CN105197909A - Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof - Google Patents
Graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of carbon aerogel which is a nano-porous material, and particularly relates to graphene nanoribbon/carbon nanotube cross-linked polyimide-based compound carbon aerogel and a preparation method thereof. The method includes the steps of preparation of an oxidized graphene nanoribbon/carbon nanotube hybrid material, synthesis of water-soluble polyamide acid, sol-gel method preparation of oxidized graphene nanoribbon/carbon nanotube/polyamide acid aerogel, preparation of graphene nanoribbon/carbon nanotube/polyimide compound carbon aerogel, activating treatment, high-temperature carbonization and the like. The method is easy to implement, low in cost and environmentally friendly. Prepared graphene nanoribbon/carbon nanotube/polyimide-based compound carbon aerogel has the advantages of being large in specific area, high in porosity, uniform in pore size and distribution and the like and can serve as a catalyst carrier material, an adsorbing material and an electrode material of supercapacitors, lithium ion batteries and other new energy devices.
Description
Technical field
The invention belongs to novel nano porous material-carbon aerogels technical field, be specifically related to a kind of graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel material and preparation method thereof.
Background technology
Carbon aerogels be a kind ofly have that porosity is high, light weight, specific surface area are large, structure-controllable and physicochemical property are stablized, the porous material of electric conductivity advantages of higher, be widely used as support of the catalyst, sorbing material and various electrode materialss etc., be considered to one of novel material of the large most potentiality of Future Ten, and become study hotspot.
Polyimide is a kind of special engineering plastics with advantages such as moulding processability is good, physical strength is high, Heat stability is goods, is widely used in the every field of national economy.For expanding the Application Areas of polyimide, this seminar is by carrying out high temperature cabonization process to polyimide aerogels, prepare a kind of novel polyimide-based carbon aerogels, and this carbon aerogels is applied to electrode materials and catalyst support material, expand the range of application of polyimide widely.But research finds, the aperture of the pure polyimide-based carbon aerogels prepared by Freeze Drying Technique is comparatively large, and hole distribution is uneven and its specific surface area is not high (without the specific surface area of the polyimide-based carbon aerogels of activation of potassium hydroxide less than 200m
2/ g, through the polyimide-based carbon aerogels only 677m of activation of potassium hydroxide
2/ g).Therefore, the pore space structure how effectively improving polyimide-based carbon aerogels and the specific surface area improving polyimide-based carbon aerogels seem very important.
Carbon nanotube is that one has typical lamellar hollow structure, and caliber is in a few nanometer to tens nanometers, and length is the one dimension c-based nanomaterial of several microns to tens microns.What form carbon nanotube is the director circle tubular construction with certain angle between layers, and its pipe shaft is made up of hexagon carbocyclic ring microstructure unit, and end cap is by the polygonized structure formed containing pentagonal carbocyclic ring.The structure of this uniqueness imparts the special physical and chemical performance of carbon nanotube, as good mechanical property, conductivity, optical property and magnetic performance etc., the fields such as the electrode materials of the activeness and quietness of matrix material, ultracapacitor and lithium ion battery, hydrogen storage material and transistor material can be widely used in.But the surface energy of carbon nanotube is higher, makes it be easy to reunite, greatly limit its using value.Graphene nanobelt is a kind of accurate one dimension c-based nanomaterial with special construction and pattern, and it not only has the excellent properties of carbon nanotube, also has the regulatable special marginal texture of pattern.The graphene nanobelt of this pattern controllable, excellent performance all has very wide application prospect in fields such as energy transformation and storage, field-effect transistor, electronic sensor, high molecule nano composite materials, therefore becomes the study hotspot in carbon nanomaterial field.
The present invention is intended to select some eco-friendly raw materials, designed by simple process, prepare that a kind of novel pore size is homogeneous, the graphene nanobelt of the uniform high porosity of hole distribution, high-specific surface area/carbon nano-tube/polyimide base composite carbon aerogel.Its innovative point is, the first, and first passage stannic oxide/graphene nano band/carbon nano-tube hybridization material is crosslinked with polyimide under the action of heat prepares graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel.Experimental design of the present invention is very ingenious, in the sub-amidated process of heat, three targets can be realized simultaneously, be respectively stannic oxide/graphene nano band and polyamic acid there occurs crosslinking reaction, polyamic acid changes polyimide into, and stannic oxide/graphene nano band is reduced to graphene nanobelt; The second, by the activation of potassium hydroxide, make prepared graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel have very large specific surface area and very high porosity.
Summary of the invention
The object of the present invention is to provide graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel that a kind of specific surface area is large, porosity is high, pore size is homogeneous, be evenly distributed and preparation method thereof; And preparation method's technique is simple, with low cost, environmental protection.
The present invention prepares by a kind of simple and green chemical synthesis method of low cost that to have porosity high, the polyimide-based composite carbon aerogel that graphene nanobelt/carbon nano-tube hybridization material that specific surface area is large is crosslinked, and the synthesis proposed from polyamic acid, the preparation being prepared into graphene nanobelt/carbon nano-tube/polyimide base composite aerogel of stannic oxide/graphene nano band/carbon nano-tube hybridization material and prepare the sequence of operations of graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel and experiment main points through activation treatment and high temperature cabonization technology.
The inventive method comprises: stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid aerogel, the preparation of graphene nanobelt/carbon nano-tube/polyimide composite aerogel and the step such as activation treatment and high temperature cabonization are prepared in the preparation of stannic oxide/graphene nano band/carbon nano-tube hybridization material, the synthesis of water-soluble polyamic acid, sol-gel method.
The preparation method of middle graphene nanobelt provided by the invention/carbon nano-tube/polyimide base composite carbon aerogel, concrete steps are as follows:
(1) stannic oxide/graphene nano band/carbon nano-tube hybridization material is prepared by solution oxide method one step, and by prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material by ultrasonic disperse in deionized water, obtain the stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid of certain density stable dispersion;
(2) water-soluble polyamic acid is dissolved in the stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid prepared by step (1), obtains stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid solution;
(3) potassium hydroxide solution configured being joined the graphene oxide that step (2) obtains receives in band rice/carbon nano tube/polyamide 6 amino acid solution, for some time is placed after rapid stirring, by sol-gel process, obtain stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid hydrogel;
(4) by freezing in refrigerator or liquid nitrogen for above-mentioned stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid hydrogel be solid, then dry in freeze drier, obtain stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid composite aerogel, be denoted as GONR/CNT/PAA;
(5) by temperature programming, hot sub-amidation is carried out to above-mentioned stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid composite aerogel, obtain graphene nanobelt/carbon nano-tube/polyimide composite aerogel, be denoted as GNR/CNT/PI;
(6) graphene nanobelt/carbon nano-tube/polyimide composite aerogel that step (5) obtains is carried out activation treatment and high temperature cabonization according to specific heating schedule, namely obtain the graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel with high-specific surface area.
In the present invention, the concrete operation step preparing stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid described in step (1) is:
A multi-walled carbon nano-tubes is scattered in (mass concentration of multi-walled carbon nano-tubes is 3-5mg/mL) in the vitriol oil of 95-98% by (), stir 1-2h to mixing.Dropwise add the phosphoric acid (volume ratio of phosphoric acid and the vitriol oil is 1:2-1:6) of 85%, continue to stir 30-60min;
B () under agitation, in above-mentioned mixed solution, slowly add potassium permanganate (mass ratio of potassium permanganate and multi-walled carbon nano-tubes is 1:1-1:4), 40-60min adds complete;
C above-mentioned reaction system is warming up to 60-80 DEG C by (), after temperature-stable, under agitation continue reaction 2-3h, then naturally cooling;
D the mixing solutions of above-mentioned gained is poured in the frozen water of 300mL and (is included the hydrogen peroxide of 5-10mL30%) by (), after stirring 30-60min, overnight standing, makes its natural subsidence;
E supernatant liquor in step (d) is outwelled process as spent acid by (), the hydrochloric acid soln of the sedimentable matter 15-20% of bottom is washed 3-5 time, and each uniform settling is separated; Then, centrifugal drying, namely obtains solid oxidation graphene nanobelt/carbon nano-tube hybridization material;
F solid oxidation graphene nanobelt/carbon nano-tube hybridization material is scattered in deionized water by (), ultrasonic disperse, obtains the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions of 2-8mg/mL.
The preparation method of the water-soluble polyamic acid described in step of the present invention (2) and the sub-amidation of the heat described in step (5), can adopt method in the patent application CN104355302A of applicant.
The consumption of the potassium hydroxide described in step of the present invention (3) is 0.1-0.5 times of polyamic acid quality, and described sol-gel process is 3-12h, preferred 8-12h.
High temperature cabonization described in step of the present invention (6) and activated process for: by obtained polyimide-based composite aerogel in tube furnace in nitrogen atmosphere sequence of control heat up, namely from room temperature to 400-500 DEG C, heating-up time is 1-2h, insulation 0.5-1h; And then being warmed up to 650-800 DEG C, the heating-up time is 1-3h, insulation 1-2h; Be warmed up to 1000-1400 DEG C afterwards, the heating-up time is 1-2h, insulation 0.5-2h.
In the present invention, the monomer needed for synthesis of polyimides comprises diamine, binary acid anhydride; Described diamine monomer comprises Ursol D (PPDA), 4,4 '-diaminodiphenyl ether (ODA), and described binary anhydride monomer comprises pyromellitic acid anhydride (PMDA), biphenyl tetracarboxylic dianhydride (BPDA), phenyl ether tetracarboxylic dianhydride (ODPA); Polar solvent needed for synthesis of polyimides comprise N,N-DIMETHYLACETAMIDE,
n-methyl-2-pyrrolidone, dimethyl formamide.
Use SEM(scanning electronic microscope), x-ray diffractometer, full-automatic adsorption instrument characterize stannic oxide/graphene nano band/carbon nano-tube hybridization material that the present invention obtains, the structure and morphology of graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel and specific surface area, its result is as follows:
(1) test result of SEM shows: the tube wall of original carbon nanotubes is comparatively smooth, and diameter Distribution is between 30-50nm.Stannic oxide/graphene nano band/carbon nano-tube hybridization material prepared in the present invention is then made up of the material of two kinds of structures, namely banded stannic oxide/graphene nano band and the carbon nanotube of tubulose.In stannic oxide/graphene nano band/carbon nano-tube hybridization material, unstripped carbon nanotube is overlapped on different banded stannic oxide/graphene nano band lamellas, thus has constructed the three-dimensional carbon nano-hybrid material with special construction and pattern.The advantage of this carbon nano-hybrid material is: the first, containing abundant oxy radical on stannic oxide/graphene nano band, contributes to the dispersion of carbon nanotube in deionized water and water-soluble polyamic acid; Second, carbon nanotube has function served as bridge between different stannic oxide/graphene nano band, after high temperature reduction carbonization, this carbon nanotube bridge not only can form conductive path, reduce the transmission range of electronics and ion, the contact resistance between graphene nanobelt lamella can also be reduced, thus improve the performance (see accompanying drawing 1) of material.
Adopt pure polyimide-based carbon aerogels prepared by activation of potassium hydroxide technology, as the etching pattern stayed after etching on plate material, its hole mostly is closed pore in irregular shape.Graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel then has less perforate hole and higher porosity, and its inner void size is more homogeneous, be evenly distributed (see accompanying drawing 3).
(2) XRD test show, the XRD curve of original carbon nanotubes has sharp-pointed diffraction peak at ° place, 2 θ=25.8, corresponding to carbon nanotube tube wall between spacing.Prepared stannic oxide/graphene nano band/carbon nanotube in 2 θ=10 ° and a ° place, 2 θ=25.8 all have obvious diffraction peak, illustrate that original carbon nanotubes is partly peeled off into stannic oxide/graphene nano band, define stannic oxide/graphene nano band and carbon nano-tube hybridization material.Sharp-pointed diffraction peak is had at ° place, 2 θ=25.8 with the hybrid material after experiment condition process stannic oxide/graphene nano band/carbon nano-tube hybridization material identical with sub-amidation treating processes, prove that stannic oxide/graphene nano band/carbon nano-tube hybridization material is reduced in order to graphene nanobelt/carbon nano-tube hybridization material (see accompanying drawing 2) under thermal treatment after the sub-amidation process of experience.
(3) full-automatic adsorption instrument test result shows: the specific surface area of pure polyimide-based composite carbon airsetting prepared in the present invention is 676m
2/ g, its pore size distribution concentrates on 4nm; And the specific surface area of prepared graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel can reach 2085m
2/ g, its pore size distribution concentrates on 4nm, 8nm to 16nm.As can be seen here, greatly increase by composite carbon aerogel specific surface area prepared after graphene nanobelt/carbon nanotube crosslinked polyimide, its hole increased mainly contains two kinds of aperture specifications, aperture integrated distribution at 8nm and 16nm(see accompanying drawing 4).
The present invention relates to three ultimate principles:
(1) in the building-up process of polyamic acid, add triethylamine, even if triethylamine is coated on the terminal carboxyl function of polyamic acid, synthesized polyamic acid can be made easily to be dissolved in deionized water.
(2) stannic oxide/graphene nano band contains the abundant oxy radical such as carboxyl, hydroxyl, carbonyl, epoxy group(ing), the existence of these oxy radicals, make stannic oxide/graphene nano band in water, have good dispersiveness, simultaneously, stannic oxide/graphene nano band is made to work in coordination with dispersing Nano carbon tubes, therefore by carrying out a step solution oxide to original carbon nanotubes, obtain the stannic oxide/graphene nano band/carbon nano-tube hybridization material of stable dispersion.In addition, the oxy radical on stannic oxide/graphene nano band can be used as the avtive spot of reaction, under the action of heat crosslinking reaction occurs with polyamic acid, thus reaches the inner void structure of polyimide-based aerogel.
(3) activating mechanism of KOH is between 400 to 800 DEG C, and potassium hydroxide and carbon occur to react as follows:
6KOH+2C=2K+3H
2+2K
2CO
3
K
2CO
3=K
2O+CO
2
CO
2+C=2CO
K
2CO
3+2C=2K+3CO
K
2O+C=2K+CO。
In the process of pyroprocessing, potassium hydroxide consumes part carbon, and produces a large amount of hydrogen, carbonic acid gas and carbon monoxide.This consumption part carbon the behavior producing gas improve pore size and the distribution thereof of composite carbon aerogel just, greatly increase its specific surface area.
Composite carbon aerogel prepared by the present invention has the large (2085m of specific surface area
2/ g), the advantage such as porosity is high and pore size is homogeneous, be evenly distributed, can be used as the electrode materials of desirable catalyst support material, sorbing material and the new energy devices such as ultracapacitor, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of original carbon nanotubes and the prepared graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel used in the present invention.
Fig. 2 is the original carbon nanotubes used in the present invention, prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material and the XRD diffraction spectrogram of graphene nanobelt/carbon nano-tube hybridization material that obtains after the thermal treatment of sub-amidation temperature condition.
Fig. 3 is pure polyimide-based carbon aerogels prepared in the present invention and the scanning electron microscope (SEM) photograph of graphene nanobelt/carbon nano-tube/polyimide base carbon aerogels.
Fig. 4 is pure polyimide-based carbon aerogels prepared in the present invention and the N of graphene nanobelt/carbon nano-tube/polyimide base carbon aerogels
2adsorption/desorption curve.
Embodiment
Below in conjunction with specific examples, set forth the present invention further, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.In addition should be understood that those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
embodiment 1
The present embodiment comprises the following steps:
The preparation method of water-soluble polyamic acid fiber is with our patent CN104355302A.
Being prepared as follows of graphene nanobelt/carbon nano-tube hybridization material: be scattered in by 150mg multi-walled carbon nano-tubes in 98% vitriol oil of 36mL, adds the phosphoric acid of 85% again after being uniformly dispersed, and constantly stirs in the process and obtains homogeneous dispersion liquid.In above-mentioned dispersion liquid, slowly add 450mg potassium permanganate in batches, constantly stir.Reaction system is slowly warming up to 70 DEG C, after temperature-stable, insulation for some time, and constantly stir.The mixed dispersion liquid of gained is naturally cooled to room temperature, then pours in the frozen water containing 7mL30% hydrogen peroxide, placement overnight, make its natural subsidence.By the sedimentable matter obtained with 15% salt acid elution repeatedly and wash uniform settling at every turn.Solid oxidation graphene nanobelt/carbon nano-tube hybridization material can be obtained after the sediment of bottom being carried out after washing for the last time centrifugal and drying, be designated as GONR/CNT-1.
Above-mentioned for 44mg prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material is scattered in the deionized water of 11mL, the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions of preparation 4mg/mL.
1g water-soluble polyamic acid fiber is put into the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions containing 0.5g triethylamine, stir and make it dissolve.Add 1mL potassium hydroxide solution, wherein the quality of potassium hydroxide is 0.5g, continues to stir 0.5h, finally places 10h and completes sol-gel process.Being transferred to diameter is in the container of 2cm, putting into liquid nitrogen makes its quick freeze be solid, finally put into the dry 24h of freeze drier potassium hydroxide-stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid aerogel, be designated as GONR/CNT/PAA-1.
Obtained potassium hydroxide-stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid aerogel is placed in tube furnace nitrogen atmosphere sequence of control to heat up, namely room temperature is to 100 DEG C of intensification 30min, insulation 1h; 100 DEG C to 200 DEG C, intensification 30min, insulation 1h; 200 DEG C to 300 DEG C, intensification 30min, insulation 1h, can obtain potassium hydroxide-graphene nanobelt/carbon nano-tube/polyimide aerogel, be designated as GNR/CNT/PI-1.
Obtained potassium hydroxide-graphene nanobelt/carbon nano-tube/polyimide aerogel is carried out activation treatment and high temperature cabonization in tube furnace in nitrogen atmosphere, its temperature-rise period be room temperature to 450 DEG C of intensification 1h, insulation 70min; 450 DEG C to 750 DEG C, intensification 30min, insulation 90min; 750 DEG C to 1000 DEG C, intensification 50min, insulation 2h, can obtain the graphene nanobelt with the high-specific surface area/carbon nano-tube/polyimide base composite carbon aerogel of activation of potassium hydroxide, be designated as GNR/CNT/PIbasedCA-1.
embodiment 2
The dispersion liquid concentration of the stannic oxide/graphene nano band/carbon nano-tube hybridization material in embodiment 1 is become 8mg/mL, all the other steps are with embodiment 1, the graphene nanobelt with the high-specific surface area/carbon nano-tube/polyimide base composite carbon aerogel of activation of potassium hydroxide can be obtained, be designated as GNR/CNT/PIbasedCA-2.
embodiment 3the present embodiment comprises the following steps:
The preparation method of water-soluble polyamic acid fiber is with our patent CN104355302A.
Being prepared as follows of graphene nanobelt/carbon nano-tube hybridization material: be scattered in by 150mg multi-walled carbon nano-tubes in 98% vitriol oil of 36mL, adds the phosphoric acid of 85% again after being uniformly dispersed, and constantly stirs in the process and obtains homogeneous dispersion liquid.In above-mentioned dispersion liquid, slowly add 300mg potassium permanganate in batches, constantly stir.Reaction system is slowly warming up to 70 DEG C, after temperature-stable, insulation for some time, and constantly stir.The mixed dispersion liquid of gained is naturally cooled to room temperature, then pours in the frozen water containing 7mL30% hydrogen peroxide, placement overnight, make its natural subsidence.By the sedimentable matter obtained with 15% salt acid elution repeatedly and wash uniform settling at every turn.Solid oxidation graphene nanobelt/carbon nano-tube hybridization material can be obtained after the sediment of bottom being carried out after washing for the last time centrifugal and drying, be designated as GONR/CNT-2.
Above-mentioned for 44mg prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material is scattered in the deionized water of 11mL, the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions of preparation 4mg/mL.
1g water-soluble polyamic acid fiber is put into the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions containing 0.5g triethylamine, stir and make it dissolve.Add 1mL potassium hydroxide solution, wherein the quality of potassium hydroxide is 0.5g, continues to stir 0.5h, finally places 10h and completes sol-gel process.Being transferred to diameter is in the container of 2cm, putting into liquid nitrogen makes its quick freeze be solid, finally put into the dry 24h of freeze drier potassium hydroxide-stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid aerogel, be designated as GONR/CNT/PAA-3.
Obtained potassium hydroxide-stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid aerogel is placed in tube furnace nitrogen atmosphere sequence of control to heat up, namely room temperature is to 100 DEG C of intensification 30min, insulation 1h; 100 DEG C to 200 DEG C, intensification 30min, insulation 1h; 200 DEG C to 300 DEG C, intensification 30min, insulation 1h, can obtain potassium hydroxide-graphene nanobelt/carbon nano-tube/polyimide aerogel, be designated as GNR/CNT/PI-3.
Obtained potassium hydroxide-graphene nanobelt/carbon nano-tube/polyimide aerogel is carried out activation treatment and high temperature cabonization in tube furnace in nitrogen atmosphere, its temperature-rise period be room temperature to 450 DEG C of intensification 1h, insulation 70min; 450 DEG C to 750 DEG C, intensification 30min, insulation 90min; 750 DEG C to 1000 DEG C, intensification 50min, insulation 2h, can obtain the graphene nanobelt with the high-specific surface area/carbon nano-tube/polyimide base composite carbon aerogel of activation of potassium hydroxide, be designated as GNR/CNT/PIbasedCA-3.
embodiment 4
Testing as a control group, when not adding graphene oxide nano belt/carbon nano-tube hybridization material, directly preparing the pure polyimide-based carbon aerogels of activation of potassium hydroxide.Its preparation method does not add graphene oxide nano belt/carbon nano-tube hybridization material in embodiment 1, and all the other steps are with embodiment 1, and the polyimide-based carbon aerogels of the activation of potassium hydroxide of final preparation, is designated as PIbasedCA.
embodiment 5
In order to prove in the sub-amidated process of heat, stannic oxide/graphene nano band/carbon nano-tube hybridization material there occurs reduction reaction really, the present invention's prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material heating schedule identical with embodiment 1 Central Asia amidation process is heat-treated, the material obtained is called graphene nanobelt/carbon nano-tube hybridization material, is designated as GNR/CNT.
The formability of the cylindrical carbon aerogel prepared by first three embodiment is all better, and outward appearance does not have difference substantially, and the specific surface area of full-automatic adsorption instrument test gained is at 2000 to 2100m
2between/g, difference is little equally.But embodiment 2 is compared with embodiment 1, linking agent graphene nanobelt/carbon nano-tube hybridization material used is more, and the conductive path of carbon aerogels inside is more.Embodiment 3 is compared with embodiment 1, graphene nanobelt in linking agent graphene nanobelt/carbon nano-tube hybridization material that the latter is used and the ratio of carbon nanotube reduce, mean that the stability of the aqueous dispersions of the linking agent of embodiment 3 compares the poor stability of embodiment 1, be difficult to dispersed in body material polyimide, therefore the homogeneity of composite carbon aerogel material inside obtained by embodiment 3 is not as good as embodiment 1.
Claims (7)
1. a preparation method for graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel, is characterized in that concrete steps are:
(1) stannic oxide/graphene nano band/carbon nano-tube hybridization material is prepared by solution oxide method one step, and by prepared stannic oxide/graphene nano band/carbon nano-tube hybridization material by ultrasonic disperse in deionized water, obtain the stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid of stable dispersion;
(2) water-soluble polyamic acid is dissolved in the stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid prepared by step (1), obtains stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid solution;
(3) potassium hydroxide solution configured being joined the graphene oxide that step (2) obtains receives in band rice/carbon nano tube/polyamide 6 amino acid solution, for some time is placed after rapid stirring, by sol-gel process, obtain stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid hydrogel;
(4) by freezing in refrigerator or liquid nitrogen for above-mentioned stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid hydrogel be solid, then dry in freeze drier, obtain stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid composite aerogel, be denoted as GONR/CNT/PAA;
(5) by temperature programming, hot sub-amidation is carried out to above-mentioned stannic oxide/graphene nano band/carbon nano tube/polyamide 6 amino acid composite aerogel, obtain graphene nanobelt/carbon nano-tube/polyimide composite aerogel, be denoted as GNR/CNT/PI;
(6) graphene nanobelt/carbon nano-tube/polyimide composite aerogel that step (5) obtains is carried out activation treatment and high temperature cabonization, namely obtain the graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel with high-specific surface area.
2. preparation method according to claim 1, is characterized in that the concrete operation step preparing stannic oxide/graphene nano band/carbon nano-tube hybridization material dispersion liquid described in step (1) is:
A multi-walled carbon nano-tubes is scattered in the vitriol oil of 95-98% by (), the mass concentration of multi-walled carbon nano-tubes is 3-5mg/mL; Stir 1-2h to mixing; Dropwise add the phosphoric acid of 85%, the volume ratio of phosphoric acid and the vitriol oil is 1:2-1:6; Continue to stir 30-60min;
B () under agitation, slowly adds potassium permanganate in above-mentioned mixed solution, it is complete that the mass ratio of potassium permanganate and multi-walled carbon nano-tubes is that 1:1-1:4,40-60min add;
C above-mentioned reaction system is warming up to 60-80 DEG C by (), after temperature-stable, under agitation continue reaction 2-3h, then naturally cooling;
D the mixing solutions of above-mentioned gained is poured in the frozen water of 300mL by (), this frozen water includes the hydrogen peroxide of 5-10mL30%, after stirring 30-60min, overnight standing, makes its natural subsidence;
E supernatant liquor in step (d) is outwelled process as spent acid by (), the hydrochloric acid soln of the sedimentable matter 15-20% of bottom is washed 3-5 time, and each uniform settling is separated; Then, centrifugal drying, namely obtains solid oxidation graphene nanobelt/carbon nano-tube hybridization material;
F solid oxidation graphene nanobelt/carbon nano-tube hybridization material is scattered in deionized water by (), ultrasonic disperse, obtains the stannic oxide/graphene nano band/carbon nano-tube hybridization material stable dispersions of 2-8mg/mL.
3. preparation method according to claim 2, is characterized in that in step (3), and the consumption of described potassium hydroxide is 0.1-0.5 times of polyamic acid quality, and the described sol-gel process time is 3-12h.
4. preparation method according to claim 2, it is characterized in that the high temperature cabonization described in step (6) and activated process for: by obtained polyimide-based composite aerogel in tube furnace in nitrogen atmosphere sequence of control heat up, i.e. DEG C intensification from room temperature to 400-500, time is 1-2h, insulation 0.5-1h; And then being warmed up to 650-800 DEG C, the heating-up time is 1-3h, insulation 1-2h; Be warmed up to 1000-1400 DEG C afterwards, the heating-up time is 1-2h, insulation 0.5-2h.
5. preparation method according to claim 2, is characterized in that, the monomer needed for synthesis of polyimides comprises diamine, binary acid anhydride; Described diamine monomer is selected from Ursol D, 4,4 '-diaminodiphenyl ether, and described binary anhydride monomer is selected from pyromellitic acid anhydride, biphenyl tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride; Polar solvent needed for synthesis of polyimides be selected from N,N-DIMETHYLACETAMIDE,
n-methyl-2-pyrrolidone, dimethyl formamide.
6. the graphene nanobelt prepared by the described preparation method of one of claim 1-5/carbon nano-tube/polyimide base composite carbon aerogel.
7. graphene nanobelt/carbon nano-tube/polyimide base composite carbon aerogel as claimed in claim 6 is as the application of the electrode materials of catalyst support material, sorbing material and ultracapacitor, lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510615214.4A CN105197909B (en) | 2015-09-24 | 2015-09-24 | A kind of graphene nanobelt/compound carbon aerogels of carbon nano-tube/polyimide base and preparation method thereof |
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| CN105617956A (en) * | 2016-01-28 | 2016-06-01 | 复旦大学 | Molybdenum disulfide nanosheet/polyimide based composite aerogel and preparation method thereof |
| CN105820572A (en) * | 2016-06-02 | 2016-08-03 | 黑龙江科技大学 | Preparation method of polyimide/graphene nanoribbon composite film |
| CN105845455A (en) * | 2016-05-10 | 2016-08-10 | 复旦大学 | Polyacrylonitrile nanometer fiber/polyimide-based composite carbon aerogel electrode material and preparation method thereof |
| CN107056318A (en) * | 2017-03-01 | 2017-08-18 | 山东省科学院新材料研究所 | A kind of CNT carbon aerogel composite material and preparation method thereof |
| CN107365497A (en) * | 2016-05-12 | 2017-11-21 | 复旦大学 | A kind of polyimide-based composite aerogel with high flame resistance and its preparation method and application |
| CN109092258A (en) * | 2018-10-15 | 2018-12-28 | 东华理工大学 | A kind of nanocomposite adsorbent and preparation method thereof, application |
| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
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| CN113690449A (en) * | 2021-08-17 | 2021-11-23 | 中国人民解放军军事科学院军事医学研究院 | High-performance membrane-free lactic acid biofuel cell based on enzyme and medium dual-fixation bioelectrode |
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| CN107365426B (en) * | 2016-05-12 | 2021-03-23 | 复旦大学 | Polyimide-based composite aerogel and controllable preparation method and application thereof |
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| CN105617956A (en) * | 2016-01-28 | 2016-06-01 | 复旦大学 | Molybdenum disulfide nanosheet/polyimide based composite aerogel and preparation method thereof |
| CN105617956B (en) * | 2016-01-28 | 2019-04-02 | 复旦大学 | A kind of molybdenum disulfide nano sheet/polyimide-based composite aerogel and preparation method thereof |
| CN105845455A (en) * | 2016-05-10 | 2016-08-10 | 复旦大学 | Polyacrylonitrile nanometer fiber/polyimide-based composite carbon aerogel electrode material and preparation method thereof |
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| CN109903998A (en) * | 2019-02-26 | 2019-06-18 | 内蒙古科技大学 | A kind of combination electrode and its preparation method and application |
| CN113133297A (en) * | 2021-04-20 | 2021-07-16 | 合肥工业大学 | Super-crosslinked polystyrene based composite carbon aerogel electromagnetic shielding material and preparation method thereof |
| CN113690449A (en) * | 2021-08-17 | 2021-11-23 | 中国人民解放军军事科学院军事医学研究院 | High-performance membrane-free lactic acid biofuel cell based on enzyme and medium dual-fixation bioelectrode |
| CN113460999A (en) * | 2021-08-23 | 2021-10-01 | 上海交通大学 | Preparation method of graphene nanoribbon/single-walled carbon nanotube intramolecular heterojunction |
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