed liquor speed is 1mL/h, operating distance 24cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 800 DEG C of nitrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
3. preparation method according to claim 1, is characterized in that, comprises the following steps:
Step one, adds graphene oxide in ethanol, and it is 12.1mg/mL graphene oxide ethanolic solution that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.024:0.05 in thermosetting phenolic resin, PVP and graphene oxide mass ratio, thermosetting phenolic resin and PVP are joined in graphene oxide ethanolic solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2300;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 22cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 1.5 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of argon gas atmosphere, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
4. preparation method according to claim 1, is characterized in that, comprises the following steps:
Step one, adds graphene oxide in acetone, and it is 8.3mg/mL graphene oxide acetone soln that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.018:0.02 in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl butyral resin are joined in graphene oxide acetone soln, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 24cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of hydrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
5. preparation method according to claim 1, is characterized in that, comprises the following steps:
Step one, adds graphene oxide in methyl alcohol, and it is 13.2mg/mL graphene oxide methanol solution that ultrasonic disperse is made into concentration;
Step 2, be the ratio of 1:0.024:0.05 in thermosetting phenolic resin, PVP and graphene oxide mass ratio, thermosetting phenolic resin and PVP are joined in graphene oxide methanol solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2300;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 25kV, and feed liquor speed is 1mL/h, operating distance 25cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 2 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 850 DEG C of hydrogen/argon gas atmosphere, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
6. preparation method according to claim 1, is characterized in that, comprises the following steps:
Step one, adds graphene oxide in ethanol, and ultrasonic disperse is made into concentration 15.4mg/mL graphene oxide ethanolic solution;
Step 2, be the ratio of 1:0.020:0.06 in thermosetting phenolic resin, polyvinyl alcohol and graphene oxide mass ratio, thermosetting phenolic resin and polyvinyl alcohol are joined in graphene oxide ethanolic solution, be stirred to by this mixed solution and dissolve completely, thermosetting phenolic resin molecular weight is 2000;
Step 3, becomes composite ultrafine fiber by the mixed solution electrostatic spinning of step 2, and spinning voltage is 23kV, and feed liquor speed is 1mL/h, operating distance 25cm;
Step 4, after above-mentioned fiber is warming up to 180 DEG C from the non-at the uniform velocity staged of room temperature, solidify 3 hours again, non-at the uniform velocity staged heat up namely from the heating rate of room temperature to 60 DEG C be 40 DEG C/h, should lower than 4 DEG C/h at the heating rate of 60-80 DEG C, along with temperature raises, its heating rate also progressively improves, 40 DEG C/h can be increased to time more than 140 DEG C, then carbonize under 1000 DEG C of nitrogen atmospheres, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
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