CN107673332A - A kind of method that large area 3D graphenes are prepared using composition metal template - Google Patents
A kind of method that large area 3D graphenes are prepared using composition metal template Download PDFInfo
- Publication number
- CN107673332A CN107673332A CN201710843089.1A CN201710843089A CN107673332A CN 107673332 A CN107673332 A CN 107673332A CN 201710843089 A CN201710843089 A CN 201710843089A CN 107673332 A CN107673332 A CN 107673332A
- Authority
- CN
- China
- Prior art keywords
- foam
- graphenes
- metal
- composition metal
- large area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to a kind of method that large area 3D graphenes are prepared using composition metal template, this method plates one layer of copper (or one layer of nickel is plated on foam copper) in nickel foam, then high-temperature heating makes its surface become corronil, then under the growth temperature of CVD techniques, it is passed through carbon source, graphene is grown in Intelligent Composite metal film surfaces during cooling, the number of plies of graphene is controlled using Intelligent Composite metallic film, prepares high-quality, large area 3D graphenes.Solve the problems, such as that the number of plies existing for traditional CVD method preparation 3D graphenes is unmanageable and covering is not complete, the 3D graphenes of better quality can be obtained.
Description
Technical field
The present invention relates to a kind of method that large area 3D graphenes are prepared using composition metal template, belongs to graphene preparation
Technical field.
Background technology
In firm past several years, the three-dimensional material that is formed by graphene self assembly oneself through being considered as nanosecond science and technology
One of most promising material in field, it is wide concerned in chemical field.3D graphenes are by individual layer Two-dimensional Carbon atomic unit
The three-dimensional bodies (compared to the structure of two-dimensional graphene) formed are stacked, are three-dimensional cross-linked loose structure.3D graphenes show
The excellent inherent attributes such as more preferable electric conductivity, bigger specific surface area, more powerful mechanical dominance and dynamic performance are gone out.
Preferable 3D graphenes framework forms the high conductivity for containing single-layer graphene, and several microns are generally arrived in aperture at hundreds of nanometers
Or it is smaller, and gap structure can increase specific surface area, the mechanical performance of reinforcing material, i.e., the porous flexible 3D for turning into uniqueness
The application advantage of graphene three-dimensional structure.Three-dimensional netted cross linked porous structure so that the stability of 3D graphenes is tied than two dimension
Structure is more preferable, and specific surface area and space availability ratio are bigger.The reunion of Sheet Graphite alkene can be efficiently reduced, ensures that proton translocation leads to
Freely.In addition, another greater advantages of 3D grapheme materials are easy for repeatedly processing recovery use.
The many excellent properties of the three-dimensional crosslinking structure and graphene of 3D graphenes and its composite in itself, have and inhale
The performances such as attached, catalysis so that it possesses extensively in fields such as ultracapacitor, biology sensor, electro-catalysis application and environmental protection
Wealthy application prospect.
At present, 3D graphene preparation methods can be divided into two major classes on the whole：One kind is prepared by direct method, does not need mould as
Plate come aid in prepare method.Such as：Chinese patent literature CN104730121A discloses the graphene of multi-walled carbon nanotube bridging
Conductive network and preparation method thereof, oxidation graphite solid is prepared with natural flake graphite powder, ultrasound prepares graphene oxide suspension
Liquid, reducing agent stirring reaction at 50-80 DEG C is added, obtains 3D graphenes.Chinese patent literature CN105668555A is disclosed
A kind of method for preparing three-dimensional grapheme.This method be during chemical vapor deposition, using without template without catalyst
Method is directly by controlling carbon source flow in a variety of Grown three-dimensional graphemes.Both the above method is simple to operate, still
Additional impurity is relatively more, and graphene is of low quality.
Another kind of is template auxiliary law, and template auxiliary law is a kind of conventional to prepare specific structure and pattern nano material
Method, and there is many different application potentials, particularly traditional template auxiliary law, conventional metals template CVD method work
Skill is relatively simple, cost is cheap, and the equipment and growing environment generally required becomes more readily available；Template auxiliary law mainly includes
Three big steps：(1) presoma of association reaction carrys out proofing or penetrates into template；(2) by reacting, being nucleated and being grown in shape in template
Into solid-state；(3) final product can be obtained after removing template is removed.
Relevant template auxiliary law, which prepares three-dimensional grapheme, has many patent documents to disclose, such as：Chinese patent literature
CN103854877A discloses a kind of self-supporting graphene/manganese oxide composite electrodes material and preparation method thereof, the combination electrode
The preparation method of material, using dc source by its in-situ electrolysis, obtains mainly using graphite paper as raw material on graphite paper
The graphene of self-supporting；Chinese patent literature CN105776196A discloses a kind of three-dimensional grapheme porous material of structure-controllable
Preparation method, with metal form, graphene film is grown on metal form by chemical vapour deposition technique；Configure corrosive liquid simultaneously
Backflow dissolving metal form, the porous material of three-dimensional grapheme is obtained after scrubbed and drying process at a temperature of 60 DEG C -90 DEG C
Expect product.One kind chemical vapour deposition technique is disclosed in Chinese patent literature CN102674321A in three-dimensional foam nickel template table
Face deposited graphite alkene film, and through it is molten remove porous metals substrate after obtain porous foam shape graphene disclose one kind in conductive base
The method of spontaneous deposition three-dimensional grapheme on bottom；Chinese patent literature CN103265022A discloses one kind with carbonate or carbonic acid
Hydrogen salt is that masterplate prepares method of three-dimensional grapheme of porous insertion etc.；Chinese patent literature CN106158553A is related to nanometer
Function element Flied emission technical field, there is provided a kind of 3D graphenes/monodimension nanometer material composite construction field-transmitting cathode, including
Metal foam skeleton substrate, graphene layer and monodimension nanometer material layer；Graphene layer is located at metal foam and 1-dimention nano material
Between the bed of material, graphene layer is not only as electron transfer layer but also with monodimension nanometer material layer collectively as emission layer；But above-mentioned side
The pattern of three-dimensional grapheme prepared by method, density, height etc. are difficult to controllable, and the existing number of plies is unmanageable and covers incomplete
The problem of.
The content of the invention
In view of the shortcomings of the prior art, present invention offer is a kind of prepares large area 3D graphenes using composition metal template
Method.
Invention summary：
The method of the preparation large area 3D graphenes of the present invention：One layer of copper is plated in nickel foam and (or one is plated on foam copper
Layer nickel), then high-temperature heating makes its surface become corronil, then under the growth temperature of CVD techniques, is passed through carbon source, drops
Graphene is grown in Intelligent Composite metal film surfaces when warm, the layer of graphene is controlled using Intelligent Composite metallic film
Number, prepares high-quality, large area 3D graphenes.The number of plies existing for solving traditional CVD method preparation 3D graphenes is difficult to control
The problem of system and infull covering, the 3D graphenes of better quality can be obtained.
Term is explained：
Nickel foam：Spongy porous-metal nickel.
Foam copper：Spongy porous metal copper.
Plating：Plate the process of the other metals of a thin layer on the metal surface using electrolysis principle.
Electron beam evaporation：Evaporation material is placed in cold-crucible, being directly heated using electron beam vaporizes evaporation material
And condensed on substrate and form film.
Plasma sputtering：Rare gas is ionized into plasma with the method for direct current or radio frequency, then pass through biasing etc.
Method bombards target, makes the atom on target have enough abilities to spin off, falls on substrate, forms film.
Detailed description of the invention：
The present invention is achieved through the following technical solutions：
A kind of method that large area 3D graphenes are prepared using composition metal template, is comprised the following steps：
(1) foam metal is provided, cleaned, removes surface impurity, the foam metal after being cleaned；
(2) will on the foam metal after removal of impurities using plating or depositional mode plating or deposition last layer other metals,
Obtain composition metal；
(3) composition metal is placed on the quartz boat sample stage of CVD growth stove, vacuumized, be warming up to 200-300 DEG C, led to
Enter high-purity argon gas, Stress control is in 100-300mbar, 1~5min of insulation；550-650 DEG C is then heated to, is passed through High Purity Hydrogen
Gas, Stress control are incubated 8~12min, foam metal alloy are obtained after annealing in 100-300mbar, can be to graphene growth
Play catalytic action；
(4) 1000-1100 DEG C is continuously heating to, 10-30min is incubated, is passed through high-purity carbon-source gas, Stress control is in 100-
300mbar, insulation 5-30min carries out growth graphene, after the completion of growth, closes carbon-source gas, continues logical high-purity argon gas, pressure
Heating interval is moved to opposite side in 100-300mbar by control, and fast cooling is to 500-600 DEG C, then Temperature fall to room
Temperature, go out 3D graphenes in foam composition metal superficial growth；
(5) step (4) has been grown to the foam composition metal of graphene, has removed composition metal, cleaning, drying obtain big face
Product 3D graphenes.
Currently preferred, in step (1), described foam metal is nickel foam or foam copper, the aperture of foam metal：
0.01mm-10mm, porosity 60%-99%；Described cleaning is to enter foam metal with deionized water, absolute alcohol successively
Row is cleaned by ultrasonic.
Currently preferred, in step (2), other described metals are copper or nickel, when step (1) foam metal is foam
Nickel, other metals of step (2) are copper；When step (1) foam metal is foam copper, other metals of step (2) are nickel.
Currently preferred, in step (2), the thickness of other metals of plating or deposition last layer is 10nm-800nm, is made
The mass ratio for obtaining cupro-nickel is 1:10-1:1000.
Currently preferred, in step (2), described plating is the anode of foam metal electrochemical workstation, is put into
In other metallic solutions, using copper sheet as negative electrode, one layer of other metal is electroplated on foam metal.
Currently preferred, in step (2), described deposition is using on electron beam evaporation or plasma sputter deposition one
Other metals of layer.
It is currently preferred, in step (3), vacuum is vacuumized as 10-4-10-6Pa, it is warming up to 200-300 DEG C of heating
Speed is 5-20 DEG C/min, and it is 10-100sccm that high-purity argon gas, which is passed through flow,；The heating rate for being warming up to 550-650 DEG C is 5-20
DEG C/min, it is 4-20sccm that high-purity hydrogen, which is passed through flow,；High-purity argon gas, argon gas, the hydrogen that high-purity hydrogen is more than 5N.
Currently preferred, in step (4), the heating rate that is warming up to 1000-1100 DEG C is 1-10 DEG C/min, carbon source gas
It is 1-20sccm that body, which is passed through flow, and described high-purity carbon-source gas are more than 5N methane or propane gas；It is high after the completion of growth
It is 10-100sccm that pure argon, which is passed through flow, and fast cooling rate of temperature fall is 120-240 DEG C/min.
It is currently preferred, it is in step (5) that the PMMA that 1% is added dropwise on the foam composition metal for having grown graphene is molten
Liquid, and dry, then sample is put into 1mol/L FeCl3With nitric acid (1:1) in mixed solution, at magnetic stirrer
More than 12h is managed, removes composition metal；PMMA is removed with hot acetone repeatedly, finally deionized water, alcohol are cleaned respectively, most
Dried up afterwards with nitrogen gun.
In preparation method of the present invention, step (4) vacuumizes and is warming up to 200-300 DEG C, to foam composition metal and
Prebake conditions are carried out inside reaction cavity, makes the desorbing gas on foam composition metal surface and inside cavity absorption and discharges cavity,
To reach residual oxygen in reduction cavity and further lift vacuum.
All raw materials are commercially available prod in the inventive method.The part being not particularly limited can refer to prior art.
The technical characterstic and excellent results of the present invention is：
For the present invention as a result of foam nickel copper as substrate, its production cost is very low, commercially available to have many specifications.
The foam nickel copper that the present invention uses, which is passed through, to be cleaned by ultrasonic, and after annealing, not damaged layer；And herein
Handled again by hydrogen attack in step (4) heating process afterwards, surface is very smooth.
The present invention relates to a kind of new method for preparing graphene.Traditional CVD method is combined on metallic copper and metallic nickel
The advantages of upper growth graphene, it is that one layer of copper (or one layer of nickel is plated on foam copper) is plated in nickel foam the characteristics of this method, leads to
Crossing high-temperature heating makes its surface become corronil, catalytic action can be played to graphene growth, then in the life of CVD techniques
At long temperature, additional carbon is passed through, the metal copper film of alloy can be catalyzed carbon atom in its unfolded surface, cooling intelligently multiple
Close metal film surfaces and grow graphene, using the Intelligent Composite metallic film of foam metal alloy surface (by controlling copper
Film different thickness controls the ratio of cupro-nickel metal) control the number of plies of graphene, prepare coverage rate up to 98% with
Upper, high-quality 3D graphenes.
It is of the invention compared with traditional CVD method prepares 3D graphenes in nickel foam, graphene coverage rate is higher, graphite
Alkene monocrystalline area is bigger, and scale effect is lower, and globality is stronger more preferable；This method can also solve traditional CVD method and prepare 3D
The number of plies existing for graphene is unmanageable and covers the problem of incomplete, can obtain the 3D graphenes of better quality.
The present invention utilizes the Intelligent Composite metal of foam metal alloy surface by precise control of temperature and temperature rate
Film (by controlling the different thickness of Copper thin film) is so as to adjust composition metal composition, to control the number of plies of graphene；Solve
Graphene grows disunity on nickel foam, foam copper, the number of plies is not easily controlled the problem very thick with the number of plies.This method is grown
3D graphenes be covered with whole template surface, the graphene number of plies can be controlled in 1-4 layers.
Brief description of the drawings
Fig. 1 is the schematic diagram that the present invention prepares 3D graphenes using composition metal template；
Fig. 2 is the XRD that embodiment 1 grows obtained 3D graphenes.
Fig. 3 is the Raman spectrogram of 3D graphenes that embodiment 1-3 grows to obtain.Abscissa is Raman shift (cm-1), indulge and sit
Mark is intensity (a.u.).
Fig. 4 is the SEM figures that embodiment 1 grows obtained 3D graphenes.
Embodiment
With reference to embodiment, the present invention will be further described, but not limited to this.
Slide rail tubular type CVD growth stove used is Hefei section crystalline substance OTF-1200 type CVD stoves in embodiment, and the rate of heat addition can arrive
30 DEG C/min, rate of temperature fall most soon can be to 300 DEG C/min.
The nickel foam used is commercially available prod, thickness：1-3mm, aperture：0.1-0.5mm, porosity：70-80%.
Embodiment 1：
A kind of method that large area 3D graphenes are prepared using composition metal template, is comprised the following steps：
(1) nickel foam that size is 1 square centimeter is cleaned by ultrasonic with deionized water, absolute alcohol successively, defoamed
Nickel surface impurity；
(2) by the anode of the cleaned nickel foam electrochemical workstation of step (1), it is put into 1mol/L CuCl2Solution
In, using copper sheet as negative electrode, under normal temperature, 20min is reacted, one layer of copper is electroplated in nickel foam；
(3) the foam copper nickel composite metal that step (2) has been plated is lain in the quartz boat sample of slide rail tubular type CVD growth stove
On platform；Tubular type CVD growth stove mechanical pump and molecular pump suction are to 10-4Pa, is warming up to 200 DEG C, and heating rate is 20 DEG C/
Min, high-purity argon gas is passed through, flow 20sccm, Stress control is in 100-300mbar, insulation 1min；550 DEG C are then heated to,
Heating rate is 20 DEG C/min, is passed through hydrogen, flow 10sccm, Stress control is in 100-300mbar, insulation 10min；Then
1100 DEG C are warming up to, heating rate is 10 DEG C/min, is incubated 20min；It is passed through methane gas, flow 10sccm, Stress control
In 100-300mbar, 20min is incubated；
After the completion of growth, carbon-source gas are closed, continue logical argon gas, flow 30sccm, Stress control is in 100-
300mbar, heating interval is moved to opposite side, for fast cooling to 600 DEG C, rate of temperature fall can reach 120-240 DEG C/min；So
Temperature fall goes out graphene to room temperature in foam composition metal superficial growth afterwards；
(4) step (3) has been grown to the PMMA solution of dropwise addition 1% on the foam composition metal of graphene, and dried, then
Sample is put into 1mol/L FeCl3With nitric acid (1:1) in mixed solution, more than 12h is handled with magnetic stirrer, is removed
Composition metal；PMMA is removed with hot acetone repeatedly, finally deionized water, alcohol are cleaned respectively, are finally dried up with nitrogen gun.
Embodiment 2：
A kind of method that large area 3D graphenes are prepared using composition metal template, is comprised the following steps：
(1) nickel foam that size is 1 square centimeter is cleaned by ultrasonic with deionized water, absolute alcohol successively, defoamed
Nickel surface impurity；
(2) the cleaned foam copper deposited by electron beam evaporation of step (1) is deposited to 200nm nickel；
(3) the foam copper nickel composite metal that step (2) has been plated is lain in the quartz boat sample of slide rail tubular type CVD growth stove
On platform；Tubular type CVD growth stove mechanical pump and molecular pump suction are to 10-4Pa, is warming up to 200 DEG C, and heating rate is 20 DEG C/
Min, high-purity argon gas is passed through, flow 20sccm, Stress control is in 100-300mbar, insulation 1min；550 DEG C are then heated to,
Heating rate is 20 DEG C/min, is passed through hydrogen, flow 10sccm, Stress control is in 100-300mbar, insulation 10min；Then
1000 DEG C are warming up to, heating rate is 10 DEG C/min, is incubated 20min；Methane gas, flow 5sccm are passed through, Stress control exists
100-300mbar, it is incubated 10min；
After the completion of growth, carbon-source gas are closed, continue logical argon gas, flow 30sccm, Stress control is in 100-
300mbar, heating interval is moved to opposite side, for fast cooling to 600 DEG C, rate of temperature fall can reach 120-240 DEG C/min；So
Temperature fall goes out graphene to room temperature in foam composition metal superficial growth afterwards；
(4) step (3) has been grown to the PMMA solution of dropwise addition 1% on the foam composition metal of graphene, and dried, then
Sample is put into 1mol/L FeCl3With nitric acid (1:1) in mixed solution, more than 12h is handled with magnetic stirrer, is removed
Composition metal；PMMA is removed with hot acetone repeatedly, finally deionized water, alcohol are cleaned respectively, are finally dried up with nitrogen gun.
Embodiment 3：
A kind of method that large area 3D graphenes are prepared using composition metal template, is comprised the following steps：
(1) nickel foam that size is 1 square centimeter is cleaned by ultrasonic with deionized water, absolute alcohol successively, defoamed
Nickel surface impurity；
(2) by the cleaned nickel foam deposited by electron beam evaporation of step (1) or plasma sputter deposition 300nm copper；
(3) the foam copper nickel composite metal that step (2) has been plated is lain in the quartz boat sample of slide rail tubular type CVD growth stove
On platform；Tubular type CVD growth stove mechanical pump and molecular pump suction are to 10-4Pa, is warming up to 200 DEG C, and heating rate is 20 DEG C/
Min, high-purity argon gas is passed through, flow 20sccm, Stress control is in 100-300mbar, insulation 1min；550 DEG C are then heated to,
Heating rate is 20 DEG C/min, is passed through hydrogen, flow 10sccm, Stress control is in 100-300mbar, insulation 10min；Then
1000 DEG C are warming up to, heating rate is 10 DEG C/min, is incubated 20min；Propane gas, flow 5sccm are passed through, Stress control exists
100-300mbar, it is incubated 10min；
After the completion of growth, carbon-source gas are closed, continue logical argon gas, flow 30sccm, Stress control is in 100-
300mbar, heating interval is moved to opposite side, for fast cooling to 600 DEG C, rate of temperature fall can reach 120-240 DEG C/min；So
Temperature fall goes out graphene to room temperature in foam composition metal superficial growth afterwards；
(4) step (3) has been grown to the PMMA solution of dropwise addition 1% on the foam composition metal of graphene, and dried, then
Sample is put into 1mol/L FeCl3With nitric acid (1:1) in mixed solution, more than 12h is handled with magnetic stirrer, is removed
Composition metal；PMMA is removed with hot acetone repeatedly, finally deionized water, alcohol are cleaned respectively, are finally dried up with nitrogen gun.
Experimental example：
Test experience is carried out to above-described embodiment 1-3 product.
The 3D graphene XRDs that step described in embodiment 1 obtains are as shown in Figure 2.The 3D grown by above-mentioned Fig. 2, embodiment 1
In the XRD of graphene sample, compared with nickel foam, at 25 ° -30 °, there is an obvious projection, this is to assemble spreading out for carbon
Peak is penetrated, illustrates the generation for having graphene；Embodiment 2-3 is also similar.
The 3D graphite Raman spectrograms that step described in embodiment 1-3 obtains are as shown in Figure 3.
By above-mentioned Fig. 3, the 2D peaks and G peaks of the 3D graphenes of three embodiment growths by comprehensive analysis all it is obvious that drawn
Ratio (the I at D peaks and G peaks in graceful spectrogramG/I2D=0.4~2) and 2D peaks half-peak breadth FWHM numerical value, obtain grow graphene
The number of plies at 1~4 layer.Half-peak breadth formula corresponding with the number of plies：FWHM=(- 45 × (1/n))+88 (n is the graphene number of plies).
From above-mentioned Fig. 4 SEM spectrum, the good 3D graphenes of quality have been grown.
Contrast test：
Using the method for invention, with CH4Or C3H8External carbon source, 3D graphenes are prepared under mixed gas different proportion, are obtained
Similar result (3,4,5 result is similar in table 1).Table 1 gives the result that 3D graphenes are prepared under different condition,
Contrast understands, it is too many using conventional CVD method to prepare the 3D graphene numbers of plies merely under similarity condition, and uses one kind with compound
The new method that metal form prepares 3D graphenes can prepare higher-quality 3D graphenes, illustrate the growth in graphene,
Cupro-nickel composition metal auxiliary control external carbon source so that growth is easier to control.Therefore 3D graphite is prepared using traditional CVD method
Existing for alkene be difficult to control the problem of be expected to be improved significantly, the performance of corresponding 3D graphenes is also expected to substantially be carried
It is high.
The Comparative result of graphene crystal is grown under table 1, different condition.
In summary, can be commercially available using the new method that 3D graphenes are prepared with composition metal template of the present invention
The 3D graphenes of high quality are prepared in nickel foam (foam copper), this method prepares 3D graphenes compared to conventional CVD method, and advantage shows
Write.
Claims (9)
1. a kind of method that large area 3D graphenes are prepared using composition metal template, is comprised the following steps：
(1) foam metal is provided, cleaned, removes surface impurity, the foam metal after being cleaned；
(2) on the foam metal after removal of impurities using plating or depositional mode plating or deposition last layer other metals, will obtain
Composition metal；
(3) composition metal is placed on the quartz boat sample stage of CVD growth stove, vacuumized, be warming up to 200-300 DEG C, be passed through height
Pure argon, Stress control is in 100-300mbar, 1~5min of insulation；550-650 DEG C is then heated to, is passed through high-purity hydrogen, is pressed
Power is controlled in 100-300mbar, is incubated 8~12min, foam metal alloy is obtained after annealing；
(4) 1000-1100 DEG C is continuously heating to, 10-30min is incubated, is passed through high-purity carbon-source gas, Stress control is in 100-
300mbar, insulation 5-30min carries out growth graphene, after the completion of growth, closes carbon-source gas, continues logical high-purity argon gas, pressure
Heating interval is moved to opposite side in 100-300mbar by control, and fast cooling is to 500-600 DEG C, then Temperature fall to room
Temperature, go out 3D graphenes in foam composition metal superficial growth；
(5) step (4) has been grown to the foam composition metal of graphene, has removed composition metal, cleaning, drying obtain large area 3D
Graphene.
2. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (1), described foam metal is nickel foam or foam copper, the aperture of foam metal：0.01mm-10mm, porosity are
60%-99%；Described cleaning is to be cleaned by ultrasonic foam metal with deionized water, absolute alcohol successively.
3. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (2), other described metals are copper or nickel, when step (1) foam metal is nickel foam, other metals of step (2)
For copper；When step (1) foam metal is foam copper, other metals of step (2) are nickel.
4. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (2), the thickness of other metals of plating or deposition last layer is 10nm-800nm so that the mass ratio of cupro-nickel is 1:10-
1:1000。
5. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (2), described plating is the anode of foam metal electrochemical workstation, is put into other metallic solutions, with copper sheet
As negative electrode, one layer of other metal is electroplated on foam metal.
6. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (2), described deposition is using electron beam evaporation or plasma sputter deposition last layer other metals.
7. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (3), vacuum is vacuumized as 10-4Pa, the heating rate for being warming up to 200-300 DEG C are 5-20 DEG C/min, high-purity argon gas
It is 10-100sccm to be passed through flow；The heating rate for being warming up to 550-650 DEG C is 5-20 DEG C/min, and high-purity hydrogen is passed through flow and is
4-20sccm；High-purity argon gas, argon gas, the hydrogen that high-purity hydrogen is more than 5N.
8. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
In step (4), the heating rate for being warming up to 1000-1100 DEG C is 1-10 DEG C/min, and it is 1-20sccm that carbon-source gas, which are passed through flow,
Described high-purity carbon-source gas are more than 5N methane or propane gas；It is 10- that high-purity argon gas, which is passed through flow, after the completion of growth
100sccm, fast cooling, rate of temperature fall are 120-240 DEG C/min.
9. the method according to claim 1 that large area 3D graphenes are prepared using composition metal template, it is characterised in that
1% PMMA solution will be added dropwise on the foam composition metal for having grown graphene in step (5), and dry, then put sample
Enter FeCl3, in hydrochloric acid or nitric acid mixed solution, with magnetic stirrer, remove composition metal；Then removed repeatedly with hot acetone
PMMA is removed, finally deionized water, alcohol are cleaned respectively, are finally dried up with nitrogen gun.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710843089.1A CN107673332B (en) | 2017-09-18 | 2017-09-18 | Method for preparing large-area 3D graphene by using composite metal template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710843089.1A CN107673332B (en) | 2017-09-18 | 2017-09-18 | Method for preparing large-area 3D graphene by using composite metal template |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107673332A true CN107673332A (en) | 2018-02-09 |
| CN107673332B CN107673332B (en) | 2020-09-04 |
Family
ID=61137314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710843089.1A Active CN107673332B (en) | 2017-09-18 | 2017-09-18 | Method for preparing large-area 3D graphene by using composite metal template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107673332B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368616A (en) * | 2018-09-11 | 2019-02-22 | 天津大学 | A kind of controllable method for preparing of three-dimensional grapheme carbon nano tube compound material |
| CN109573991A (en) * | 2018-12-28 | 2019-04-05 | 山东大学 | A method of lattice point thickness difference graphene array is prepared using composition metal template |
| CN110257795A (en) * | 2019-05-31 | 2019-09-20 | 上海欣材科技有限公司 | A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites |
| CN112938947A (en) * | 2021-03-30 | 2021-06-11 | 于庆凯 | Preparation method of graphene with controllable layer number |
| CN113813962A (en) * | 2021-09-06 | 2021-12-21 | 天津理工大学 | Preparation method of high-activity foamed nickel catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| CN104176731A (en) * | 2014-08-15 | 2014-12-03 | 上海交通大学 | Preparation method of through-hole graphene foam |
| US20150132565A1 (en) * | 2013-11-13 | 2015-05-14 | Massachusetts Institute Of Technology | Percolated Microstructures for Multi-Modal Transport Enhancement in Porous Active Materials |
| CN105776186A (en) * | 2014-12-25 | 2016-07-20 | 华中科技大学 | Method for preparing structure-controllable three-dimensional graphene porous material |
| CN105836735A (en) * | 2016-03-25 | 2016-08-10 | 西安电子科技大学 | Preparation method for ultra-three-dimension graphene |
| US20180346337A1 (en) * | 2015-11-25 | 2018-12-06 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
-
2017
- 2017-09-18 CN CN201710843089.1A patent/CN107673332B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN102674321A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院金属研究所 | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof |
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| US20150132565A1 (en) * | 2013-11-13 | 2015-05-14 | Massachusetts Institute Of Technology | Percolated Microstructures for Multi-Modal Transport Enhancement in Porous Active Materials |
| CN104176731A (en) * | 2014-08-15 | 2014-12-03 | 上海交通大学 | Preparation method of through-hole graphene foam |
| CN105776186A (en) * | 2014-12-25 | 2016-07-20 | 华中科技大学 | Method for preparing structure-controllable three-dimensional graphene porous material |
| US20180346337A1 (en) * | 2015-11-25 | 2018-12-06 | William Marsh Rice University | Formation of three-dimensional materials by combining catalytic and precursor materials |
| CN105836735A (en) * | 2016-03-25 | 2016-08-10 | 西安电子科技大学 | Preparation method for ultra-three-dimension graphene |
Non-Patent Citations (3)
| Title |
|---|
| JING NING等: "Three-dimensional multilevel porous thin graphite nanosuperstructures for Ni(OH)2-based energy storage devices", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| QIURONG SHI等: "3D graphene-based hybrid materials: synthesis and applications in energy storage and conversion", 《NANOSCALE》 * |
| XUN LIU等: "Segregation Growth of Graphene on Cu Ni Alloy for Precise Layer Control", 《J.PHYS.CHEM.C》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368616A (en) * | 2018-09-11 | 2019-02-22 | 天津大学 | A kind of controllable method for preparing of three-dimensional grapheme carbon nano tube compound material |
| CN109573991A (en) * | 2018-12-28 | 2019-04-05 | 山东大学 | A method of lattice point thickness difference graphene array is prepared using composition metal template |
| CN109573991B (en) * | 2018-12-28 | 2022-04-22 | 山东大学 | Method for preparing graphene arrays with different lattice point thicknesses by using composite metal template |
| CN110257795A (en) * | 2019-05-31 | 2019-09-20 | 上海欣材科技有限公司 | A kind of preparation method of three-dimensional structure graphene enhancing Cu-base composites |
| CN112938947A (en) * | 2021-03-30 | 2021-06-11 | 于庆凯 | Preparation method of graphene with controllable layer number |
| CN112938947B (en) * | 2021-03-30 | 2022-08-26 | 于庆凯 | Preparation method of graphene with controllable layer number |
| CN113813962A (en) * | 2021-09-06 | 2021-12-21 | 天津理工大学 | Preparation method of high-activity foamed nickel catalyst |
| CN113813962B (en) * | 2021-09-06 | 2024-02-02 | 天津理工大学 | Preparation method of high-activity foam nickel catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107673332B (en) | 2020-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107673332A (en) | A kind of method that large area 3D graphenes are prepared using composition metal template | |
| Tang et al. | CaO‐templated growth of hierarchical porous graphene for high‐power lithium–sulfur battery applications | |
| Wu et al. | A review of graphene synthesis by indirect and direct deposition methods | |
| CN105293483B (en) | A kind of method that original position prepares transient metal doped porous graphene | |
| Dong et al. | Synthesis of a MnO2–graphene foam hybrid with controlled MnO2 particle shape and its use as a supercapacitor electrode | |
| CN102515152B (en) | Method for preparing spheroidal graphene | |
| CN102092710B (en) | Regular graphene and preparation method thereof | |
| Delpeux et al. | High yield of pure multiwalled carbon nanotubes from the catalytic decomposition of acetylene on in situ formed cobalt nanoparticles | |
| CN106185896B (en) | The preparation method of three-dimensional grapheme and its composite material | |
| CN105752969B (en) | The method for preparing polyatom auto-dope graphene using natural porous and layer structure vegetables | |
| Zhou et al. | Low-temperature Ni particle-templated chemical vapor deposition growth of curved graphene for supercapacitor applications | |
| CN107934965B (en) | Ti3C2-Co(OH)(CO3)0.5Process for preparing nano composite material | |
| CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
| US20150004329A1 (en) | Short-time growth of large-grain hexagonal graphene and methods of manufacture | |
| CN103407988A (en) | Method for preparing graphene film at low temperature | |
| Hsieh et al. | Pulse electrodeposition of Pt nanocatalysts on graphene-based electrodes for proton exchange membrane fuel cells | |
| CN102842354A (en) | Graphene-based back electrode material with three-dimensional network structure and preparation method thereof | |
| CN106744859A (en) | Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking | |
| Chen et al. | Bioinspired synthesis of CVD graphene flakes and graphene-supported molybdenum sulfide catalysts for hydrogen evolution reaction | |
| CN109368616A (en) | A kind of controllable method for preparing of three-dimensional grapheme carbon nano tube compound material | |
| CN106629690A (en) | Method for reinforcing three-dimensional graphene porous material structure | |
| KR101195869B1 (en) | Method for preparing porous fullerene using by catalytic combustion | |
| CN102320597A (en) | A kind of preparation method of graphene | |
| CN107161989A (en) | A kind of preparation method of cellular three-dimensional grapheme | |
| CN110092420A (en) | A kind of Fe3O4The preparation method of/porous graphene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |