CN106145085A - The graphene aerogel of a kind of crushing resistance high conductivity and low density and the preparation method of doped carbon nanometer pipe composite - Google Patents
The graphene aerogel of a kind of crushing resistance high conductivity and low density and the preparation method of doped carbon nanometer pipe composite Download PDFInfo
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Abstract
The invention discloses graphene aerogel and the doped carbon nanometer pipe composite of a kind of crushing resistance high conductivity and low density, contrast hydrothermal reduction and ascorbic acid chemistry reduction, draw hydrothermal reduction can more preferable thorough redox graphene, obtain structural integrity, the Graphene hydrogel of even compact.The intensity that can not only be improved graphene aerogel by the MWNTs that adulterates can also improve electric conductivity.The aeroge being formed after the Graphene hydrogel of immersion ammoniacal liquor is lyophilized simultaneously also further increases mechanical strength, principle first ammoniacal liquor replaces water in freezing system, the freezing point of reduction system, thus alleviate and freeze-drying process expands the structural deterioration bringing, it two is graphene sheet layer surface and ammoniacal liquor generation chemical reaction in hydrogel, introduce new covalent bond between lamella, thus further enhance the mechanical strength of graphene aerogel.
Description
Technical field
The present invention relates to the graphene aerogel of a kind of crushing resistance high conductivity and low density and the preparation method of doped carbon nanometer pipe composite.
Background technology
The Graphene of two dimension and one-dimensional multi-walled carbon nano-tubes MWNTs are the material with carbon elements of nano-scale, have the characteristics such as great specific surface area, good electric conductivity and outstanding mechanical performance.And aeroge is the novel light nanoporous amorphous solid-state material of a kind of structure-controllable, there is many special natures, thus contain wide application prospect.[see: Zhao Ping Hui, Chen Lideng, journal of Zhejiang university, 1991,25:538] select suitable method to prepare graphene/carbon nano-tube composite aerogel, a kind of cooperative effect can be produced between them, make its various physical and chemical performances be strengthened, thus this composite has great application prospect in a lot of fields.[see: Rao C N R, Sood, A K Subrahmanyam K S, Govindaraj, A. Angew. Chem. Int.
Ed. 2009,48,7752.] this composite is not only successfully applied in capacitor, photoelectric device, energy-storage battery, electrochemical sensor and other fields, and can deepen in these fields and extend to other fields.
Content of the invention
It is an object of the invention to prepare graphene aerogel and the doped carbon nanometer pipe composite of a kind of crushing resistance high conductivity and low density, prepare by the following method:
Step one: native graphite is prepared graphite oxide solution by improved Hummers method；
Step 2: ultrasonic for the graphite oxide solution obtaining in step one stripping is prepared graphene oxide solution；
Step 3: by hydrothermal reduction method, takes pure zirconia graphene solution and the variable concentrations of variable concentrations, after doping different quality fraction MWNTs(acidifying) combined oxidation graphene solution under the conditions of different temperatures, different time, form Graphene hydrogel；
Step 4: by ascorbic acid chemistry reduction, same to step 3, obtain Graphene hydrogel；
Graphene hydrogel is soaked in ammoniacal liquor by step 5: in order to improve the intensity of graphene aerogel, 90 DEG C, takes out freezing after 1h, and frozen dried prepares graphene aerogel；
Step 6: in order to improve the conductance of graphene aerogel further, by graphene aerogel charing process；
The present invention is to prepare graphene aerogel and the doped carbon nanometer pipe composite of a kind of crushing resistance high conductivity and low density, with native graphite as carbon source, preparation graphene oxide solution, in step 2, the concentration of solution is 0.1mg/ml ~ 3mg/ml, and in step 3, hydrothermal reduction reaction temperature is: 100 DEG C ~ 200 DEG C；Reaction time is: 1h ~ 12h；In step 4, ascorbic acid reduction reaction temperature is: 40 DEG C ~ 80 DEG C；Reaction time is: 12h ~ 36h;In step three and four, carbon-doped nanometer tube mass fraction is 0% ~ 30%；
The present invention has the advantage that: in the graphene aerogel and doped carbon nanometer pipe composite of described crushing resistance high conductivity and low density, contrast hydrothermal reduction and ascorbic acid chemistry reduction, show that hydrothermal reduction can more preferable thorough redox graphene, obtain structural integrity, the Graphene hydrogel of even compact.The intensity that can not only be improved graphene aerogel by the MWNTs that adulterates can also improve electric conductivity.The aeroge being formed after the Graphene hydrogel of immersion ammoniacal liquor is lyophilized simultaneously also further increases mechanical strength, principle first ammoniacal liquor replaces water in freezing system, the freezing point of reduction system, thus alleviate and freeze-drying process expands the structural deterioration bringing, it two is graphene sheet layer surface and ammoniacal liquor generation chemical reaction in hydrogel, introduce new covalent bond between lamella, thus further enhance the mechanical strength of graphene aerogel.
Brief description:
Fig. 1 is that the present invention prepares the graphene aerogel of a kind of crushing resistance high conductivity and low density and the schematic flow sheet of doped carbon nanometer pipe composite；
Fig. 2 is the graphene aerogel photomacrograph that the present invention prepares a kind of crushing resistance high conductivity and low density；
Fig. 3 is the crushing resistance high conductivity and low density composite graphite alkene aeroge photomacrograph of doped carbon nanometer pipe；
Fig. 4, Fig. 5 are the electron scanning micrograph of pure graphene aerogel and the electron scanning micrograph that Fig. 6 is doped carbon nanometer pipe composite graphite alkene aeroge.
Detailed description of the invention
Embodiment 1
Native graphite is prepared graphite oxide solution by improved Hummers method by the first step；
Ultrasonic for graphite oxide solution 0.5h is peeled off and prepares graphene oxide solution by second step, and being made into concentration is 1.5mg/ml;
3rd step, takes graphene oxide solution 30ml of 1.5mg/ml, and the CNT of 0% doping is put in the water heating kettle with polytetrafluoroethylene (PTFE) as substrate, and regulation oven temperature is 180 DEG C, and the reaction time is that 12h carries out hydrothermal reduction and prepares Graphene hydrogel；
Graphene hydrogel in 3rd step, in order to improve the intensity of graphene aerogel, is soaked in ammoniacal liquor by the 4th step, and temperature is 90 DEG C, takes out and puts into refrigerator and carry out freezing 24h, place into and prepare graphene aerogel after carrying out frozen dried in freeze dryer after reaction 1h；
1000 DEG C of charings of graphene aerogel, in order to improve the conductance of graphene aerogel further, are processed 2h by the 5th step;
Pure graphene aerogel photomacrograph is as in figure 2 it is shown, structural integrity, and there is the hole of densification on internal and surface, lightweight and also there is elasticity.Its Electronic Speculum figure as shown in Figure 4, separates the single-layer graphene sheet thing of larger area, and structural integrity continuity is good；Having continuity good 3D pore network structure as shown in Figure 5, pore network size is in micron level, and hole thickness is the thickness of multi-layer graphene lamella stacking material.
Embodiment 2
Method of operating is identical with example 1, and difference is the CNT of the 3rd step 20% doping.The composite graphite alkene aeroge photomacrograph of doped carbon nanometer pipe is as it is shown on figure 3, structural integrity is not so good as pure graphene aerogel, and also there is the hole of densification on same internal and surface, lightweight and also there is elasticity.Its Electronic Speculum figure as shown in Figure 6, has continuity good 3D pore network structure, and pore network size is typically in sub-micron rank, and hole thickness is the thickness of multi-layer graphene lamella stacking material, and there is finely dispersed carbon nanotube particulate on Graphene tablet surface.
Embodiment 3
Method of operating is identical with example 1, and difference is that in second step and the 3rd step, graphene oxide concentration is 2.0mg/ml.Knowable to the Electronic Speculum figure of pure graphene aerogel, it has the good 3D pore network structure of continuity equally, due to the raising of graphene oxide concentration, separates individual layer and multi-layer graphene lamella stacking material.
Embodiment 4
Method of operating is identical with example 1, and difference is that in second step and the 3rd step, graphene oxide concentration is 2.0mg/ml, the CNT of the 3rd step 20% doping.The compound graphene aerogel Electronic Speculum figure of doped carbon nanometer pipe, there is continuity preferable 3D pore network structure equally, pore network size is typically in sub-micron rank, increase due to graphene oxide concentration, separating multi-layer graphene lamella stacking material, there is finely dispersed carbon nanotube particulate on Graphene tablet surface simultaneously.
Embodiment 5
Method of operating is identical with example 1, and difference is that in second step and the 3rd step, graphene oxide concentration is 2.0mg/ml, and in the 3rd step, the reaction time is 6h.Knowable to the Electronic Speculum figure of pure graphene aerogel, it has continuity good 3D pore network structure equally, major part is still made up of multi-layer graphene lamella stacking material, but the shortening due to the reaction time, it less is reduced into Graphene, therefore nonwoven fabric from filaments reduces, and also has unstripped flakey graphene oxide.
Embodiment 6
Method of operating is identical with example 1, and difference is that in second step and the 3rd step, graphene oxide concentration is 2.0mg/ml, and the CNT of the 3rd step 20% doping, in the 3rd step, the reaction time is 6h.The compound graphene aerogel Electronic Speculum figure of doped carbon nanometer pipe, there is continuity good 3D pore network structure equally, increase due to concentration and the reaction time shortens, have more unstripped flakey graphene oxide, and there is finely dispersed carbon nanotube particulate on Graphene tablet surface.
Embodiment 7
Native graphite is prepared graphite oxide solution by improved Hummers method by the first step；
Ultrasonic for graphite oxide solution 0.5h is peeled off and prepares graphene oxide solution by second step, and being made into concentration is 1.5mg/ml;
3rd step, takes graphene oxide solution 20ml of 1.5mg/ml, and the CNT of 0% doping is put in beaker, adds the ascorbic acid of 150mg, and regulation oven temperature is 40 DEG C, and the reaction time is that 16h carries out the prepared Graphene hydrogel of ascorbic acid reduction；
Graphene hydrogel in 3rd step, in order to improve the intensity of graphene aerogel, is soaked in ammoniacal liquor by the 4th step, and temperature is 90 DEG C, takes out and puts into refrigerator and carry out freezing 24h, place into and prepare graphene aerogel after carrying out frozen dried in freeze dryer after reaction 1h；
1000 DEG C of charings of graphene aerogel, in order to improve the conductance of graphene aerogel further, are processed 2h by the 5th step;
Knowable to the Electronic Speculum figure of pure graphene aerogel, it has successional 3D pore network structure but is not so good as hydrothermal reduction, therefore deduces that hydrothermal reduction has greater advantages, and pore network size is in micron level, and hole thickness is the thickness of multi-layer graphene lamella stacking material.
Embodiment 8
Method of operating is identical with example 7, and difference is that in second step and the 3rd step, graphene oxide concentration is 2.0mg/ml.Knowable to the Electronic Speculum figure of pure graphene aerogel, it has successional 3D pore network structure and is not so good as hydrothermal reduction, due to the raising of graphene oxide concentration, separates a small amount of single-layer graphene lamella thing.
Embodiment 9
Method of operating is identical with example 7, and difference is the CNT of 20% doping in the 3rd step.The compound graphene aerogel Electronic Speculum figure of doped carbon nanometer pipe, has continuity good 3D pore network structure equally, and pore network size is typically in sub-micron rank, and there is finely dispersed carbon nanotube particulate on Graphene tablet surface.
Embodiment 10
Method of operating is identical with example 7, and difference is that in the 3rd step, the reaction time is 36h.Knowable to the Electronic Speculum figure of pure graphene aerogel, it has successional 3D pore network structure and is not so good as hydrothermal reduction, due to the increase in reaction time, the effective layer structure peeling off graphene oxide, forms more single-layer graphene.
Embodiment 11
Method of operating is identical with example 7, and difference is that in the 3rd step, reaction temperature is 80 DEG C.Knowable to the Electronic Speculum figure of pure graphene aerogel, it has successional 3D pore network structure and is not so good as hydrothermal reduction, due to the raising of temperature, separates single-layer graphene lamella thing further.
Below presently preferred embodiments of the present invention is illustrated, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modification or replacement on the premise of without prejudice to present invention spirit, and these equivalent modification or replacement are all contained in the application claim limited range.
Claims (6)
1. the graphene aerogel of a crushing resistance high conductivity and low density and doped carbon nanometer pipe composite, it is characterized in that: this material belongs to fields of nano material application, there is classification aperture, superhigh specific surface area and three-dimensional structure, in conjunction with Graphene in electricity, optics, calorifics, the excellent properties of mechanics etc. and the ultralight porosity characteristic of aeroge.
2. a kind of graphene aerogel according to claim 1 and doped carbon nanometer pipe composite, it is characterized in that: described graphene aerogel is a kind of novel light nanoporous amorphous solid-state material, hole ratio is up to 80% ~ 99.8%, aperture is 1 ~ 100nm, and specific surface area is 200 ~ 1000m2/ g, density is 0.5 ~ 15mg/cm3, intensity is 90 ~ 150 kN m/kg, and electric conductivity is 1.6 × 102~3.5×102S/m。
3. the low-density graphene aerogel of a high-strength highly-conductive and doped carbon nanometer pipe composite, it is characterised in that comprise the following steps:
The first step: native graphite is prepared graphite oxide solution by improved Hummers method；
Second step: ultrasonic for graphite oxide solution stripping is prepared graphene oxide solution；
3rd step: by hydrothermal reduction method, takes pure zirconia graphene solution and the variable concentrations of variable concentrations, after doping different quality fraction MWNTs(acidifying) combined oxidation graphene solution under the conditions of different temperatures, different time, form Graphene hydrogel；
4th step: by ascorbic acid chemistry reduction, operation, with the 3rd step, obtains Graphene hydrogel；
Graphene hydrogel is soaked in ammoniacal liquor by the 5th step: in order to improve the intensity of graphene aerogel, 90 DEG C, takes out freezing after 1h, and frozen dried prepares graphene aerogel；
6th step: in order to improve the conductance of graphene aerogel further, by graphene aerogel charing process.
4. preparation method according to claims 3, it is characterized in that: with native graphite as carbon source, by to graphene oxide solution concentration, reaction temperature, reaction time, after doping different quality fraction MWNTs(acidifying), different method of reducing, the control of charing treatment conditions etc., thus prepare a kind of low-density graphene aerogel of high-strength highly-conductive and doped carbon nanometer pipe composite.
5. a kind of low-density graphene aerogel of high-strength highly-conductive according to claim 3 and doped carbon nanometer pipe composite, it is characterised in that: after doping different quality fraction MWNTs(acidifying), hydrothermal reduction, ascorbic acid reduces, and ammoniacal liquor strengthens.
6. a kind of low-density graphene aerogel of high-strength highly-conductive according to claim 3 and doped carbon nanometer pipe composite, it is characterised in that: solution concentration is: 0.1mg/ml ~ 3mg/ml, and hydrothermal reduction reaction temperature is: 100 DEG C ~ 200 DEG C；Reaction time is: 1h ~ 12h；Ascorbic acid reduction reaction temperature is: 40 DEG C ~ 80 DEG C；Reaction time is: 12h ~ 36h;Carbon-doped nanometer tube mass fraction is 0% ~ 30%.
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| CN108906005A (en) * | 2018-07-12 | 2018-11-30 | 山东佳星环保科技有限公司 | A kind of graphene silica gel solid phase extraction material and preparation method thereof |
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Application publication date: 20161123 |