CN106629668B - A kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material - Google Patents
A kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material, which includes the following steps：First divalent metal salt, carbon source precursor, precipitating reagent are completely dissolved in water, obtain mixed liquor；Mixed liquor is subjected to hydro-thermal reaction again, obtains suspension；Then suspension centrifuged successively, washed, be dried, take the powdered presoma of the sepia after drying；Then carbonization treatment will be carried out after presoma and cyanamide compound mixed grinding, obtains black powder；Black powder is finally passed through into pickling processes, obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.Preparation method of the present invention prepares three-dimensional structure graphene/carbon nano-tube hydridization carbon material using self-template in-situ carburization catalysis technique, and carbon nanotube directly grows out from graphene surface, and passes through sp between the two2Covalent carbon key connection, rather than the simple physical mixed of the two, simple, at low cost, the suitable large-scale production of this method.
Description
Technical field
The present invention relates to the technical fields of nano material, in particular to a kind of three-dimensional structure graphene/carbon nano-tube hydridization
The preparation method of carbon material.
Background technology
Carbon nanomaterial is always the hot spot of scientific research, and carbon material type is various, according to its dimension can be divided into zero dimension,
One-dimensional, two and three dimensions carbon material.The fullerene of the zero-dimension structural found such as 1985；Japanese Scientists Sumio in 1991
Iijima is found that the carbon nanotube of one-dimentional structure, Russian two physicist 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
The flat film that hexagon is in honeycomb lattice is formed, only there are one carbon atom thickness 2D carbon materials, and the carbon material of other dimensions is such as
Carbon nanotube, 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 make stone
Black alkene has broad application prospects in fields such as energy storage, catalysis and environmental protections.The carbon material of three-dimensional structure be by zero dimension,
One-dimensional or two-dimentional carbon material, which spatially assembles, forms specific structure, especially in recent years three-dimensional grapheme material attracted it is numerous
Research.Due to the strong interaction between graphene sheet layer, it be easy to cause π-π heaps and falls, reduce its specific surface area.For this purpose, will
Graphene assembles to form three-dimensional structure, and preventing it, heap is fallen layer by layer, effectively improves its surface area and active site, and generate one
A little new performances.
Carbon nanotube and graphene are all novel carbon nanomaterials, and carbon nanotube is a kind of one-dimensional with special construction
Quantum material, its radial dimension can reach nanoscale, and axial dimension is micron order, have high specific surface area and electric conductivity.
Graphene and carbon nanotube have similar property in electricity and mechanics etc., but due to structure difference, they also have very much
Difference.The graphene of the carbon nanotube of one-dimentional structure and two-dimensional structure is compound, it on the one hand can be to avoid the group of graphene
It is poly-；On the other hand a kind of synergistic effect can be generated between them, its various physicochemical properties is made to be enhanced, thus it is 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 carbon nanotube, 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 grows graphene and carbon nanotube in foam nickel surface.But for CVD method, complex process is of high cost, pure to gas
Degree requires high.
Du (Chemistry of Materials, 2011,23,4810-4816) et al. is by ordered graphitic acidification
Reason, then high-temperature heat expansion, obtains thermally expanding high-sequential pyrolytic graphite (HOPG)；Then growth of vertical arranges carbon for convenience
Nanotube has coated one layer of SiO on Expandable graphite sheet surface2, finally it is pyrolyzed phthalocyanine dye and is pyrolyzed stone to high-sequential is thermally expanded
It is inserted into the carbon nanotube of growth of vertical arrangement (VACNT) in black (HOPG), prepares adjustable three-dimensional column graphene/carbon nanometer
Pipe nanostructure.It can be found that this method step is comparatively laborious, operating process is complicated.
Carbon nanotube is distributed in graphene oxide solution by patent CN102674315, is then freeze-dried or is surpassed
Critical drying obtains graphene oxide-carbon nanotube composite aerogel, heat-treats, obtains finally by electronation or high temperature
Graphene/carbon nano-tube composite all-carbon aeroge.However, the above method need by graphene and carbon nanotube it is separately synthesized go out
Come, then by assembling form three-dimensional structure, carbon nanotube is not directly to grow out from graphene surface, the two simply by
The physics of electrostatic interaction is compound rather than by chemical bonds, and therefore, the graphene/carbon nano-tube of this composite construction is at some
Using especially having prodigious contact resistance in electrochemical energy storage field, to limit its application field.
Invention content
Present invention aim to provide a kind of preparation side of three-dimensional structure graphene/carbon nano-tube hydridization carbon material
Method, the preparation method prepare three-dimensional structure graphene/carbon nano-tube hydridization carbon material using self-template in-situ carburization catalysis technique,
Its carbon nanotube directly grows out from three-dimensional grapheme surface, rather than simple physical mixed, the carbon nanometer in addition grown
Tubular looks and length are controllable, simple, at low cost, the suitable large-scale production of this method.
To achieve the above object, a kind of three-dimensional structure graphene/carbon nano-tube hydridization carbon material provided by the present invention
Preparation method includes the following steps：First divalent metal salt, carbon source precursor, precipitating reagent are completely dissolved in water, obtain mixing
Liquid；Mixed liquor is subjected to hydro-thermal reaction again, obtains suspension；Then suspension centrifuged successively, washed, be dried,
Obtain the powdered presoma after drying；Then carbonization treatment will be carried out after presoma and cyanamide compound mixed grinding, obtained
Black powder；Black powder is finally passed through into pickling processes, obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
Further, the divalent metal salt, carbon source precursor, precipitating reagent additive amount by mole the ratio between be divalent metal
Salt：Carbon source precursor：Precipitating reagent=1：2-5：3-5.
Further, the hydro-thermal reaction the specific steps are：Mixed liquor is placed in hydrothermal reaction kettle and is in temperature
10-48h is reacted under conditions of 150-200 DEG C.
Further, the carbonization treatment the specific steps are：It will be put into after presoma and cyanamide compound mixed grinding
Tube furnace with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and keeps 1-6h, naturally cools to room under an inert atmosphere
Temperature obtains black powder.
Further, it is presoma that the presoma and the additive amount of cyanamide compound, which press 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 the specific steps are：It is 3-10mol/L's that black powder, which is put into molar concentration,
In hydrochloric acid solution, it is stirred to react 24-48h under conditions of temperature is 60-100 DEG C, is cooled to room temperature later, at centrifugation
Reason is used in combination the multiple washing precipitate of water up to the pH=6.8-7.2 of solution, is finally putting into the baking oven that temperature is 60-80 DEG C and does
Dry 10-24h is to get to three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
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 of nickel, nickel nitrate, nickel acetate；The cobalt salt be selected from cobalt nitrate, cobalt chloride, cobalt acetate it is a kind of or more
Kind；The ferrous salt is selected from frerrous chloride or ferrous sulfate.
Further, the carbon source precursor is selected from resorcinol, hydroquinone, Glucosamine, glucose, sucrose, fruit
One or more of sugar.
Still further, the precipitating reagent is in urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride
One kind.
Further, the carbon source precursor be selected from resorcinol, hydroquinone, Glucosamine, glucose, sucrose,
One or more of fructose；The precipitating reagent is selected from urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride
In one kind.
The preparation method of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of the present invention, specifically comprises the following steps：
1) dissolving of reactant：
First by divalent metal salt, carbon source precursor, precipitating reagent by mole the ratio between 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 of sour nickel, nickel acetate；The cobalt salt is selected from the one or more of cobalt nitrate, cobalt chloride, cobalt acetate；Institute
It states ferrous salt and is selected from frerrous chloride or ferrous sulfate；The carbon source precursor be selected from resorcinol, hydroquinone, Glucosamine,
One or more of glucose, sucrose, fructose；The precipitating reagent is selected from urea, potassium hydroxide, sodium hydroxide, six first
One kind in urotropine, ammonium chloride；
2) hydro-thermal reaction：
Mixed liquor is placed in hydrothermal reaction kettle and reacts 10-48h under conditions of temperature is 150-200 DEG C, takes suspension
It centrifuged, washed, be dried successively, obtain the powdered presoma after drying；
3) carbonization treatment：
It is presoma that presoma and cyanamide compound, which are pressed mass ratio,：Cyanamide compound=1：It is 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 keeps 1-6h, naturally cool to
Room temperature obtains black powder；
4) pickling processes：
Black powder is put into the hydrochloric acid solution that molar concentration is 3-10mol/L, the condition for being 60-100 DEG C in temperature
Under be stirred to react 24-48h, be cooled to room temperature later, using centrifugal treating, and be washed with distilled water to the pH=6.8- of solution
7.2, finally will centrifugation obtain sediment be put into temperature be in 60-80 DEG C of baking oven dry 10-24h to get to three-dimensional structure stone
Black alkene/carbon nano-tube hybridization carbon material.
Compared with prior art, the invention has the advantages that：
First, the preparation method of the present invention is not necessarily to previously prepared template, it is self-assembly of with three-dimensional 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,
It can be as the catalyst of growth carbon nanotube；By regulating and controlling cyanamide compound amount, length, the shape of carbon nanotube can be regulated and controled
Looks and growth population, and then obtain the hydridization carbon material of high conductivity and high-specific surface area.
Second, the carbon nanotube of the present invention is grown out from graphene surface, carbon nanotube and graphene skeleton structure
Between be sp by being carried out on atom level2Covalent carbon bond is closed, and obtains being a kind of with three-dimensional structure in configuration aspects
Graphene/carbon nano-tube hydridization carbon material, obtain the innovation in structure, rather than two kinds of ingredients simply lean on electrostatic interaction
Physics is compound, advantageously reduces junction electrical resistance in this way, promotes the conductivity of material.
Third, three-dimensional grapheme/carbon nano-tube hybridization carbon material 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 is simple for process, it is extensive raw to be suitable for industrialization
Production, and it is at low cost, substantially without environmental pollution.
Description of the drawings
Fig. 1 is the SEM figures of powdered predecessor in embodiment 1；
Fig. 2 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 1；
Fig. 3 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 2；
Fig. 4 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 3；
Fig. 5 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 4；
Fig. 6 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 5；
Fig. 7 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 6；
Fig. 8 is the SEM figures of three-dimensional grapheme/carbon nanotube prepared by embodiment 7.
Specific implementation mode
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 30mL water
In, obtain mixed liquor；Mixed liquor is transferred in 50mL polytetrafluoro reaction kettles again, reaction 18h is stood at 150 DEG C, is cooled to
After room temperature, suspension is obtained；By above-mentioned suspension centrifuge washing, at room temperature it is dry for 24 hours, take it is dry after powdered presoma with
Melamine is 1 according to mass ratio:It is put into 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；Cooled to room temperature obtains black powder；By this
Black powder is put into 100mL beakers, and the hydrochloric acid 50mL that molar concentration is 8mol/L is added, 48h is stirred at 60 DEG C；Later,
It filters, it is 6.8-7.2 to be used in combination distilled water repeatedly to wash to pH value of solution, and what is obtained is deposited at 80 DEG C dry 16h, finally obtains three
Tie up structure graphite alkene/carbon nano-tube hybridization carbon material.
By the scanned Electronic Speculum characterization of the material of above-mentioned preparation, the method for sem test is：Sample powder is adhered to
On conductive carbon paste, it is put into progress metal spraying 60s on vacuum coating equipment, is then scanned Electronic Speculum test, the setting of accelerating potential range
In 10kV, 25k times of enlargement ratio.
Fig. 1 be above-mentioned powdered presoma SEM scheme, as can be seen from the figure sample it is microcosmic on show by many sheet knots
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 carbon material of above-mentioned preparation
Electron micrograph (SEM) is retouched, the graphene being apparent that from figure assembles to form three-dimensional flower ball-shaped structure, ruler
It is very little at 3-4 μm；There are some a small amount of carbon nano tube growths to come 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 reaction kettles again, the hydro-thermal reaction 12h at 180 DEG C after being cooled to room temperature, takes
Obtain suspension；Above-mentioned suspension is subjected to centrifuge washing, is dried at room temperature for 24 hours, by the powdered presoma and trimerization after drying
Cyanamide is 1 according to mass ratio:4 mixing, are 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 cooled to room temperature, black powder is obtained；By this black powder
End is put into 100mL beakers, and addition molar concentration is 6mol/L hydrochloric acid 50mL, and 48h is stirred at 50 DEG C；Later, 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 12h at 60 DEG C, finally obtains three-dimensional structure
Graphene/carbon nano-tube hydridization carbon material.
By the scanned Electronic Speculum characterization of the material of above-mentioned preparation, the method for sem test is：Sample powder is adhered to
On conductive carbon paste, it is put into progress metal spraying 60s on vacuum coating equipment, is then scanned Electronic Speculum test, the setting of accelerating potential range
In 10kV, 20k times of enlargement ratio.
Fig. 3 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), it can be seen from the figure that obtained composite material is in three-dimensional flower ball-shaped structure and has certain agglomeration, three-dimensional sheet
Body structure surface grows some carbon nanotubes, 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 reaction kettles again, hydro-thermal reaction is for 24 hours at 180 DEG C；It is cooled to room temperature
Afterwards, suspension is obtained；Above-mentioned suspension is subjected to centrifuge washing, at room temperature it is dry for 24 hours, take it is dry after powdered presoma with
Dicyandiamide is 1 according to mass ratio:4 mixing, are 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 keeps 1h at this temperature；After cooled to room temperature, black powder is obtained；This is black
Color powder is put into 100mL beakers, and addition molar concentration is 6mol/L hydrochloric acid 50mL, and 36h is stirred at 80 DEG C；Later, it centrifuges
And it is 6.8-7.2 to be repeatedly washed with distilled water to pH value of solution, and centrifugal sediment is dried 10h at 60 DEG C, finally obtains three-dimensional
Structure graphite alkene/carbon nano-tube hybridization carbon material.
By the scanned Electronic Speculum characterization of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation, scanning electron microscope
The method of test is：Sample powder is adhered on conductive carbon paste, progress metal spraying 60s on vacuum coating equipment is put into, then carries out
Sem test, accelerating potential range are arranged in 10kV, 10k times of enlargement ratio.
Fig. 4 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), it can be seen from the figure that three-dimensional flower-shaped structure is presented in obtained carbon material, 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 nickel nitrate of 0.005mol, the amino of 0.005mol nickel sulfates, 0.04mol hexamethylenetetramines and 0.02mol
Glucose is dissolved in 30mL distilled water, obtains mixed liquor；It by mixed liquor and is transferred in 50mL polytetrafluoro reaction kettles again, 200
Hydro-thermal stands reaction for 24 hours at DEG C, after being cooled to room temperature, obtains suspension；Above-mentioned suspension is subjected to centrifuge washing, is done at room temperature
It is dry for 24 hours, take it is dry after powdered presoma with dicyandiamide be 1 according to mass ratio:3 mixing, are put into tube furnace, in argon atmospher
Under enclosing (gas flow 50mL/min), 900 DEG C are warming up to from room temperature with 2 DEG C/min, and keep 2h at this temperature；Natural cooling
To room temperature, black powder is obtained.This black powder is put into 100mL beakers, addition molar concentration is 6mol/L hydrochloric acid
50mL stirs 48h at 40 DEG C；Later, it is 6.8-7.2 to centrifuge and be repeatedly washed with distilled water to pH value of solution, after centrifugation
Sediment dry 12h at 80 DEG C, finally obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
By the scanned Electronic Speculum characterization of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation, scanning electron microscope
The method of test is：Sample powder is adhered on conductive carbon paste, progress metal spraying 60s on vacuum coating equipment is put into, then carries out
Sem test, accelerating potential range are arranged in 10kV, 20k times of enlargement ratio.
Fig. 5 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), it can be seen from the figure that obtained composite material is in multilevel hierarchy, and the diameter of ball is at 1 μm.It can be with bright from figure
Aobvious to observe that carbon nanotube grows out from graphene surface, carbon nanotube 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；It by mixed liquor and is transferred in 50mL polytetrafluoro reaction kettles again, at 200 DEG C
Hydro-thermal stands reaction 16h, after being cooled to room temperature, obtains suspension；Above-mentioned suspension is subjected to centrifuge washing, is dried at room temperature
For 24 hours, take it is dry after powdered presoma with dicyandiamide be 1 according to mass ratio:4 mixed grindings, are 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 cooled to room temperature, black powder is obtained；This black powder is put into 100mL beakers, molar concentration, which is added, is
5mol/L hydrochloric acid solution 50mL, 48h is stirred at 50 DEG C；Later, it is 6.8- to centrifuge and be repeatedly washed with distilled water to pH value of solution
7.2, centrifugal sediment is dried into 12h at 60 DEG C, finally obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
By the scanned Electronic Speculum characterization of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation, scanning electron microscope
The method of test is：Sample powder is adhered on conductive carbon paste, progress metal spraying 60s on vacuum coating equipment is put into, then carries out
Sem test, accelerating potential range are arranged in 10kV, 10k times of enlargement ratio.
Fig. 6 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), it can be seen from the figure that many carbon nanotubes are grown in the form of cluster on the surface of graphene, length is at 1 μm or so.
Embodiment 6：
The Glucosamine of the cobalt chloride of 0.01mol, 0.03mol sodium hydroxides and 0.05mol is dissolved in 50mL distilled water
In, obtain mixed liquor；It by mixed liquor and is transferred in 50mL polytetrafluoro reaction kettles again, hydro-thermal stands reaction 16h at 150 DEG C；
After being cooled to room temperature, above-mentioned suspension is filtered, drying at room temperature for 24 hours, takes the powdered presoma and trimerization after drying
Cyanamide is 1 according to mass ratio:7 mixed grindings, are 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 cooled to room temperature, black powder is obtained；By this
Black powder is put into 100mL beakers, and addition molar concentration is 10mol/L hydrochloric acid 50mL, is stirred for 24 hours at 60 DEG C；Later from
The heart is simultaneously repeatedly washed with distilled water to pH value of solution as 6.8-7.2, and by centrifugal sediment, drying for 24 hours, finally obtains three at 60 DEG C
Tie up structure graphite alkene/carbon nano-tube hybridization carbon material.
By the scanned Electronic Speculum characterization of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation, scanning electron microscope
The method of test is：Sample powder is adhered on conductive carbon paste, progress metal spraying 60s on vacuum coating equipment is put into, then carries out
Sem test, accelerating potential range are arranged in 3kV, 10k times of enlargement ratio.
Fig. 7 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), it can be seen from the figure that three-dimensional structure graphene surface grown many carbon nanotubes, carbon nanotube " jungle " is formed,
Carbon length of tube is at 1 μm, and diameter is in 20-40nm.
Embodiment 7：
The cobalt acetate of 0.01mol, 0.03mol urea, 0.02mol fructose and 0.02mol sucrose are dissolved in 40mL distilled water
In, obtain mixed liquor；It by mixed liquor and is transferred in 50mL polytetrafluoro reaction kettles again, hydro-thermal stands reaction for 24 hours at 180 DEG C；
After being cooled to room temperature, suspension is obtained；Above-mentioned suspension is subjected to centrifuge washing, drying at room temperature for 24 hours, takes the powder after drying
Shape presoma is 1 according to mass ratio with dicyandiamide:6 mixed grindings, are put into tube furnace, under nitrogen atmosphere (nitrogen flow
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 into 100mL beakers, addition molar concentration is 5mol/L hydrochloric acid solutions
50mL is stirred for 24 hours at 80 DEG C.Later, it is 6.8-7.2 to centrifuge and be repeatedly washed with distilled water to pH value of solution, by centrifugation
Object dry 10h at 80 DEG C, finally obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
By the scanned Electronic Speculum characterization of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation, scanning electron microscope
The method of test is：Sample powder is adhered on conductive carbon paste, progress metal spraying 60s on vacuum coating equipment is put into, then carries out
Sem test, accelerating potential range are arranged in 10kV, 15k times of enlargement ratio.
Fig. 8 is the electron scanning micrograph of the three-dimensional structure graphene/carbon nano-tube hydridization carbon material of above-mentioned preparation
(SEM), as can be seen from Figure 8, three-dimensional structure surface grows many bamboo-like carbon nano tubes, is 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 reaction kettle, hydro-thermal stands reaction 12h at 180 DEG C；After being cooled to room temperature, suspension is obtained；By above-mentioned suspension
Carry out centrifuge washing, at room temperature it is dry for 24 hours, take it is dry after powdered presoma with melamine be 1 according to mass ratio:7 is mixed
Grinding is closed, is 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 5h at this temperature to 900 DEG C；After cooled 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 48h is stirred at 80 DEG C.Later, it centrifuges and multiple
It is 6.8-7.2 to be washed with distilled water to pH value of solution, and centrifugal sediment is dried 12h at 80 DEG C, finally obtains three-dimensional structure stone
Black alkene/carbon nano-tube hybridization carbon material.
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；It by mixed liquor and is transferred in 100mL polytetrafluoro reaction kettles again,
Hydro-thermal stands reaction 48h at 180 DEG C；After being cooled to room temperature, suspension is obtained；Above-mentioned suspension is subjected to centrifuge washing, room
Temperature is lower dry for 24 hours, take it is dry after powdered presoma with melamine be 1 according to mass ratio: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 cooled to room temperature, black powder is obtained；This black powder is put into 100mL beakers, is added
Molar concentration is 10mol/L hydrochloric acid solution 50mL, is stirred for 24 hours at 90 DEG C.Later, it centrifuges and is repeatedly washed with distilled water to molten
Liquid pH is 6.8-7.2, and centrifugal sediment is dried 16h at 80 DEG C, finally obtains three-dimensional structure graphene/carbon nano-tube hydridization
Carbon material.
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 reaction kettle, hydro-thermal stands reaction 48h at 200 DEG C；After being cooled to room temperature, suspension is obtained；Above-mentioned suspension is carried out
Centrifuge washing, it is 1 according to mass ratio to dry the powdered presoma after taking drying for 24 hours at room temperature with melamine:4 mixing are ground
Mill, be 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 cooled to room temperature, black powder is obtained；This black powder is put into 100mL
In beaker, addition molar concentration is 6mol/L hydrochloric acid solution 50mL, is stirred for 24 hours at 100 DEG C.Later, it centrifuges and repeatedly with steaming
It is 6.8-7.2 that distilled water, which is washed to pH value of solution, by centrifugal sediment at 80 DEG C dry 20h, finally obtain three-dimensional structure graphene/
Carbon nano-tube hybridization carbon material.
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；It by mixed liquor and is transferred in 50mL polytetrafluoro reaction kettles again, hydro-thermal stands reaction 48h at 180 DEG C；It is cooled to room
Wen Hou obtains suspension；Above-mentioned suspension is subjected to centrifuge washing, drying at room temperature for 24 hours, takes the powdered presoma after drying
With dicyandiamide according to mass ratio be 1:6 mixed grindings, are 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 cooled to room temperature, obtain black
Color powder；This black powder is put into 100mL beakers, addition molar concentration is 10mol/L hydrochloric acid solution 50mL, at 80 DEG C
Stirring is for 24 hours.Later, it is 6.8-7.2 to centrifuge and be repeatedly washed with distilled water to pH value of solution, and centrifugal sediment is dry at 80 DEG C
16h finally obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
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；It by mixed liquor and is transferred in 100mL polytetrafluoro reaction kettles again, hydro-thermal is quiet at 180 DEG C
Set reaction for 24 hours；After being cooled to room temperature, suspension is obtained；Above-mentioned suspension is subjected to centrifuge washing, drying at room temperature for 24 hours, takes dry
Powdered presoma after dry is 1 according to mass ratio with dicyandiamide:5 mixed grindings, are 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 6h at this temperature；It is natural
After being cooled to room temperature, black powder is obtained；This black powder is put into 100mL beakers, addition molar concentration is 10mol/L salt
Acid solution 50mL is stirred for 24 hours at 60 DEG C.Later, it centrifuges and is repeatedly washed with distilled water to pH value of solution as 6.8-7.2, it will be from
Heart sediment dry 16h at 80 DEG C, finally obtains three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
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 reaction kettles again
In, hydro-thermal stands reaction 36h at 180 DEG C；After being cooled to room temperature, suspension is obtained；Above-mentioned suspension is subjected to centrifuge washing,
It is 1 according to mass ratio that the powdered presoma after taking drying for 24 hours is dried at room temperature 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 herein
At a temperature of keep 2h；After cooled to room temperature, black powder is obtained；This black powder is put into 100mL beakers, addition rubs
You are a concentration of 7mol/L hydrochloric acid solutions 50mL, and 48h is stirred at 60 DEG C.Later, it centrifuges and is repeatedly washed with distilled water to solution
PH is 6.8-7.2, and centrifugal sediment is dried 10h at 80 DEG C, finally obtains 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 are dissolved in 50mL distilled water, obtain 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 centrifugation to wash
It washs, it is 1 according to mass ratio to dry the powdered presoma after taking drying for 24 hours at room temperature 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 cooled to room temperature, black powder is obtained；This black powder is put into 100mL beakers, is added
It is 10mol/L hydrochloric acid solution 50mL to enter molar concentration, is stirred for 24 hours at 60 DEG C.Later, it centrifuges and is repeatedly washed with distilled water to
PH value of solution is 6.8-7.2, and centrifugal sediment is dried 16h at 80 DEG C, it is miscellaneous to finally obtain three-dimensional structure graphene/carbon nano-tube
Change carbon material.
The above description is merely a specific embodiment, it is noted that any technical person familiar with the field exists
Disclosed herein technical scope in, the change or replacement that can be readily occurred in, should all cover protection scope of the present invention it
It is interior.
Claims (8)
1. a kind of preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material, which is characterized in that including walking as follows
Suddenly：First divalent metal salt, carbon source precursor, precipitating reagent are completely dissolved in water, obtain mixed liquor；Mixed liquor is subjected to hydro-thermal again
Reaction obtains suspension；Then suspension centrifuged successively, washed, be dried, obtain the powdered forerunner after drying
Body；Then carbonization treatment will be carried out after presoma and cyanamide compound mixed grinding, obtains black powder；Finally by black powder
By pickling processes, three-dimensional structure graphene/carbon nano-tube hydridization carbon material is obtained；
Wherein, the divalent metal salt, carbon source precursor, precipitating reagent additive amount by mole the ratio between be divalent metal salt：Before carbon source
Body：Precipitating reagent=1：2-5：3-5；
The divalent metal salt is nickel salt, ferrous salt or cobalt salt；Wherein, the nickel salt is selected from nickel chloride, nickel sulfate, nitric acid
One or more of nickel, nickel acetate；The cobalt salt is selected from the one or more of cobalt nitrate, cobalt chloride, cobalt acetate；It is described
Ferrous salt is selected from frerrous chloride or ferrous sulfate.
2. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1, feature exist
In, the hydro-thermal reaction the specific steps are：Mixed liquor is placed in hydrothermal reaction kettle under conditions of temperature is 150-200 DEG C
React 10-48h.
3. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1, feature exist
In, the carbonization treatment the specific steps are：It will be put into tube furnace 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, cooled to room temperature obtains black powder
End.
4. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1 or 3, special
Sign is that it is presoma that the additive amount of the presoma and cyanamide compound, which presses mass ratio,：Cyanamide compound=1：3-7.
5. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1 or 3, special
Sign is that the cyanamide compound is selected from dicyandiamide or melamine.
6. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1, feature exist
In, pickling processes the specific steps are：Black powder is put into the hydrochloric acid solution that molar concentration is 3-10mol/L,
Temperature is stirred to react 24-48h under conditions of being 60-100 DEG C, is cooled to room temperature later, using centrifugal treating, distilled water is used in combination
It washs to the pH=6.8-7.2 of solution, centrifugation, which is finally obtained sediment, is put into dry 10- in the baking oven that temperature is 60-80 DEG C
For 24 hours to get to three-dimensional structure graphene/carbon nano-tube hydridization carbon material.
7. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1 or 2, special
Sign is, the one kind of the carbon source precursor in resorcinol, hydroquinone, Glucosamine, glucose, sucrose, fructose
Or it is a variety of；The one kind of the precipitating reagent in urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride.
8. the preparation method of three-dimensional structure graphene/carbon nano-tube hydridization carbon material according to claim 1, feature exist
In specifically comprising the following steps：
1) dissolving of reactant：
First by divalent metal salt, carbon source precursor, precipitating reagent by mole the ratio between 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 of nickel, nickel acetate；The cobalt salt is selected from the one or more of cobalt nitrate, cobalt chloride, cobalt acetate；It is described
Ferrous salt is selected from frerrous chloride or ferrous sulfate；The carbon source precursor is selected from resorcinol, hydroquinone, Glucosamine, Portugal
One or more of grape sugar, sucrose, fructose；The precipitating reagent is selected from urea, potassium hydroxide, sodium hydroxide, six methines
One kind in tetramine, ammonium chloride；
2) hydro-thermal reaction：
Mixed liquor is placed in hydrothermal reaction kettle and reacts 10-48h under conditions of temperature is 150-200 DEG C, takes suspension successively
It centrifuged, washed, be dried, obtain the powdered presoma after drying；
3) carbonization treatment：
It is presoma that presoma and cyanamide compound, which are pressed mass ratio,：Cyanamide compound=1：It is put into pipe after 3-7 mixed grindings
Formula stove with 2-5 DEG C/min from room temperature to 700-1000 DEG C, and keeps 1-6h, naturally cools to room under an inert atmosphere
Temperature obtains black powder；
4) pickling processes：
Black powder is put into the hydrochloric acid solution that molar concentration is 3-10mol/L, is stirred under conditions of temperature is 60-100 DEG C
Reaction 24-48h is mixed, is cooled to room temperature later, using centrifugal treating, and is washed with distilled water to the pH=6.8-7.2 of solution,
Finally will centrifugation obtain sediment be put into temperature be in 60-80 DEG C of baking oven dry 10-24h to get to three-dimensional structure graphene/
Carbon nano-tube hybridization carbon material.
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