CN105621400A - Method for preparing graphene by using carbonate as raw material - Google Patents
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Abstract
The invention belongs to the technical field of carbon material preparation, and particularly relates to a method for preparing graphene by using carbonate as a raw material. The method comprises the steps that firstly, carbonate and a high-molecular compound are mixed to be used as a carbon source precursor, the carbon source precursor is pumped into a double-screw extruder, the carbonate is coated with a network structure formed by the high-molecular compound by dispersing screw elements, the carbon source precursor is changed into a thermal plasticity material on the high warm stretching condition by mixing the screw elements, volatiles are removed on the high-temperature hyperpyretic condition by devolatilizing the screw elements to form the loose and porous structure, finally sheets are formed through extrusion, and graphene is obtained by washing and drying through a high-temperature catalytic reaction. The graphene preparation technology is simple, raw materials are wide in source, the cost is low, the yield is high, the purity is high, and large-scale production can be achieved.
Description
Technical field
The invention belongs to material with carbon element technical field, particularly to a kind of method preparing Graphene for raw material with carbonate.
Background technology
Graphene, as a kind of novel two-dimensional material, is arranged according to hexagon by carbon atom, is connected with each other, and forms a carbon molecule, and its structure is highly stable; Along with the amount of carbon atom connected is on the increase, the carbon planes of molecules of this two dimension constantly expands, and molecule also constantly becomes big. The thickness of single-layer graphene only one of which carbon atom, namely 0.335 nanometer, be equivalent to a hair 200,000/ thickness, the graphite of 1 millimeters thick will nearly have the Graphene of about 1,500,000 layers. And Graphene is the unique Two Dimensional Free state atomic crystal existed having now been found that. The research worker such as AKGeim, the KSNovoselov since Univ Manchester UK are since 2004 utilize adhesive tape to peel off oriented graphite discovery Graphene, this material with various excellent specific property, illustrates wide application prospect in fields such as electronics, sensing, the energy, composite, medical treatment, energy storage, catalysis, Aero-Space.
Up to now, have been found that Graphene has outstanding physics and electrical properties, its thickness is only monolayer carbon atomic diameter, be in the world the thinnest, specific surface area is maximum, intensity is the highest, thermal conductivity is the highest, mean free path is the longest under room temperature, be prone to modify and large-scale production etc.
At present, multiple method can be adopted to prepare grapheme material powder body, such as mechanical stripping method, oxidation-reduction method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and stripping CNT method etc. In these methods, to prepare Graphene destructible graphene-structured, productivity relatively low for mechanical stripping method and epitaxial growth method, it is difficult to meets large-scale production. Although chemical vapour deposition technique can obtain large scale continuous print graphene film, but is applicable to micro-nano electronic device or transparent conductive film, the extensive demand in market can not be met. Oxidation-reduction method prepares the relatively costly of grapheme material powder body, complex process.
China Patent Publication No. 103466608A discloses the ball milling of a kind of Graphene and prepares method, the mass volume ratio of hexa-atomic to graphitic carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant is 1:2��1:15 by the present invention and deionized water mixes and is loaded on ball grinder, is fixed on ball mill rotating speed ball milling 5-30 hour with 200-500rpm; Proceed to again in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, prepare variable concentrations graphene aqueous solution. The present invention utilizes ball mill destructible Graphene crystal structure, and productivity is relatively low, it is impossible to large-scale production.
China Patent Publication No. 104528696A discloses preparation method and the Graphene of a kind of Graphene, comprise the following steps: A) carbon source and metal agent for capturing are mixed, obtaining modified carbon source, described carbon source includes one or more in ion exchange resin, starch, cellulose and amorphous carbon; B) by metallic catalyst and described step A) in modified carbon source mix, adsorb, obtain being adsorbed with the carbon source of metallic catalyst; C) by described step B) in the carbon source being adsorbed with metallic catalyst be heated, obtain Graphene. The present invention utilizes metal agent for capturing adsorbing metal catalysts influence many factors, it is impossible to effectively obtaining Graphene, productivity is relatively low, and cost is high, is unfavorable for large-scale production.
Summary of the invention
The present invention is directed to the problems referred to above, it is proposed to a kind of method preparing Graphene for raw material with carbonate. To mix as carbon source predecessor with macromolecular compound using carbonate, carbon source predecessor is pumped into double screw extruder, by disperseing screwing element, carbonate is made to be coated in the network structure that macromolecular compound is formed, then pass through mixing screwing element, carbon source predecessor is made to become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, form loose and porous structure, form thin slice finally by extruding, high-temperature catalytic, and wash and dry obtain Graphene. Preparation method of the present invention is reproducible, environmentally friendly, prepares that Graphene technique is simple, the extensive cost of raw material sources is low, and productivity is high, and purity is high, it may be achieved large-scale production, has broad application prospects.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of method preparing Graphene for raw material with carbonate, it is characterised in that comprise the following steps:
(1) by carbonate with macromolecular compound it is 8:(2 ~ 3 in mass ratio) add in high-speed mixer and disperse 5 ~ 10min to obtain carbon source predecessor with the speed high-speed stirred of 2000 ~ 3000rpm;
(2) the carbon source predecessor obtained in step (1) is pumped in screw extruder charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 130 ~ 180 DEG C, carbon source predecessor, by disperseing screwing element, makes carbonate be coated in the network structure that macromolecular compound is formed; Then pass through mixing screwing element, arranging this section of reaction temperature is 180 ~ 220 DEG C, carbon source predecessor is made to become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, making volatile matter get rid of, form loose and porous structure, arranging temperature is 200 ~ 230 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 15 ~ 30min under the air atmosphere of 180 ~ 250 DEG C;
(4) when inert gas shielding, by the temperature of tube furnace to 800 ~ 1000 DEG C, add catalyst reaction 120 ~ 150min, atmosphere of inert gases is cooled to 25 DEG C, obtains Graphene Primary product;
(5) the Graphene Primary product that step (4) obtains is reacted 8 ~ 12min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene;
Described carbonate is at least one in calcium carbonate, magnesium carbonate, brium carbonate, sodium carbonate, aluminium carbonate, and described macromolecular compound is at least one in polyvinyl pyrrolidone, polyacrylamide, polyethylene terephthalate, Polyethylene Glycol, styrene butadiene styrene triblock copolymer, polyimides;
Described catalyst is the one in cesium salt, aluminum isopropylate., manganese dioxide, antimony oxide, Cu-lyt.;
High-speed mixer described in above-mentioned steps (1) is conical screw spiral ribbon mixer, this mixer is made up of cycloidal planetary gear speed reducer, screw rod, outer layer ribbon etc., carbonate and macromolecular compound are tangentially thrown to space by the centrifugal force produced by quick rotation, make it produce strong convection current to shear, spreading, thus reaching the purpose of quick mix homogeneously.
Screw extruder described in above-mentioned steps (2) is conical parallel dual-screw extruding machine, screw slenderness ratio is 60 ~ 75:1, screw rod is set gradually as dispersion screwing element, mixing screwing element, devolatilization screwing element, compression screwing element, in the same direction screwing element by feed end terminad, this extruder, extrusion force is big, plasticizing capacity good, yield is high, energy consumption is low, the extruding of carbon source predecessor is obtained thin slice, making the effective regular uniform growth of Graphene, Graphene purity, productivity that it finally obtains are high.
Catalyst its addition catalyst in mass ratio described in above-mentioned steps (4): carbonate=(0.03 ~ 0.05): 3.
A kind of method preparing Graphene for raw material with carbonate of the present invention, first carbon source predecessor will be formed with carbonate and macromolecular compound when high-speed stirred for carbon source, it is made to be sufficiently mixed uniformly, carbon source predecessor is pumped into double screw extruder, by disperseing screwing element, carbonate is made to be coated in the network structure that macromolecular compound is formed, the graphene-structured making formation is uniform, then pass through mixing screwing element, carbon source predecessor is made to become thermoplastic under high-temperature hot stretching condition, it is beneficial to thermoplasticity processing and obtains thin slice, again through devolatilization screwing element, utilize when high temperature high heat, volatile matter is made to get rid of, impurity reduces, make the Graphene purity obtained high, form loose and porous structure to add and catalyst reaction surface, its abundant reaction yield is made to be improved, then pass through extruding and form thin slice, Graphene can be obtained by homoepitaxial.
A kind of method preparing Graphene for raw material with carbonate of the present invention, compared with prior art prominent feature and beneficial effect are in that:
1, a kind of method preparing Graphene for raw material with carbonate of the present invention, processed by double screw extruder and make carbonate be coated in the network structure that macromolecular compound is formed, volatile matter is got rid of, form loose and porous structure extruding and increase the reaction surface with catalyst in flakes, reactivity is improved, it can effectively make Graphene regular uniform grow, and the Graphene purity obtained is high, productivity is high.
2, a kind of method preparing Graphene for raw material with carbonate of the present invention, its raw material sources is extensive, and its preparation technology is simple, cost is low, utilizes double screw extruder easy to spread and the advantage such as continuous prodution.
Detailed description of the invention
Embodiment 1
(1) calcium carbonate and polyvinyl pyrrolidone 8:2 in mass ratio addition conical screw spiral ribbon mixer will disperse 5min to obtain carbon source predecessor with the speed high-speed stirred of 2000rpm;
(2) the carbon source predecessor obtained in step (1) is pumped in conical parallel dual-screw extruding machine charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 130 DEG C, carbon source predecessor, by disperseing screwing element, makes calcium carbonate be coated in the network structure that polyvinyl pyrrolidone is formed; Then passing through mixing screwing element, arranging this section of reaction temperature is 180 DEG C, makes carbon source predecessor become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, forming loose and porous structure, arranging temperature is 200 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 15min under the air atmosphere of 180 DEG C;
(4) when inert gas shielding, by the temperature in tube furnace to 800 DEG C, cesium salt in mass ratio: calcium carbonate=0.03:3 adds cesium salt reaction 120min, is cooled to 25 DEG C, obtains Graphene Primary product in atmosphere of inert gases.
(5) product that step (4) obtains is reacted 8min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene
Embodiment 2
(1) magnesium carbonate and polyacrylamide solution are obtained carbon source predecessor for the 8:2.1 speed high-speed stirred dispersion 6min added in conical screw spiral ribbon mixer with 2100rpm in mass ratio;
(2) the carbon source predecessor obtained in step (1) is pumped in conical parallel dual-screw extruding machine charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 140 DEG C, carbon source predecessor, by disperseing screwing element, makes magnesium carbonate be coated in the network structure that polyacrylamide is formed; Then passing through mixing screwing element, arranging this section of reaction temperature is 185 DEG C, makes carbon source predecessor become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, forming loose and porous structure, arranging temperature is 205 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 16min under the air atmosphere of 190 DEG C;
(4) when inert gas shielding, by the temperature in tube furnace to 850 DEG C, aluminum isopropylate. in mass ratio: calcium carbonate=0.032:3 adds aluminum isopropylate. reaction 130min, is cooled to 25 DEG C, obtains Graphene Primary product in atmosphere of inert gases;
(5) product that step (4) obtains is reacted 9min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene.
Embodiment 3
(1) for 8:2.2, brium carbonate being added conical screw spiral ribbon mixer in mass ratio with polyethylene terephthalate solution disperses 7min to obtain carbon source predecessor with the speed high-speed stirred of 2200rpm;
(2) the carbon source predecessor obtained in step (1) is pumped in conical parallel dual-screw extruding machine charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 150 DEG C, carbon source predecessor, by disperseing screwing element, makes brium carbonate be coated in the network structure that polyethylene terephthalate is formed; Then passing through mixing screwing element, arranging this section of reaction temperature is 195 DEG C, makes carbon source predecessor become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, forming loose and porous structure, arranging temperature is 210 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 20min under the air atmosphere of 220 DEG C;
(4) when inert gas shielding, by the temperature in tube furnace to 900 DEG C, manganese dioxide in mass ratio: brium carbonate=0.04:3 adds manganese dioxide reaction 140min, is cooled to 25 DEG C, obtains Graphene Primary product in atmosphere of inert gases;
(5) product that step (4) obtains is reacted 10min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene.
Embodiment 4
(1) sodium carbonate and polyglycol solution are obtained carbon source predecessor for the 8:2.5 speed high-speed stirred dispersion 9min added in conical screw spiral ribbon mixer with 2900rpm in mass ratio;
(2) slurry obtained in step (1) is pumped in conical parallel dual-screw extruding machine charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 170 DEG C, carbon source predecessor, by disperseing screwing element, makes sodium carbonate be coated in the network structure that Polyethylene Glycol is formed; Then passing through mixing screwing element, arranging this section of reaction temperature is 210 DEG C, makes carbon source predecessor become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, forming loose and porous structure, arranging temperature is 210 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 28min under the air atmosphere of 240 DEG C;
(4) when inert gas shielding, by the temperature in tube furnace to 950 DEG C, antimony oxide in mass ratio: sodium carbonate=0.045:3 adds antimony oxide reaction 145min, is cooled to 25 DEG C, obtains Graphene Primary product in atmosphere of inert gases;
(5) product that step (4) obtains is reacted 11min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene.
Embodiment 5
(1) aluminium carbonate and styrene butadiene styrene triblock copolymer solution are obtained carbon source predecessor for the 8:3 speed high-speed stirred dispersion 10min added in conical screw spiral ribbon mixer with 3000rpm in mass ratio;
(2) slurry obtained in step (1) is pumped in double screw extruder charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 180 DEG C, carbon source predecessor, by disperseing screwing element, makes aluminium carbonate be coated in the network structure that styrene butadiene styrene triblock copolymer is formed; Then passing through mixing screwing element, arranging this section of reaction temperature is 220 DEG C, makes carbon source predecessor become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, make volatile matter get rid of, forming loose and porous structure, arranging temperature is 230 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in high-temperature reactor, dry 30min under the air atmosphere of 250 DEG C;
(4) when inert gas shielding, by the temperature in high-temperature reactor to 1000 DEG C, Cu-lyt. in mass ratio: aluminium carbonate=0.05:3 adds Cu-lyt. reaction 150min, is cooled to 25 DEG C, obtains Graphene Primary product in atmosphere of inert gases;
(5) product that step (4) obtains is reacted 12min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene.
Claims (4)
1. the method preparing Graphene for raw material with carbonate, it is characterised in that comprise the following steps:
(1) by carbonate with macromolecular compound it is 8:(2 ~ 3 in mass ratio) add in high-speed mixer and disperse 5 ~ 10min to obtain carbon source predecessor with the speed high-speed stirred of 2000 ~ 3000rpm;
(2) the carbon source predecessor obtained in step (1) is pumped in screw extruder charge door, screw rod is set gradually dispersion screwing element, mixing screwing element, devolatilization screwing element by feed end terminad, arranging dispersion screwing element section reaction temperature is 130 ~ 180 DEG C, carbon source predecessor, by disperseing screwing element, makes carbonate be coated in the network structure that macromolecular compound is formed; Then pass through mixing screwing element, arranging this section of reaction temperature is 180 ~ 220 DEG C, carbon source predecessor is made to become thermoplastic under high-temperature hot stretching condition, again through devolatilization screwing element, utilize when high temperature high heat, making volatile matter get rid of, form loose and porous structure, arranging temperature is 200 ~ 230 DEG C; Thin slice is formed finally by extruding;
(3) by the thin slice obtained in step (2) in aqueous by washing, vibrating, put in tube furnace, dry 15 ~ 30min under the air atmosphere of 180 ~ 250 DEG C;
(4) when inert gas shielding, by the temperature of tube furnace to 800 ~ 1000 DEG C, add catalyst reaction 120 ~ 150min, atmosphere of inert gases is cooled to 25 DEG C, obtains Graphene Primary product;
(5) the Graphene Primary product that step (4) obtains is reacted 8 ~ 12min in hydrochloric acid solution, be then washed with water to neutrality and dry, finally obtaining Graphene;
Described carbonate is at least one in calcium carbonate, magnesium carbonate, brium carbonate, sodium carbonate, aluminium carbonate, and described macromolecular compound is at least one in polyvinyl pyrrolidone, polyacrylamide, polyethylene terephthalate, Polyethylene Glycol, styrene butadiene styrene triblock copolymer, polyimides; Described catalyst is the one in cesium salt, aluminum isopropylate., manganese dioxide, antimony oxide, Cu-lyt..
2. a kind of method preparing Graphene for raw material with carbonate according to claim 1, it is characterized in that the high-speed mixer described in step (1) is conical screw spiral ribbon mixer, this mixer is made up of cycloidal planetary gear speed reducer, screw rod, outer layer ribbon etc., carbonate and macromolecular compound are tangentially thrown to space by the centrifugal force produced by quick rotation, make it produce strong convection current to shear, spreading, thus reaching the purpose of quick mix homogeneously.
3. a kind of method preparing Graphene for raw material with carbonate according to claim 1, it is characterised in that the screw extruder described in step (2) is conical parallel dual-screw extruding machine, and screw slenderness ratio is 60 ~ 75:1.
4. a kind of method preparing Graphene for raw material with carbonate according to claim 1, it is characterised in that catalyst its addition catalyst in mass ratio described in step (4): carbonate=(0.03 ~ 0.05): 3.
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Cited By (3)
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| CN106582816A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Three-dimensional nitrogen doped graphene with multistage porous channels and prepared of polybenzimidazole |
| CN106587026A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Preparation method of reinforced mass transfer type 3D nitrogen-doped graphene with multi-stage pores communicated |
| CN109264706A (en) * | 2018-10-16 | 2019-01-25 | 李红莉 | A kind of method of the three-D nano-porous graphene powder of chemical vapour deposition technique controllable preparation |
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| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene powder |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
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| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN101993065A (en) * | 2010-12-17 | 2011-03-30 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene powder |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106582816A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Three-dimensional nitrogen doped graphene with multistage porous channels and prepared of polybenzimidazole |
| CN106587026A (en) * | 2016-12-28 | 2017-04-26 | 山东理工大学 | Preparation method of reinforced mass transfer type 3D nitrogen-doped graphene with multi-stage pores communicated |
| CN106587026B (en) * | 2016-12-28 | 2019-04-02 | 山东理工大学 | Strengthen the preparation method of the three-dimensional nitrogen-doped graphene of quality transmission type multistage pore canal perforation |
| CN106582816B (en) * | 2016-12-28 | 2019-04-02 | 山东理工大学 | The three-dimensional nitrogen-doped graphene of multistage pore canal is prepared with polybenzimidazoles |
| CN109264706A (en) * | 2018-10-16 | 2019-01-25 | 李红莉 | A kind of method of the three-D nano-porous graphene powder of chemical vapour deposition technique controllable preparation |
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