CN104860304A - High specific surface area of silicon oxide hybridized graphene aerogel and production method thereof - Google Patents
High specific surface area of silicon oxide hybridized graphene aerogel and production method thereof Download PDFInfo
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Abstract
The invention discloses high specific surface area of silicon oxide hybridized graphene aerogel and a production method thereof. The high specific surface area of silicon oxide hybridized graphene aerogel and the production method aim at solving the problem that the specific surface area is reduced when hybridization is performed on graphene aerogel. The high specific surface area of silicon oxide hybridized graphene aerogel is formed by grapheme through building, wherein a large quantity of silicon oxide particles are distributed on the surface of the grapheme; the high specific surface area of silicon oxide hybridized graphene aerogel comprises a porous structure, wherein the pore diameter of the porous structure is concentrated to be 1 to 500 nm; the porous structure comprises a microporous structure and a macroporous structure. The production method comprises serving graphite powder, siloxane and the like as main raw materials, producing graphene oxide, preparing a graphene oxide dispersing agent and producing silicon oxide hybridized graphene gel and obtaining the high specific surface area of silicon oxide hybridized graphene aerogel after drying. According to the high specific surface area of silicon oxide hybridized graphene aerogel and the production method thereof, tiny particle size of silicon oxide nanoparticles are produced through liquid mixing of the raw materials and a reaction, the introduction on the silicon oxide particles is implemented, meanwhile the partition effect on the grapheme is achieved, and accordingly the high specific surface area of silicon oxide hybridized graphene aerogel is large in specific surface area, small in silicon oxide particle and uniform in distribution.
Description
Technical field
The present invention relates to a kind of graphene aerogel, particularly relate to a kind of silica with great specific surface area hydridization graphene aerogel and preparation method thereof.
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.But the impact of the Some features due to itself, graphene aerogel is very limited in the application in some fields separately.
Carrying out modification by some other compound to graphene aerogel is a kind of way more common at present, existing a large amount of documents and materials are reported this method and the effect that obtains thereof, result display can improve some performances of graphene aerogel really by modification, but still has larger gap with notional result.One of main reason wherein causing this phenomenon is, the hybridized aerogel material specific surface area prepared is low, such as document [Li Xiao, Dongqing Wu, Sheng Han, Yanshan Huang, Shuang Li, MingzhongHe, Fan Zhang, and Xinliang Feng.Self-Assembled Fe
2o
3/ Graphene Aerogel withHigh Lithium Storage Performance.ACS Appl.Mater.Interfaces 2013,5,3764-3769] (there is the self-assembly Fe of high lithium memory property
2o
3/ graphene aerogel) by one step hydro thermal method with Fe
2o
3hydridization graphene aerogel, the Fe prepared
2o
3hydridization graphene aerogel BET (Brunauer – Emmett – Teller) specific surface area only 77m
2/ g.This has had a strong impact on the performance of graphene aerogel performance, and therefore acquired results and theoretical value have a long way to go.So, while hydridization is carried out to graphene aerogel, and don't obviously reduce its specific surface area, even improve its specific surface area and just become particularly important.
Summary of the invention
The technical problem to be solved in the present invention is while carrying out hydridization to graphene aerogel, and its specific surface area of not obvious reduction, even improves its specific surface area, provides a kind of silica with great specific surface area hydridization graphene aerogel and preparation method thereof.
A kind of silica with great specific surface area hydridization graphene aerogel, it is characterized in that silica with great specific surface area hydridization graphene aerogel has the Graphene of a large amount of silicon oxide particle to build by surface arrangement, there is vesicular structure, its aperture concentrates on 1 ~ 500nm, or has micropore (aperture <50nm) and macropore (aperture >5 μm) simultaneously.
Described silicon oxide particle size distribution is between several nanometer to tens nanometers.
A preparation method for silica with great specific surface area hydridization graphene aerogel, mainly comprises the preparation of graphene oxide, the preparation of graphene oxide dispersion, the preparation of silicon oxide hydridization Graphene gel, dry four steps.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 >85%) 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, triethoxyl silane and 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.
Adopt the present invention can reach following technique effect:
For the problem that being difficult to of existing of current graphene aerogel specific surface area that separately application and hydridization graphene aerogel exist is little, the present invention proposes to realize raw material by the mode mixed with liquid state and fully and uniformly mixes, the minimum monox nanometer particle of particle diameter is generated through reaction, while silicon oxide particle is introduced in realization, compartmentation is played to Graphene, thus it is high to make the silica with great specific surface area hydridization graphene aerogel obtained have specific surface area simultaneously, silicon oxide particle is little, the feature such as be evenly distributed, in electrochemistry, absorption, catalysis, the fields such as thermal control have a good application prospect.
(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, and make the silicon oxide particle particle diameter that obtains less, thus make the silicon oxide introduced can fully play its function.
(2) due to the present invention the 3rd step introduce silicon oxide particle particle diameter little, be uniformly dispersed, can be separated by Graphene fully, the silica with great specific surface area hydridization graphene aerogel specific surface area therefore obtained is high, and specific surface area can reach 1548m
2/ g.
(3) silicone/silica that the present invention the 3rd step is introduced 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.
(4) the present invention the 4th step can make the silica with great specific surface area hydridization graphene aerogel obtained have macropore and microvoid structure by lyophilize simultaneously, be conducive to the generation of the mass transfer processes such as the circulation of gas, thus promote its application in absorption, catalysis etc.; And pass through CO
2supercritical drying can make the silica with great specific surface area hydridization graphene aerogel obtained have uniform internal structure, and aperture concentrates on 1 ~ 500nm, and has larger specific surface area, thus promotes its application in electrochemistry, thermal control etc.
Therefore, preparation method's technique of the present invention is simple, cost is low, has a good application prospect in fields such as electrochemistry, absorption, catalysis, thermal controls.
Accompanying drawing explanation
Fig. 1 is the overview flow chart of the inventive method.
Fig. 2 is SEM (field emission scanning electron microscope) photo of the silica with great specific surface area hydridization graphene aerogel that embodiment 1 obtains.
Fig. 3 is the N2 adsorption curve of the silica with great specific surface area hydridization graphene aerogel that embodiment 1 obtains.
Fig. 4 is the SEM photo of the silica with great specific surface area hydridization graphene aerogel that embodiment 37 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 18g 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 10ml 30% 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, repeat to be dissolved in 200ml ethanol from effluent and with the rotating speed centrifugal process 3 times of 2000r/min, 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 put into freeze drier, dry 48h at the temperature of-50 DEG C, taking-up can obtain silica with great specific surface area hydridization 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 silica with great specific surface area hydridization graphene aerogel that embodiment 1 obtains is 0.0116g/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, projection is silicon oxide particle, forms small hole between particle.
The N2 adsorption curve (as shown in Figure 3) of the silica with great specific surface area hydridization 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 method to calculate its specific surface area, the specific surface area of the silica with great specific surface area hydridization graphene aerogel that embodiment 1 obtains is 1135m
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 these parameters are little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact; 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 density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact; 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 these parameters are little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.
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 these parameters are little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.
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 little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.
The speed of the 4th step lyophilize temperature and time major effect drying and abundant degree, can not have an impact to the structure of silica with great specific surface area hydridization graphene aerogel, therefore lyophilize temperature and time is little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.
Embodiment 2 ~ 36
The processing parameter that embodiment 2 ~ 36 adopts is as shown in table 1, its technological process is identical with embodiment 1, difference is the parameter that siloxanes kind, deionized water and graphene oxide portion rate, siloxanes and graphene oxide dispersion portion rate etc. 3 are larger to silica with great specific surface area hydridization graphene aerogel performance impact, except writing except processing parameter in table, all the other processing parameters are identical with embodiment 1.
Table 1 embodiment 2 ~ 36 prepares preparation technology parameter and the performance of silica with great specific surface area hydridization graphene aerogel
Embodiment 37
Embodiment 37 is the 4th step with the difference of embodiment 1, and all the other processing parameters are identical with embodiment 1.Embodiment 37 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 silica with great specific surface area hydridization graphene aerogel.
The SEM photo of the silica with great specific surface area hydridization graphene aerogel that embodiment 37 obtains as shown in Figure 4, wherein particle is silicon oxide particle, translucent paper-like thing is Graphene, as can be seen from the figure the aperture in the hole of aerogel inside is less than 500nm, and has a large amount of nano level silicon oxide particle to be distributed between Graphene.
The performance of the silica with great specific surface area hydridization graphene aerogel that embodiment 37 obtains is in table 2.
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 ethanol, 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 ethanol, therefore these parameters are little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.Supercritical state CO
2the thorough degree that in time swap major effect gel, ethanol is displaced, time in the scope provided, ethanol is thoroughly replaced, therefore supercritical state CO
2time swap is little on the density of silica with great specific surface area hydridization graphene aerogel, specific surface area impact.
Embodiment 38 ~ 72
The processing parameter that embodiment 38 ~ 72 adopts is as shown in table 2, its technological process is identical with embodiment 37, difference is the parameter that siloxanes kind, deionized water and graphene oxide portion rate, siloxanes and graphene oxide dispersion portion rate etc. 3 are larger to silica with great specific surface area hydridization graphene aerogel performance impact, except writing except processing parameter in table, all the other processing parameters are identical with embodiment 37.
Table 2 embodiment 37 ~ 72 prepares preparation technology parameter and the performance of silica with great specific surface area hydridization graphene aerogel
Claims (13)
1. a silica with great specific surface area hydridization graphene aerogel, is characterized in that silica with great specific surface area hydridization graphene aerogel is built by the Graphene of surface arrangement silica particle, has vesicular structure.
2. silica with great specific surface area hydridization graphene aerogel as claimed in claim 1, is characterized in that the aperture of described vesicular structure concentrates on 1 ~ 500nm.
3. silica with great specific surface area hydridization graphene aerogel as claimed in claim 1, is characterized in that described vesicular structure has the micropore of aperture <50nm and the macropore of aperture >5 μm.
4. silica with great specific surface area hydridization graphene aerogel as claimed in claim 1, is characterized in that described silicon oxide particle size distribution is between several nanometer to tens nanometers.
5. prepare a method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1, it 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 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, 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: joined by the graphene oxide that 1 part of the first step obtains in 30 ~ 1000 parts of deionized waters, stirs 20 ~ 150min, then supersound process 20 ~ 600min, 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.
6. prepare the method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, it is characterized in that the alr mode described in the first step, second step is mechanical stirring or magnetic agitation, speed during stirring is 100 ~ 1000r/min.
7. prepare the method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, it is characterized in that described in the first step being vacuum-drying or constant pressure and dry from effluent drying mode, drying temperature is 0 ~ 50 DEG C.
8. prepare the method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, the siloxanes that it is characterized in that described in the 3rd step is the one of tetraethoxy, methyl silicate, triethoxyl silane and Trimethoxy silane.
9. prepare the method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, 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 namely obtains silica with great specific surface area hydridization graphene aerogel.
10. prepare the method for silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, it is characterized in that when wishing concentrate on the silica with great specific surface area hydridization graphene aerogel of 1 ~ 500nm to aperture, the 4th step adopts CO
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, takes out and namely obtains silica with great specific surface area hydridization graphene aerogel.
11. methods preparing silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, it is characterized in that strong phosphoric acid concentration >85% described in the first step, vitriol oil concentration >95%, described ethanol is technical pure.
12. methods preparing silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, it is characterized in that described centrifugal time rotating speed be 1000 ~ 15000r/min.
13. methods preparing silica with great specific surface area hydridization graphene aerogel as claimed in claim 1 as claimed in claim 5, is characterized in that the frequency of second step supersound process is 10 ~ 100KHZ.
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| CN112479188A (en) * | 2020-11-23 | 2021-03-12 | 陕西理工大学 | Silicon-doped graphene aerogel and preparation method and application thereof |
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