CN103215693A - 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 PDF

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CN103215693A
CN103215693A CN2013100426476A CN201310042647A CN103215693A CN 103215693 A CN103215693 A CN 103215693A CN 2013100426476 A CN2013100426476 A CN 2013100426476A CN 201310042647 A CN201310042647 A CN 201310042647A CN 103215693 A CN103215693 A CN 103215693A
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graphene oxide
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thermosetting phenolic
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CN103215693B (en
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黄正宏
白宇
康飞宇
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Tsinghua University
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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

Alkyd resin based ultra-fine porous carbon fiber and preparation method that graphene oxide is modified
Technical field
The invention belongs to the porous carbon fiber technical field, relate to alkyd resin based ultra-fine porous carbon fiber and preparation method that a kind of graphene oxide is modified.
Background technology
Ultra-fine porous carbon fiber by the preparation of electrostatic spinning and subsequent heat treatment is subjected to paying close attention to widely in Application Areass such as adsoption catalysis, biologic medical and energy energy storage because of advantages such as pore structure with high specific area, prosperity and self supporting structures.Up to the present the precursor that is used to prepare ultra-fine porous carbon fiber is mainly polyacrylonitrile (PAN).But PAN fiber carbonization yield is low, and is very low without its specific area of activation, almost do not have pore structure.And alkyd resin based charcoal fine fibre charcoal productive rate height, only promptly obtain flourishing pore structure after the charing, cause that people more and more pay close attention to.
Graphene oxide becomes good nano-filled dose owing to having excellent character, and oxygen-containing functional group that it is abundant and pleated structure can impel with macromolecule matrix and form stronger interface.Therefore we propose to prepare the method for compound charcoal fiber by method of electrostatic spinning in a kind of employing graphene oxide interpolation phenolic resins.Electrostatic spinning is the effective ways of preparation superfine fibre, and graphene oxide good dispersiveness in solvent can not influence the spinnability of Polymer Solution.Can regulate and control the pore structure and the surperficial oxygen functional group content of ultrafine carbon fiber by adding graphene oxide.
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the alkyd resin based ultra-fine porous carbon fiber and the preparation method that the object of the present invention is to provide a kind of graphene oxide to modify, commercially available thermosetting phenolic resin mixed with graphene oxide be dissolved in organic solvent and form precursor solution, utilize method of electrostatic spinning to prepare evenly continuous graphene oxide/phenolic resins composite fibre.Through the ultrafine carbon fiber that solidifies, charing makes have specific area height, microcellular structure prosperity, advantage such as structural stability is strong 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 μ m, specific area is 500 ~ 900m 2/ g has the loose structure based on micropore, and the micropore pore volume is 0.20 ~ 0.50cm 3/ g, surperficial oxygen atom ratio is lower than 10%.
The preparation method of the alkyd resin based ultra-fine porous carbon fiber of modifying based on above-mentioned graphene oxide may further comprise the steps:
Step 1 adds graphene oxide in the organic solvent, and it is 2.0~16.4mg/ml graphene oxide solution that ultrasonic dispersion is made into concentration, and described organic solvent is ethanol, methyl alcohol, acetone, normal propyl alcohol or N, dinethylformamide;
Step 2, in thermosetting phenolic resin, high molecular weight linear polymer and graphene oxide mass ratio is the ratio of 1:0.010~0.024:0.01~0.10, thermosetting phenolic resin and high molecular weight linear polymer are joined in the graphene oxide solution, this mixed solution is stirred to dissolving fully; Described high molecular weight linear polymer is PVP, polyvinyl butyral resin, polyvinyl alcohol, polyacrylonitrile or the above-mentioned mixture of several arbitrary proportions arbitrarily; Described thermosetting phenolic resin is the commercially available prod, molecular weight 600<M w<3000
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 1~3 hour, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 800 ℃~1000 ℃ inert atmospheres or reducing atmosphere, carry out charing then, obtain graphene oxide/alkyd resin based charcoal composite superfine porous fibre, inert atmosphere is nitrogen or argon gas; Reducing atmosphere is a hydrogen, or the arbitrary proportion mist of hydrogen and nitrogen, or the arbitrary proportion mist of hydrogen and argon gas.
The thermosetting phenolic resin molecular weight is less among the present invention, and the spinnability of solution is relatively poor, therefore need mix the high molecular weight linear polymer to improve spinnability.Less its softening point of phenolic resins of molecular weight is low in addition, and directly curing can make fiber adhesion when higher temperature, destroys fibre structure.Therefore need the staged technology that is heating and curing, the heating long period when low temperature, guarantee the phenolic resins molecule full cross-linked can not take place molten also, when high temperature, improve speed and shorten hardening time.
The present invention has the following advantages: the formation of hydrogen bond impels graphene oxide to be dispersed in the macromolecule matrix and the two strong interface interaction of promotion formation between graphene oxide oxygen-containing functional group and the phenolic resins molecule hydroxyl, thereby formed more stable network structure, heat endurance is improved, and gained charcoal/graphene oxide composite ultrafine fiber pliability improves; After graphene oxide added, composite fibre had flourishing pore structure, and the specific area of charcoal/graphene oxide composite ultrafine fiber and pore structure can realize controllable variations by adjusting carbonization temperature; Used atmosphere can prepare the composite ultrafine fiber with different surfaces oxygen content during by adjusting graphene oxide addition or charing; Used phenolic resins molecular weight is low, and preparation cost is low, and the graphene oxide raw material sources are extensive, and fiber has the slabbing structure and morphology of self-supporting, and these favourable characteristics all will be suitable for this composite fibre in the practical application better of fields such as adsoption catalysis.
Description of drawings
Fig. 1 is the embodiment of the invention one and the phenolic resins/graphene oxide composite fibre (a) of Comparative Examples 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 modified of the graphene oxide of the embodiment of the invention one preparation.
Fig. 3 is the pattern photo of the ultra-fine porous carbon fiber of alkyd resin based charcoal of Comparative Examples one preparation of the present invention.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment one
Present embodiment may further comprise the steps:
Step 1 adds graphene oxide in the acetone, and it is 7.0mg/ml graphene oxide acetone soln that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio is the ratio of 1:0.020:0.03, thermosetting phenolic resin and polyvinyl butyral resin are joined in the graphene oxide acetone soln, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 800 ℃ of nitrogen atmospheres, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
The thermogravimetric curve of phenolic resins/graphene oxide composite fibre that step 3 obtains as shown in Figure 1a, the microscopic appearance of step 4 gained composite fibre as shown in Figure 2, diameter range is 0.4 ~ 1.6 μ m, specific area is 553m 2/ g, micropore pore volume are 0.22cm 3/ g, surperficial oxygen atom ratio is 4.95%.
Embodiment two
Present embodiment may further comprise the steps:
Step 1 adds graphene oxide in the ethanol, and it is 12.1mg/ml graphene oxide ethanolic solution that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, PVP and graphene oxide mass ratio is the ratio of 1:0.024:0.05, thermosetting phenolic resin and PVP are joined in the graphene oxide ethanolic solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2300;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 1.5 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of argon gas atmosphere, carry out charing then, 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 μ m, and specific area is 658m 2/ g, micropore pore volume are 0.32cm 3/ g, surperficial oxygen atom ratio is 8.32%.
Embodiment three
Present embodiment may further comprise the steps:
Step 1 adds graphene oxide in the acetone, and it is 8.3mg/ml graphene oxide acetone soln that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio is the ratio of 1:0.018:0.02, thermosetting phenolic resin and polyvinyl butyral resin are joined in the graphene oxide acetone soln, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of hydrogen atmospheres, carry out charing then, 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 μ m, and specific area is 628m 2/ g, micropore pore volume are 0.28cm 3/ g, surperficial oxygen atom ratio is 4.63%.
Embodiment four
Present embodiment may further comprise the steps:
Step 1 adds graphene oxide in the methyl alcohol, and it is 13.2mg/ml graphene oxide methanol solution that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, PVP and graphene oxide mass ratio is the ratio of 1:0.024:0.05, thermosetting phenolic resin and PVP are joined in the graphene oxide methanol solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2300;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of hydrogen/argon gas atmosphere, carry out charing then, 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 μ m, and specific area is 524m 2/ g, micropore pore volume are 0.20cm 3/ g, surperficial oxygen atom ratio is 6.70%.
Embodiment five
Present embodiment may further comprise the steps:
Step 1 adds graphene oxide in the ethanol, and ultrasonic dispersion is made into concentration 15.4mg/ml graphene oxide ethanolic solution;
Step 2, in thermosetting phenolic resin, polyvinyl alcohol and graphene oxide mass ratio is the ratio of 1:0.020:0.06, thermosetting phenolic resin and polyvinyl alcohol are joined in the graphene oxide ethanolic solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 3 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 1000 ℃ of nitrogen atmospheres, carry out charing then, 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 μ m, and specific area is 900m 2/ g, micropore pore volume are 0.50cm 3/ g, surperficial oxygen atom ratio is 3.08%.
Comparative Examples one
According to the method for embodiment one, do not add graphene oxide, directly electrospinning thermosetting phenolic resin fiber obtains pure thermosetting phenolic resin base charcoal superfine fibre through curing, charing.The thermogravimetric curve of pure phenolic resin fiber is shown in Fig. 1 b, and the heat endurance of comparing visible pure phenolic resin fiber with embodiment one Fig. 1 a is not as phenolic resins/graphene oxide composite fibre.Pure charcoal superfine fibre microscopic appearance as shown in Figure 3, diameter range is 0.4 ~ 1.6 μ m, specific area is 615m 2/ g, micropore pore volume are 0.26cm 3/ g, surperficial oxygen atom ratio is 4.11%, this shows that the pure fiber surface oxygen content of not adding graphene oxide is lower.The pliability of pure in addition porous charcoal superfine fibre does not have the good of composite fibre yet.

Claims (7)

1. the alkyd resin based ultra-fine porous carbon fiber of graphene oxide modification is characterized in that the diameter range of this fiber is 0.3 ~ 1.7 μ m, and specific area is 500 ~ 900m 2/ g has the loose structure based on micropore, and the micropore pore volume is 0.20 ~ 0.50cm 3/ g, surperficial oxygen atom ratio is lower than 10%.
2. the preparation method of the alkyd resin based ultra-fine porous carbon fiber of modifying based on the described graphene oxide of claim 1 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the organic solvent, and it is 2.0~16.4mg/ml graphene oxide solution that ultrasonic dispersion is made into concentration, and described organic solvent is ethanol, methyl alcohol, acetone, normal propyl alcohol or N, dinethylformamide;
Step 2, in thermosetting phenolic resin, high molecular weight linear polymer and graphene oxide mass ratio is the ratio of 1:0.010~0.024:0.01~0.10, thermosetting phenolic resin and high molecular weight linear polymer are joined in the graphene oxide solution, this mixed solution is stirred to dissolving fully; Described high molecular weight linear polymer is PVP, polyvinyl butyral resin, polyvinyl alcohol, polyacrylonitrile or above-mentioned several mixture arbitrarily; Described thermosetting phenolic resin is the commercially available prod, molecular weight 600<M w<3000
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 1~3 hour, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 800 ℃~1000 ℃ inert atmospheres or reducing atmosphere, carry out charing then, obtain graphene oxide/alkyd resin based charcoal composite superfine porous fibre, inert atmosphere is nitrogen or argon gas; Reducing atmosphere is a hydrogen, or the arbitrary proportion mist of hydrogen and nitrogen, or the arbitrary proportion mist of hydrogen and argon gas.
3. preparation method according to claim 2 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the acetone, and it is 7.0mg/ml graphene oxide acetone soln that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio is the ratio of 1:0.020:0.03, thermosetting phenolic resin and polyvinyl butyral resin are joined in the graphene oxide acetone soln, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 800 ℃ of nitrogen atmospheres, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
4. preparation method according to claim 2 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the ethanol, and it is 12.1mg/ml graphene oxide ethanolic solution that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, PVP and graphene oxide mass ratio is the ratio of 1:0.024:0.05, thermosetting phenolic resin and PVP are joined in the graphene oxide ethanolic solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2300;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified again 1.5 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate, along with temperature raises, its heating rate also progressively improves, can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of argon gas atmosphere, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
5. preparation method according to claim 2 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the acetone, and it is 8.3mg/ml graphene oxide acetone soln that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, polyvinyl butyral resin and graphene oxide mass ratio is the ratio of 1:0.018:0.02, thermosetting phenolic resin and polyvinyl butyral resin are joined in the graphene oxide acetone soln, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of hydrogen atmospheres, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
6. preparation method according to claim 2 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the methyl alcohol, and it is 13.2mg/ml graphene oxide methanol solution that ultrasonic dispersion is made into concentration;
Step 2, in thermosetting phenolic resin, PVP and graphene oxide mass ratio is the ratio of 1:0.024:0.05, thermosetting phenolic resin and PVP are joined in the graphene oxide methanol solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2300;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 2 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 850 ℃ of hydrogen/argon gas atmosphere, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
7. preparation method according to claim 2 is characterized in that, may further comprise the steps:
Step 1 adds graphene oxide in the ethanol, and ultrasonic dispersion is made into concentration 15.4mg/ml graphene oxide ethanolic solution;
Step 2, in thermosetting phenolic resin, polyvinyl alcohol and graphene oxide mass ratio is the ratio of 1:0.020:0.06, thermosetting phenolic resin and polyvinyl alcohol are joined in the graphene oxide ethanolic solution, this mixed solution is stirred to dissolving fully, and the thermosetting phenolic resin molecular weight is 2000;
Step 3 becomes composite ultrafine fiber with 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 ℃ from the non-at the uniform velocity staged of room temperature, solidified 3 hours, it is 40 ℃/h that non-at the uniform velocity staged heats up promptly from the heating rate of room temperature to 60 ℃, should be lower than 4 ℃/h at 60-80 ℃ heating rate again, along with temperature raises, its heating rate also progressively improves, and can be increased to 40 ℃/h in time more than 140 ℃, under 1000 ℃ of nitrogen atmospheres, carry out charing then, obtain the alkyd resin based ultra-fine porous carbon fiber that graphene oxide is modified.
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