CN107903575B - A kind of preparation method of graphene phenolic resin-based composite fiber membrane for capacitor electrode - Google Patents
A kind of preparation method of graphene phenolic resin-based composite fiber membrane for capacitor electrode Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000012528 membrane Substances 0.000 title claims abstract description 66
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 58
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 58
- 239000000835 fiber Substances 0.000 title claims abstract description 38
- 239000003990 capacitor Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002028 Biomass Substances 0.000 claims abstract description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000011324 bead Substances 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000006260 foam Substances 0.000 claims abstract description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 244000146553 Ceiba pentandra Species 0.000 claims description 4
- 235000003301 Ceiba pentandra Nutrition 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 241000219000 Populus Species 0.000 claims description 3
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- 238000000576 coating method Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 7
- 240000001398 Typha domingensis Species 0.000 claims 1
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract description 14
- 238000004146 energy storage Methods 0.000 abstract description 6
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
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- 241000234435 Lilium Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
一种电容器电极用石墨烯酚醛树脂基复合纤维膜的制备方法是以生物质活性炭纤维为骨架，乳液小球为模板剂，与氧化石墨烯水溶胶一起加入水和有机溶剂组成的混合溶剂中形成悬浮液，悬浮液进行沉积复合，获得复合柔性膜，复合柔性膜铺覆于石墨夹具中抽真空或惰性气氛下，经热压处理得3D大孔泡状复合膜，3D大孔泡状复合膜铺覆于预浸料酚醛树脂中，室温下抽真空，经热压，在碱液中浸渍、活化，得石墨烯酚醛树脂基复合纤维膜。本发明具有电容器电极储能密度高、循环稳定性好的优点。
A preparation method of a graphene phenolic resin-based composite fiber membrane for capacitor electrodes takes biomass activated carbon fiber as a skeleton, emulsion beads as a template agent, and graphene oxide hydrosol is added to a mixed solvent composed of water and an organic solvent to form The suspension is deposited and compounded to obtain a composite flexible film. The composite flexible film is laid in a graphite fixture under vacuum or an inert atmosphere, and is subjected to hot pressing to obtain a 3D macroporous foam composite film. 3D macroporous foam composite film It is covered in prepreg phenolic resin, evacuated at room temperature, impregnated and activated in alkali solution after hot pressing to obtain a graphene phenolic resin-based composite fiber membrane. The invention has the advantages of high energy storage density of the capacitor electrode and good cycle stability.
Description
Technical Field
The invention belongs to the field of new energy materials, relates to a preparation method of a supercapacitor electrode material, and particularly relates to a preparation method of a graphene phenolic resin based composite fiber membrane for a capacitor electrode.
Technical Field
The graphene is in a single layer or few layers sp2A two-dimensional structure of carbon. Was sent out since 2004Since now, due to its good conductivity (103-104S ∙ m)-1) High electron mobility (20000 cm at room temperature)2∙V-1∙S-1) And a high theoretical specific surface area (2630 m)2∙g-1) With excellent properties, people have begun to explore such sp2Possibility of application of carbon material with structure in super capacitor (Zhang LL, Zhou R, Zhao XS. Graphene-based material assupercapacitor electrodes]J Mater Chem 2010;20(29): 5983-92) (Stoller MD, Park SJ, Zhu YW, An JH, Ruoff RS. Graphene-based supercapacitors [ J].Nano Lett 2008;8(10):3498-502.）。
The prior art graphene-based supercapacitor materials have been widely researched and focused. Royal jelly et al (patent publication No. CN 103723722A) prepared a graphene-modified activated carbon electrode material with a high specific surface area by mixing the decontaminated activated carbon with graphene in an organic solvent for high-temperature activation, which exhibited a high specific mass capacity. Lily (patent publication No. CN 103253658A) is prepared by mixing graphene oxide with activator and carbon source material, and activating in protective atmosphere to obtain graphene with high volume specific capacity. The graphene-based electrode material fully exerts the advantage that the two-dimensional surface of graphene is easy to fully contact with electrolyte, and the inter-sheet macroporous structure can provide sufficient buffer space for the electrolyte and provide a smooth channel for ion migration. In addition, conjugated pi electrons (high-density carriers) facing graphene can provide a low-resistance channel for charge transmission, so that the energy storage requirement of large-current rapid charge and discharge is met. However, the graphene-based electrode material is mostly solid powder, and when the graphene-based electrode material is applied to a supercapacitor, the graphene-based electrode material must be uniformly mixed with acetylene black, a binder and other substances, and then the mixture is coated on a current collector, so that powder agglomeration and caking are caused in the process, and the conductivity of the electrode material is reduced, so that the prepared graphene-based electrode material is low in energy storage density and poor in cycle stability, and the requirements of practical application cannot be met.
Disclosure of Invention
The invention aims to overcome the defects of the existing graphene-based electrode material and provides a preparation method of a graphene phenolic resin-based composite fiber membrane for a capacitor electrode, which has high energy storage density and good cycling stability.
The invention obtains a 3D macroporous graphene/biomass activated carbon fiber composite membrane by a hard template guiding ordered assembly method; and then the composite membrane is paved in prepreg phenolic resin emulsion, and then the graphene phenolic resin matrix composite fiber membrane is prepared through vacuum hot press molding and alkali activation processes. The film combines the advantages of the graphene, the biomass active carbon and the phenolic resin, fully exerts the good conductivity of the graphene, the porous structure of the biomass active carbon fiber, the high specific surface area, the space skeleton structure and the high carbon residue rate of the phenolic resin, and accordingly effectively improves the energy storage of the supercapacitor. Meanwhile, the composite film has good flexibility, can be directly used as a super capacitor electrode, and effectively avoids internal resistance caused by adding a binder in the process of preparing the electrode from powder.
In order to achieve the purpose, the invention is realized by the following technical scheme:
(1) the method is characterized in that biomass active carbon fibers are used as a framework, emulsion beads are used as a template agent, and the emulsion beads and graphene oxide hydrosol are added into a mixed solvent consisting of water and an organic solvent together to form a suspension, wherein the mass ratio of graphene oxide to the biomass active carbon fibers is 1: 0.1-20, wherein the mass ratio of the graphene oxide to the emulsion globules is 1: 0.5-5, wherein the volume ratio of water to the organic solvent is 1: 0.5-10, and the mass ratio of the sum of the mass of the biomass activated carbon fibers, the emulsion beads and the graphene oxide to the mixed solvent is as follows: 1.6-26: 50-500;
(2) depositing and compounding the graphene oxide hydrosol, the emulsion globule and the biomass activated carbon fiber suspension to obtain a composite flexible membrane;
(3) paving the composite flexible film obtained in the step (2) in a graphite clamp, vacuumizing or under an inert atmosphere, and performing hot-pressing treatment at 500-1000 ℃ for 0.1-15h to obtain a 3D macroporous bubble-shaped composite film;
(4) and (3) paving the 3D macroporous bubble-shaped composite membrane prepared in the step (3) in prepreg phenolic resin, vacuumizing at room temperature, carrying out hot pressing at 150-180 ℃ for 30-120min, and further soaking and activating in alkali liquor to obtain the graphene phenolic resin based composite fiber membrane.
The organic solvent in the step (1) is one of absolute ethyl alcohol, acetone, N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
The biomass activated carbon fiber in the step (1) comprises a biomass activated carbon fiber prepared from one of poplar seed, willow seed, cattail and kapok.
And (2) carrying out ultrasonic treatment on the graphene oxide hydrosol in the step (1) in deionized water, wherein the ultrasonic time is 10-120min, and the ultrasonic power is 100-800W, so as to obtain the graphene oxide hydrosol with the concentration of 0.1-10 mg/ml.
The emulsion beads in step (1) described above are polymethyl methacrylate emulsion beads (PMMA) or polystyrene emulsion beads (PS).
And (3) depositing and compounding the graphene oxide hydrosol, the emulsion balls and the biomass activated carbon fiber suspension in the step (2), wherein the deposition and compounding adopts spraying, coating, filter pressing or vacuum filtration.
The inert atmosphere in step (3) is argon, nitrogen or helium as described above.
The mass ratio of the graphene to the phenolic resin in the step (4) is 0.5-10: 100.
The mass ratio of the membrane to the alkali in the alkali liquor immersion in the step (4) is 1: 0.5-6, and the immersion time is 6-12 h.
The activation temperature of the step (4) is 500-900 ℃, and the activation time is 0.5-6 h.
The invention has the beneficial effects that:
according to the preparation method of the graphene phenolic resin-based composite fiber membrane for the capacitor electrode, the 3D macroporous foam graphene/biomass activated carbon fiber composite membrane is obtained through a hard template guiding ordered assembly method; and then the composite membrane is paved in prepreg phenolic resin emulsion, and then the graphene phenolic resin matrix composite fiber membrane is prepared through vacuum hot press molding and alkali activation processes. The composite membrane prepared by the method combines the advantages of the graphene, the biomass activated carbon and the phenolic resin, fully exerts the good conductivity of the graphene, the porous structure of the biomass activated carbon fiber, the high specific surface area, the space framework structure and the high carbon residue rate of the phenolic resin, and thus effectively improves the energy storage of the supercapacitor. Meanwhile, the composite film has good flexibility, can be directly used as a super capacitor electrode, and effectively avoids internal resistance caused by adding a binder in the process of preparing the electrode from powder. The specific capacity is between 100-300F/g; after 2000 cycles, the capacitance can still reach 90-98.5% of the initial capacitance.
Drawings
Fig. 1 shows an adsorption/desorption curve and a pore size distribution curve of the graphene phenolic resin-based composite fiber membrane prepared in example 1.
FIG. 2 the graphene phenolic resin-based composite fiber membrane prepared in example 1 is directly used as an electrode to assemble a cyclic voltammetry curve of a supercapacitor at different sweep rates.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
Example 1
(1) Carrying out ultrasonic treatment on graphite oxide in deionized water, wherein the ultrasonic time is 10min, and the ultrasonic power is 800W, so as to obtain 10mg/ml graphene oxide hydrosol;
(2) adding a poplar catkin-based biomass activated carbon fiber as a framework and polymethyl methacrylate emulsion globules (PMMA) as a template agent and graphene oxide hydrosol into a mixed solvent of water and absolute ethyl alcohol to form a suspension, wherein the mass ratio of graphene oxide to the biomass activated carbon fiber is 1:0.1, the mass ratio of graphene oxide to emulsion globules is 1:0.5, the volume ratio of water to an organic solvent is 1:0.5, and the mass ratio of the sum of the mass of the biomass activated carbon fiber, the emulsion globules and the graphene oxide to the mixed solvent is as follows: 1.6: 50;
(3) carrying out vacuum filtration on the suspension to obtain a composite flexible membrane;
(4) paving the composite flexible membrane obtained in the step (3) in a graphite clamp, vacuumizing, and carrying out hot-pressing treatment at 500 ℃ for 15 hours to obtain a 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane;
(5) and (3) paving the 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane prepared in the step (4) in a prepreg phenolic resin (the mass ratio of graphene to phenolic resin is 4: 100), vacuumizing at room temperature, performing hot pressing at 150 ℃ for 120min, further soaking in alkali liquor for 12h (the mass ratio of the membrane to alkali is 1: 2), and activating at 800 ℃ for 1h to obtain the graphene phenolic resin matrix composite fiber membrane.
The specific surface area of the graphene phenolic resin-based composite fiber membrane prepared in example 1 is 698 m2(ii) in terms of/g. The prepared graphene phenolic resin matrix composite fiber film is directly used as an electrode to assemble a super capacitor. Tests show that the current density of the composite film is 1Ag-1The specific capacity of the battery is 284 Fg-1After 2000 cycles, the capacitance still reaches 98.5% of the initial capacitance.
Example 2
(1) Carrying out ultrasonic treatment on graphite oxide in deionized water, wherein the ultrasonic time is 120min, and the ultrasonic power is 100W, so as to obtain 0.1mg/ml graphene oxide hydrosol;
(2) the method comprises the following steps of taking cattail-based biomass active carbon fiber as a framework, taking polymethyl methacrylate emulsion globule (PMMA) as a template agent, adding the cattail-based biomass active carbon fiber and graphene oxide hydrosol into a mixed system of water and N-methyl pyrrolidone to form suspension, wherein the mass ratio of graphene oxide to the biomass active carbon fiber is 1: 20, the mass ratio of graphene oxide to emulsion globule is 1: 5, the volume ratio of water to organic solvent is 1: 10, and the mass ratio of the sum of the mass of the biomass active carbon fiber, the emulsion globule and the graphene oxide to the mixed solvent is as follows: 26: 500;
(3) coating and compounding the graphene oxide hydrosol, the emulsion globule and the biomass active carbon fiber suspension to obtain a graphene oxide/emulsion globule/biomass active carbon fiber composite flexible membrane;
(4) laying the graphene oxide/biomass active carbon fiber composite flexible membrane obtained in the step (3) in a graphite clamp, vacuumizing, and carrying out hot pressing treatment at 1000 ℃ for 0.1h to obtain a 3D macroporous bubble graphene/biomass active carbon fiber composite membrane;
(5) and (3) paving the 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane prepared in the step (4) in a prepreg phenolic resin (the mass ratio of graphene to phenolic resin is 2: 100), vacuumizing at room temperature, performing hot pressing at 180 ℃ for 30min, further soaking in alkali liquor for 6h (the mass ratio of the membrane to alkali is 1: 6), and activating at 500 ℃ for 2h to obtain the graphene phenolic resin matrix composite fiber membrane.
The specific surface area of the graphene phenolic resin-based composite fiber membrane prepared in example 2 is 542 m2(ii) in terms of/g. The prepared graphene phenolic resin matrix composite fiber film is directly used as an electrode to assemble a super capacitor. Tests show that the current density of the composite film is 1Ag-1Specific capacity of 211 Fg-1After 2000 cycles, the capacitance still reaches 90.5% of the initial capacitance.
Example 3
(1) Carrying out ultrasonic treatment on graphite oxide in deionized water, wherein the ultrasonic time is 30min, and the ultrasonic power is 500W, so as to obtain 3mg/ml graphene oxide hydrosol;
(2) adding a bio-active carbon fiber based on catkin as a framework and a polystyrene emulsion bead (PS) as a template agent together with graphene oxide hydrosol into a mixed system of water and N, N-dimethylformamide to form a suspension, wherein the mass ratio of the graphene oxide to the bio-active carbon fiber is 1: 10, the mass ratio of the graphene oxide to the emulsion bead is 1:3, the volume ratio of the water to an organic solvent is 1: 5, and the mass ratio of the sum of the mass of the bio-active carbon fiber, the emulsion bead and the graphene oxide to the mixed solvent is as follows: 14: 300;
(3) spraying and compounding the graphene oxide hydrosol, the emulsion globule and the biomass active carbon fiber suspension to obtain a graphene oxide/emulsion globule/biomass active carbon fiber composite flexible membrane;
(4) laying the graphene oxide/biomass activated carbon fiber composite flexible membrane obtained in the step (3) in a graphite clamp for vacuumizing, and performing hot pressing treatment at 800 ℃ for 1h to obtain a 3D macroporous bubble-shaped graphene/biomass activated carbon fiber composite membrane;
(5) and (3) paving the 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane prepared in the step (4) in a prepreg phenolic resin (the mass ratio of graphene to phenolic resin is 10: 100), vacuumizing at room temperature, performing hot pressing at 140 ℃ for 100min, further soaking in alkali liquor for 12h (the mass ratio of the membrane to alkali is 1: 4), and activating at 900 ℃ for 0.5h to obtain the graphene phenolic resin matrix composite fiber membrane.
The specific surface area of the graphene phenolic resin-based composite fiber membrane prepared in example 3 is 980 m2(ii) in terms of/g. The prepared graphene phenolic resin matrix composite fiber film is directly used as an electrode to assemble a super capacitor. Tests show that the current density of the composite film is 1Ag-1Specific capacity of 103 Fg-1After 2000 cycles, the capacitance still reaches 98.5% of the initial capacitance.
Example 4
(1) And (3) carrying out ultrasonic treatment on the graphite oxide in deionized water, wherein the ultrasonic time is 45min, and the ultrasonic power is 300W, so as to obtain 3.5mg/ml graphene oxide hydrosol.
(2) The preparation method comprises the following steps of taking kapok-based biomass active carbon fibers as a framework, taking polystyrene emulsion beads (PS) as a template agent, adding the kapok-based biomass active carbon fibers and graphene oxide hydrosol into a mixed system of water and N, N-dimethylacetamide to form suspension, wherein the mass ratio of the graphene oxide to the biomass active carbon fibers is 1: 5, the mass ratio of the graphene oxide to the emulsion beads is 1:2, the volume ratio of the water to an organic solvent is 1: 1, and the mass ratio of the sum of the mass of the biomass active carbon fibers, the emulsion beads and the graphene oxide to the mixed solvent is as follows: 8: 200;
(3) carrying out vacuum filtration on the graphene oxide hydrosol, the emulsion globule and the biomass active carbon fiber suspension to obtain a graphene oxide/emulsion globule/biomass active carbon fiber composite flexible membrane;
(4) laying the graphene oxide/biomass activated carbon fiber composite flexible membrane obtained in the step (3) in a graphite clamp for vacuumizing, and performing hot-pressing treatment at 600 ℃ for 4 hours to obtain a 3D macroporous bubble-shaped graphene/biomass activated carbon fiber composite membrane;
(5) and (3) paving the 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane prepared in the step (4) in a prepreg phenolic resin (the mass ratio of graphene to phenolic resin is 8: 100), vacuumizing at room temperature, performing hot pressing at 170 ℃ for 60min, further soaking in alkali liquor for 8h (the mass ratio of the membrane to alkali is 1: 2), and activating at 850 ℃ for 1h to obtain the graphene phenolic resin based composite fiber membrane.
The specific surface area of the graphene phenolic resin-based composite fiber membrane prepared in example 4 is 720 m2(ii) in terms of/g. The prepared graphene phenolic resin matrix composite fiber film is directly used as an electrode to assemble a super capacitor. The test shows that the current density of the composite film is 1Ag-1The specific hourly capacity is 189 Fg-1After 2000 cycles, the capacitance still reaches 95.2% of the initial capacitance.
Example 5
(1) And (3) carrying out ultrasonic treatment on the graphite oxide in deionized water, wherein the ultrasonic time is 60min, and the ultrasonic power is 100W, so as to obtain the graphene oxide hydrosol of 4 mg/ml.
(2) Taking a biological activated carbon fiber based on catkin as a framework, taking a polystyrene emulsion bead (PS) as a template agent, adding the template agent and graphene oxide hydrosol into a mixed system of water and acetone to form a suspension, wherein the mass ratio of graphene oxide to the biological activated carbon fiber is 1: 15, the mass ratio of graphene oxide to an emulsion bead is 1:4, the volume ratio of water to an organic solvent is 1:6, and the mass ratio of the sum of the mass of the biological activated carbon fiber, the emulsion bead and the graphene oxide to the mixed solvent is as follows: 20: 400;
(3) carrying out filter pressing on the graphene oxide hydrosol, the emulsion globule and the biomass active carbon fiber suspension to obtain a graphene oxide/emulsion globule/biomass active carbon fiber composite flexible membrane;
(4) laying the graphene oxide/biomass activated carbon fiber composite flexible membrane obtained in the step (3) in a graphite clamp for vacuumizing, and performing hot-pressing treatment at 600 ℃ for 2 hours to obtain a 3D macroporous bubble-shaped graphene/biomass activated carbon fiber composite membrane;
(5) and (3) paving the 3D macroporous bubble graphene/biomass activated carbon fiber composite membrane prepared in the step (4) in a prepreg phenolic resin (the mass ratio of graphene to phenolic resin is 0.5: 100), vacuumizing at room temperature, performing hot pressing at 170 ℃ for 70min, further soaking in alkali liquor for 8h (the mass ratio of the membrane to alkali is 1: 3), and activating at 900 ℃ for 6h to obtain the graphene phenolic resin matrix composite fiber membrane.
The specific surface area of the graphene phenolic resin-based composite fiber membrane prepared in example 5 is 685 m2(ii) in terms of/g. The prepared graphene phenolic resin matrix composite fiber film is directly used as an electrode to assemble a lithium ion supercapacitor. The prepared graphene/biomass activated carbon fiber composite flexible membrane is directly used as an electrode to assemble a supercapacitor. The current density of the composite film is 1Ag through testing-1The specific capacity of the specific energy per hour is 220 Fg-1After 2000 cycles, the capacitance still reaches 95.3% of the initial capacitance.
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