CN104925787A - Method for preparing graphene aerogel through constant pressure drying - Google Patents
Method for preparing graphene aerogel through constant pressure drying Download PDFInfo
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- CN104925787A CN104925787A CN201510121119.9A CN201510121119A CN104925787A CN 104925787 A CN104925787 A CN 104925787A CN 201510121119 A CN201510121119 A CN 201510121119A CN 104925787 A CN104925787 A CN 104925787A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 111
- 239000004964 aerogel Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000001035 drying Methods 0.000 title claims abstract description 13
- 239000000017 hydrogel Substances 0.000 claims abstract description 33
- 230000008014 freezing Effects 0.000 claims abstract description 21
- 238000007710 freezing Methods 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 230000002829 reductive effect Effects 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000010257 thawing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000001599 direct drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000000352 supercritical drying Methods 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 13
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000012425 Freezing-thawing process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention provides a method for preparing a graphene aerogel through constant pressure drying. The method comprises the following steps of: firstly, preparing a hydrogel by using aqueous dispersions of oxidized graphene as raw materials; processing the hydrogel by freezing and melting so as to reassemble the internal structure of the hydrogel, wherein the formed structure is strong enough to resist the structure collapse caused by air-liquid interface tension during constant pressure drying; and finally, realizing the preparation of the graphene aerogel through constant pressure drying. Compared with a freeze drying method and a supercritical drying method, the method disclosed by the invention has the advantages that the efficiency for preparing the graphene aerogel is greatly improved, the production cost is reduced, and the industrialized production of the graphene aerogel is hopeful to realize. In addition, the invention further provides a novel graphene aerogel, and the characteristics of macropores and super resilience, of the graphene aerogel, can be applied in many fields.
Description
[technical field]
The present invention relates to a kind of method that constant pressure and dry prepares graphene aerogel, belong to aerogel preparing technical field.
[background technology]
Aerogel (Aerogel) is also called xerogel, it is the nano material of the multi-branched nanoporous three-dimensional net structure with extra-low density, high-specific surface area, high hole ratio and superelevation pore volume rate, the medium be full of in its space net structure is gas, and appearance is solid state.The appearance of carbon aerogels has initiative progress in aerogel material research, and aerogel material be extend to electrical conductor from the poor conductor of electricity by it, has started the Application Areas that aerogel material is new.
Graphene (Graphene) is made up of sp2 hydbridized carbon atoms, in cycle honeycomb lattice structure, has the physicalies such as good conduction, heat conduction, mechanics.The thickness of Graphene is only 0.34 ran, and its two-dimensional is not from tens nanometers to tens microns etc., therefore can be assembled into porous, ultralight graphene aerogel by certain method.Different preparation methods determines the different internal networking structure of graphene aerogel, also gives the performance that they are different, the fragility aerogel of such as high strength and soft elasticity aerogel.Graphene aerogel has ultralight, porous, conduction, hydrophobic oleophilic oil and the characteristic such as mechanical property flexibly, can be applied in fields such as support of the catalyst, conductive devices, oily waste treatment and energy snubbers.
First Graphene can obtain graphene oxide (Oxidegraphene) by graphite by oxidation style, and then is obtained by chemistry or the reduction of hot method.Surface of graphene oxide has abundant oxy radical, can in water stable dispersion.Therefore the preparation of graphene aerogel is all be that first raw material prepares graphene oxide dispersion or Graphene wet gel with graphene oxide usually, and then removes solvent by lyophilize or supercritical drying and obtain.Such as, Chinese patent CN102239114A uses the dispersion liquid of graphene oxide or wet gel to prepare graphene oxide and graphene aerogel by lyophilize or supercritical drying first.
Use reductive agent that the reduction of graphene oxide aqueous dispersions is obtained Graphene hydrogel in CN101941693A first, then prepare aerogel by lyophilize.The hole of method mainly because of graphene sheet layer assembling that people are dry under why not using normal pressure is less, and capillary action is obvious, and in gas evaporation process, liquid-gas interface tension force easily makes pore space structure cave in, and the post shrinkage of drying is obvious; And lyophilize and supercritical drying can avoid this point, volume and the shape of aerogel therefore can be kept well.But lyophilize needs the environment providing low temperature and low pressure, overcritically need the environment providing high pressure, and all need special equipment, cost is high, and production efficiency is low, can not prepare in large quantity, therefore constrains the widespread use of graphene aerogel.Provide a kind of method that constant pressure and dry prepares Graphene cross-linking type organic aerogel and charcoal-aero gel in patent CN102774824A, describe the significance that constant pressure and dry prepares aerogel.But in this patent, Graphene is just as linking agent, is not the material of main part of aerogel, performance and graphene aerogel difference larger.Therefore the aerogel using atmosphere pressure desiccation to prepare full Graphene has very important practical significance.
[summary of the invention]
[technical problem that will solve]
A kind of constant pressure and dry is the object of the present invention is to provide to prepare the method for graphene aerogel;
The present invention also aims to provide a kind of purposes the method being used for graphene aerogel and preparing.
[technical scheme]
As previously mentioned, all need special equipment in the preparation technology of the graphene aerogel of prior art, cost is high, and production efficiency is low, can not prepare in large quantity, therefore constrains the widespread use of graphene aerogel.Only have and adopt constant pressure and dry to prepare the production technique that graphene aerogel fundamentally could simplify graphene aerogel, reduce costs, realize suitability for industrialized production.But time dry under condition of normal pressure, due to the tension force that liquid-gas interface produces, gel network structure easily produce cave in, the phenomenon such as contraction.But when graphene sheet layer assembles that the three-dimensional network hole built is enough large, hole wall is enough thick, just can resist this tension force, the volume substantially during maintenance hydrogel and shape, obtain the graphene aerogel of constant pressure and dry.Technical scheme of the present invention provides a kind of method that constant pressure and dry prepares graphene aerogel, the method with the aqueous dispersions of graphene oxide for reaction system, add reductive agent or linking agent or use high pressure hydrothermal method, the aqueous dispersions of redox graphene, and the reducing degree of controlled oxidization Graphene can be carried out by the time and temperature controlling prereduction reaction, first the graphene oxide hydrogel of prereduction is prepared, then by making Graphene three-dimensional net structure re-assembly freezing for hydrogel method of melting again, obtain resisting liquid-gas interface in constant pressure and dry process produce the structure of tension force, further reductive water gel again, consolidate the three-dimensional structure of hydrogel, dry Graphene hydrogel under finally realizing normal pressure, preparation almost non-shrinking graphene aerogel.
The present invention is achieved through the following technical solutions.
A kind of constant pressure and dry prepares the method for graphene aerogel, it is characterized in that the method with the aqueous dispersions of graphene oxide for reaction system, by adding reductive agent or linking agent in this aqueous dispersions, or adopt high pressure hydro-thermal legal system for the hydrogel of prereduction graphene oxide, prereduction degree needs to control in certain limit, can pass through fixation reaction temperature, the change reaction times realizes.Then melted again after this hydrogel is freezing under-30 to 0 degrees Celsius, this freezing thaw process is carried out repeatedly once above after, then reduced further by this hydrogel and become Graphene hydrogel, finally drying obtains graphene aerogel at ambient pressure.
According to another kind of preferred implementation of the present invention, the monolithic layer of wherein said graphene oxide is 0.2 ~ 50 micron, and the concentration of graphene oxide aqueous dispersions is 0.5 ~ 10 milligram every milliliter.
According to another kind of preferred implementation of the present invention, wherein said reductive agent is hydrazine hydrate, vitamins C and hydrogen iodide.
According to another kind of preferred implementation of the present invention, wherein said linking agent is quadrol.
According to another kind of preferred implementation of the present invention, wherein drying means is selected from direct drying under normal pressure.
Foregoing method, is characterized in that the method comprises the steps:
(1) graphene oxide aqueous dispersions is prepared;
(2) in this graphene oxide aqueous dispersions by adding reductive agent or linking agent, or use high pressure hydro-thermal legal system for the hydrogel of prereduction graphene oxide;
(3) hydrogel of prereduction graphene oxide step (2) prepared is freezing under-30 to-10 degrees Celsius, then at room temperature makes it melt, repeated freezing thawing step more than 1 time;
(4) reduced further by hydrogel prepared by step (3), the prereduction method in the same step of method of reducing (2), continues reacting by heating and terminates to reduction reaction;
(5) hydrogel prepared by step (4) washing by soaking more than 2 times in a solvent, solvent be selected from water, ethanol and acetone one or more;
(6) hydrogel that 20-100 degree Celsius of drying step (5) prepares at ambient pressure obtains graphene aerogel.
According to another kind of preferred implementation of the present invention, it is characterized in that in described step (1), the preparation method of graphene oxide aqueous dispersions does not limit, wherein Hummer ' s chemical method prepares graphite oxide is method conventional in this area.
According to another kind of preferred implementation of the present invention, it is characterized in that in described step (2), the method preparing prereduction graphene oxide hydrogel is not limit, as preferably, use the method adding reductive agent or high pressure hydro-thermal.
According to another kind of preferred implementation of the present invention, it is characterized in that in described step (2), the C/O mole atom ratio controlled in prereduction graphene oxide is 3.0 to 5.0.
According to another kind of preferred implementation of the present invention, it is characterized in that in described step (3), control freezing temp at-20 to-15 degrees Celsius, freezing thawing number of times controls at 1 to 3 times.
According to another kind of preferred implementation of the present invention, it is characterized in that in described step (4), the C/O atomic molar ratio controlled in the rear Graphene of reduction is 6.0 to 10.0.
Described method is preparing the application in graphene aerogel.
[beneficial effect]
The present invention, owing to taking technique scheme, has the following advantages:
1, constant pressure and dry prepares graphene aerogel, volume before can most keeping dry and shape, prepare graphene aerogel with lyophilize and supercritical drying to compare, technique is simpler, cost is lower, and solve the difficult problem that graphene aerogel prepares production in enormous quantities, be expected to realize suitability for industrialized production.
2, the graphene aerogel prepared by the present invention has extraordinary mechanical property and conductivity.The graphene aerogel such as prepared has super rebound resilience, and maximum compression ratio can reach 93%, and can reply well, is the graphene aerogel that current compression ratio is maximum, produces permanentset hardly after compression reaction more than 1,000 times.Specific conductivity when it is uncompressed can to reach 13S m
-1.Therefore the graphene aerogel prepared by the present invention can be applied to the conductive sensor field of large deformation.
3, the graphene aerogel prepared by the present invention has oleophilic drainage characteristic, can be used as oil suction scrubbing material, and can recycle.
4, the graphene aerogel prepared by the present invention has ultralight characteristic, and density range is 1 to 10mg cm
-3.
5, the present invention can prepare difform graphene aerogel, meets the demand of different field.
[accompanying drawing explanation]
Fig. 1 is the photo in kind of aerogel after the Graphene hydrogel that obtains of the present invention and constant pressure and dry;
Fig. 2 is the difform graphene aerogel that the present invention obtains;
Fig. 3 is the scanning electron microscope (SEM) photograph of the graphene aerogel that the present invention obtains;
Fig. 4 is the compression reaction test curve figure of the graphene aerogel that the present invention obtains;
Fig. 5 is the exploded view that graphene aerogel that the present invention obtains has oleophilic drainage performance, and its oil can extruding absorption by compression recycle;
Fig. 6 is the photo in kind of graphene aerogel prepared by embodiment 5 and comparative example 1;
[embodiment]
Below in conjunction with embodiment, the present invention is further described, it should be understood that these embodiments are only for illustration of the present invention, and be not used in and limit the scope of the invention.
Embodiment 1.
Use 325 object crystalline flake graphites as raw material, graphene oxide is prepared by Hummer ' the s chemical method improved, obtain graphene oxide (GO) solution of 10 milligrams every milliliter, getting 5 milliliters of GO solution joins in cylindrical glass bottle, add 5 ml deionized water, GO strength of solution is made into 5 milligrams every milliliter, get the hydrazine hydrate solution of 100 microlitre massfractions 35% again, join in GO solution, supersound process 5 minutes, hydrazine hydrate is uniformly dispersed, sealing of being jumped a queue by circular glass bottle, reacts under being put into 95 degrees Celsius and form gel in 0.5 hour.Then stopped reaction, drop to after room temperature until gel, this gel is put into refrigerator and cooled and freezes, the temperature of refrigerator approximately-18 degrees Celsius, after two hours, after gel freezes completely, under this gel is taken room temperature, after melting completely, again with the freezing thawing of identical condition once, and then react 2 hours under hydrogel is placed in 95 degrees Celsius, after reaction terminates, hydrogel alcohol rinse is washed twice, finally within 24 hours, obtain graphene aerogel by dry under hydrogel in an oven 60 degrees Celsius.
Embodiment 2.
Technical process, with embodiment 1, is made into 4 milligrams every milliliter unlike by GO strength of solution, total amount 10 milliliters, and hydrazine hydrate adds 80 microlitres, 1 hour reaction times, and after forming gel, freezing temp is-30 degrees Celsius.After freezing thawing processes, then react 1.5 hours.
Embodiment 3.
Technical process, with embodiment 1, is made into 3 milligrams every milliliter unlike by GO strength of solution, total amount 10 milliliters, and hydrazine hydrate add-on is 90 microlitres.
Embodiment 4.
Technical process, with embodiment 1, changes 180 order crystalline flake graphites into unlike by 325 order crystalline flake graphites.
Embodiment 5.
Technical process, with embodiment 1, is made into 4 milligrams every milliliter unlike by GO strength of solution, total amount 10 milliliters, add 80 milligrams of vitamins Cs and replace hydrazine hydrate, within ultrasonic 2 minutes, vitamins C dissolves completely, then 1 hour reaction times, form gel, after freezing thawing processes, then react 5 hours.
Embodiment 6.
Technical process, with embodiment 5, unlike 2 hours reaction times, forms gel, after freezing thawing processes, then reacts 4 hours.
Embodiment 7.
Technical process, with embodiment 5, is-30 degrees Celsius unlike freezing temp.
Embodiment 8.
Technical process, with embodiment 1, is made into 3 milligrams every milliliter unlike by GO strength of solution, total amount 10 milliliters, adds 40 microlitre quadrols and replaces hydrazine hydrate, and then 90 degrees Celsius are reacted 8 hours, form gel, after freezing thawing processes, then react 8 hours.
Embodiment 9.
Technical process is with embodiment 8, and unlike adding 80 microlitre quadrols, in 12 hours reaction times, form gel, freezing temp-30 degrees Celsius, after freezing thawing processes, then reacts 4 hours.
Embodiment 10.
Technical process, with embodiment 1, is made into 3 milligrams every milliliter unlike by GO strength of solution, total amount 10 milliliters, do not add any reductive agent and linking agent, react 2 hours under 180 degrees Celsius in autoclave, form gel, freezing dissolve process after, then react 13 hours.
Comparative example 1.
Technical process, with embodiment 5, processes this step, direct reaction 6 hours, then oven drying unlike not carrying out freezing thawing.
As can be seen from Figure 1, this invention can prepare graphene aerogel by constant pressure and dry, and can the overwhelming majority keep dry before volume and shape.Fig. 2 illustrates that this invention can prepare difform graphene aerogel.Fig. 3 illustrates the morphological structure of the graphene aerogel prepared by this invention, the three-dimensional hole of Graphene assembling is between 100 to 500 microns, belong to larger hole, and Graphene wall orientations, the tension force that in constant pressure and dry process, liquid-gas interface produces can be resisted well, the volume before the overwhelming majority keeps dry and shape.The graphene aerogel that Fig. 4 illustrates this patent to be provided has super-elasticity, and its maximum compression ratio can reach 93%, is the maximum compression ratio of current graphene aerogel, produces permanentset hardly after compression reaction 1,000 times.The graphene aerogel that Fig. 5 illustrates this patent to be provided has the performance of oleophilic drainage, and can recycle by compressing the oil extruding absorption.Fig. 6 embodies freezing keying action of melting process as a comparison case.Its left figure is through the aerogel pictorial diagram of freezing thawing process prepared by this step, and right figure eliminates the comparative example 1 of this step, has occurred serious shrinkage phenomenon in constant pressure and dry process.
Claims (10)
1. a constant pressure and dry prepares the method for graphene aerogel, it is characterized in that the method with the aqueous dispersions of graphene oxide for reaction system, by adding reductive agent or linking agent in this aqueous dispersions, or adopt high pressure hydro-thermal legal system for the hydrogel of prereduction graphene oxide; Then at room temperature melt again after this hydrogel is freezing under-30 to-10 degrees Celsius, this freezing thaw process is carried out repeatedly after once, reduced further by this hydrogel and become Graphene hydrogel, finally this Graphene hydrogel dry obtains graphene aerogel at ambient pressure.
2. the method for claim 1, the control of the reducing degree of prereduction graphene oxide was realized by the fixation reaction temperature change reaction times.
3. the method for claim 1, the monolithic layer of wherein said graphene oxide is 0.2 ~ 50 micron, and the concentration of graphene oxide aqueous dispersions is 0.5 ~ 10 milligram every milliliter.
4. the method for claim 1, wherein said reductive agent is selected from one or more in hydrazine hydrate, vitamins C and hydrogen iodide, and wherein said linking agent is quadrol.
5. the method for claim 1, wherein drying means is selected from direct drying under normal pressure.
6. the method for claim 1, is characterized in that the method comprises the steps:
(1) graphene oxide aqueous dispersions is prepared;
(2) in this graphene oxide aqueous dispersions by adding reductive agent or linking agent, or use high pressure hydro-thermal legal system for the hydrogel of prereduction graphene oxide;
(3) hydrogel of prereduction graphene oxide step (2) prepared is freezing under-30 to-10 degrees Celsius, then at room temperature makes it melt, repeated freezing thawing step more than 1 time;
(4) reduced further by hydrogel prepared by step (3), the prereduction method in the same step of method of reducing (2), continues reacting by heating and terminates to reduction reaction;
(5) hydrogel prepared by step (4) washing by soaking more than 2 times in a solvent, solvent be selected from water, ethanol and acetone one or more;
(6) hydrogel that 20-100 degree Celsius of drying step (5) prepares at ambient pressure obtains graphene aerogel.
7. method as claimed in claim 6, is characterized in that in described step (2), and the C/O atomic molar ratio controlled in prereduction graphene oxide is 3.0 to 5.0.
8. method as claimed in claim 6, is characterized in that in described step (3), and control freezing temp at-20 to-15 degrees Celsius, freezing thawing number of times controls at 1 to 3 times.
9. method as claimed in claim 6, is characterized in that in described step (4), and the C/O atomic molar ratio controlled in the rear Graphene of reduction is 6.0 to 10.0.
10. method according to claim 1 is preparing the application in graphene aerogel.
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