CN107673332B - Method for preparing large-area 3D graphene by using composite metal template - Google Patents
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Abstract
The invention relates to a method for preparing large-area 3D graphene by using a composite metal template, which comprises the steps of plating a layer of copper on foamed nickel (or plating a layer of nickel on the foamed copper), heating at high temperature to enable the surface of the foamed nickel to be changed into a copper-nickel alloy, introducing a carbon source at the growth temperature of a CVD (chemical vapor deposition) process, growing graphene on the surface of an intelligent composite metal film when the temperature is reduced, and controlling the number of layers of the graphene by using the intelligent composite metal film to prepare the high-quality large-area 3D graphene. The method solves the problems that the number of layers is difficult to control and the coverage is incomplete in the 3D graphene prepared by the traditional CVD method, and can obtain the 3D graphene with better quality.
Description
Technical Field
The invention relates to a method for preparing large-area 3D graphene by using a composite metal template, and belongs to the technical field of graphene preparation.
Background
In the last few years, three-dimensional materials self-assembled from graphene have been considered as one of the most promising materials in the field of nanotechnology, and have attracted much attention in the field of chemistry. The 3D graphene is a three-dimensional space body (compared to the structure of two-dimensional graphene) formed by stacking single-layer two-dimensional carbon atom units, and is a three-dimensional cross-linked porous structure. The 3D graphene has the excellent intrinsic properties of better conductivity, larger specific surface area, stronger mechanical advantage and dynamic performance. The ideal 3D graphene framework structure comprises the high conductivity of single-layer graphene, the pore size is usually from hundreds of nanometers to several micrometers or less, and the void structure can increase the specific surface area, enhance the mechanical properties of the material, i.e. the porous flexibility becomes the application advantage of the unique 3D graphene three-dimensional structure. Due to the three-dimensional reticular porous cross-linked structure, the stability of the 3D graphene is better than that of a two-dimensional structure, and the specific surface area and the space utilization rate are higher. The method can effectively reduce the agglomeration of the lamellar graphene and ensure the smooth transfer of protons. In addition, another great advantage of the 3D graphene material is that it is convenient to recycle for multiple treatments.
The three-dimensional cross-linked structure of the 3D graphene and the composite material thereof and a plurality of excellent performances of the graphene have the performances of adsorption, catalysis and the like, so that the graphene has wide application prospects in the fields of supercapacitors, biosensors, electrocatalysis application, environmental protection and the like.
Currently, 3D graphene preparation methods can be broadly divided into two main categories: one is direct preparation, that is, preparation without the need for a template. Such as: chinese patent document CN104730121A discloses a multiwalled carbon nanotube-bridged graphene conductive network and a preparation method thereof, wherein natural crystalline flake graphite powder is used for preparing a graphite oxide solid, a graphene oxide suspension is prepared by ultrasonic treatment, and a reducing agent is added to the graphene oxide suspension to be stirred and reacted at 50-80 ℃ to obtain 3D graphene. Chinese patent document CN105668555A discloses a method for preparing three-dimensional graphene. The method is characterized in that in the chemical vapor deposition process, three-dimensional graphene is directly grown on various substrates by controlling the flow of a carbon source by a template-free and catalyst-free method. The two methods are simple to operate, but the additional impurities are more, and the quality of the graphene is not high.
The other is a template-assisted method, which is a commonly used method for preparing nano materials with specific structures and morphologies and has many different application potentials, the traditional template-assisted method, especially the traditional metal template CVD method, has the advantages of simple process, low cost and easily obtained equipment and growth environment which are generally needed; the template auxiliary method mainly comprises three steps: (1) soaking or infiltrating the template in combination with the reacted precursor; (2) forming a solid state on the template by reaction, nucleation and growth; (3) and removing the template to obtain the final product.
Many patent documents are disclosed about template-assisted methods for preparing three-dimensional graphene, such as: chinese patent document CN103854877A discloses a self-supporting graphene/manganese oxide composite electrode material and a preparation method thereof, the preparation method of the composite electrode material mainly uses graphite paper as a raw material, and adopts a direct current power supply to electrolyze the graphite paper in situ, so as to obtain self-supporting graphene on the graphite paper; chinese patent document CN105776196A discloses a method for preparing a three-dimensional graphene porous material with a controllable structure, wherein a graphene film is grown on a metal template by a chemical vapor deposition method through the metal template; preparing corrosive liquid, refluxing and dissolving the metal template at the temperature of 60-90 ℃, and washing and drying to obtain the three-dimensional graphene porous material product. Chinese patent document CN102674321A discloses a method for depositing a graphene film on the surface of a three-dimensional foam nickel template by a chemical vapor deposition method, and obtaining porous foam-like graphene after dissolving out a porous metal substrate, and discloses a method for spontaneously depositing three-dimensional graphene on a conductive substrate; chinese patent document CN103265022A discloses a method for preparing porous through three-dimensional graphene with carbonate or bicarbonate as a template, and the like; chinese patent document CN106158553A relates to the field emission technology field of nano-functional devices, and provides a 3D graphene/one-dimensional nanomaterial composite structure field emission cathode, which comprises a metal foam skeleton substrate, a graphene layer and a one-dimensional nanomaterial layer; the graphene layer is positioned between the metal foam and the one-dimensional nano material layer, and the graphene layer is used as an electron transmission layer and is used as an emission layer together with the one-dimensional nano material layer; however, the three-dimensional graphene prepared by the method has the problems that the shape, density, height and the like are difficult to control, the number of layers is difficult to control, and the coverage is incomplete.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing large-area 3D graphene by using a composite metal template.
Brief description of the invention:
the method for preparing the large-area 3D graphene comprises the following steps: plating a layer of copper on the foamed nickel (or plating a layer of nickel on the foamed copper), then heating at high temperature to change the surface of the foamed nickel into copper-nickel alloy, then introducing a carbon source at the growth temperature of the CVD process, growing graphene on the surface of the intelligent composite metal film when cooling, and controlling the number of layers of the graphene by utilizing the intelligent composite metal film to prepare the high-quality large-area 3D graphene. The method solves the problems that the number of layers is difficult to control and the coverage is incomplete in the 3D graphene prepared by the traditional CVD method, and can obtain the 3D graphene with better quality.
Interpretation of terms:
foamed nickel: sponge-like porous metallic nickel.
Foam copper: spongy porous metallic copper.
Electroplating: the process of plating a thin layer of other metal on the metal surface by using the principle of electrolysis.
Electron beam evaporation: the evaporation material is placed in a water-cooled crucible, and is directly heated by electron beams to be vaporized and condensed on the substrate to form a thin film.
Plasma sputtering: the rare gas is ionized into plasma by a direct current or radio frequency method, and then the target material is bombarded by a bias method and the like, so that atoms on the target have enough capacity to be separated out and fall on the substrate to form a film.
Detailed description of the invention:
the invention is realized by the following technical scheme:
a method for preparing large-area 3D graphene by using a composite metal template comprises the following steps:
(1) providing a foam metal, cleaning, and removing surface impurities to obtain the foam metal after impurity removal;
(2) electroplating or depositing a layer of other metal on the foam metal subjected to impurity removal in an electroplating or depositing manner to obtain a composite metal;
(3) placing the composite metal on a quartz boat sample table of a CVD growth furnace, vacuumizing, heating to 200-; then heating to 550-650 ℃, introducing high-purity hydrogen, controlling the pressure at 100-300mbar, keeping the temperature for 8-12 min, and annealing to obtain a foam metal alloy which can play a catalytic role in the growth of graphene;
(4) continuously heating to 1000-class 1100 ℃, keeping the temperature for 10-30min, introducing high-purity carbon source gas, controlling the pressure at 300mbar of 100-class, keeping the temperature for 5-30min to grow graphene, after the growth is finished, closing the carbon source gas, continuously introducing high-purity argon, controlling the pressure at 300mbar of 100-class, pulling the heating interval to the other side, rapidly cooling to 600 ℃ of 500-class, then naturally cooling to room temperature, and growing 3D graphene on the surface of the foam composite metal;
(5) and (4) removing the composite metal of the foam of the graphene grown in the step (4), cleaning and drying to obtain the large-area 3D graphene.
Preferably, in step (1), the foam metal is nickel foam or copper foam, and the pore diameter of the foam metal is: 0.01mm-10mm, porosity 60% -99%; the cleaning is to perform ultrasonic cleaning on the foam metal by using deionized water and absolute alcohol in sequence.
Preferably, in the step (2), the other metal is copper or nickel, and when the foam metal in the step (1) is foam nickel, the other metal in the step (2) is copper; and (3) when the foam metal in the step (1) is foam copper, and the other metal in the step (2) is nickel.
Preferably, in the step (2), the thickness of the other metal layer is electroplated or deposited to be 10nm-800nm, so that the mass ratio of copper to nickel is 1:10-1: 1000.
Preferably, in the step (2), the electroplating is to use an anode of an electrochemical workstation for the foam metal, put the anode into other metal solution, use a copper sheet as a cathode, and electroplate a layer of other metal on the foam metal.
Preferably, in step (2), the deposition is carried out by depositing a layer of other metal by electron beam evaporation or plasma sputtering.
Preferably, in step (3), the vacuum degree is 10-4-10-6Pa, the heating rate is 5-20 ℃/min when the temperature is increased to 200-300 ℃, and the flow of high-purity argon is 10-100 sccm; the temperature rise rate is 5-20 ℃/min when the temperature rises to 550-650 ℃, and the flow of the high-purity hydrogen is 4-20 sccm; the high-purity argon and the high-purity hydrogen are argon and hydrogen with the purity of more than 5N.
Preferably, in the step (4), the heating rate of the temperature rise to 1000-1100 ℃ is 1-10 ℃/min, the flow rate of the carbon source gas is 1-20sccm, and the high-purity carbon source gas is methane or propane gas with the purity of more than 5N; after the growth is finished, high-purity argon is introduced with the flow rate of 10-100sccm, and the rapid cooling rate is 120-240 ℃/min.
Preferably, in the step (5), 1% PMMA solution is dripped on the foam composite metal with the grown graphene, the foam composite metal is dried, and then the sample is placed into 1mol/L FeCl3Mixing with nitric acid (1:1), stirring with magnetic stirrer for more than 12 hr to remove composite metal; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
In the preparation method, the step (4) is vacuumized and heated to 200 ℃ and 300 ℃, and the foam composite metal and the interior of the reaction cavity are pre-baked, so that the gas adsorbed on the surface of the foam composite metal and the interior of the cavity is desorbed and discharged out of the cavity, and the purposes of reducing the residual oxygen content in the cavity and further improving the vacuum degree are achieved.
All the raw materials in the method are commercial products. The prior art can be referred to for any part not specifically defined.
The invention has the technical characteristics and excellent effects that:
the invention adopts foamed nickel/copper as the substrate, so the production cost is low, and the foamed nickel/copper is sold in various specifications.
The foam nickel/copper adopted by the invention is subjected to ultrasonic cleaning and annealing treatment, so that a layer is not damaged; and the surface is smooth after hydrogen etching treatment in the heating process of the step (4).
The invention relates to a novel method for preparing graphene. The method is characterized in that a layer of copper is plated on the foamed nickel (or a layer of nickel is plated on the foamed copper), the surface of the foamed nickel is changed into copper-nickel alloy through high-temperature heating, the growth of graphene can be catalyzed, then an external carbon source is introduced at the growth temperature of the CVD process, the metal copper film of the alloy can catalyze carbon atoms to spread on the surface of the metal copper film, graphene grows on the surface of the intelligent composite metal film when the temperature is reduced, the number of layers of graphene is controlled by utilizing the intelligent composite metal film on the surface of the foamed metal alloy (the proportion of copper-nickel metal is controlled by controlling different thicknesses of the copper film), and the high-quality 3D graphene with the coverage rate of more than 98% is prepared.
Compared with the traditional CVD method for preparing 3D graphene on the foamed nickel, the method has the advantages that the graphene coverage rate is higher, the graphene single crystal area is larger, the flake effect is lower, and the integrity is stronger and better; the method can also solve the problems that the number of layers is difficult to control and the coverage is incomplete in the traditional CVD method for preparing the 3D graphene, and the 3D graphene with better quality can be obtained.
According to the invention, the number of layers of graphene is controlled by accurately controlling the temperature and the temperature rise and fall rate and adjusting the composition of the composite metal by utilizing the intelligent composite metal film (different thicknesses of the copper film) on the surface of the foam metal alloy; the method solves the problems that the growth of the graphene on the foam nickel and the foam copper is not uniform, the number of layers is not easy to control, and the number of layers is very thick. The 3D graphene grown by the method is distributed on the surface of the whole template, and the number of graphene layers can be controlled to be 1-4.
Drawings
FIG. 1 is a schematic diagram of the preparation of 3D graphene by using a composite metal template according to the present invention;
fig. 2 is an XRD pattern of 3D graphene grown in example 1.
FIG. 3 is a Raman spectrum of 3D graphene grown in examples 1-3. The abscissa is the Raman shift (cm)-1) And the ordinate is intensity (a.u.).
Fig. 4 is an SEM image of 3D graphene grown in example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The slide rail tube type CVD growth furnace used in the embodiment is a combined fertilizer and crystal OTF-1200 type CVD furnace, the heating rate can reach 30 ℃/min, and the cooling rate can reach 300 ℃/min at the fastest speed.
The adopted foamed nickel is a commercial product, and the thickness is as follows: 1-3mm, pore diameter: 0.1-0.5mm, porosity: 70-80 percent.
Example 1:
a method for preparing large-area 3D graphene by using a composite metal template comprises the following steps:
(1) ultrasonically cleaning foamed nickel with the size of 1 square centimeter by using deionized water and absolute alcohol in sequence to remove impurities on the surface of the foamed nickel;
(2) putting the anode of the electrochemical workstation for the foam nickel cleaned in the step (1) into 1mol/L CuCl2In the solution, a copper sheet is used as a cathode, the reaction is carried out for 20min at normal temperature, and a layer of copper is plated on the foamed nickel;
(3) horizontally placing the plated copper-nickel foam composite metal in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 ℃, heating at a rate of 20 ℃/min, introducing high-purity argon at a flow rate of 20sccm and a pressure of 100-300mbar, and keeping the temperature for 1 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1100 deg.C, heating rate 10 deg.C/min, and keeping the temperature for 20 min; introducing methane gas with the flow rate of 10sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing graphene on the surface of the foam composite metal;
(4) dripping 1% PMMA solution on the foam composite metal with the graphene grown in the step (3), drying, and then putting the sample into 1mol/L FeCl3Mixing with nitric acid (1:1), stirring with magnetic stirrer for more than 12 hr to remove composite metal; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
Example 2:
a method for preparing large-area 3D graphene by using a composite metal template comprises the following steps:
(1) ultrasonically cleaning foamed nickel with the size of 1 square centimeter by using deionized water and absolute alcohol in sequence to remove impurities on the surface of the foamed nickel;
(2) depositing nickel with the thickness of 200nm on the foam copper cleaned in the step (1) by electron beam evaporation;
(3) horizontally placing the plated copper-nickel foam composite metal in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 ℃, heating at a rate of 20 ℃/min, introducing high-purity argon at a flow rate of 20sccm and a pressure of 100-300mbar, and keeping the temperature for 1 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1000 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 20 min; introducing methane gas with the flow rate of 5sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing graphene on the surface of the foam composite metal;
(4) dripping 1% PMMA solution on the foam composite metal with the graphene grown in the step (3), drying, and then putting the sample into 1mol/L FeCl3Mixing with nitric acid (1:1), stirring with magnetic stirrer for more than 12 hr to remove composite metal; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
Example 3:
a method for preparing large-area 3D graphene by using a composite metal template comprises the following steps:
(1) ultrasonically cleaning foamed nickel with the size of 1 square centimeter by using deionized water and absolute alcohol in sequence to remove impurities on the surface of the foamed nickel;
(2) depositing 300nm copper on the cleaned foam nickel in the step (1) by using electron beam evaporation or plasma sputtering;
(3) horizontally placing the plated copper-nickel foam composite metal in the step (2) on a quartz boat sample table of a slide rail tube type CVD growth furnace; the mechanical pump and the molecular pump for the tubular CVD growth furnace are pumped to the vacuum degree of 10-4Pa, heating to 200 deg.C, heating rateIntroducing high-purity argon at the speed of 20 ℃/min, controlling the flow rate of 20sccm and the pressure at 100-300mbar, and preserving the heat for 1 min; then heating to 550 ℃, wherein the heating rate is 20 ℃/min, introducing hydrogen, controlling the flow rate to 10sccm, controlling the pressure to be 100-; then heating to 1000 ℃, wherein the heating rate is 10 ℃/min, and keeping the temperature for 20 min; introducing propane gas with the flow rate of 5sccm and the pressure of 100-;
after the growth is finished, closing the carbon source gas, continuously introducing argon gas with the flow rate of 30sccm and the pressure controlled at 300mbar, pulling the heating area to the other side, rapidly cooling to 600 ℃, wherein the cooling rate can reach 240 ℃/min in case of 120 sccm; then naturally cooling to room temperature, and growing graphene on the surface of the foam composite metal;
(4) dripping 1% PMMA solution on the foam composite metal with the graphene grown in the step (3), drying, and then putting the sample into 1mol/L FeCl3Mixing with nitric acid (1:1), stirring with magnetic stirrer for more than 12 hr to remove composite metal; and (3) repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and alcohol, and finally drying with a nitrogen gun.
Experimental example:
the products of examples 1-3 above were tested.
The XRD pattern of the 3D graphene obtained by the procedure described in example 1 is shown in fig. 2. From the above fig. 2, the XRD pattern of the 3D graphene sample grown in example 1 has a distinct protrusion at 25 ° -30 ° compared to nickel foam, which is a diffraction peak of aggregated carbon, indicating the formation of graphene; examples 2-3 are also similar.
The raman spectrum of the 3D graphene obtained by the steps described in examples 1-3 is shown in fig. 3.
From the above fig. 3, the 2D peak and the G peak of the 3D graphene grown in the three examples are evident, and the ratio (I) of the D peak and the G peak in the raman spectrum is analyzed by integrationG/I2D0.4-2) and 2D peak half-width FWHM, obtaining the number of layers of the grown graphene, wherein the number of the layers corresponds to the half-width FWHM (-45 × (1/n)) +88(n is the number of graphene layers).
As can be seen from the SEM spectrum of fig. 4, 3D graphene with good quality is grown.
And (3) comparison test:
by the process of the invention, with CH4Or C3H8Similar results were obtained for 3D graphene prepared with different ratios of external carbon source and mixed gas (results of 3, 4, 5 in table 1 are similar). Table 1 shows the results of preparing 3D graphene under different conditions, and a comparison shows that the number of 3D graphene layers prepared by the conventional CVD method is too large under the same conditions, but 3D graphene with higher quality can be prepared by a new method for preparing 3D graphene by using a composite metal template, which indicates that in the growth of graphene, copper-nickel composite metal assists in controlling an external carbon source, so that the growth is easier to control. Therefore, the problem that the 3D graphene is difficult to control in the traditional CVD method is expected to be obviously improved, and the performance of the corresponding 3D graphene is also expected to be obviously improved.
Table 1, comparison of the results of graphene crystal growth under different conditions.
In conclusion, by using the novel method for preparing 3D graphene by using the composite metal template, high-quality 3D graphene can be prepared on commercially available nickel foam (copper foam), and the method has significant advantages compared with the conventional CVD method for preparing 3D graphene.
Claims (4)
1. A method for preparing large-area 3D graphene by using a composite metal template comprises the following steps:
(1) providing a foam metal, cleaning, and removing surface impurities to obtain the foam metal after impurity removal;
(2) electroplating or depositing a layer of other metal on the foam metal subjected to impurity removal in an electroplating or depositing manner to obtain a composite metal; when the foam metal in the step (1) is foam nickel, and other metals are copper; when the foam metal in the step (1) is foam copper and other metals are nickel, the thickness of the other metals which are electroplated or deposited with a layer of other metals is 10nm-800nm, so that the mass ratio of copper to nickel is 1:10-1: 1000;
(3) placing the composite metal on a quartz boat sample table of a CVD growth furnace, and vacuumizing to 10 DEG C-4Pa, heating to 200-300 ℃ at a heating rate of 5-20 ℃/min, introducing high-purity argon, controlling the pressure at 300mbar of 100-100 ℃ and the flow rate of 10-100sccm, and keeping the temperature for 1-5 min; then heating to 550-650 ℃ at the heating rate of 5-20 ℃/min, introducing high-purity hydrogen, controlling the flow rate of the high-purity hydrogen to be 4-20sccm, controlling the pressure to be 300mbar, and carrying out heat preservation for 8-12 min to obtain the foam metal alloy after annealing; the high-purity argon and the high-purity hydrogen are argon and hydrogen with the purity of more than 5N;
(4) continuously heating to 1000-class 1100 ℃, keeping the temperature for 10-30min, introducing high-purity carbon source gas, controlling the pressure at 300mbar of 100-class, keeping the temperature for 5-30min to grow graphene, after the growth is finished, closing the carbon source gas, continuously introducing high-purity argon, controlling the pressure at 300mbar of 100-class, pulling the heating interval to the other side, rapidly cooling to 600 ℃ of 500-class, then naturally cooling to room temperature, and growing 3D graphene on the surface of the foam composite metal; the heating rate is 1-10 ℃/min when the temperature is increased to 1000-1100 ℃, the flow rate of the carbon source gas is 1-20sccm, and the high-purity carbon source gas is methane or propane gas with the flow rate of more than 5N; after the growth is finished, introducing high-purity argon at a flow rate of 10-100sccm, and rapidly cooling at a cooling rate of 120-;
(5) dripping 1% PMMA solution on the foam composite metal with the graphene grown in the step (4), drying, and then putting the sample into FeCl3In the mixed solution of hydrochloric acid or nitric acid, stirring by a magnetic stirrer to remove the composite metal; and then, repeatedly using hot acetone to remove PMMA, finally respectively cleaning with deionized water and alcohol, and finally blow-drying with a nitrogen gun to obtain the large-area 3D graphene.
2. The method for preparing large-area 3D graphene by using the composite metal template as claimed in claim 1, wherein in the step (1), the foam metal is foam nickel or foam copper, and the pore diameter of the foam metal is as follows: 0.01mm-10mm, porosity 60% -99%; the cleaning is to perform ultrasonic cleaning on the foam metal by using deionized water and absolute alcohol in sequence.
3. The method for preparing large-area 3D graphene by using the composite metal template as claimed in claim 1, wherein in the step (2), the electroplating is performed by using an anode of an electrochemical workstation for the foam metal, putting the anode into other metal solution, using a copper sheet as a cathode, and electroplating a layer of other metal on the foam metal.
4. The method for preparing large-area 3D graphene by using the composite metal template as claimed in claim 1, wherein in the step (2), the deposition is carried out by depositing a layer of other metal by electron beam evaporation or plasma sputtering.
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| 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 |
| CN112938947B (en) * | 2021-03-30 | 2022-08-26 | 于庆凯 | Preparation method of graphene with controllable layer number |
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