CN113593769A - Graphene composite film and preparation method thereof - Google Patents
Graphene composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene composite film and a preparation method thereof, wherein the method comprises the following steps: mixing graphene nanoplatelets, low-melting-point metal salt and a solvent to obtain mixed slurry; carrying out hot-pressing film forming treatment on the mixed slurry to form molten metal with the low-melting-point metal salt, and filling the molten metal into the sheet layer of the graphene microchip to form metal microstructure welding graphene to obtain a graphene composite film; wherein the melting point of the low-melting-point metal salt is lower than the heat treatment temperature in the hot-pressing film-forming process; by applying the method, the graphene composite film with high conductivity can be prepared at low cost.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a graphene composite film and a preparation method thereof.
Background
Graphene Nanoplatelets (Graphene Nanoplatelets) refer to ultra-thin Graphene layered stacks having more than 10 carbon layers and a thickness in the range of 5 to 100 nm. The graphene nanoplatelets maintain the original planar carbon six-membered ring conjugated crystal structure of graphite, have excellent mechanical strength, electric conduction and heat conduction properties and good lubricating, high temperature resistant and corrosion resistant properties, and are widely applied to various fields, such as the field of electronic components, by preparing graphene nanoplatelets to obtain graphene films.
The conductivity of the graphene and the composite film prepared by the existing mass-produced graphene microchip technology is usually about 1000s/cm, and is usually less than 2000s/cm after further treatment, so that the graphene and the composite film cannot meet application requirements with higher conductivity requirements, such as application as an electrode substrate, a radio frequency antenna material and the like, and the application of the graphene film in the field of electronic components is limited.
Disclosure of Invention
The embodiment of the invention provides a graphene composite film and a preparation method thereof, and the graphene composite film has higher conductivity.
An embodiment of the present invention provides a method for preparing a graphene composite film, where the method includes: mixing graphene nanoplatelets, low-melting-point metal salt and a solvent to obtain mixed slurry; carrying out hot-pressing film forming treatment on the mixed slurry to form molten metal with the low-melting-point metal salt, and filling the molten metal into the sheet layer of the graphene microchip to form metal microstructure welding graphene to obtain a graphene composite film; wherein the melting point of the low-melting-point metal salt is lower than the heat treatment temperature in the hot-pressing film-forming process.
In one embodiment, the graphene nanoplatelets are graphene nanoplatelets dispersed in water; correspondingly, the solvent at least comprises a first component and a second component, and the first component is water; the second component is an acidic solution.
In one embodiment, the second component is an acidic surfactant; the acidic surfactant comprises at least one of ortho-hydroxybenzoic acid, rosin, natural resin, succinic acid and sebacic acid.
In one embodiment, the solvent further comprises a third component, and the third component comprises at least one of ethanol, N-dimethylformamide and N-methylpyrrolidone.
In one embodiment, the low melting point metal salt includes at least one of a tin salt, a zinc salt, an aluminum salt, and a magnesium salt.
In one embodiment, in the mixed slurry, the molar ratio of the metal ions corresponding to the low melting point metal salt to the graphene nanoplatelets is 0.01 to 0.1: 1; further, the molar ratio of the metal ions corresponding to the low-melting-point metal salt to the graphene nanoplatelets is 0.05-0.1: 1.
in an embodiment, before obtaining the mixed slurry, the method further comprises: adding a surfactant to the solvent so that the surfactant is mixed with the graphene nanoplatelets and the low melting point metal salt.
In an embodiment, in the mixed slurry, the mass ratio of the surfactant to the graphene nanoplatelets is 0.01 to 0.2: 1; further, the mass ratio of the surfactant to the graphene nanoplatelets is 0.05-0.15: 1.
in an embodiment, the performing the hot-pressing film formation process on the mixed slurry includes: carrying out primary film forming treatment on the mixed slurry to obtain a mixed slurry film; placing the mixed slurry film in an atmosphere furnace, controlling the temperature to be 750-850 ℃ in a reducing atmosphere, and preserving the heat for 3.5-4.5 hours to obtain a heat treatment film; and carrying out isostatic pressing heat treatment or conventional heat treatment on the heat-treated film, and then carrying out rolling treatment to obtain the graphene composite film.
In another aspect, the present invention provides a graphene composite film, which is prepared by the preparation method according to any one of the above embodiments.
According to the method, low-melting-point metal salt is reduced into metal and adsorbed on the surface of a graphene microchip sheet, when mixed slurry is subjected to hot pressing to form a film, the metal is heated and melted, the hot pressing pressure is filled in the graphene microchip sheet to form micro-structure welding between the metal and graphene, the compactness of the sheet is increased, the contact resistance of the graphene composite film is reduced, and meanwhile, the contact resistance between the inner sheet layers of the graphene composite film is further reduced due to the fact that the metal has the characteristic of small sheet resistance, so that the graphene composite film with high conductivity is obtained.
Drawings
The above and other objects, features and advantages of exemplary embodiments of the present invention will become readily apparent from the following detailed description read in conjunction with the accompanying drawings. Several embodiments of the invention are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:
in the drawings, the same or corresponding reference numerals indicate the same or corresponding parts.
Fig. 1 is a first flow chart of an implementation principle of a preparation method of a graphene composite film according to an embodiment of the present invention;
fig. 2 is a second flow chart illustrating an implementation principle of a method for preparing a graphene composite film according to an embodiment of the present invention;
fig. 3 is a third flow chart of an implementation principle of the preparation method of the graphene composite film according to the embodiment of the invention;
fig. 4 is a fourth flow chart of an implementation principle of a preparation method of a graphene composite film according to an embodiment of the present invention;
FIG. 5 is an electron microscope image of a graphene composite film according to an embodiment of the present invention;
fig. 6 is an electron microscope image of a graphene composite film according to another embodiment of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An embodiment of the present invention provides a method for preparing a graphene composite film, including: operation 101, mixing graphene nanoplatelets, low-melting-point metal salt and a solvent to obtain mixed slurry; operation 102, performing hot-pressing film forming treatment on the mixed slurry to form molten metal with a low-melting-point metal salt, filling the molten metal into a sheet layer of the graphene microchip to form metal microstructure welded graphene, and obtaining a graphene composite film; wherein the melting point of the low-melting metal salt is lower than the heat treatment temperature in the hot-pressing film-forming process.
According to the method, the graphene microchip and the low-melting-point metal salt are used as raw materials, the low-melting-point metal salt is reduced into metal in a solvent and adsorbed on the surface of a graphene microchip sheet layer, when the mixed slurry is subjected to hot pressing to form a film, the metal is heated and melted, and the position with a large gap of the graphene microchip sheet layer is filled due to the pressure of the hot pressing, so that microstructure welding between the metal and the graphene is formed. The contact resistance of the graphene composite film is reduced, and the contact resistance of the graphene composite film is reduced due to the fact that metal is welded to the sheet layer of the graphene microchip under the action of hot pressing, so that the compactness of the sheet layer is improved, and the contact resistance of the graphene composite film is reduced. Specifically, the conductivity of the graphene composite film prepared by the method can reach 3000-6000 s/cm.
In operation 101, the graphene nanoplatelets may be commercially available mass-produced graphene nanoplatelets, i.e., ultra-thin graphene layered stacks having more than 10 carbon layers and a thickness in the range of 5 to 100 nm. The low-melting-point metal salt can be reduced into low-melting-point metal under the influence of at least one of a solvent, a graphene microchip or an atmosphere in a hot pressing process, and meanwhile, the melting point of the low-melting-point metal salt is lower than the heat treatment temperature in the hot pressing film forming process, so that the low-melting-point metal is melted in the hot pressing process. The solvent contains a solvent component capable of dispersing the graphene nanoplatelets and the low melting point metal salt, and also contains a component capable of reducing the low melting point metal salt, so that the graphene nanoplatelets and the low melting point metal salt are dispersed in the solvent.
In operation 102, the mixed slurry is subjected to a hot-pressing film-forming process, so that the metal reduced by the low-melting-point metal salt is melted under the heat treatment and adsorbed on the surface of the graphene sheet layer, and the graphene sheet layer is in a stacked state; under the pressure state, the graphene sheet layers become more compact, meanwhile, the molten metal flows and flows to the place with larger gaps of the graphene microchip layers, the molten metal tends to fill the gaps between the graphene microchip layers to form microstructure welding, and therefore the contact resistance of the graphene composite film obtained by hot-pressing film forming is greatly reduced. It is supplementary to need, generally, there are more gaps in the stacked structure edge that the graphite alkene lamella formed, and consequently, low melting point metal can carry out the micro-structure welding in the edge junction of graphite alkene microchip to not only reduce the inside contact resistance of graphite alkene composite film by a wide margin, still be favorable to improving the connection compactness between the graphite alkene microchip.
In one embodiment, the low melting metal salt comprises at least one of a tin salt, a zinc salt, an aluminum salt, and a magnesium salt. The metal tin, the metal zinc, the metal aluminum and the metal magnesium formed by the metal salt have the characteristics of low melting point, good weldability and high conductivity, and are favorable for reducing the contact resistance of the graphene composite film.
In one embodiment, the graphene nanoplatelets are graphene nanoplatelets dispersed in water; correspondingly, the solvent at least comprises a first component and a second component, wherein the first component is water; the second component is an acidic solution. Specifically, in the method, the solvent may be selected as a water-soluble solvent including the first component water, and the graphene nanoplatelets may be selected as graphene nanoplatelets of an aqueous dispersion system, so that the graphene nanoplatelets can be sufficiently dispersed in the solvent. The solvent also comprises an acidic solution which is used for dissolving metal ions of the low-melting-point metal salt in the solution, so that the metal ions can be reduced by carbon provided by graphene or gas atmosphere during hot-pressing treatment to form the low-melting-point metal.
In an embodiment, before obtaining the mixed slurry, the method further comprises: and adding a surfactant into the solvent so that the surfactant is mixed with the graphene nanoplatelets and the low-melting-point metal salt. Specifically, the second component is an acidic surfactant; the acidic surfactant comprises at least one of ortho-hydroxybenzoic acid, rosin, natural resin, succinic acid and sebacic acid. The acidic solution is preferably an acidic surfactant, the surfactant can also enable metal to be soaked on the surface of the graphene, so that the graphene micro-sheets and the metal are dispersed in the mixed slurry more uniformly, the conductivity of the graphene composite film is more uniform, and the graphene composite film has better flatness.
In one embodiment, the solvent further comprises a third component, and the third component comprises at least one of ethanol, N-dimethylformamide and N-methylpyrrolidone. Furthermore, in order to promote the dissolution of the graphene micro-sheets and the metal salt, a third component can be added into the solvent in the method so as to achieve the purpose of dissolution aiding.
In one embodiment, the molar ratio of the metal ions corresponding to the low-melting metal salt to the graphene nanoplatelets in the mixed slurry is 0.01 to 0.1: 1; under the proportion, the molten metal can basically fill lamellar gaps of the welded graphene micro-sheets, so that the contact resistance caused by the lamellar gaps is reduced, and the high-conductivity graphene composite film is obtained. Further, the molar ratio of the metal ions corresponding to the low-melting-point metal salt to the graphene nanoplatelets is 0.05-0.1: 1. under the proportion, the molten metal can completely fill the lamellar gaps of the welded graphene micro-sheets, so that the contact resistance caused by the lamellar gaps is reduced, and the conductivity of the graphene composite film is further improved.
In one embodiment, in the mixed slurry, the mass ratio of the surfactant to the graphene nanoplatelets is 0.01 to 0.2: 1. under the proportion, the surfactant can enable most of metal to be soaked on the surface of the graphene microchip, and formation of microstructure welding between the molten metal and the graphene sheet layer is facilitated. Further, the mass ratio of the surfactant to the graphene nanoplatelets is 0.05-0.15: 1. under the proportion, the surfactant can enable all metals to be infiltrated on the surfaces of the graphene micro-sheets, and the formation of microstructure welding between the molten metal and the graphene sheet layers is facilitated.
In one embodiment, operation 102, a hot-pressing film forming process is performed on the mixed slurry, including: firstly, carrying out primary film forming treatment on mixed slurry to obtain a mixed slurry film; then, placing the mixed slurry film in an atmosphere furnace, controlling the temperature to be 750-850 ℃ in a reducing atmosphere, and preserving the temperature for 3.5-4.5 hours to obtain a heat treatment film; and then, carrying out isostatic pressing heat treatment or conventional heat treatment on the heat-treated film, and then carrying out rolling treatment to obtain the graphene composite film.
Specifically, the hot-pressing film forming process of the method comprises a film forming process, a heat treatment and a rolling process. Firstly, the method carries out film forming treatment on the mixed slurry, the film forming treatment can adopt a coating and rolling mode to carry out film forming, specifically, the mixed slurry can be coated on a substrate by a coating method and directly compacted by a roller press, and can also be compacted by the roller press after being dried. The substrate can be a copper foil or other metal material substrate, forming a mixed slurry film. Wherein, the method can also directly form the mixed slurry film which is not adhered to the substrate.
Then, the mixed slurry film is placed in an atmosphere furnace and heat-treated in a reducing atmosphere. Wherein, the heat treatment mode comprises but is not limited to an isostatic pressure heat treatment mode or a conventional compaction mode after heat sintering; reducing atmospheres include, but are not limited to, hydrogen atmospheres or carbothermic atmospheres. It can be understood that, through heat treatment, the low-melting-point metal salt infiltrated on the surface of the graphene can be reduced into a metal simple substance and melted, and the melted metal can fully fill the gap part between the sheets to form microstructure welding, so that the obtained heat-treated film can greatly reduce the contact resistance. It is further necessary to supplement that, when the substrate is selected to be a metal material containing a low-melting-point metal, the low-melting-point metal on the substrate is also melted, so as to increase the adhesion between the substrate and the graphene composite film, and simultaneously, the metal filling of the graphene sheet layer is more sufficient. Further, the method can carry out heat treatment under the condition of loading pressure on the surface of the mixed slurry film so as to further improve the tightness between graphene sheet layers, and the loading pressure can be 10-100 MPa.
The heat treatment temperature of the method is controlled to be 750-850 ℃, and compared with the traditional graphitization treatment temperature (more than 3000 ℃), the heat treatment temperature can be greatly reduced, and the production cost of the graphene composite film is reduced.
And then, performing roll-in treatment on the heat-treated film to increase the compactness between the graphene sheet layers, further reducing the contact resistance of the graphene composite film and obtaining the graphene composite film with high conductivity.
To facilitate a further understanding of the above embodiments, a description of a specific implementation principle is provided below.
First, graphene nanoplatelets are added to a solvent, wherein the solvent may be water or a mixed solvent of water and other solvents (such as ethanol, DMF, NMP, etc.), and the graphene nanoplatelets may be graphene nanoplatelets of a commercially available aqueous dispersion system. As shown in fig. 1, the lines in fig. 1 are used to indicate the sheets of the graphene nanoplatelets, and the sheets of the graphene nanoplatelets are in an unapplied state.
Then, the low-melting-point metal salt and the surfactant are added into the solvent, and the components are uniformly mixed to obtain mixed slurry. Wherein, the metal salt with low melting point can be one or a combination of a plurality of tin salts (stannic chloride, stannous chloride and stannous oxalate), zinc salts (zinc chloride, zinc nitrate and zinc citrate) and aluminum salts (alum and aluminum chloride), the molar ratio of the metal ions to the graphene is 0.01-0.1: 1, preferably 0.05 to 0.1: 1. the surfactant can be selected from one or more of ortho-hydroxybenzoic acid, rosin, natural resin, succinic acid and sebacic acid, and the mass ratio of the surfactant to the graphene is (0.01-0.2): 1, preferably 0.05 to 0.15: 1. as shown in fig. 2, the lines in fig. 2 are used to indicate the sheets of the graphene nanoplatelets, and the dots are used to indicate the low melting point metal salt and the surfactant, and at this time, the graphene nanoplatelets, the low melting point metal salt and the surfactant are respectively dispersed in water to form a mixed slurry.
And then, carrying out coating and rolling treatment on the mixed slurry to obtain a mixed slurry film. The film may be self-supporting or supported on a substrate such as copper foil. As shown in fig. 3, the lines in fig. 3 are used to indicate the sheets of the graphene nanoplatelets, and the dots are used to indicate the low-melting metal salt and the surfactant, at this time, after the graphene nanoplatelets are rolled, the graphene sheets are in a stacked state, a film with tightly stacked sheets is formed between the graphene sheets due to the pressure, and the metal salt and the surfactant are adsorbed on the surfaces of the graphene sheets.
And then, heating the mixed slurry film through an atmosphere furnace for heat treatment, wherein the temperature is 500-800 ℃, hydrogen is preferably introduced, and the surface of the film is preferably loaded with pressure for sintering, and the pressure is 10-100 MPa. At this time, as shown in fig. 4, the long lines in fig. 4 are used to represent the sheets of the graphene nanoplatelets, the short lines are low-melting-point metals used to weld the graphene sheets after melting, the low-melting-point metal salts are reduced to metals by carbon provided by the graphene or introduced hydrogen atmosphere, and the metals are infiltrated on the surface of the graphene with the help of the surfactant; under the heat treatment, the metal is melted, and the melted metal tends to fill the gap part between the sheet layers to form microstructure welding, so that the contact resistance is greatly reduced, and the graphene composite film is formed.
And finally, after the graphene composite film is cooled, compacting the graphene composite film by using a roller press again to obtain the high-conductivity graphene composite film.
To facilitate a further understanding of the above-described implementation principles, a variety of implementation scenarios are provided below for explanation.
Example 1
Firstly, taking 5 wt% graphene water-based slurry, adding ethanol to dilute the graphene water-based slurry to 2 wt%, and adding rosin and o-hydroxybenzoic acid; wherein the mass ratio of the rosin, the ortho-hydroxybenzoic acid and the graphene in the slurry is 0.08: 0.06: 1.
and then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding tin tetrachloride until the dispersed graphene slurry is stirred continuously, wherein the molar ratio of the added tin tetrachloride to the graphene is 0.1: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an atmosphere furnace for heat treatment, introducing gas as hydrogen, and keeping the temperature at 800 ℃ for 4 hours.
And finally, compacting the film by using a roller press again after the film is cooled to obtain the high-conductivity graphene composite film shown in the figure 5, wherein the conductivity of the graphene composite film is 5800s/cm through measurement.
Example 2
Firstly, taking 5 wt% graphene water-based slurry, adding ethanol to dilute the graphene water-based slurry to 2 wt%, and adding rosin and o-hydroxybenzoic acid; wherein the mass ratio of the rosin, the ortho-hydroxybenzene and the graphene in the slurry is 0.08: 0.06: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding tin tetrachloride until the dispersed graphene slurry is stirred continuously, wherein the molar ratio of the added tin tetrachloride to the graphene is 0.05: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an atmosphere furnace for heat treatment, introducing gas as hydrogen, and keeping the temperature at 800 ℃ for 4 hours.
And finally, compacting the film by using a roller press again after the film is cooled to obtain the high-conductivity graphene composite film shown in fig. 6, wherein the conductivity of the graphene composite film is 5200s/cm through measurement.
Example 3
Firstly, taking 5 wt% graphene water-based slurry, adding ethanol to dilute the graphene water-based slurry to 2.5 wt%, and adding rosin; wherein the mass ratio of the rosin to the graphene in the slurry is 0.05: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding tin tetrachloride until the dispersed graphene slurry is stirred continuously, wherein the molar ratio of the added tin tetrachloride to the graphene is 0.05: 1, obtaining mixed slurry.
And coating the obtained dispersion liquid on the surface of the aluminum foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an atmosphere furnace for heat treatment, introducing gas as hydrogen, and keeping the temperature at 500 ℃ for 5 hours.
And finally, compacting the film by using a roller press again after the film is cooled to obtain the high-conductivity graphene composite film, wherein the conductivity of the graphene composite film is 4200s/cm through measurement.
Example 4
Firstly, taking 5 wt% graphene water-based slurry, adding NMP to dilute the graphene water-based slurry to 2 wt%, and adding ortho-hydroxybenzoic acid and succinic acid; wherein the mass ratio of the o-hydroxybenzoic acid to the succinic acid to the graphene in the slurry is 0.02: 0.03: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding zinc chloride until the dispersed graphene slurry is stirred continuously, wherein the molar ratio of the added zinc chloride to the graphene is 0.06: 1, obtaining mixed slurry.
And coating the obtained mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an atmosphere furnace for heat treatment, introducing gas as hydrogen, and preserving heat for 3 hours at 800 ℃.
And finally, compacting the film by using a roller press again after the film is cooled to obtain the high-conductivity graphene composite film, wherein the conductivity of the graphene composite film is 5500s/cm through measurement.
Example 5
Firstly, taking 5 wt% graphene water-based slurry, adding ethanol to dilute the graphene water-based slurry to 3 wt%,
adding sebacic acid, wherein the mass ratio of the sebacic acid to the graphene in the slurry is 0.08: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding aluminum chloride until the dispersed graphene slurry is stirred continuously, wherein the molar ratio of the added aluminum chloride to the graphene is 0.08: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an isostatic pressing sintering furnace for heat treatment, and preserving heat at 800 ℃ for 2 hours to obtain the high-conductivity graphene composite film.
After cooling, the conductivity of the graphene composite film is 4500s/cm through measurement.
Example 6.
Firstly, taking 5 wt% graphene water-based slurry, adding DMP to dilute the slurry to 3.5 wt%, and then adding rosin and natural resin, wherein the mass ratio of the added rosin and natural resin to graphene in the slurry is 0.03: 0.02: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding stannous oxalate and aluminum chloride into the dispersed graphene slurry, and continuously stirring, wherein the molar ratio of the added stannous oxalate to the added aluminum chloride to the graphene is 0.03: 0.02: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an isostatic pressing sintering furnace for heat treatment, and preserving heat at 600 ℃ for 4 hours to obtain the high-conductivity graphene composite film.
After cooling, the conductivity of the graphene composite film is 5200s/cm through measurement.
Example 7.
Firstly, taking 5 wt% graphene water-based slurry, adding a mixed solvent (2: 1 vol%) of DMF and NMP to dilute the graphene water-based slurry to 2.5 wt%, adding rosin and natural resin, wherein the mass ratio of sebacic acid to graphene in the slurry is 0.06: 0.04: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding stannic chloride and zinc citrate into the dispersed graphene slurry, and continuously stirring, wherein the molar ratio of the added stannic chloride to the added zinc citrate to the graphene is 0.03: 0.03: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an atmosphere furnace for heat treatment, introducing gas as hydrogen, and keeping the temperature at 600 ℃ for 3 hours.
And finally, compacting the film by using a roller press again after the film is cooled to obtain the high-conductivity graphene composite film, wherein the conductivity of the graphene composite film is 5000s/cm through measurement.
Example 8.
Firstly, taking 5 wt% graphene water-based slurry, adding a mixed solvent (1: 1 vol%) of DMP and ethanol to dilute the graphene water-based slurry to 3 wt%, and then adding rosin, wherein the mass ratio of the rosin to the graphene in the slurry is 0.08: 1.
then, uniformly dispersing the graphene slurry by using a dispersion machine, slowly adding alum into the dispersed graphene slurry, and continuously stirring, wherein the molar ratio of the added alum to the added graphene is 0.1: 1, obtaining mixed slurry.
And coating the mixed slurry on the surface of the copper foil by a coating method, drying and compacting by using a roller press to obtain the mixed slurry film.
And then, placing the mixed slurry film in an isostatic pressing sintering furnace for heat treatment, and preserving heat at 800 ℃ for 3 hours to obtain the high-conductivity graphene composite film.
Through measurement, the conductivity of the graphene composite film is 5500 s/cm.
In another aspect, the embodiments of the present invention provide a graphene composite film, which is prepared by any one of the preparation methods described above. The graphene composite film obtained by the invention can greatly improve the conductivity to 3000-6000 s/cm on the basis of keeping the flexibility, the flatness and the like of the graphene composite film, and the graphene composite film prepared by the invention is suitable for application requirements with higher requirements on the conductivity, such as electrode substrates, radio frequency antenna materials and the like.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a graphene composite film is characterized by comprising the following steps:
mixing graphene nanoplatelets, low-melting-point metal salt and a solvent to obtain mixed slurry;
carrying out hot-pressing film forming treatment on the mixed slurry to reduce the mixed slurry and the low-melting-point metal salt into a metal simple substance and form molten metal, wherein the molten metal is filled into a sheet layer of a graphene microchip to form metal microstructure welding graphene, so that a graphene composite film is obtained;
wherein the melting point of the low-melting-point metal salt is lower than the heat treatment temperature in the hot-pressing film-forming process.
2. The preparation method according to claim 1, wherein the graphene nanoplatelets are graphene nanoplatelets of an aqueous dispersion system;
correspondingly, the solvent at least comprises a first component and a second component, and the first component is water;
the second component is an acidic solution.
3. The method of claim 1, wherein the second component is an acidic surfactant; the acidic surfactant comprises at least one of ortho-hydroxybenzoic acid, rosin, natural resin, succinic acid and sebacic acid.
4. The method of claim 1, wherein the solvent further comprises a third component comprising at least one of ethanol, N-dimethylformamide, N-methylpyrrolidone.
5. The method according to claim 1, wherein the low melting point metal salt includes at least one of a tin salt, a zinc salt, an aluminum salt, and a magnesium salt.
6. The method according to claim 1, wherein a molar ratio of metal ions corresponding to the low-melting metal salt to graphene nanoplatelets in the mixed slurry is 0.01 to 0.1: 1;
further, the molar ratio of the metal ions corresponding to the low-melting-point metal salt to the graphene nanoplatelets is 0.05-0.1: 1.
7. the method of manufacturing according to claim 1, wherein before obtaining the mixed slurry, the method further comprises:
adding a surfactant to the solvent so that the surfactant is mixed with the graphene nanoplatelets and the low melting point metal salt.
8. The preparation method according to claim 7, wherein in the mixed slurry, the mass ratio of the surfactant to the graphene nanoplatelets is 0.01 to 0.2: 1;
further, the mass ratio of the surfactant to the graphene nanoplatelets is 0.05-0.15: 1.
9. the method according to claim 1, wherein the hot-pressing film formation of the mixed slurry comprises:
carrying out primary film forming treatment on the mixed slurry to obtain a mixed slurry film;
placing the mixed slurry film in an atmosphere furnace, controlling the temperature to be 750-850 ℃ in a reducing atmosphere, and preserving the heat for 3.5-4.5 hours to obtain a heat treatment film;
and carrying out isostatic pressing heat treatment or conventional heat treatment on the heat-treated film, and then carrying out rolling treatment to obtain the graphene composite film.
10. A graphene composite film, which is prepared by the preparation method according to any one of claims 1 to 9.
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