CN112582105A - Preparation method of high-conductivity and internally continuous graphene hybrid film - Google Patents
Preparation method of high-conductivity and internally continuous graphene hybrid film Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 239000000243 solution Substances 0.000 claims description 60
- 229910052709 silver Inorganic materials 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
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- H—ELECTRICITY
- H01—BASIC ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
A preparation method of a high-conductivity and internally continuous graphene hybrid film comprises the steps of hybridizing graphene oxide and metal nanoparticles, wrapping and crosslinking adjacent graphene oxide sheets through the metal nanoparticles, and reducing the interface resistance between the graphene oxide sheets; then carrying out pre-reduction on the hybrid film by utilizing chemical reduction or low-temperature heat treatment to ensure that the hybrid film has conductive performance; finally, the hybrid membrane is thermally reduced at 800-2000 ℃ by electric heating, and the conductivity of the reduced graphene hybrid membrane and the graphene membrane subjected to ultra-high temperature graphitization treatment are in the same order of magnitude of 105S/m; the invention reduces the time cost and solves the problem of the limitation of the size of the high-temperature furnace to the size of the hybrid membrane.
Description
Technical Field
The invention relates to the technical field of graphene hybrid membrane preparation, in particular to a preparation method of a highly-conductive and internally-continuous graphene hybrid membrane.
Background
The graphene is a poly (p-phenylene ether)2The hybridized and connected carbon atoms are tightly stacked to form a new material with a single-layer two-dimensional honeycomb lattice structure, and the new material has excellent electric conduction and heat conduction properties; the graphene film is a macroscopic film formed by assembling graphene sheets layer by layer, has strong electric and heat conducting capabilities and excellent flexibility, and can be applied to heat dissipation of a new-generation flexible device and electromagnetic shielding, wave absorption and lightning stroke protection in aerospace.
Most of graphene films are prepared by taking a graphene oxide film as a precursor through low-temperature chemical reduction or high-temperature physical reduction, and oxygen-containing functional groups and other defects in the graphene oxide often scatter or capture SP2The electric charge carriers in the large pi bonds formed by hybridization seriously affect the electric conductivity and the thermal conductivity of the graphene film. The chemical reduction at low temperature can remove most of oxygen-containing functional groups in the graphene oxide, and reduce the graphene oxide film into a graphene film; however, the electrical conductivity of the graphene film obtained by the low-temperature chemical reduction at present is difficult to exceed 2 multiplied by 104S/m, mainly because many defects in graphene have not been repaired. In order to further improve the conductivity of the graphene film and repair defects in the graphene, the graphene film needs to be placed in a vacuum atmosphere furnace and subjected to high-temperature reduction under the protection of vacuum or inert atmosphere, when the reduction temperature reaches 2000-3000 ℃, oxygen-containing functional groups in the graphene are completely removed, the defects in the graphene are repaired, and the conductivity of the graphene film can be increased to 105Of the order of S/m.
However, when high-temperature thermal reduction is performed, the size of the graphene film is often limited by the size of the furnace chamber, the temperature rise and decrease rate of the traditional high-temperature furnace is limited, and a large amount of time cost is required for preparing the graphene film.
Disclosure of Invention
In order to overcome the technical defects, the invention aims to provide a preparation method of a graphene hybrid film with high conductivity and continuous inside, reduce graphene oxide by electric heating, reduce time cost and simultaneously solve the problem of limitation of the size of a high-temperature furnace on the size of the hybrid film.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a highly conductive and internally continuous graphene hybrid film comprises the steps of hybridizing graphene oxide with metal nanoparticles, wrapping and crosslinking adjacent graphene oxide sheets through the metal nanoparticles, and reducing the interface resistance between the graphene oxide sheets; then carrying out pre-reduction on the hybrid film by utilizing chemical reduction or low-temperature heat treatment to ensure that the hybrid film has conductive performance; finally, the hybrid membrane is thermally reduced at 800-2000 ℃ by electric heating, and the conductivity of the reduced hybrid membrane and the graphene membrane after the ultrahigh-temperature graphitization treatment are in the same order of magnitude of 105S/m。
A preparation method of a highly conductive and internally continuous graphene hybrid film comprises the following steps:
(1) firstly, uniformly mixing a graphene oxide solution and a metal salt solution according to a ratio, pouring the mixed solution into a vacuum filtration device for filtration to obtain a graphene oxide hybrid membrane containing metal ions;
(2) pouring the solution with reducibility into the vacuum filtration device in the step (1) for secondary filtration, and reducing metal ions into metal nano particles in situ;
(3) pre-reducing the hybrid membrane prepared in the step (2) to endow the hybrid membrane with conductivity; and then carrying out high-temperature thermal reduction on the hybrid film at 800-2000 ℃ by electric heating, and reducing the graphene oxide into graphene.
The specific steps of the step (1) are as follows: firstly, mixing a graphene oxide solution and a metal salt solution in proportion, uniformly mixing the graphene oxide solution and the metal salt solution through magnetic stirring and ultrasonic dispersion, then pouring the mixed solution into a vacuum filtration device, forming a layer of graphene oxide hybrid membrane containing metal ions on the surface of filter paper after the mixed solution is drained, and at the moment, stacking and assembling graphene oxide sheets layer by layer to form the hybrid membrane, wherein the metal ions are adsorbed on the graphene oxide sheets through strong electrostatic force.
The thickness of the graphene oxide hybrid membrane containing the metal ions can be controlled by adjusting the volume of the mixed solution according to requirements.
The specific steps of the step (2) are as follows: pouring a solution with reducibility into a vacuum filtration device, wherein the solution with reducibility preferentially flows through the nanochannels existing between the adjacent graphene oxide sheets because the nanochannels exist between the adjacent graphene oxide sheets in the hybrid membrane in the step (1) and the resistance to the solution with reducibility is small; when the reducing solution flows through the nano channel, metal ions are firstly reduced into metal atoms in situ, then clusters are formed, nucleation and growth are finally carried out to form metal nano particles, adjacent graphene oxide sheets are wrapped and crosslinked, and the interface resistance between the graphene oxide sheets is improved.
The specific steps of the step (3) are as follows: carrying out pre-reduction on the hybrid membrane obtained in the step (2) through chemical reduction or low-temperature thermal reduction at the temperature of 300-500 ℃, wherein the pre-reduced hybrid membrane has conductivity; and finally, placing the hybrid membrane between the graphite electrodes in a vacuum operation box, and loading pulse current at two ends of the graphite electrodes by adopting a programmable direct current power supply to quickly heat the hybrid membrane to 800-2000 ℃ under the action of joule heat, removing oxygen-containing functional groups in the graphene oxide, and reducing the graphene oxide into graphene.
The metal ions are silver ions, copper ions, aluminum ions or iron ions and the like.
The reducing solution in the step (2) adopts ascorbic acid solution or citric acid solution and the like.
The graphene oxide solution can be replaced by a surface-modified carbon nanotube solution, and the carbon nanotube is carboxylated and negatively charged.
The graphene oxide hybrid membrane containing the metal ions can be prepared by a spin coating method or a coating method.
Compared with the prior art, the invention has the following beneficial effects:
the prepared graphene hybrid membrane is formed by assembling and stacking graphene sheets layer by layer and has a good layered structure; the metal nanoparticles wrap and crosslink adjacent graphene sheets, so that the interface resistance between the graphene sheets is improved, and a conductive path is formed inside the hybrid membrane.
By mixing graphene with metal nanoparticlesThe electric conductivity of the prepared hybrid membrane can be in the same order of magnitude (10) as that of the graphene membrane subjected to high-temperature graphitization treatment after electric heating reduction at 800-2000 DEG C5S/m)。
The hybrid membrane is subjected to high-temperature reduction by adopting electric heating, the temperature rising and reducing speed is high, the time cost is reduced, and the limitation of the size of the hybrid membrane by the size of a high-temperature furnace is also solved.
Drawings
FIG. 1 is a schematic process scheme of example 1 of the present invention.
Fig. 2 is a schematic structural diagram of a graphene oxide hybrid film containing silver ions in example 1 of the present invention.
FIG. 3 is a schematic view showing the flow of a reducing solution through nanochannels in example 1 of the present invention.
Fig. 4 is a schematic diagram of in-situ reduction of silver ions into silver atom clusters and silver nanoparticles in example 1 of the present invention.
FIG. 5 is a schematic diagram of the electrical heating of the pre-reduced hybrid membrane in example 1 of the present invention.
Fig. 6(a) is a scanning electron microscope picture of graphene sheets wrapped by silver nanoparticles in example 1 of the present invention; fig. 6(b) is a scanning electron microscope image of the silver atom cluster in example 1 of the present invention.
FIG. 7 is a scanning electron micrograph of a cross section of the hybrid membrane in example 1 of the present invention.
FIG. 8 is a scanning electron microscope image of silver nanoparticles after melt-crosslinking in example 3 of the present invention.
Wherein: 1 is a mixed solution of graphene oxide/silver nitrate; 2 is a vacuum filtration device; 3 is a graphene oxide hybrid membrane containing silver ions; 4 is ascorbic acid solution; 5 is silver ion; 6 is a graphene oxide sheet; 7 is a silver atom cluster; 8 is silver nanoparticles; 9 is an upper graphite plate; 10 is a lower graphite plate; 11 is a pre-reduced hybrid membrane; 12 are bolts.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Embodiment 1, a method for preparing a highly conductive and internally continuous graphene hybrid film, comprising the steps of:
(1) weighing 10ml of graphene oxide solution (8mg/ml) and 1ml of silver nitrate solution (0.1mol/L) to mix according to a volume ratio of 10:1, dropwise and slowly adding the silver nitrate solution into the graphene oxide solution which is magnetically stirred during mixing, and then continuously magnetically stirring for 1 h; continuously placing the uniformly mixed solution in an ultrasonic bath for ultrasonic treatment for 30min to perform one-step dispersion; due to a large number of oxygen-containing functional groups on the surface of the graphene oxide, the graphene oxide is negatively charged, and silver ions are uniformly loaded on the surface and the edge of the graphene oxide sheet through strong electrostatic action; firstly, pouring a dispersed graphene oxide/silver nitrate mixed solution 1 into a vacuum filtration device 2, wherein the filter paper is cellulose acetate filter paper with the diameter of 50mm and the aperture of 0.22um, the vacuum filtration device 2 is externally connected with a vacuum pump, and the negative pressure of the vacuum pump is 0.09MPa during filtration;
(2) as shown in fig. 2, when the graphene oxide/silver nitrate mixed solution 1 is drained in step (1), a layer of graphene oxide hybrid film 3 containing silver ions is formed on the surface of the filter paper, and at this time, the graphene oxide hybrid film 3 containing silver ions has a good hierarchical structure, and the silver ions 5 are uniformly adsorbed on the graphene oxide sheets 6; weighing 5g of ascorbic acid powder, and dissolving the ascorbic acid powder in 50ml of deionized water to prepare an ascorbic acid solution; then pouring the ascorbic acid solution into the vacuum filtration device 2 for continuous filtration, wherein as shown in fig. 3, the resistance to the ascorbic acid solution 4 is small because of the existence of the nano-channel between the adjacent graphene oxide sheets 6, and the ascorbic acid solution 4 can preferentially flow through the nano-channel; as shown in fig. 4, since the dienol group in the ascorbic acid molecule has very strong reducibility, when the ascorbic acid solution 4 flows through the nanochannel, the ascorbic acid is dehydrogenated and oxidized, silver ions are firstly reduced in situ to silver atoms, then silver atom clusters 7 are formed, finally nucleation and growth are carried out to form silver nanoparticles 8, and adjacent graphene oxide sheets are wrapped and crosslinked; after 5h of suction filtration, pouring out the redundant ascorbic acid solution 4 from the vacuum suction filtration device 2, and then putting the hybrid membrane and the filter paper into an autoclave;
(3) because the ascorbic acid solution 4 is fully soaked in the hybrid membrane, the high-pressure kettle is placed in an oven and heated to 90 ℃, the hybrid membrane is pre-reduced by a chemical method, and the hybrid membrane is endowed with certain conductivity; after the reaction is finished, taking down the hybrid membrane from the filter paper and naturally airing; as shown in fig. 5, the pre-reduced hybrid film 11 is then placed between two sets of graphite electrodes in a vacuum operation box, each set of graphite electrodes is composed of an upper graphite plate 9 and a lower graphite plate 10, and the upper graphite plate 9 and the lower graphite plate 10 are connected by bolts 12 to increase the contact reliability of the graphite electrodes and the pre-reduced hybrid film 11; the two groups of graphite electrodes are respectively connected with the positive electrode and the negative electrode of a direct current power supply, the direct current power supply has a programmable function, the experiment adopts pulse waveform loading, an infrared temperature measuring sensor is adopted to monitor the surface temperature of the hybrid membrane in real time, the temperature is controlled to be always below the melting point of silver, flash burning of the pre-reduced hybrid membrane 11 is realized through the pulse waveform of the direct current power supply, the highest temperature of flash burning is 800 ℃, and the appearance and the size of silver nanoparticles cannot be influenced while oxygen-containing functional groups of graphene oxide are removed at high temperature;
as shown in fig. 6(a), two pieces of graphene are wrapped and crosslinked by silver nanoparticles with the diameter of about 210 nm; as shown in fig. 6(b), it can be observed that some silver nanoclusters occur between two sheets of adjacent graphene; as shown in fig. 7, the finally obtained graphene hybrid membrane has a good layered structure, and the silver nanoparticles wrap and crosslink adjacent graphene sheets, so that the interface resistance between the graphene sheets is greatly improved.
Embodiment 2, a method for preparing a highly conductive and internally continuous graphene hybrid film, comprising the steps of:
(1) weighing 8ml of graphene oxide solution (8mg/ml) and 1ml of ferric chloride solution (0.1mol/L) to mix according to a volume ratio of 8:1, dropwise and slowly adding the ferric chloride solution into the graphene oxide solution which is being magnetically stirred during mixing, and then continuously magnetically stirring for 1 hour; continuously placing the uniformly mixed solution in an ultrasonic bath for ultrasonic treatment for 30min to perform one-step dispersion; due to a large number of oxygen-containing functional groups on the surface of the graphene oxide, the graphene oxide is negatively charged, and iron ions are uniformly loaded on the surface and the edge of a graphene oxide sheet through strong electrostatic action; pouring the dispersed mixed solution into a vacuum filtration device, wherein the filter paper is cellulose acetate filter paper with the diameter of 50mm and the aperture of 0.22um, the vacuum filtration device is externally connected with a vacuum pump, and the negative pressure of the vacuum pump is 0.09MPa during filtration;
(2) when the mixed solution in the step (1) is pumped to be dry, a layer of graphene oxide hybrid film containing iron ions is formed on the surface of the filter paper, the hybrid film has a good hierarchical structure, and the iron ions are uniformly adsorbed on the graphene oxide sheet; weighing 3g of citric acid powder, and dissolving in 30ml of deionized water to prepare a citric acid solution; pouring the citric acid solution into a vacuum filtration device for continuous filtration, wherein the resistance to the citric acid solution is small because a nano channel exists between adjacent graphene oxide sheets, and the citric acid solution can preferentially flow through the nano channel; because citric acid has reducibility, when the citric acid solution flows through the nano channel, iron ions are firstly reduced into iron atoms in situ, then clusters are formed, nucleation and growth are finally carried out to form iron nano particles, and adjacent graphene oxide sheets are wrapped and crosslinked; after 5h of suction filtration, pouring out the redundant citric acid solution from the vacuum suction filtration device, and then taking down the hybrid membrane from the filter paper and naturally drying the hybrid membrane;
(3) placing the hybrid membrane prepared in the step (2) in a vacuum atmosphere furnace, heating to 300 ℃ at a heating rate of 5 ℃/min in a vacuum environment, preserving heat for 2h, and pre-reducing the hybrid membrane to endow the hybrid membrane with certain conductivity; then, in a vacuum operation box, placing the pre-reduced hybrid film between two groups of graphite electrodes, wherein each group of graphite electrodes consists of an upper graphite plate and a lower graphite plate which are connected through bolts so as to increase the contact reliability of the graphite electrodes and the pre-reduced hybrid film; the two groups of graphite electrodes are respectively connected with the positive electrode and the negative electrode of a direct current power supply, the direct current power supply has a programmable function, the experiment adopts pulse waveform loading, an infrared temperature measuring sensor is adopted to monitor the surface temperature of the hybrid membrane in real time, the temperature is controlled to be always below the melting point of iron, flash combustion of the pre-reduced hybrid membrane is realized through the pulse waveform of the direct current power supply, the highest temperature of flash combustion is 1500 ℃, and the shape and the size of iron nanoparticles cannot be influenced while oxygen-containing functional groups of graphene oxide are removed at high temperature;
the finally obtained graphene hybrid membrane has a good layered structure, and the iron nanoparticles wrap and crosslink adjacent graphene sheets, so that the interface resistance between the graphene sheets is greatly improved.
Embodiment 3, a method for preparing a highly conductive and internally continuous graphene hybrid film, comprising the steps of:
(1) weighing 10ml of graphene oxide solution (8mg/ml) and 1ml of silver nitrate solution (0.1mol/L) to mix according to a volume ratio of 10:1, dropwise and slowly adding the silver nitrate solution into the graphene oxide solution which is magnetically stirred during mixing, and then continuously magnetically stirring for 1 h; continuously placing the uniformly mixed solution in an ultrasonic bath for ultrasonic treatment for 30min to perform one-step dispersion; due to a large number of oxygen-containing functional groups on the surface of the graphene oxide, the graphene oxide is negatively charged, and silver ions are uniformly loaded on the surface and the edge of the graphene oxide sheet through strong electrostatic action; firstly, pouring the dispersed mixed solution into a vacuum filtration device, wherein the filter paper is cellulose acetate filter paper with the diameter of 50mm and the aperture of 0.22um, the vacuum filtration device is externally connected with a vacuum pump, and the negative pressure of the vacuum pump is 0.09MPa during filtration;
(2) when the mixed solution in the step (1) is dried by pumping, a layer of graphene oxide hybrid film containing silver ions is formed on the surface of the filter paper, and the graphene oxide hybrid film containing silver ions has a good hierarchical structure, and the silver ions are uniformly adsorbed on graphene oxide sheets; weighing 5g of ascorbic acid powder, and dissolving the ascorbic acid powder in 50ml of deionized water to prepare an ascorbic acid solution; pouring the ascorbic acid solution into a vacuum filtration device for continuous filtration, wherein the resistance to the ascorbic acid solution is small because a nano channel exists between adjacent graphene oxide sheets, and the ascorbic acid solution can preferentially flow through the nano channel; because dienol groups in ascorbic acid molecules have extremely strong reducibility, when ascorbic acid solution flows through a nano channel, ascorbic acid is dehydrogenated and oxidized, silver ions are firstly reduced into silver atoms in situ, then clusters are formed, finally nucleation and growth are carried out to form silver nano particles, and adjacent graphene oxide sheets are wrapped and crosslinked; after 5h of suction filtration, pouring out the redundant ascorbic acid solution from the vacuum suction filtration device, and then putting the hybrid membrane and the filter paper into an autoclave;
(3) because the ascorbic acid solution fully infiltrates the hybrid membrane, the high-pressure kettle is placed in an oven and heated to 90 ℃, the hybrid membrane is pre-reduced by a chemical method, and the hybrid membrane is endowed with certain conductivity; after the reaction is finished, taking down the hybrid membrane from the filter paper and naturally airing; then, in a vacuum operation box, placing the pre-reduced hybrid film between two groups of graphite electrodes, wherein each group of graphite electrodes consists of an upper graphite plate and a lower graphite plate which are connected through bolts so as to increase the contact reliability of the graphite electrodes and the pre-reduced hybrid film; two groups of graphite electrodes are respectively connected with the positive electrode and the negative electrode of a direct current power supply, the direct current power supply has a programmable function, the experiment adopts pulse waveform loading, an infrared temperature measuring sensor is adopted to monitor the surface temperature of the hybrid membrane in real time, flash burning of the pre-reduced hybrid membrane is realized through the pulse waveform of the direct current power supply, the maximum temperature of flash burning is 2000 ℃, and rapid heating and cooling can be realized through flash burning because the heating temperature at the moment exceeds the melting point of silver; therefore, the silver nanoparticles are instantly melted and recrystallized, and continuously infiltrate into gaps between adjacent graphene sheets in the melting process, and finally, the two graphene sheets are wrapped by recrystallization.
As shown in fig. 8, it can be seen that the morphology of the silver nanoparticles is changed from spherical particles to flat particles, which is mainly caused by rapid melting and instant crystallization, but at this time, the flat silver aggregates still wrap and cross-link the adjacent graphene sheets to form a conductive network.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a graphene hybrid film with high conductivity and continuous inside is characterized by comprising the following steps: firstly, graphene oxide and metal nano-particles are hybridized, adjacent graphene oxide sheets are wrapped and crosslinked through the metal nano-particles, and the number of the graphene oxide sheets is reducedThe interfacial resistance therebetween; then carrying out pre-reduction on the hybrid film by utilizing chemical reduction or low-temperature heat treatment to ensure that the hybrid film has conductive performance; finally, the hybrid membrane is thermally reduced at 800-2000 ℃ by electric heating, and the conductivity of the reduced hybrid membrane and the graphene membrane after the ultrahigh-temperature graphitization treatment are in the same order of magnitude of 105S/m。
2. A preparation method of a graphene hybrid film with high conductivity and continuous inside is characterized by comprising the following steps:
(1) firstly, uniformly mixing a graphene oxide solution and a metal salt solution according to a ratio, pouring the mixed solution into a vacuum filtration device for filtration to obtain a graphene oxide hybrid membrane containing metal ions;
(2) pouring the solution with reducibility into the vacuum filtration device in the step (1) for secondary filtration, and reducing metal ions into metal nano particles in situ;
(3) pre-reducing the hybrid membrane prepared in the step (2) to endow the hybrid membrane with conductivity; and then carrying out high-temperature thermal reduction on the pre-reduced hybrid film at 800-2000 ℃ by electric heating, and reducing the graphene oxide into graphene.
3. The preparation method of the highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the specific steps of the step (1) are as follows: firstly, mixing a graphene oxide solution and a metal salt solution in proportion, uniformly mixing the graphene oxide solution and the metal salt solution through magnetic stirring and ultrasonic dispersion, then pouring the mixed solution into a vacuum filtration device, forming a layer of graphene oxide hybrid membrane containing metal ions on the surface of filter paper after the mixed solution is drained, and at the moment, stacking and assembling graphene oxide sheets layer by layer to form the hybrid membrane, wherein the metal ions are adsorbed on the graphene oxide sheets through strong electrostatic force.
4. The preparation method of the highly conductive and internally continuous graphene hybrid film according to claim 3, is characterized in that: the thickness of the graphene oxide hybrid membrane containing the metal ions is controlled by adjusting the volume of the mixed solution according to requirements.
5. The preparation method of the highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the specific steps of the step (2) are as follows: pouring a solution with reducibility into the vacuum filtration device, wherein the solution with reducibility can preferentially flow through the nanochannels between adjacent graphene oxide sheets; when the reducing solution flows through the nano channel, metal ions are firstly reduced into metal atoms in situ, then clusters are formed, nucleation and growth are finally carried out to form metal nano particles, adjacent graphene oxide sheets are wrapped and crosslinked, and the interface resistance between the graphene oxide sheets is improved.
6. The preparation method of the highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the step (3) comprises the following specific steps: after the reductive solution is dried, the hybrid membrane is subjected to pre-reduction through chemical reduction or low-temperature thermal reduction at 300-500 ℃, and the pre-reduced hybrid membrane has conductivity; and finally, placing the pre-reduced hybrid film between graphite electrodes in a vacuum operation box, and loading pulse current at two ends of the graphite electrodes by adopting a programmable direct current power supply to quickly heat the pre-reduced hybrid film to 800-2000 ℃ under the action of joule heat, removing oxygen-containing functional groups in the graphene oxide, and reducing the graphene oxide into graphene.
7. The method for preparing a highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the metal ions are silver ions, copper ions, aluminum ions or iron ions.
8. The method for preparing a highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the reducing solution in step (2) is ascorbic acid solution or citric acid solution.
9. The method for preparing a highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the graphene oxide solution can be replaced by a surface-modified carbon nanotube solution, and the carbon nanotubes are carboxylated and negatively charged.
10. The method for preparing a highly conductive and internally continuous graphene hybrid film according to claim 2, wherein the graphene oxide hybrid film containing metal ions can be prepared by spin coating or coating.
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