CN104401977A - Preparation method of graphene aerogel and graphene-carbon nanotube aerogel - Google Patents
Preparation method of graphene aerogel and graphene-carbon nanotube aerogel Download PDFInfo
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Abstract
The invention relates to a preparation method of graphene aerogel and graphene-carbon nanotube aerogel. According to the method, graphene oxide or a mixture of graphene oxide and carbon nanotube is subjected to drying treatment; graphene oxide is reduced through a magnesium thermal reaction; the material is soaked in an acidic water solution; and impurities are removed, and the material is dried, such that graphene aerogel or graphene-carbon nanotube aerogel is obtained. Compared with prior arts, the method provided by the invention has the advantages of simple process, and is green and environment-friendly. Magnesium powder is adopted as a reducing agent. Compared to reducing agents such as hydrazine hydrate, sodium borohydride, formaldehyde, carbohydrate compounds, ascorbic acid and hydroiodic acid, magnesium powder has higher reducibility, such that the graphene aerogel or graphene-carbon nanotube aerogel with high carbon-oxygen ratio can be prepared. The electrical conductivity of the graphene aerogel or graphene-carbon nanotube aerogel can reach 10<4>s/cm. The graphene aerogel or graphene-carbon nanotube aerogel has large specific surface area, and is non-toxic and harmless. The graphene aerogel or graphene-carbon nanotube aerogel can be widely applied.
Description
Technical field
The invention belongs to aerogel technical field, relate to the preparation method of a kind of graphene aerogel and Graphene-CNT (carbon nano-tube) aerogel.
Background technology
Aerogel has the more low-density porous nanometer material of high-ratio surface sum.General by supercritical drying or the acquisition of frozen drying wet gel.At first, carbon aerogels is with Resorcinol and formaldehyde for raw material, after forming gel in the basic conditions, by the aerogel that supercritical drying is obtained, is prepared from by carbonization.Carbon aerogels is as a kind of novel mesoporous and porous structural material, and its porosity rate reaches 80% ~ 99.8%, and specific surface area is up to 200 ~ 1500m
2/ g.Carbon aerogels has a wide range of applications in a lot of field, as catalyzer and support of the catalyst, gas filtering material, high efficiency heat insulation material etc., also can be used for electrode materials.And using carbon aerogels as electrode of electric double layer capacitor material time, its ratio capacitance is up to more than 50F/g.
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.The structures shape of this uniqueness its there is abundant physical and chemical performance, such as, up to 2630m
2the theoretical specific surface area of/g, there is outstanding heat conductivility (3000W/ (mK)) and mechanical property (Young's modulus 1060GPa, breaking tenacity 130GPa), and the feature such as electronic mobility (1500cm/ (Vs)) at a high speed under room temperature condition.Graphene can be used for a series of technical fields such as sensor, energy storage material, transistor, sorbing material, support of the catalyst.At present, the preparation method of Graphene mainly contains four kinds: chemical Vapor deposition process, mechanically peel method, plane of crystal epitaxial growth method, chemical reduction method.Wherein, chemical reduction method is the graphite oxide utilizing the reduction of the method for chemistry to be stripped into single layer structure.Such as, adopt the reductive agents such as hydrazine hydrate, sodium borohydride, lithium aluminum hydride, formaldehyde, saccharide compound, xitix, hydroiodic acid HI to carry out reduction-oxidation graphite, just can obtain stable Graphene aqueous colloid solution.But, the carbon-to-oxygen ratio lower (< 20) of Graphene is obtained by above-mentioned reductive agent, electroconductibility is not high yet, and the carbon-to-oxygen ratio of being assembled the graphene aerogel made by this Graphene is also lower, and this directly can affect the final performance of graphene aerogel.In addition, above-mentioned reductive agent, except saccharide compound and xitix, other reductive agent all has toxicity or corrodibility, and this is to bad environmental.
Summary of the invention
Object of the present invention is exactly provide a kind of technological process simple to overcome defect that above-mentioned prior art exists, adopts magnesium reduction process to prepare the method for graphene aerogel and Graphene-CNT (carbon nano-tube) aerogel.
Object of the present invention can be achieved through the following technical solutions:
The preparation method of a kind of graphene aerogel and Graphene-CNT (carbon nano-tube) aerogel, the method is the mixing solutions by graphene oxide solution or graphene oxide and CNT (carbon nano-tube), drying process, by magnesium thermit, graphene oxide is reduced again, and be soaked in acidic aqueous solution, and remove impurity, dry, i.e. obtained graphene aerogel or Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, through ultrasonic disperse or mechanical stirring until mix, obtained mass concentration is the graphene oxide water solution of 0.05 ~ 20mg/ml;
(2) be (0 ~ 10) by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1): 1, CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and through ultrasonic disperse or mechanical stirring until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) graphene oxide graphene oxide solution obtained for step (1) or step (2) obtained and the mixing solutions of CNT (carbon nano-tube), carry out lyophilize or supercritical drying, obtained graphite oxide aerogel or graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphite oxide aerogel obtained for step (3) or graphene oxide-CNT (carbon nano-tube) aerogel being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained graphene aerogel or Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and the CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube, the external diameter < 8nm of this multiple-wall carbon nanotube.
The mass ratio of the magnesium powder described in step (4) and graphite oxide aerogel and graphene oxide-CNT (carbon nano-tube) aerogel is (1 ~ 100): 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 5 ~ 10 DEG C/min, reactor is heated to 550 ~ 1000 DEG C, and isothermal reaction 5 ~ 24h.
Described supercritical drying is that ethanol supercritical drying or CO 2 supercritical are dry.
When carrying out supercritical drying to the mixing solutions of graphene oxide and CNT (carbon nano-tube), first by the mixing solutions of graphene oxide and CNT (carbon nano-tube) under the temperature condition of 25 ~ 99 DEG C, placement for some time obtains corresponding hydrogel, a large amount of ethanol or acetone is adopted to replace the aqueous solvent existed in corresponding hydrogel and other soluble reaction thing and reaction product again, to obtain corresponding ethanol gel or acetone gel, then Supercritical Ethanol or supercritical co mode is adopted, drying is carried out to described corresponding ethanol gel or acetone gel, obtain graphite oxide aerogel and Graphene. CNT (carbon nano-tube) aerogel.
Described supercritical drying process is not by the restriction of supercritical drying equipment, can any business or non-commercial supercritical drying equipment in complete the supercritical drying of ethanol gel or acetone gel, to obtain graphite oxide aerogel and Graphene. CNT (carbon nano-tube) aerogel.
Described lyophilize is directed lyophilize or non-directional lyophilize, and freezing temp is-1 DEG C ~ liquid nitrogen temperature, and drying temperature is 0 ~ 60 DEG C, and dry vacuum tightness is 5 ~ 50000Pa, and time of drying is 2 ~ 48h.
When carrying out lyophilize to the mixing solutions of graphene oxide and CNT (carbon nano-tube), first can adopt liquid nitrogen freezing, then proceeding to vacuum-drying in lyophilizer; Also can direct lyophilize in lyophilizer.
Acidic aqueous solution described in step (4) adopts hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid formulated, and concentration is O.05 ~ 4mol/L.
The ultrasonic power of described ultrasonic disperse is 40 ~ 1000W, and ultrasonic frequency is 20 ~ 80KHz; Described churned mechanically rotating speed is 40 ~ 4000 revs/min.
The present invention prepares graphene aerogel and the Graphene of gained. and CNT (carbon nano-tube) aerogel is a kind of inorganic conductive aerogel being made up of three-dimensional net structure two-dimensional graphene: graphene aerogel and Graphene. and the carbon-to-oxygen ratio of CNT (carbon nano-tube) aerogel is (20 ~ 4000): 1, aperture is 1nm ~ 100 μm, porosity is 50 ~ 99.9%, and density is 0.00005 ~ 0.5g/cm
3, specific surface area is 5 ~ 3000m
2/ g, specific conductivity is 10
-5~ 10
4s/cm.
The present invention prepares graphene aerogel and the Graphene of gained. and when CNT (carbon nano-tube) aerogel is used as electrode material for electric double layer capacitor, its ratio capacitance is 90 ~ 250F/g; During as electromagnetic shielding material, within the scope of 10KHz ~ 18GHz, its electromagnet shield effect is 10 ~ 90dB.
Compared with prior art, the present invention has following characteristics:
1) when preparing graphite oxide aerogel, compare additive method, do not adopt any linking agent, make full use of graphene oxide special construction and abundant functional group, direct formation aerogel, while reduction preparation cost, ensure that the purity of graphene aerogel, and the structural unit that Graphene is intrinsic, farthest play the physical and chemical performance that it is excellent;
2) magnesiothermic reduction graphene oxide mainly utilizes the steam of magnesium low, and there is very strong reductibility, with the oxygen-containing functional group generation chemical reaction in graphene oxide, generate the Graphene that carbon-to-oxygen ratio is very high, simultaneously, reaction conditions is controlled, the pattern of aerogel is not impacted, and high temperature reduction under direct shielding gas, require temperature higher (about 1000 DEG C) on the one hand, and the oxygen-containing functional group in graphene oxide can be caused to discharge in a gaseous form, and cause popping of aerogel, cannot be shaping;
3) owing to adopting magnesium powder as reductive agent, compared to reductive agents such as hydrazine hydrate, sodium borohydride, formaldehyde, saccharide compound, xitix, hydroiodic acid HIs, its reductibility is stronger, obtained graphene aerogel and the carbon-to-oxygen ratio of Graphene-CNT (carbon nano-tube) aerogel higher, electroconductibility is also better, and nontoxic;
4) magnesiothermic reduction reaction is adopted, not only energy consumption is low pollution-free, and preparation graphene aerogel and Graphene-CNT (carbon nano-tube) aerogel morphology controllable, there is good mechanical property, its microcosmic vesicular structure, has larger application prospect in absorption and catalysis;
5) in the preparation process of composite aerogel, can carbon nanotube be added, increase the conductivity of aerogel further.
Accompanying drawing explanation
The atomic force microscope spectrogram of the graphene oxide of Fig. 1 prepared by the embodiment of the present invention 1;
The digital photograph of the graphite oxide aerogel of Fig. 2 prepared by the embodiment of the present invention 1;
The digital photograph of the graphene aerogel of Fig. 3 prepared by the embodiment of the present invention 1;
The electron microscope picture of the graphene aerogel of Fig. 4 prepared by the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
The present embodiment prepares graphene aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, ultrasonic disperse is until mix, and obtained mass concentration is the graphene oxide water solution of 4.0mg/ml;
(2) graphene oxide water solution that step (1) is obtained is carried out supercritical drying, obtained graphite oxide aerogel;
(3) after the graphite oxide aerogel that step (2) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained graphene aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from.
Hummers chemical method is adopted to prepare the concrete technology flow process of graphene oxide: the reaction flask of 500mL is placed in ice bath, add the appropriate vitriol oil, stir, and add the solid mixture of 4g Graphite Powder 99 and 2g SODIUMNITRATE, gradation adds 12g potassium permanganate again, control temperature of reaction and be no more than 20 DEG C, after stirring reaction for some time, be warming up to about 35 DEG C, continue to stir 30min, slowly add a certain amount of deionized water again, after continuing to stir 20min, add appropriate hydrogen peroxide, the oxygenant that reduction is residual, filtered while hot, and with 5% HCl solution and deionized water wash.Finally, vacuum drying oven filter cake being placed in 60 DEG C is fully dry, saves backup.
Magnesium powder described in step (3) and the mass ratio of graphite oxide aerogel are 100: 1.
The condition of the magnesium thermit described in step (3) is under an argon atmosphere, with the temperature rise rate of 8 DEG C/min, reactor is heated to 550 DEG C, and isothermal reaction 24h.
Described supercritical drying is ethanol supercritical drying.
The ultrasonic power of described ultrasonic disperse is 40W, and ultrasonic frequency is 20KHz.
Graphene oxide water solution is carried out overcritical freezing time, first by graphene oxide solution under the temperature condition of 25 DEG C, placement for some time obtains corresponding hydrogel, a large amount of ethanol is adopted to replace the aqueous solvent existed in corresponding hydrogel and other soluble reaction thing and reaction product again, to obtain corresponding ethanol gel, then Supercritical Ethanol mode is adopted, drying is carried out to described corresponding ethanol gel, obtains graphite oxide aerogel and Graphene-CNT (carbon nano-tube) aerogel.
Acidic aqueous solution described in step (3) is the aqueous acetic acid of 0.05mol/L.
As shown in Figure 1, the present embodiment prepares the thickness of gained graphite oxide aerogel at about 1nm, shows that prepared graphene oxide keeps good two-dimensional layered structure.
Fig. 2 is the optical photograph of graphite oxide aerogel prepared by the present embodiment; Fig. 3 is the optical photograph of graphene aerogel prepared by the present embodiment; Fig. 4 is the stereoscan photograph of the graphene aerogel of this enforcement preparation.
Can be found by Fig. 2, Fig. 3, before and after magnesiothermic reduction, the one-piece construction of aerogel has almost no change, and adopts additive method to reduce and prepare graphene aerogel and often cause aerogel one-piece construction to change, and causes aerogel unstable.Can be found by Fig. 4, graphene aerogel still maintains good vesicular structure after magnesiothermic reduction, and this hole is macropore, shows that this material has special mechanical property and very high absorption property, has very large using value.
The aperture that the present embodiment prepares the graphene aerogel of gained is 1 ~ 40 μm, and density is 1.8g/cm
3, specific conductivity is 27.7S/m, and during as electrode material for electric double layer capacitor, its ratio capacitance is up to 130 ~ 250F/g, and internal resistance is less than 0.2 ohm, and leakage current is less than 1mA, and circulate after 5000 times, ratio capacitance can keep original more than 90%.Using the graphene aerogel of preparation as electromagnetic shielding material, within the scope of 10KHz ~ 18GHz, electromagnet shield effect reaches 15 ~ 90dB.Using the graphene aerogel of preparation as lagging material, its normal-temperature vacuum thermal conductivity is 0.012Wm
-1k
-1, when 2500 DEG C, Vacuum Heat conductance is 0.15Wm
-1k
-1.
The graphene aerogel that the embodiment of the present invention proposes, combines the photoelectricity feature of Graphene and the light porous feature of aerogel, will at the energy, optical, electrical sub-device, the component of nano-machine, transistor, rectifier, photodiode, (biology) sensor, molecular device, electric double layer capacitance material, electromagnetic shielding, stealthy technique, life science, catalytic field, adsorb be separated, the aspect such as high temperature insulating protection is widely used.
Embodiment 2:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, ultrasonic disperse is until mix, and obtained mass concentration is the graphene oxide water solution of 0.5mg/ml;
(2) be 5: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and ultrasonic disperse is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out lyophilize, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
In the present embodiment, the graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 40: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 5 DEG C/min, reactor is heated to 700 DEG C, and isothermal reaction 5h.
Described lyophilize is directed lyophilize, and freezing temp is-16 DEG C, and drying temperature is 25 DEG C, and dry vacuum tightness is 8Pa, and time of drying is 24h.
Acidic aqueous solution described in step (4) is the aqueous hydrochloric acid of 3mol/L.
The ultrasonic power of described ultrasonic disperse is 500W, and ultrasonic frequency is 60KHz.
Embodiment 3:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, ultrasonic disperse is until mix, and obtained mass concentration is the graphene oxide water solution of 8mg/ml;
(2) be 5: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and ultrasonic disperse is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube):
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out supercritical drying, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 20: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 5 DEG C/min, reactor is heated to 850 DEG C, and isothermal reaction 10h.
Described supercritical drying is that CO 2 supercritical is dry.
The ultrasonic power of described ultrasonic disperse is 1000W, and ultrasonic frequency is 80KHz.
The mixing solutions of graphene oxide and CNT (carbon nano-tube) is carried out overcritical freezing time, first by the mixing solutions of graphene oxide and CNT (carbon nano-tube) under the temperature condition of 60 DEG C, placement for some time obtains corresponding hydrogel, a large amount of ethanol is adopted to replace the aqueous solvent existed in corresponding hydrogel and other soluble reaction thing and reaction product again, to obtain corresponding ethanol gel, then supercritical co mode is adopted, drying is carried out to described corresponding ethanol gel, obtains graphite oxide aerogel and Graphene-CNT (carbon nano-tube) aerogel.
Acidic aqueous solution described in step (4) is the aqueous sulfuric acid of 4mol/L.
Embodiment 4:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, mechanical stirring is until mix, and obtained mass concentration is the graphene oxide water solution of 0.05mg/ml;
(2) be 10: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and mechanical dispersion is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out lyophilize, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 80: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 10 DEG C/min, reactor is heated to 1000 DEG C, and isothermal reaction 5h.
Described churned mechanically rotating speed is 4000 revs/min.
Described lyophilize is directed lyophilize, and freezing temp is-1 DEG C, and drying temperature is 60 DEG C, and dry vacuum tightness is 5Pa, and time of drying is 48h.
Acidic aqueous solution described in step (4) is the aqueous sulfuric acid of 4mol/L.
Embodiment 5:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, mechanical stirring is until mix, and obtained mass concentration is the graphene oxide water solution of 20mg/ml;
(2) be 2: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and mechanical dispersion is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out lyophilize, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 1: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 8 DEG C/min, reactor is heated to 950 DEG C, and isothermal reaction 8h.
Described churned mechanically rotating speed is 3000 revs/min.
Described lyophilize is directed lyophilize, and freezing temp is liquid nitrogen temperature, and drying temperature is 0 DEG C, and dry vacuum tightness is 50000Pa, and time of drying is 2h.
Acidic aqueous solution described in step (4) is the aqueous hydrochloric acid of 3mol/L.
Embodiment 6:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, mechanical stirring is until mix, and obtained mass concentration is the graphene oxide water solution of 1mg/ml;
(2) be 6: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and mechanical dispersion is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out lyophilize, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 60: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 5 DEG C/min, reactor is heated to 600 DEG C, and isothermal reaction 12h.
Described churned mechanically rotating speed is 40 revs/min.
Described lyophilize is directed lyophilize, and freezing temp is liquid nitrogen temperature, and drying temperature is 0 DEG C, and dry vacuum tightness is 10000Pa, and time of drying is 5h.
Acidic aqueous solution described in step (4) is the aqueous hydrochloric acid of 3mol/L.
Embodiment 7:
The present embodiment prepares Graphene-CNT (carbon nano-tube) aerogel, specifically comprises the following steps:
(1) join in deionized water by graphene oxide, ultrasonic disperse is until mix, and obtained mass concentration is the graphene oxide water solution of 2mg/ml;
(2) be 8: 1 by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1), CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and ultrasonic disperse is until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) mixing solutions of graphene oxide obtained for step (2) and CNT (carbon nano-tube) is carried out supercritical drying, obtained graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphene oxide-CNT (carbon nano-tube) aerogel that step (3) is obtained being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained Graphene-CNT (carbon nano-tube) aerogel.
Graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, and concrete preparation process is with embodiment 1.
CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube (external diameter < 8nm), buys in Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
The mass ratio of the magnesium powder described in step (4) and graphene oxide-CNT (carbon nano-tube) aerogel is 20: 1.
The condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 6 DEG C/min, reactor is heated to 720 DEG C, and isothermal reaction 18h.
Described supercritical drying is that CO 2 supercritical is dry.
The ultrasonic power of described ultrasonic disperse is 200W, and ultrasonic frequency is 20KHz.
The mixing solutions of graphene oxide and CNT (carbon nano-tube) is carried out overcritical freezing time, first by the mixing solutions of graphene oxide and CNT (carbon nano-tube) under the temperature condition of 99 DEG C, placement for some time obtains corresponding hydrogel, a large amount of ethanol is adopted to replace the aqueous solvent existed in corresponding hydrogel and other soluble reaction thing and reaction product again, to obtain corresponding ethanol gel, then supercritical co mode is adopted, drying is carried out to described corresponding ethanol gel, obtains graphite oxide aerogel and Graphene-CNT (carbon nano-tube) aerogel.
Acidic aqueous solution described in step (4) is the phosphate aqueous solution of 4mol/L.
Claims (8)
1. the preparation method of a graphene aerogel and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, the method is the mixing solutions by graphene oxide solution or graphene oxide and CNT (carbon nano-tube), drying process, then by magnesium thermit, graphene oxide is reduced, and be soaked in acidic aqueous solution, remove impurity, drying, i.e. obtained graphene aerogel or Graphene-CNT (carbon nano-tube) aerogel, specifically comprise the following steps:
(1) join in deionized water by graphene oxide, through ultrasonic disperse or mechanical stirring until mix, obtained mass concentration is the graphene oxide water solution of 0.05 ~ 20mg/ml;
(2) be (0 ~ 10) by the mass ratio of graphene oxide in CNT (carbon nano-tube) and step (1): 1, CNT (carbon nano-tube) is joined in the obtained graphene oxide water solution of step (1), and through ultrasonic disperse or mechanical stirring until mix, the mixing solutions of obtained graphene oxide and CNT (carbon nano-tube);
(3) graphene oxide graphene oxide solution obtained for step (1) or step (2) obtained and the mixing solutions of CNT (carbon nano-tube), carry out lyophilize or supercritical drying, obtained graphite oxide aerogel or graphene oxide-CNT (carbon nano-tube) aerogel;
(4) after graphite oxide aerogel obtained for step (3) or graphene oxide-CNT (carbon nano-tube) aerogel being mixed with magnesium powder, be placed in reactor and carry out magnesium thermit, after question response terminates, reaction product is soaked in acidic aqueous solution, again through lyophilize, i.e. obtained graphene aerogel or Graphene-CNT (carbon nano-tube) aerogel.
2. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, graphene oxide described in step (1) adopts Hummers chemical method to be prepared from, CNT (carbon nano-tube) described in step (2) is multiple-wall carbon nanotube, the external diameter < 8nm of this multiple-wall carbon nanotube.
3. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, the mass ratio of the magnesium powder described in step (4) and graphite oxide aerogel and graphene oxide-CNT (carbon nano-tube) aerogel is (1 ~ 100): 1.
4. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, the condition of the magnesium thermit described in step (4) is under an argon atmosphere, with the temperature rise rate of 5 ~ 10 DEG C/min, reactor is heated to 550 ~ 1000 DEG C, and isothermal reaction 5 ~ 24h.
5. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, is characterized in that, described supercritical drying is that ethanol supercritical drying or CO 2 supercritical are dry.
6. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, described lyophilize is directed lyophilize or non-directional lyophilize, freezing temp is-1 DEG C ~ liquid nitrogen temperature, drying temperature is 0 ~ 60 DEG C, dry vacuum tightness is 5 ~ 50000Pa, and time of drying is 2 ~ 48 hours.
7. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, acidic aqueous solution described in step (4) adopts hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid formulated, and concentration is 0.05 ~ 4mol/L.
8. the preparation method of a kind of graphene aerogel according to claim 1 and Graphene-CNT (carbon nano-tube) aerogel, it is characterized in that, the ultrasonic power of described ultrasonic disperse is 40 ~ 1000W, and ultrasonic frequency is 20 ~ 80KHz, and described churned mechanically rotating speed is 40 ~ 4000 revs/min.
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