CN104828810A - Preparation method of graphene aerogel with ultrahigh specific surface area - Google Patents
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Abstract
The invention discloses a preparation method of graphene aerogel with an ultrahigh specific surface area, and aims to enlarge the specific surface area of graphene aerogel without affecting the chemical structure of graphene. The preparation method comprises the following steps: taking graphite powder and siloxane as the main raw materials, preparing oxidized graphene, preparing a dispersion liquid of oxidized graphene, preparing silicon oxide hybridized graphene gel, drying the gel, and finally carrying out high-temperature decomposition to obtain the graphene aerogel with an ultrahigh specific surface area. The raw materials are mixed in liquid, after reactions, silicon oxide nano particles with an extremely small particle size can be evenly dispersed, thus the graphene is dispersed, and the agglomeration is prohibited. Furthermore, high-temperature decomposition is performed to remove the silicon oxide, at the same time the high-temperature decomposition has a certain activating effect, thus the prepared graphene aerogel has an ultrahigh specific surface area, which can reach 2491 m<2>/g, and at the same time the chemical structure is barely influenced.
Description
Technical field
The present invention relates to a kind of preparation method of graphene aerogel, particularly relate to a kind of preparation method of superhigh specific surface area graphene aerogel.
Technical background
Graphene aerogel is the three-dimensional porous structure material mutually overlapped by Graphene, this material has that ultralight, high-elastic, specific surface area is large, the high a series of feature of conductive and heat-conductive rate, has huge application potential in many fields such as catalysis, electrochemistry, the energy, sensor, super capacitor, absorption, thermal controls.Redox graphene dispersion liquid or aerogel are a kind of methods preparing graphene aerogel the most conventional at present, and this method has the features such as method is simple, cost is low, performance is comparatively excellent.But in reduction process, (oxidation) Graphene is easy to reunite, the specific surface area of the graphene aerogel therefore prepared is much smaller than the specific surface area (2600m of Graphene
2/ g), this performance for Graphene has great impact, has had a strong impact on graphene aerogel application in a lot of fields.Therefore, that improves that the specific surface area of graphene aerogel just becomes very is important.
At present, improving a kind of the most effective method of graphene aerogel is activation method, namely first prepares graphene aerogel, and then utilizes water vapour, CO
2, KOH etc. activates graphene aerogel.Document [Zhu-YinSui, Qing-Han Meng, Ji-Tao Li, Jian-Hua Zhu, Yi Cui, Bao-Hang Han.High surface areaporous carbons produced by steam activation of graphene aerogels.J.Mater.Chem.A 2014] (preparing high specific surface area porous carbon by steam activation graphene aerogel), specific surface area is maximum reached 1230m by steam activation legal system for the graphene aerogel of bigger serface
2/ g, but the specific surface area of this value and Graphene still has larger gap.
Document [Shuwen Wang, Ferdinando Tristan, Daiki Minami, Toshihiko Fujimori, Rodolfo Cruz-Silva, Mauricio Terrones, Kenji Takeuchi, Katsuya Teshima, FranciscoRodri ' guez-Reinoso, Morinobu Endo, Katsumi Kaneko.Activation routes for highsurface area graphene monoliths from graphene oxide colloids.CARBON, 76 (2014) 220 – 231] (from graphene oxide colloid to the activation method of graphene with high specific surface block) pass through CO
2activation and chemical activation (ZnCl
2, H
3pO
4, KOH) prepared the graphene aerogel of bigger serface, find with KOH carry out activate preparation graphene aerogel specific surface area maximum, its maximum value can reach 2150m
2/ g, the specific surface area of this value and Graphene still has larger gap.Reactivation process itself can produce certain impact to the chemical structure of Graphene simultaneously, makes Graphene to produce more defect and room, thus produces adverse influence to some performances of Graphene (aerogel).
In addition, the method increasing graphene aerogel specific surface area also comprises template (namely with other bigger serface materials for Template preparation graphene aerogel) and introduces the methods such as stopper (namely stoping the reunion being oxidized (Graphene) with some compound), but these methods are for the increase effect of graphene aerogel specific surface area all not as good as activation method, and the specific surface area of the graphene aerogel of preparation is generally no more than 1200m
2/ g.
How both to have improved the specific surface area of graphene aerogel, not producing obviously impact to the chemical structure of Graphene is again the technical problem that those skilled in the art very pay close attention to.
Summary of the invention
The technical problem to be solved in the present invention is the preparation method providing a kind of superhigh specific surface area graphene aerogel, and the specific surface area improving graphene aerogel does not produce obviously impact to the chemical structure of Graphene again simultaneously.
A preparation method for superhigh specific surface area graphene aerogel, is characterized in that the preparation comprising graphene oxide, the preparation of graphene oxide dispersion, the preparation of silicon oxide hydridization Graphene gel, dry, Pintsch process five step.Concrete steps are as follows:
The first step, the preparation of graphene oxide: Graphite Powder 99 and potassium permanganate are mixed according to portion rate 1:3 ~ 10 and obtains Graphite Powder 99/potassium permanganate mixture, strong phosphoric acid (concentration >85%) and the vitriol oil (concentration >95%) are mixed according to portion rate 1:5 ~ 15 and obtains nitration mixture, the nitration mixture of 10 ~ 40 parts is joined in the Graphite Powder 99/potassium permanganate mixture of 1 part under the condition of ice bath and stirring, be warming up to 40 ~ 90 DEG C, reaction 5 ~ 24h under the condition stirred, the mixture be obtained by reacting is added 10 ~ 50 parts containing in the frozen water of 0.1 ~ 3 part of 30% hydrogen peroxide, with the centrifugal 1h of the rotating speed of 1000 ~ 15000r/min, obtain from effluent, the deionized water of 10 ~ 100 parts will be dissolved in and with the centrifugal 1h of the rotating speed of 1000 ~ 15000r/min from effluent, again by be dissolved in from effluent 10 ~ 100 parts 10% ~ 35% hydrochloric acid and with the centrifugal 1h of the rotating speed of 1000 ~ 15000r/min, finally will be dissolved in the ethanol (technical pure) of 10 ~ 100 parts from effluent and with the centrifugal 1h of the rotating speed of 1000 ~ 15000r/min (repeating 3 ~ 10 times), get and obtain graphene oxide from effluent drying.
Described part is milliliter for liquid, for solid is gram, lower with.
Described alr mode is mechanical stirring or magnetic agitation.
Described stirring velocity is 100 ~ 1000r/min.
Described drying mode is vacuum-drying or constant pressure and dry.
Described drying temperature is 0 ~ 50 DEG C.
Second step, the preparation of graphene oxide dispersion: the graphene oxide that 1 part of the first step obtains is joined in 30 ~ 1000 parts of deionized waters, stir 20 ~ 150min, then with the frequency ultrasound process 20 ~ 600min of 10 ~ 100KHZ, again with the centrifugation 10 ~ 120min of 1000 ~ 15000r/min, get supernatant liquor and obtain graphene oxide dispersion.
Described alr mode is mechanical stirring or magnetic agitation, and stirring velocity is 100 ~ 1000r/min.
3rd step, the preparation of silicon oxide hydridization Graphene gel: the graphene oxide dispersion obtained by 1 part of second step mixes with 0.001 ~ 0.1 part of siloxanes, is warming up to 60 ~ 180 DEG C of insulation 1 ~ 48h, obtains silicon oxide hydridization Graphene gel by mixture.
Described siloxanes is the one of tetraethoxy, methyl silicate, methyltrimethoxy silane, triethoxyl silane, methyltrimethoxy silane or Trimethoxy silane.
4th step, dry: drying can adopt lyophilize or CO
2supercritical drying, adopted lyophilize when hope has the silica with great specific surface area hydridization graphene aerogel of micropore and macroporous structure simultaneously, must arrive when aperture concentrates on the silica with great specific surface area hydridization graphene aerogel of 1 ~ 500nm when hope and adopt CO
2supercritical drying.
Described lyophilize is the silicon oxide hydridization Graphene gel liquid nitrogen freezing the 3rd step obtained, and then puts into freeze drier, and dry 12 ~ 240h at the temperature of 0 ~-50 DEG C, taking-up can obtain silica with great specific surface area hydridization graphene aerogel.
Described CO
2supercritical drying is that the deionized water of hydridization Graphene gel 3 ~ 50 times of volumes the 3rd step obtained is replaced 3 ~ 15 times, use the ethanol replacement 3 ~ 15 times of 3 ~ 50 times of volumes again, each time swap is 3 ~ 12h, obtain the silicon oxide hydridization Graphene gel after solvent exchange, then the silicon oxide hydridization Graphene gel after solvent exchange is put into CO
2in the drying kettle of supercritical drying device, then pass into the CO of supercritical state
2, replace 2 ~ 20 hours, finally with the speed relief pressure of 100KPa/min, furnace cooling, taking-up can obtain silica with great specific surface area hydridization graphene aerogel.
5th step, Pintsch process: the silicon oxide hydridization graphene aerogel the 4th step obtained puts into pyrolyzer, rare gas element is passed into the flow velocity of 20 ~ 600ml/min, then with ramp to 1000 ~ 2000 DEG C of 0.5 DEG C/min ~ 50 DEG C/min, insulation 0.5 ~ 10h, furnace cooling can obtain superhigh specific surface area graphene aerogel.
Described rare gas element is the mixture of one or more in nitrogen, argon gas, helium, neon, Krypton.
Adopt the present invention can reach following technique effect:
The present invention realizes raw material by the mode mixed with liquid state and fully and uniformly mixes, and generates minimum, the finely dispersed monox nanometer particle of particle diameter, thus graphene dispersion is come, stop it to reunite through reaction; The present invention removes silicon oxide by Pintsch process again, play the effect of similar activation simultaneously, thus make the superhigh specific surface area graphene aerogel specific surface area superelevation that obtains and high temperature stability performance is excellent, have a good application prospect in fields such as catalysis, electrochemistry, the energy, sensor, super capacitor, absorption, thermal controls.
(1) the present invention the 3rd step is by siloxanes and graphene oxide dispersion liquid-phase mixing, can ensure that silicon oxide particle is uniform in whole reaction system to generate and distribution, make the silicon oxide particle particle diameter that obtains less, be uniformly dispersed, thus fully Graphene is separated, the superhigh specific surface area graphene aerogel specific surface area therefore obtained is high.
(2) silicon oxide that the siloxanes introduced of the present invention the 3rd step and siloxane reactions generate contains silicone hydroxyl or alkoxyl group can react with the oxy radical of surface of graphene oxide, thus ensures that the silicon oxide particle introduced can play compartmentation fully.
(3) the present invention the 5th step can remove the silicon oxide particle of the inner graphenic surface of silicon oxide hydridization graphene aerogel by Pintsch process, the specific surface area of graphene aerogel is got a promotion, this process can play the effect similar with reactivation process simultaneously, thus its specific surface area is improved further, therefore the superhigh specific surface area graphene aerogel specific surface area superelevation obtained, can reach 2491m
2/ g.
(4) the present invention the 5th step can make silicon oxide and Graphene react by Pintsch process and gasify to overflow, and the superhigh specific surface area graphene aerogel silicone content therefore obtained is low.
(5) the present invention the 5th step makes the group of the inner graphenic surface of graphene aerogel remove by Pintsch process, and therefore structure is more stable, can at high temperature apply and the change of not shedder sum structure etc.
Therefore, preparation method's technique of the present invention is simple, cost is low, and the product prepared has a good application prospect in fields such as catalysis, electrochemistry, the energy, sensor, super capacitor, absorption, thermal controls.
Accompanying drawing explanation
Fig. 1 is the overview flow chart of the inventive method.
Fig. 2 is superhigh specific surface area graphene aerogel SEM (field emission scanning electron microscope) photo that embodiment 1 obtains.
Fig. 3 is the N2 adsorption curve of the superhigh specific surface area graphene aerogel that embodiment 1 obtains.
Embodiment
The invention will be further described below to use embodiment, but these embodiments do not produce any restriction to protection scope of the present invention.
Embodiment 1
(1) 3g Graphite Powder 99 is mixed with 15g potassium permanganate, 40ml strong phosphoric acid is mixed with the 360ml vitriol oil and obtains nitration mixture, gained nitration mixture is joined in gained Graphite Powder 99/potassium permanganate mixture under the mechanical agitation of ice bath and 300r/min, be warming up to 50 DEG C, 12h is reacted under the mechanical agitation of 300r/min, the mixture be obtained by reacting being joined 400ml contains in the frozen water of 10ml30% hydrogen peroxide, centrifugal with the rotating speed of 2000r/min, obtain from effluent, the deionized water of 200ml will be dissolved in and with the centrifugal 1h of the rotating speed of 2000r/min from effluent, again by be dissolved in from effluent 200ml 30% hydrochloric acid and with the centrifugal 1h of the rotating speed of 2000r/min, finally will be dissolved in the ethanol of 200ml from effluent and with the centrifugal 1h of the rotating speed of 2000r/min (3 times), get and obtain graphene oxide from effluent 50 DEG C of vacuum-dryings.
(2) graphene oxide that 1g step (1) obtains is joined in 100ml deionized water, 60min is stirred under the magnetic agitation condition of 300r/min, then with the frequency ultrasound process 60min of 50KHZ, again with the centrifugation 120min of 8000r/min, get supernatant liquor and obtain graphene oxide dispersion.
(3) graphene oxide dispersion that 5ml step (2) obtains is mixed with 0.05ml tetraethoxy, mixture is warming up to 110 DEG C of insulation 24h, obtains silicon oxide hydridization Graphene gel.
(4) silicon oxide hydridization Graphene gel liquid nitrogen freezing step (3) obtained, then puts into freeze drier, dry 48h at the temperature of-50 DEG C, takes out and obtains silicon oxide hydridization graphene aerogel.
(5) the silicon oxide hydridization graphene aerogel that step (4) obtains is put into pyrolyzer, argon gas is passed into the flow velocity of 100ml/min, then with the ramp to 1000 DEG C of 2 DEG C/min, insulation 1h, furnace cooling can obtain superhigh specific surface area graphene aerogel.
Adopt the quality of the extremely-low density hydridization graphene aerogel lagging material that weighs with scale, adopt the physical dimension of vernier caliper measurement extremely-low density hydridization graphene aerogel lagging material, by quality divided by its volume, the density calculating the superhigh specific surface area graphene aerogel that embodiment 1 obtains is 0.0060g/cm
3.
Adopt the microtexture of Hitachi S4800 field emission scanning electron microscope test extremely-low density hydridization graphene aerogel lagging material, the SEM photo of the silica with great specific surface area hydridization graphene aerogel that embodiment 1 obtains as shown in Figure 2, wherein (a) figure magnification is 3000 times, the darker part of color is hole, the more shallow part of color is for being distributed with the Graphene of silicon oxide particle, b () figure magnification is 30000 times, granular substance is silicon oxide particle, the paper-like thing being full of fold is Graphene, as can be seen from the figure there is a large amount of aperture in the hole of several micron to some tens of pm in aerogel inside, and the silicon oxide particle of the graphene aerogel surface overwhelming majority removes in Pintsch process process, surface only remains few silicon oxide particle.The photoelectron spectrum figure of the superhigh specific surface area graphene aerogel adopting ESCALAB 250Xi type x-ray photoelectron spectroscopy testing example 1 to obtain, by analysis its silicone content only 1.74%.
The N2 adsorption curve (as shown in Figure 3) of the superhigh specific surface area graphene aerogel adopting the autosorb-1 type Full-automatic physical adsorption instrument testing example 1 of Kang Ta company of the U.S. to obtain, wherein X-coordinate is relative pressure, ordinate zou is adsorptive capacity, adopt BET (Brunauer – Emmett – Teller) method to calculate its specific surface area, the specific surface area of the superhigh specific surface area graphene aerogel that embodiment 1 obtains is 2332m
2/ g.
The first step Graphite Powder 99 and potassium permanganate portion rate, strong phosphoric acid and vitriol oil portion rate, nitration mixture and Graphite Powder 99/potassium permanganate mixture portion rate, temperature of reaction and time, the number major effect of frozen water and hydrogen peroxide obtains degree of oxidation and the lamellar spacing of graphene oxide, when parameters value is all in given range, the graphene oxide degree of oxidation obtained and lamellar spacing not quite influenced, all comparatively suitable, therefore the specific surface area impact of these parameters on superhigh specific surface area graphene aerogel is little; The first step alr mode, stirring velocity, drying mode and temperature do not affect reaction process, time only needed for influence process, can not have an impact to the graphene oxide degree of oxidation obtained and lamellar spacing, therefore little on the specific surface area impact of superhigh specific surface area graphene aerogel; The consumption of the first step deionized water, the concentration of hydrochloric acid and consumption, the consumption of ethanol, centrifugal rotating speed and time, be dissolved in ethanol and centrifugal number of times on the graphene oxide degree of oxidation obtained and lamellar spacing without impact, only produce a little impact to the purity of the graphene oxide obtained, therefore the specific surface area impact of these parameters on superhigh specific surface area graphene aerogel is little.
Second step alr mode, stirring velocity, churning time, ultrasonic frequency, ultrasonic time, centrifugal rotational speed, the degree of uniformity of centrifugation time major effect graphene oxide dispersion dispersion, when parameters is in the scope provided, little on the degree of uniformity impact of graphene oxide dispersion dispersion, all can obtain uniform graphene oxide dispersion, therefore the specific surface area impact of these parameters on superhigh specific surface area graphene aerogel is little.
The abundant degree that 3rd step holding temperature and time major effect siloxanes and graphene oxide dispersion are reacted, carry out to react fully, the temperature range provided and time have exceeded siloxanes and graphene oxide dispersion fully reacts required temperature and time, and therefore holding temperature and time are on the specific surface area impact of superhigh specific surface area graphene aerogel not quite.
The speed of the 4th step lyophilize temperature and time major effect drying and abundant degree, to superhigh specific surface area graphene aerogel structure can not have an impact, therefore lyophilize temperature and time is little on the impact of the specific surface area of superhigh specific surface area graphene aerogel.
Embodiment 2 ~ 162
The processing parameter that embodiment 2 ~ 162 adopts is as shown in table 1, its technological process is identical with embodiment 1, difference is 4 parameters such as siloxanes kind, deionized water and graphene oxide portion rate, siloxanes and graphene oxide dispersion portion rate, cracking temperature, except writing except processing parameter in table, all the other processing parameters are identical with embodiment 1.
Table 1 embodiment 2 ~ 162 prepares preparation technology parameter and the performance of superhigh specific surface area graphene aerogel
Embodiment 163
Embodiment 163 is the 4th step with the difference of embodiment 1, and all the other processing parameters are identical with embodiment 1.Embodiment 163 the 4th step is: deionized water, the ethanol of hydridization Graphene gel 10 times of volumes step (3) obtained replace 10 times respectively, each time swap is 6h, obtain the silicon oxide hydridization Graphene gel after solvent exchange, then the silicon oxide hydridization Graphene gel after solvent exchange is put into CO
2in the drying kettle of supercritical drying device, then pass into the CO of supercritical state
2, replace 5 hours, finally with the speed relief pressure of 100KPa/min, furnace cooling can obtain superhigh specific surface area graphene aerogel.
The performance of the superhigh specific surface area graphene aerogel that embodiment 163 obtains is in table 3.
The degree that in the thorough degree of the removal of impurity in the volume of the 4th step deionized water and ethanol and displacement number of times and time major effect gel and gel, solvent is replaced by alcohol, on the structures and characteristics of gel without impact, when parameters is in the scope provided, all can remove the impurity in gel thoroughly and the solvent in gel can also thoroughly replace by alcohol, therefore these parameters are little on the impact of the specific surface area of superhigh specific surface area graphene aerogel.Supercritical state CO
2the thorough degree that in time swap major effect gel, alcohol is displaced, time in the scope provided, alcohol is thoroughly replaced, therefore supercritical state CO
2the specific surface area impact of time swap on superhigh specific surface area graphene aerogel is little.
Embodiment 164 ~ 324
The processing parameter that embodiment 164 ~ 324 adopts is as shown in table 2, its technological process is identical with embodiment 163, difference is the parameter that siloxanes kind, deionized water and graphene oxide portion rate, siloxanes and graphene oxide dispersion portion rate, cracking temperature etc. 4 are larger to superhigh specific surface area graphene aerogel performance impact, except writing except processing parameter in table, all the other processing parameters are identical with embodiment 163.
Table 2 embodiment 163 ~ 324 prepares preparation technology parameter and the performance of superhigh specific surface area graphene aerogel
Claims (10)
1. a preparation method for superhigh specific surface area graphene aerogel, is characterized in that comprising the steps:
The first step, the preparation of graphene oxide: Graphite Powder 99 and potassium permanganate are mixed according to portion rate 1:3 ~ 10 and obtains Graphite Powder 99/potassium permanganate mixture, strong phosphoric acid and the vitriol oil are mixed according to portion rate 1:5 ~ 15 and obtains nitration mixture, the nitration mixture of 10 ~ 40 parts is joined in 1 part of Graphite Powder 99/potassium permanganate mixture under the condition of ice bath and stirring, be warming up to 40 ~ 90 DEG C, reaction 5 ~ 24h under the condition stirred, the mixture be obtained by reacting is added 10 ~ 50 parts containing in the frozen water of 0.1 ~ 3 part of 30% hydrogen peroxide, centrifugal 1h, obtain from effluent, the deionized water of 10 ~ 100 parts will be dissolved in and centrifugal 1h from effluent, again by be dissolved in from effluent 10 ~ 100 parts 10% ~ 35% hydrochloric acid and centrifugal 1h, finally will be dissolved in the ethanol of 10 ~ 100 parts from effluent and centrifugal 1h, repeat 3 ~ 10 times, get and obtain graphene oxide from effluent drying,
Described part is milliliter for liquid, for solid is gram;
Second step, the preparation of graphene oxide dispersion: the graphene oxide that 1 part of the first step obtains is joined in 30 ~ 1000 parts of deionized waters, stir 20 ~ 150min, then with the frequency ultrasound process 20 ~ 600min of 10 ~ 100KHZ, centrifugal 10 ~ 120min again, gets supernatant liquor and obtains graphene oxide dispersion;
3rd step, the preparation of silicon oxide hydridization Graphene gel: the graphene oxide dispersion obtained by 1 part of second step mixes with 0.001 ~ 0.1 part of siloxanes, is warming up to 60 ~ 180 DEG C of insulation 1 ~ 48h, obtains silicon oxide hydridization Graphene gel by mixture;
4th step, dry: drying to be carried out to the silicon oxide hydridization Graphene gel that the 3rd step obtains, obtains silica with great specific surface area hydridization graphene aerogel;
5th step, Pintsch process: the silicon oxide hydridization graphene aerogel the 4th step obtained puts into pyrolyzer, passes into rare gas element, is then warming up to 1000 ~ 2000 DEG C, insulation 0.5 ~ 10h, furnace cooling obtains superhigh specific surface area graphene aerogel.
2. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, is characterized in that alr mode described in the first step, second step is mechanical stirring or magnetic agitation; Stirring velocity during stirring is 100 ~ 1000r/min.
3. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, is characterized in that the mode when the first step is dry from effluent is vacuum-drying or constant pressure and dry; Drying temperature is 0 ~ 50 DEG C.
4. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, it is characterized in that the strong phosphoric acid concentration >85% described in the first step, vitriol oil concentration >95%, ethanol is technical pure.
5. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, the siloxanes that it is characterized in that described in the 3rd step is the one of tetraethoxy, methyl silicate, methyltrimethoxy silane, triethoxyl silane, methyltrimethoxy silane or Trimethoxy silane.
6. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, it is characterized in that when wishing that be there is the silica with great specific surface area hydridization graphene aerogel of micropore and macroporous structure simultaneously, 4th step adopts lyophilize, by the silicon oxide hydridization Graphene gel liquid nitrogen freezing that the 3rd step obtains, then freeze drier is put into, at the temperature of 0 ~-50 DEG C, dry 12 ~ 240h, takes out and obtains silica with great specific surface area hydridization graphene aerogel.
7. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, is characterized in that adopting CO when wishing concentrate on the silica with great specific surface area hydridization graphene aerogel of 1 ~ 500nm to aperture
2supercritical drying, the deionized water displacement of hydridization Graphene gel 3 ~ 50 times of volumes obtained by the 3rd step 3 ~ 15 times, use the ethanol replacement 3 ~ 15 times of 3 ~ 50 times of volumes again, each time swap is 3 ~ 12h, obtain the silicon oxide hydridization Graphene gel after solvent exchange, then the silicon oxide hydridization Graphene gel after solvent exchange is put into CO
2in the drying kettle of supercritical drying device, then pass into the CO of supercritical state
2, replace 2 ~ 20 hours, finally with the speed relief pressure of 100KPa/min, furnace cooling, taking-up can obtain silica with great specific surface area hydridization graphene aerogel.
8. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, the rare gas element that it is characterized in that described in the 5th step is the mixture of one or more in nitrogen, argon gas, helium, neon, Krypton.
9. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, is characterized in that described centrifugal rotating speed is 1000 ~ 15000r/min.
10. the preparation method of superhigh specific surface area graphene aerogel as claimed in claim 1, is characterized in that the flow velocity that the 5th step passes into rare gas element is 20 ~ 600ml/min, the speed of intensification is 0.5 DEG C/and min ~ 50 DEG C/min.
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