CN106629668A - Preparation method of three-dimensional-structure graphene/carbon nanotube hybrid carbon material - Google Patents

Preparation method of three-dimensional-structure graphene/carbon nanotube hybrid carbon material Download PDF

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CN106629668A
CN106629668A CN201611225498.7A CN201611225498A CN106629668A CN 106629668 A CN106629668 A CN 106629668A CN 201611225498 A CN201611225498 A CN 201611225498A CN 106629668 A CN106629668 A CN 106629668A
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carbon
dimensional structure
preparation
structure graphene
graphene
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CN106629668B (en
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梁济元
闫继
曹元成
汤舜
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Jianghan University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00Structure or properties of carbon nanotubes
    • C01B2202/20Nanotubes characterized by their properties
    • C01B2202/34Length
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/32Size or surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • C01P2004/03Particle morphology depicted by an image obtained by SEM

Abstract

The invention discloses a preparation method of a three-dimensional-structure graphene/carbon nanotube hybrid carbon material. The preparation method comprises the following steps: sufficiently dissolving a divalent metal salt, a carbon source precursor and a precipitant in water to obtain a mixed solution; carrying out hydrothermal reaction on the mixed solution to obtain a suspension; sequentially carrying out centrifugation, washing and drying, and taking the dried brown powdery precursor; mixing and grinding the precursor and a cyanamide compound, and carrying out carbonization to obtain the black powder; and finally, carrying out pickling treatment on the black powder to obtain the three-dimensional-structure graphene/carbon nanotube hybrid carbon material. According to the preparation method, the self-template in-situ carbonization catalytic technique is adopted to prepare the three-dimensional-structure graphene/carbon nanotube hybrid carbon material. The carbon nanotubes directly grow out of the graphene surface, and the carbon nanotubes and graphene are connected through sp2 covalent carbon bonds instead of simple physical mixing. The method is simple, is low in cost, and is suitable for large-scale production.

Description

A kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element
Technical field
The present invention relates to the technical field of nano material, in particular to a kind of three-dimensional structure graphene/carbon nano-tube hydridization The preparation method of material with carbon element.
Background technology
Carbon nanomaterial is always the focus of scientific research, and material with carbon element species is various, according to its dimension can be divided into zero dimension, One-dimensional, two and three dimensions material with carbon element.Such as the fullerene of the zero-dimension structural that 1985 find;Japanese Scientists Sumio in 1991 Iijima is found that the CNT of one-dimentional structure, Muscovite two physicists in 2004, Andrei Geim and Kostya Novoselov obtains two-dimension single layer plumbago alkene by using adhesive tape stripping means.Graphene is one kind by carbon atom SP2Hydridization Flat film of the composition hexagon in honeycomb lattice, only one of which carbon atom thickness 2D material with carbon elements, the material with carbon element of other dimensions is such as CNT, fullerene and graphite etc. can regard the derivative of Graphene as.Graphene has higher specific surface area (2630m2/ g), superior electric conductivity (200-3000S/cm), BREATHABLE BANDWIDTH and high mechanical strength, these features cause stone Black alkene has broad application prospects in fields such as energy storage, catalysis and environmental protection.The material with carbon element of three-dimensional structure be by zero dimension, One-dimensional or two-dimentional material with carbon element spatially assembles to form ad hoc structure, and particularly in recent years three-dimensional grapheme material has attracted numerous Research.Due to the strong interaction between graphene sheet layer, easily cause π-π heaps and fall, reduce its specific surface area.For this purpose, will Graphene assembles to form three-dimensional structure, prevent its layer by layer heap fall, effectively improve its surface area and avtive spot, and produce one A little new performances.
CNT and Graphene are all novel carbon nanomaterials, and CNT is a kind of with the one-dimensional of special construction Quantum material, its radial dimension can reach nanoscale, and axial dimension is micron order, with high specific surface area and electric conductivity. Graphene and CNT have similar property at the aspect such as electricity and mechanics, but because structure is different, they also have a lot Difference.The CNT of one-dimentional structure is combined with the Graphene of two-dimensional structure, the group of Graphene on the one hand can be avoided It is poly-;On the other hand a kind of cooperative effect can be produced between them so as to which various physicochemical properties are strengthened, thus this The material of composite construction has broad prospect of application in many fields.
In recent years, work that there are reports describes the compound of Graphene and CNT, Wang (Nano energy, 2013,2,294-303) et al. by the nickel foam surface plasma etching oxidation of three-dimensional structure, then electronics is utilized on its surface Beam evaporation deposits one layer of iron catalyst, then passes through chemical vapor deposition (Chemical Vapor Deposition, CVD) side Formula is in nickel foam superficial growth Graphene and CNT.But for CVD method, its complex process, high cost is pure to gas Degree has high demands.
Du (Chemistry of Materials, 2011,23,4810-4816) et al. is by ordered graphitic acidifying Reason, then high-temperature heat expansion, obtains thermal expansion high-sequential pyrolytic graphite (HOPG);Then for convenience growth of vertical arranges carbon Nanotube, one layer of SiO in Expandable graphite sheet Surface coating2, finally it is pyrolyzed phthalocyanine dye and is pyrolyzed stone to thermal expansion high-sequential The CNT of insertion growth of vertical arrangement (VACNT), prepares adjustable three-dimensional column graphene/carbon nanometer in black (HOPG) Pipe nanostructured.It can be found that the method step is comparatively laborious, operating process is complicated.
Patent CN102674315 is distributed to CNT in graphene oxide solution, then carries out freeze-drying or super Critical drying, obtains graphene oxide-CNT composite aerogel, finally by electronation or high temperature thermal reduction, obtains Graphene/carbon nano-tube composite all-carbon aeroge.However, said method need by Graphene and CNT it is separately synthesized go out Come, then by assembling form three-dimensional structure, CNT is not directly to grow out from graphenic surface, both simply by The physics of electrostatic interaction is combined rather than by chemical bonds, therefore, the graphene/carbon nano-tube of this composite construction is at some Using particularly there is very big contact resistance in electrochemical energy storage field, so as to limit its application.
The content of the invention
Present invention aim to provide a kind of preparation side of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element Method, the preparation method prepares three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element using self-template in-situ carburization catalysis technique, Its CNT directly from three-dimensional grapheme superficial growth out, rather than simple physical mixed, the carbon nanometer for growing in addition Tubular looks and length are controllable, and the method is simple, low cost, be adapted to large-scale production.
For achieving the above object, a kind of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element provided by the present invention Preparation method, comprises the steps:First divalent metal salt, carbon source precursor, precipitating reagent are completely dissolved in water, mixing is obtained Liquid;Again mixed liquor is carried out into hydro-thermal reaction, obtain suspension;Then suspension is centrifuged successively, washed, dried process, Obtain dried powder presoma;Then carbonization treatment will be carried out after presoma and cyanamide compound mixed grinding, is obtained Black powder;Finally by black powder through pickling processes, three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element is obtained.
Further, the divalent metal salt, carbon source precursor, precipitating reagent addition by mole ratio be divalent metal Salt:Carbon source precursor:Precipitating reagent=1:2-5:3-5.
Further, the hydro-thermal reaction is concretely comprised the following steps:Mixed liquor is inserted in hydrothermal reaction kettle and is in temperature 10-48h is reacted under conditions of 150-200 DEG C.
Further, the carbonization treatment is concretely comprised the following steps:To be put into after presoma and cyanamide compound mixed grinding Tube furnace, under an inert atmosphere, with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and keeps 1-6h, naturally cools to room Temperature, obtains black powder.
Further, the presoma and the addition of cyanamide compound are presoma by mass ratio:Cyanamide compound =1:3-7.
Further, the cyanamide compound is selected from dicyandiamide or melamine.
Further, the one kind of the inert gas in nitrogen, argon gas, helium.
Further, the pickling processes are concretely comprised the following steps:Black powder is put into into molar concentration for 3-10mol/L's In hydrochloric acid solution, stirring reaction 24-48h under conditions of temperature is for 60-100 DEG C is cooled to afterwards room temperature, then at centrifugation Reason, and with the multiple washing precipitate of water until the pH=6.8-7.2 of solution, is finally putting in the baking oven that temperature is 60-80 DEG C and does Dry 10-24h, that is, obtain three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
Further, the divalent metal salt is nickel salt, ferrous salt or cobalt salt;The nickel salt is selected from nickel chloride, sulfuric acid One or more in nickel, nickel nitrate, nickel acetate;The cobalt salt selected from cobalt nitrate, cobalt chloride, cobalt acetate it is a kind of or many Kind;The ferrous salt is selected from frerrous chloride or ferrous sulfate.
Further, the carbon source precursor is selected from resorcinol, hydroquinones, Glucosamine, glucose, sucrose, fruit One or more in sugar.
Yet further, the precipitating reagent is in urea, potassium hydroxide, NaOH, hexamethylenetetramine, ammonium chloride One kind.
Further, the carbon source precursor selected from resorcinol, hydroquinones, Glucosamine, glucose, sucrose, One or more in fructose;The precipitating reagent is selected from urea, potassium hydroxide, NaOH, hexamethylenetetramine, ammonium chloride In one kind.
The preparation method of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of the present invention, specifically includes following steps:
1) dissolving of reactant:
First by divalent metal salt, carbon source precursor, precipitating reagent by mole ratio be divalent metal salt:Carbon source precursor:Precipitating reagent =1:2-5:3-5 is completely dissolved in water, obtains mixed liquor;
Wherein, the divalent metal salt is nickel salt, ferrous salt or cobalt salt;The nickel salt is selected from nickel chloride, nickel sulfate, nitre One or more in sour nickel, nickel acetate;The cobalt salt selected from cobalt nitrate, cobalt chloride, cobalt acetate one or more;Institute Ferrous salt is stated selected from frerrous chloride or ferrous sulfate;The carbon source precursor selected from resorcinol, hydroquinones, Glucosamine, One or more in glucose, sucrose, fructose;The precipitating reagent is selected from urea, potassium hydroxide, NaOH, six first One kind in urotropine, ammonium chloride;
2) hydro-thermal reaction:
Mixed liquor is inserted in hydrothermal reaction kettle and reacts 10-48h under conditions of temperature is for 150-200 DEG C, take suspension Be centrifuged successively, washed, dried process, obtain dried powder presoma;
3) carbonization treatment:
It is presoma by mass ratio by presoma and cyanamide compound:Cyanamide compound=1:Put after 3-7 mixed grindings Enter tube furnace, under an inert atmosphere, with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and keep 1-6h, naturally cool to Room temperature, obtains black powder;
4) pickling processes:
Black powder is put in the hydrochloric acid solution that molar concentration is 3-10mol/L, in the condition that temperature is 60-100 DEG C Lower stirring reaction 24-48h, is cooled to afterwards room temperature, then through centrifugal treating, and it is washed with distilled water to the pH=6.8- of solution 7.2, finally centrifugation is precipitated into thing and is put into temperature to be dried 10-24h in 60-80 DEG C of baking oven, that is, obtain three-dimensional structure stone Black alkene/carbon nano-tube hybridization material with carbon element.
Compared with prior art, the invention has the advantages that:
First, the preparation method of the present invention is self-assembly of with three-dimensional without the need for previously prepared template by hydro-thermal reaction The presoma self-template of structure, in carbonisation, the metal in presoma had both prepared the catalyst of Graphene as catalysis, Can be used as the catalyst of growth CNT;By regulating and controlling cyanamide compound amount, length, the shape of CNT can be regulated and controled Looks and growth population, and then obtain the hydridization material with carbon element of high conductivity and high-specific surface area.
Second, the CNT of the present invention is grown out from graphenic surface, CNT and Graphene skeleton structure Between be sp by carrying out on atom level2Covalently carbon bond is closed, and it is that one kind has three-dimensional structure to obtain in configuration aspects Graphene/carbon nano-tube hydridization material with carbon element, obtain the innovation in structure, rather than two kinds of compositions are simply by electrostatic interaction Physics is combined, and so advantageously reduces junction electrical resistance, lifts the conductance of material.
Third, three-dimensional grapheme/carbon nano-tube hybridization material with carbon element prepared by the present invention, in energy storage, catalysis, bio-sensing The fields such as device, environmental protection have a wide range of applications, and this preparation method process is simple, extensive raw suitable for industrialization Produce, and low cost, substantially no environmental pollution.
Description of the drawings
Fig. 1 is the SEM figures of powder predecessor in embodiment 1;
Fig. 2 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 1;
Fig. 3 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 2;
Fig. 4 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 3;
Fig. 5 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 4;
Fig. 6 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 5;
Fig. 7 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 6;
Fig. 8 is the SEM figures of the three-dimensional grapheme/CNT prepared by embodiment 7.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1:
The resorcinol of the nickel chloride of 0.005mol, 0.015mol hexamethylenetetramines and 0.02mol is dissolved in into 30mL water In, obtain mixed liquor;Mixed liquor is transferred in 50mL polytetrafluoro reactors again, reaction 18h is stood at 150 DEG C, be cooled to After room temperature, suspension is obtained;By above-mentioned suspension centrifuge washing, under room temperature 24h is dried, take dried powder presoma with Melamine is 1 according to mass ratio:It is put in tube furnace after 5 mixing, under the protection of nitrogen (nitrogen flow 50mL/min), from Room temperature is warming up to 700 DEG C with 2 DEG C/min, and keeps 3h at this temperature;Room temperature is naturally cooled to, black powder is obtained;By this Black powder is put in 100mL beakers, the hydrochloric acid 50mL for adding molar concentration to be 8mol/L, and at 60 DEG C 48h is stirred;Afterwards, Suction filtration, and it is 6.8-7.2 repeatedly to be washed to pH value of solution with distilled water, obtain be deposited in 80 DEG C at be dried 16h, finally give three Dimension structure graphite alkene/carbon nano-tube hybridization material with carbon element.
The scanned Electronic Speculum of the material of above-mentioned preparation is characterized, the method for sem test is:Sample powder is sticked to On conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, is then scanned Electronic Speculum test, and accelerating potential scope is arranged In 10kV, 25k times of enlargement ratio.
Fig. 1 is the SEM figures of above-mentioned powder presoma, as can be seen from the figure manifests on sample microcosmic and is tied by many sheets Structure carries out being assembled into three-dimensional flower-shaped structure.Fig. 2 is sweeping for the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation Electron micrograph (SEM) is retouched, is apparent that the Graphene for obtaining assembles to form three-dimensional flower ball-shaped structure, chi from figure It is very little at 3-4 μm;There are a small amount of some carbon nano tube growths out in schistose surface simultaneously, carbon length of tube is in 500nm.
Embodiment 2:
The glucose of 0.005mol nickel acetates, 0.015mol urea and 0.01mol is dissolved in 30mL distilled water, is mixed Close liquid;Mixed liquor is transferred in 50mL polytetrafluoro reactors again, hydro-thermal reaction 12h at 180 DEG C after being cooled to room temperature, takes Obtain suspension;Above-mentioned suspension is carried out to be dried 24h under centrifuge washing, room temperature, by dried powder presoma and trimerization Cyanamide is 1 according to mass ratio:4 mixing, in being put into tube furnace, under argon atmosphere (argon flow amount 50mL/min), from room temperature with 2 DEG C/min is warming up to 800 DEG C, and keeps 2h at this temperature;After naturally cooling to room temperature, black powder is obtained;By this black powder End is put in 100mL beakers, and addition molar concentration is 6mol/L hydrochloric acid 50mL, and at 50 DEG C 48h is stirred;Afterwards, centrifugation is simultaneously more The secondary pH value of solution that is washed with distilled water to is 6.8-7.2, and centrifugal sediment is dried into 12h at 60 DEG C, finally gives three-dimensional structure Graphene/carbon nano-tube hydridization material with carbon element.
The scanned Electronic Speculum of the material of above-mentioned preparation is characterized, the method for sem test is:Sample powder is sticked to On conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, is then scanned Electronic Speculum test, and accelerating potential scope is arranged In 10kV, 20k times of enlargement ratio.
Fig. 3 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), it can be seen that the composite for obtaining is in three-dimensional flower ball-shaped structure and has certain agglomeration, three-dimensional sheet Body structure surface grows some CNTs, and carbon length of tube is at 1-2 μm.
Embodiment 3:
The sucrose of 0.005mol nickel sulfates, 0.015mol potassium hydroxide and 0.015mol is dissolved in 35mL distilled water, is taken Obtain mixed liquor;Mixed liquor is transferred in 50mL polytetrafluoro reactors again, hydro-thermal reaction 24h at 180 DEG C;It is cooled to room temperature Afterwards, suspension is obtained;Above-mentioned suspension is carried out to be dried 24h under centrifuge washing, room temperature, take dried powder presoma with Dicyandiamide is 1 according to mass ratio:4 mixing, in being put into tube furnace, under nitrogen atmosphere (nitrogen flow 50mL/min), from room temperature 900 DEG C are warming up to 2 DEG C/min, and keep 1h at this temperature;After naturally cooling to room temperature, black powder is obtained;This is black Color powder is put in 100mL beakers, and addition molar concentration is 6mol/L hydrochloric acid 50mL, and at 80 DEG C 36h is stirred;Afterwards, it is centrifuged And pH value of solution is repeatedly washed with distilled water to for 6.8-7.2, and centrifugal sediment is dried into 10h at 60 DEG C, finally give three-dimensional Structure graphite alkene/carbon nano-tube hybridization material with carbon element.
The scanned Electronic Speculum of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation is characterized, ESEM The method of test is:Sample powder is sticked on conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, then carries out Sem test, accelerating potential scope is arranged on 10kV, 10k times of enlargement ratio.
Fig. 4 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), it can be seen that the material with carbon element for obtaining is presented three-dimensional flower-shaped structure, the growth of some places carbon pipe is fewer, has Local carbon pipe growth is in much cluster-shaped, and carbon length of tube is at 1-2 μm.
Embodiment 4:
By the amino of the nickel nitrate of 0.005mol, 0.005mol nickel sulfates, 0.04mol hexamethylenetetramines and 0.02mol Glucose is dissolved in 30mL distilled water, obtains mixed liquor;By mixed liquor and it is transferred in 50mL polytetrafluoro reactors, 200 again Hydro-thermal stands reaction 24h at DEG C, after being cooled to room temperature, obtains suspension;Above-mentioned suspension is carried out into centrifuge washing, is done under room temperature Dry 24h, it is 1 according to mass ratio to take dried powder presoma with dicyandiamide:3 mixing, in being put into tube furnace, in argon atmospher Under enclosing (gas flow 50mL/min), 900 DEG C are warming up to 2 DEG C/min from room temperature, and keep 2h at this temperature;Natural cooling To room temperature, black powder is obtained.This black powder is put in 100mL beakers, addition molar concentration is 6mol/L hydrochloric acid 50mL, at 40 DEG C 48h is stirred;Afterwards, pH value of solution is centrifuged and is repeatedly washed with distilled water to for 6.8-7.2, after centrifugation Sediment is dried 12h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
The scanned Electronic Speculum of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation is characterized, ESEM The method of test is:Sample powder is sticked on conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, then carries out Sem test, accelerating potential scope is arranged on 10kV, 20k times of enlargement ratio.
Fig. 5 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), it can be seen that the composite for obtaining is in multilevel hierarchy, and the diameter of ball is at 1 μm.Can be with bright from figure Aobvious to observe that CNT grows out from graphenic surface, CNT is shorter and thick, length in 600-800nm, Diameter is in 200nm or so.
Embodiment 5:
By the cobalt nitrate of 0.01mol, 0.05mol hexamethylenetetramines and 0.01mol hydroquinones, 0.02mol isophthalic two Phenol is dissolved in 40mL distilled water, obtains mixed liquor;By mixed liquor and it is transferred in 50mL polytetrafluoro reactors, at 200 DEG C again Hydro-thermal stands reaction 16h, after being cooled to room temperature, obtains suspension;Above-mentioned suspension is carried out into centrifuge washing, is dried under room temperature 24h, it is 1 according to mass ratio to take dried powder presoma with dicyandiamide:4 mixed grindings, in being put into tube furnace, in nitrogen Under atmosphere (nitrogen flow 50mL/min), with 5 DEG C/min heating rates from room temperature to 700 DEG C, and keep at this temperature 3h;After naturally cooling to room temperature, black powder is obtained;This black powder is put in 100mL beakers, addition molar concentration is 5mol/L hydrochloric acid solution 50mL, at 50 DEG C 48h is stirred;Afterwards, pH value of solution is centrifuged and is repeatedly washed with distilled water to for 6.8- 7.2, centrifugal sediment is dried into 12h at 60 DEG C, finally give three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
The scanned Electronic Speculum of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation is characterized, ESEM The method of test is:Sample powder is sticked on conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, then carries out Sem test, accelerating potential scope is arranged on 10kV, 10k times of enlargement ratio.
Fig. 6 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), it can be seen that many CNTs are grown on graphenic surface in cluster form, length is at 1 μm or so.
Embodiment 6:
The Glucosamine of the cobalt chloride of 0.01mol, 0.03mol NaOH and 0.05mol is dissolved in into 50mL distilled water In, obtain mixed liquor;By mixed liquor and it is transferred in 50mL polytetrafluoro reactors again, hydro-thermal stands reaction 16h at 150 DEG C; After being cooled to room temperature, above-mentioned suspension is carried out to be dried 24h under suction filtration, room temperature, take dried powder presoma and trimerization Cyanamide is 1 according to mass ratio:7 mixed grindings, in being put into tube furnace, under helium atmosphere (helium gas flow 30mL/min), from room Temperature is warming up to 1000 DEG C with 5 DEG C/min, and keeps 3h at this temperature;After naturally cooling to room temperature, black powder is obtained;By this Black powder is put in 100mL beakers, and addition molar concentration is 10mol/L hydrochloric acid 50mL, and at 60 DEG C 24h is stirred;Afterwards from The heart is simultaneously repeatedly washed with distilled water to pH value of solution for 6.8-7.2, and centrifugal sediment is dried into 24h at 60 DEG C, finally gives three Dimension structure graphite alkene/carbon nano-tube hybridization material with carbon element.
The scanned Electronic Speculum of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation is characterized, ESEM The method of test is:Sample powder is sticked on conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, then carries out Sem test, accelerating potential scope is arranged on 3kV, 10k times of enlargement ratio.
Fig. 7 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), it can be seen that three-dimensional structure graphenic surface grown many CNTs, CNT " jungle " is formed, , at 1 μm, diameter is in 20-40nm for carbon length of tube.
Embodiment 7:
The cobalt acetate of 0.01mol, 0.03mol urea, 0.02mol fructose and 0.02mol sucrose are dissolved in into 40mL distilled water In, obtain mixed liquor;By mixed liquor and it is transferred in 50mL polytetrafluoro reactors again, hydro-thermal stands reaction 24h at 180 DEG C; After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out to be dried 24h under centrifuge washing, room temperature, dried powder is taken Shape presoma is 1 according to mass ratio with dicyandiamide:6 mixed grindings, in being put into tube furnace, (nitrogen flow under nitrogen atmosphere 50mL/min), with 5 DEG C/min heating rates from room temperature to 700 DEG C, and 6h is kept at this temperature;Naturally cool to room Wen Hou, obtains black powder;This black powder is put in 100mL beakers, addition molar concentration is 5mol/L hydrochloric acid solutions 50mL, at 80 DEG C 24h is stirred.Afterwards, pH value of solution is centrifuged and is repeatedly washed with distilled water to for 6.8-7.2, by centrifugation Thing is dried 10h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
The scanned Electronic Speculum of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation is characterized, ESEM The method of test is:Sample powder is sticked on conductive carbon paste, being put on vacuum coating equipment carries out metal spraying 60s, then carries out Sem test, accelerating potential scope is arranged on 10kV, 15k times of enlargement ratio.
Fig. 8 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element of above-mentioned preparation (SEM), as can be seen from Figure 8, many bamboo-like carbon nano tubes of three-dimensional structure superficial growth, are gone out with divergence expression structure growth Come, length is at 1-1.5 μm.
Embodiment 8:
By the cobalt acetate of 0.005mol, 0.005mol cobalt nitrates, 0.03mol potassium hydroxide, 0.005mol glucose, 0.01mol sucrose, 0.01mol resorcinols are dissolved in 40mL distilled water, obtain mixed liquor;By mixed liquor and it is transferred to 50mL again In polytetrafluoro reactor, hydro-thermal stands reaction 12h at 180 DEG C;After being cooled to room temperature, suspension is obtained;By above-mentioned suspension Carry out being dried 24h under centrifuge washing, room temperature, it is 1 according to mass ratio to take dried powder presoma with melamine:7 mix Grinding is closed, in being put into tube furnace, under helium atmosphere (helium gas flow 50mL/min), with 2 DEG C/min heating rates from room temperature liter Temperature keeps at this temperature 5h to 900 DEG C;After naturally cooling to room temperature, black powder is obtained;This black powder is put into In 100mL beakers, addition molar concentration is 7mol/L hydrochloric acid solution 50mL, and at 80 DEG C 48h is stirred.Afterwards, centrifugation is simultaneously multiple It is 6.8-7.2 to be washed with distilled water to pH value of solution, and centrifugal sediment is dried into 12h at 80 DEG C, finally gives three-dimensional structure stone Black alkene/carbon nano-tube hybridization material with carbon element.
Embodiment 9:
By the nickel chloride of 0.01mol, 0.01mol nickel nitrates, 0.06mol urea, 0.02mol Glucosamines and 0.02mol sucrose is dissolved in 50mL distilled water, obtains mixed liquor;By mixed liquor and it is transferred in 100mL polytetrafluoro reactors again, Hydro-thermal stands reaction 48h at 180 DEG C;After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out into centrifuge washing, room 24h is dried under temperature, it is 1 according to mass ratio to take dried powder presoma with melamine:4 mixed grindings, are put into tubular type In stove, under argon atmosphere (argon flow amount 50mL/min), with 5 DEG C/min heating rates from room temperature to 1000 DEG C, and 1h is kept at a temperature of this;After naturally cooling to room temperature, black powder is obtained;This black powder is put in 100mL beakers, is added Molar concentration is 10mol/L hydrochloric acid solution 50mL, and at 90 DEG C 24h is stirred.Afterwards, it is centrifuged and is repeatedly washed with distilled water to molten Liquid pH is 6.8-7.2, and centrifugal sediment is dried into 16h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube hydridization Material with carbon element.
Embodiment 10:
By the nickel chloride of 0.01mol, 0.01mol nickel sulfates, 0.005mol nickel acetates, 0.1mol urea, 0.025mol ammonia Base glucose and 0.025mol sucrose are dissolved in 50mL distilled water, obtain mixed liquor;By mixed liquor and it is transferred to 100mL poly- four again In fluorine reactor, hydro-thermal stands reaction 48h at 200 DEG C;After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out 24h is dried under centrifuge washing, room temperature, it is 1 according to mass ratio to take dried powder presoma with melamine:4 mixing are ground Mill, in being put into tube furnace, under nitrogen atmosphere (nitrogen flow 50mL/min), with 4 DEG C/min heating rates from room temperature to 900 DEG C, and 6h is kept at this temperature;After naturally cooling to room temperature, black powder is obtained;This black powder is put into into 100mL In beaker, addition molar concentration is 6mol/L hydrochloric acid solution 50mL, and at 100 DEG C 24h is stirred.Afterwards, it is centrifuged and repeatedly with steaming Distilled water wash to pH value of solution be 6.8-7.2, centrifugal sediment is dried into 20h at 80 DEG C, finally give three-dimensional structure Graphene/ Carbon nano-tube hybridization material with carbon element.
Embodiment 11:
The fructose of the frerrous chloride of 0.01mol, 0.03mol ammonium chlorides and 0.02mol is dissolved in 40mL distilled water, is obtained Mixed liquor;By mixed liquor and it is transferred in 50mL polytetrafluoro reactors again, hydro-thermal stands reaction 48h at 180 DEG C;It is cooled to room Wen Hou, obtains suspension;Above-mentioned suspension is carried out to be dried 24h under centrifuge washing, room temperature, dried powder presoma is taken With dicyandiamide according to mass ratio be 1:6 mixed grindings, in being put into tube furnace, under nitrogen atmosphere (nitrogen flow 50mL/min), With 2 DEG C/min heating rates from room temperature to 900 DEG C, and 6h is kept at this temperature;After naturally cooling to room temperature, obtain black Color powder;This black powder is put in 100mL beakers, addition molar concentration is 10mol/L hydrochloric acid solution 50mL, at 80 DEG C Stirring 24h.Afterwards, pH value of solution is centrifuged and be repeatedly washed with distilled water to for 6.8-7.2, centrifugal sediment is dried at 80 DEG C 16h, finally gives three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
Embodiment 12:
The ferrous sulfate of 0.02mol, 0.06mol urea, 0.02mol glucose, 0.02mol Glucosamines are dissolved in In 50mL distilled water, mixed liquor is obtained;By mixed liquor and it is transferred in 100mL polytetrafluoro reactors again, hydro-thermal is quiet at 180 DEG C Put reaction 24h;After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out to be dried 24h under centrifuge washing, room temperature, is taken dry Powder presoma after dry is 1 according to mass ratio with dicyandiamide:5 mixed grindings, in being put into tube furnace, under nitrogen atmosphere (nitrogen flow 50mL/min), with 5 DEG C/min heating rates from room temperature to 800 DEG C, and keeps at this temperature 6h;It is natural After being cooled to room temperature, black powder is obtained;This black powder is put in 100mL beakers, addition molar concentration is 10mol/L salt Acid solution 50mL, at 60 DEG C 24h is stirred.Afterwards, centrifugation and to be repeatedly washed with distilled water to pH value of solution be 6.8-7.2, will be from Heart sediment is dried 16h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
Embodiment 13:
By the cobaltous sulfate of 0.01mol, 0.01mol cobalt chlorides, 0.01mol cobalt nitrates, 0.1mol urea, 0.03mol grapes Sugar, 0.03mol sucrose are dissolved in 60mL distilled water, obtain mixed liquor;By mixed liquor and it is transferred to 100mL polytetrafluoro reactors again In, hydro-thermal stands reaction 36h at 180 DEG C;After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out into centrifuge washing, 24h is dried under room temperature, it is 1 according to mass ratio to take dried powder presoma with dicyandiamide:5 mixed grindings, are put into tubular type In stove, under nitrogen atmosphere (nitrogen flow 20mL/min), with 2 DEG C/min heating rates from room temperature to 800 DEG C, and here At a temperature of keep 2h;After naturally cooling to room temperature, black powder is obtained;This black powder is put in 100mL beakers, addition rubs Your concentration is 7mol/L hydrochloric acid solution 50mL, and at 60 DEG C 48h is stirred.Afterwards, it is centrifuged and is repeatedly washed with distilled water to solution PH is 6.8-7.2, and centrifugal sediment is dried into 10h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube hydridization carbon Material.
Embodiment 14:
By the nickel chloride of 0.01mol, 0.03mol hexamethylenetetramines and 0.02mol fructose, 0.02mol sucrose, 0.01mol hydroquinones is dissolved in 50mL distilled water, obtains mixed liquor;Again by mixed liquor and be transferred to 100mL polytetrafluoros reaction In kettle, hydro-thermal stands reaction 48h at 150 DEG C;After being cooled to room temperature, suspension is obtained;Above-mentioned suspension is carried out into centrifugation to wash Wash, under room temperature 24h is dried, it is 1 according to mass ratio to take dried powder presoma with melamine:3 mixed grindings, are put into In tube furnace, under argon atmosphere (argon flow amount 50mL/min), with 2 DEG C/min heating rates from room temperature to 900 DEG C, and 6h is kept at this temperature;After naturally cooling to room temperature, black powder is obtained;This black powder is put in 100mL beakers, plus It is 10mol/L hydrochloric acid solution 50mL to enter molar concentration, and at 60 DEG C 24h is stirred.Afterwards, it is centrifuged and is repeatedly washed with distilled water to PH value of solution is 6.8-7.2, and centrifugal sediment is dried into 16h at 80 DEG C, finally gives three-dimensional structure graphene/carbon nano-tube miscellaneous Change material with carbon element.
The above, specific embodiment only of the invention, it is noted that any those of ordinary skill in the art exist Disclosed herein technical scope in, the change or replacement that can be readily occurred in, all should cover protection scope of the present invention it It is interior.

Claims (10)

1. a kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element, it is characterised in that including following step Suddenly:First divalent metal salt, carbon source precursor, precipitating reagent are completely dissolved in water, mixed liquor is obtained;Again mixed liquor is carried out into hydro-thermal Reaction, obtains suspension;Then suspension is centrifuged successively, washed, dried process, obtain dried powder forerunner Body;Then carbonization treatment will be carried out after presoma and cyanamide compound mixed grinding, obtains black powder;Finally by black powder Through pickling processes, three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element is obtained.
2. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1, its feature exists In, the divalent metal salt, carbon source precursor, precipitating reagent addition by mole ratio be divalent metal salt:Carbon source precursor:Precipitation Agent=1:2-5:3-5.
3. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1, its feature exists In concretely comprising the following steps for, the hydro-thermal reaction:By mixed liquor insert in hydrothermal reaction kettle temperature be 150-200 DEG C under conditions of Reaction 10-48h.
4. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1, its feature exists In concretely comprising the following steps for, the carbonization treatment:Tube furnace will be put into after presoma and cyanamide compound mixed grinding, in indifferent gas Under atmosphere, with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and 1-6h is kept, naturally cool to room temperature, obtain black powder End.
5. the preparation method of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1 or 4, it is special Levy and be, the presoma is presoma by mass ratio with the addition of cyanamide compound:Cyanamide compound=1:3-7.
6. the preparation method of the three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1 or 4, it is special Levy and be, the cyanamide compound is selected from dicyandiamide or melamine.
7. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1, its feature exists In concretely comprising the following steps for, pickling processes:Black powder is put in the hydrochloric acid solution that molar concentration is 3-10mol/L, Temperature is stirring reaction 24-48h under conditions of 60-100 DEG C, and room temperature is cooled to afterwards, then through centrifugal treating, and use distilled water Wash to the pH=6.8-7.2 of solution, finally centrifugation is precipitated into thing and is put into temperature to be dried 10- in 60-80 DEG C of baking oven 24h, that is, obtain three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element.
8. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1 and 2, it is special Levy and be, the divalent metal salt is nickel salt, ferrous salt or cobalt salt;Wherein, the nickel salt is selected from nickel chloride, nickel sulfate, nitre One or more in sour nickel, nickel acetate;The cobalt salt selected from cobalt nitrate, cobalt chloride, cobalt acetate one or more;Institute Ferrous salt is stated selected from frerrous chloride or ferrous sulfate.
9. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1 and 2, it is special Levy and be, the one kind of the carbon source precursor in resorcinol, hydroquinones, Glucosamine, glucose, sucrose, fructose Or it is various;The one kind of the precipitating reagent in urea, potassium hydroxide, NaOH, hexamethylenetetramine, ammonium chloride.
10. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization material with carbon element according to claim 1, its feature It is to specifically include following steps:
1) dissolving of reactant:
First by divalent metal salt, carbon source precursor, precipitating reagent by mole ratio be divalent metal salt:Carbon source precursor:Precipitating reagent=1: 2-5:3-5 is completely dissolved in water, obtains mixed liquor;
Wherein, the divalent metal salt is nickel salt, ferrous salt or cobalt salt;The nickel salt is selected from nickel chloride, nickel sulfate, nitric acid One or more in nickel, nickel acetate;The cobalt salt selected from cobalt nitrate, cobalt chloride, cobalt acetate one or more;It is described Ferrous salt is selected from frerrous chloride or ferrous sulfate;The carbon source precursor is selected from resorcinol, hydroquinones, Glucosamine, Portugal One or more in grape sugar, sucrose, fructose;The precipitating reagent is selected from urea, potassium hydroxide, NaOH, six methines One kind in tetramine, ammonium chloride;
2) hydro-thermal reaction:
Mixed liquor is inserted in hydrothermal reaction kettle and reacts 10-48h under conditions of temperature is for 150-200 DEG C, take suspension successively Be centrifuged, washed, dried process, obtain dried powder presoma;
3) carbonization treatment:
It is presoma by mass ratio by presoma and cyanamide compound:Cyanamide compound=1:Pipe is put into after 3-7 mixed grindings Formula stove, under an inert atmosphere, with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and keeps 1-6h, naturally cools to room Temperature, obtains black powder;
4) pickling processes:
Black powder is put in the hydrochloric acid solution that molar concentration is 3-10mol/L, is stirred under conditions of temperature is for 60-100 DEG C Reaction 24-48h is mixed, room temperature is cooled to afterwards, then through centrifugal treating, and be washed with distilled water to the pH=6.8-7.2 of solution, Finally will centrifugation be precipitated thing to be put into temperature be to be dried 10-24h in 60-80 DEG C of baking oven, that is, obtain three-dimensional structure Graphene/ Carbon nano-tube hybridization material with carbon element.
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