CN118441290A - Application of metal doped graphene film prepared at low temperature as heat dissipation film - Google Patents
Application of metal doped graphene film prepared at low temperature as heat dissipation film Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 194
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 172
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- 230000017525 heat dissipation Effects 0.000 title claims abstract description 29
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- 239000010949 copper Substances 0.000 claims description 15
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011135 tin Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
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- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 34
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Abstract
The invention relates to an application of a metal doped graphene film prepared at a low temperature as a heat dissipation film, and belongs to the technical field of heat dissipation films. The preparation of the graphene composite film is realized by the thermodynamic induction of spontaneous redox reaction of the metal substrate and the graphene solution, the spontaneous graphene assembly and the in-situ doping assembly are realized, a large number of ultrafine metal oxide nanoparticles are doped in the graphene film which is spontaneously assembled on the surface of the metal substrate, and the metal oxide nanoparticles loaded on the surface of the graphene nanosheet have the in-situ carbothermic reduction pore-forming effect at high temperature. Compared with the traditional graphene film electrode, the porous structure of the graphene nano sieve surface is abundant, so that the graphene nano sieve has larger specific surface area when being used as an electrode material. And by utilizing the printing technology, the heat dissipation film is prepared at low temperature, and has a higher heat dissipation coefficient.
Description
Technical Field
The invention relates to the field of heat dissipation films, in particular to an application of a metal doped graphene film prepared at a low temperature as a heat dissipation film.
Background
Graphene is a two-dimensional material with high thermal conductivity, and the thermal conductivity of the graphene is far higher than that of other materials, so that the graphene is an excellent heat dissipation material. The graphene film also has lower surface energy and higher transparency, so that the graphene film can be fully contacted with air or other heat dissipation media, and heat conduction and dissipation are increased. The invention discloses a graphene film with high electrical conductivity and high thermal conductivity as well as a preparation method and application thereof in a Chinese invention patent specification CN116675221A, wherein large-size graphite oxide is used as a raw material, and the graphene oxide film with adjustable thickness is obtained by adopting the steps of high-speed shearing dispersion pulping, vacuum defoaming, coating film forming, temperature-adaptive drying and the like; then carrying out gradient pressure-variable hot-pressing prereduction on the graphene oxide film by using a plate vulcanizing machine; and then graphitizing the film after hot pressing at high temperature, and finally obtaining the graphene film through cold pressing. The invention patent CN105899053A discloses a graphene heat dissipation film prepared from graphite, graphene and metal ions, and a graphene distribution pattern in a longitudinal and transverse mode is formed by combining the graphene with the metal ions so as to achieve the effects of overall heat dissipation and heat conduction, so that the graphene heat dissipation film has a good heat dissipation effect. The preparation process of the two graphene heat dissipation films involves the processes of slurry preparation, vacuum defoaming, high-temperature hot pressing, compound addition and the like, and the preparation process is complex. Development of a corresponding technical means is urgently needed to prepare a green, simple and efficient graphene film preparation method.
In the patent application with publication number CN107089656B, graphene nano-sieve films are formed in situ by combining oxidation-reduction reaction between graphene oxide and active metal with high-temperature calcination and acid washing, and are used for flexible ac linear filter capacitors. However, the patent relates to the disadvantages of complex preparation method, environment friendliness and the like of high-temperature calcination (450-900 ℃) and metal pickling processes.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides application of a metal doped graphene film prepared at low temperature as a heat dissipation film, and the metal doped graphene film adopts a finite field chemical printing preparation technology, wherein a metal substrate is adopted as a carrier of graphene oxide and a composite film layer thereof, a self-redox reaction is induced based on thermodynamics, and the reduction process and metal doping of the graphene oxide can be smoothly realized by regulating the reaction temperature, so that the large-area metal loaded graphene composite film can be prepared by printing, and mechanical stripping can be conveniently and rapidly realized to obtain the self-supporting graphene composite film. The manufacturing method is simple in process and convenient to operate, dependence on high-temperature conditions or other toxic reducing agents can be eliminated, and the large-area ultrahigh-performance graphene composite film is prepared by printing, has high heat dissipation coefficient and flexibility, and can solve the technical problems of heat dissipation of products such as high-power electronic devices, integrated circuits, LED illumination, OLED and the like.
According to a first aspect of the present invention, there is provided an application of a metal doped graphene film prepared at a low temperature as a heat dissipation film, wherein the preparation method of the metal doped graphene film comprises: immersing a metal plate into an aqueous solution containing graphene oxide, and carrying out oxidation-reduction reaction on the graphene oxide and the metal plate at a low temperature of 20-40 ℃, so that a uniform and continuous reduced graphene oxide film is formed on the surface of the metal plate, and metal oxide nano particles obtained by the oxidation-reduction reaction are spontaneously deposited on the reduced graphene oxide film in situ.
Preferably, the metal plate is a copper plate, an iron plate, a cobalt plate, a nickel plate, a zinc plate, or a tin plate, or an alloy plate of at least two metals of copper, iron, cobalt, nickel, zinc, and tin.
Preferably, the aqueous solution further contains an additive.
Preferably, the additive is one or more of carbon nano tube, carbon nano sphere, rhodanine and polyvinylpyrrolidone.
Preferably, the reaction time is 5min-24h.
Preferably, the concentration of graphene oxide in the aqueous solution is 0.1 mg/mL-20 mg/mL.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) According to the preparation method, the graphene composite film is prepared by realizing the spontaneous graphene assembly and in-situ doping assembly through the thermodynamic induction spontaneous redox reaction of the metal substrate and the graphene solution, a large number of ultrafine metal oxide nanoparticles are doped in the graphene film which is spontaneously assembled on the surface of the metal substrate, and the metal oxide nanoparticles loaded on the surface of the graphene nanosheet have the in-situ carbothermic reduction pore-forming effect at high temperature. Compared with the traditional graphene film electrode, the porous structure of the graphene nano sieve surface is abundant, so that the graphene nano sieve has larger specific surface area when being used as an electrode material. And by utilizing the printing technology, the heat dissipation film is prepared at low temperature, and has a higher heat dissipation coefficient.
(2) According to the graphene heat dissipation film prepared by the method, a uniform and continuous reduced graphene oxide film is formed on the surface of a metal sheet by utilizing the oxidation-reduction reaction between graphene oxide and metal foil, and spontaneous in-situ deposition of metal oxide nano particles on the graphene sheet is realized. The preparation process is simple, and the method can be used for preparing the composite graphene film on a large scale.
(3) According to the invention, the metal substrate is selected as the carrier of the graphene oxide composite film, on one hand, the graphene oxide is promoted to be assembled through the spontaneous redox reaction induced by thermodynamics, and meanwhile, metal doping is carried out, on the other hand, the dried composite film has high mechanical property, the film layer is easily peeled from the metal substrate without damage to the metal substrate, and the metal substrate can be recycled after being cleaned.
(4) According to the technical scheme of the 'limited-area chemical printing technology', the dependence on high-temperature conditions or toxic reducing agents in the prior art is eliminated, meanwhile, the material selection, the area, the reaction time and the temperature of a substrate are accurately controlled, the film product with controllable area and thickness can be accurately regulated and controlled, and in addition, the technical problem that a graphene film and a composite film thereof are difficult to transfer in the prior art can be well solved.
(5) According to the preparation method disclosed by the invention, the preparation of the graphene film based on the flexible substrate and other various graphene composite films can be realized at normal temperature, the operation is simple, the control is convenient, the cost is low, the environment is not polluted, and the prepared film product has the technical characteristics of flexibility, flatness, high heat dissipation coefficient and the like, so that the preparation method is especially suitable for large-scale industrial production.
(6) Preferably, the graphene film grown on the copper foil has a heat conductivity coefficient of over 1600W m -1K-1, and can effectively conduct heat from heat sources such as electronic devices and the like, so that the graphene film grown on the copper foil has a wide application prospect in the fields of high-power electronic devices, integrated circuits, LED illumination, OLED and the like.
Drawings
FIG. 1 shows a galvanic model of the invention using the metal foil and GO solution of example 1 (pH. Apprxeq.6).
Fig. 2 is a schematic diagram of a metal-doped graphene composite film product according to example 1.
Fig. 3 is an SEM image of the surface and cross section of the metal-doped graphene composite film of example 1 used in the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
According to the graphene heat dissipation film prepared by the method, a uniform and continuous reduced graphene oxide film is formed on the surface of a metal sheet by utilizing the oxidation-reduction reaction between graphene oxide and metal foil, and spontaneous in-situ deposition of metal oxide nano particles on the graphene sheet is realized. Fig. 1 shows that in the primary cell model in the embodiment of the invention, as shown in fig. 1, GO is an efficient oxidant, the surface of GO has rich oxidation functional groups, and a single metal sheet (Cu, ni, fe, co, zn, sn, etc.) or a metal alloy sheet (NiCu, cuFe, coFe, coZn, niCoCu, cuFeCo, cuNiFe, etc.) has reducibility, so that a uniform continuous reduced graphene oxide film can be formed on the surface of the metal sheet by utilizing the oxidation-reduction reaction between GO and the metal sheet, and spontaneous in-situ deposition of oxide nanoparticles on a graphene sheet layer is realized.
According to a first aspect of the present invention, there is provided a method for preparing a metal-doped graphene composite film based on a metal substrate, characterized in that the method sequentially comprises the steps of:
(a) Immersing a metal plate into graphene oxide aqueous solution with the mass concentration of 0.1-20 mg/mL, and growing a film layer which is uniformly covered and has adjustable thickness on a metal substrate by accurately regulating the reaction temperature to 20-40 ℃ and the time to 5min-24 h;
(b) Taking out the metal plate obtained in the step (a), cleaning the surface with deionized water, and naturally drying;
(c) And (3) separating the film in the step (b) from the metal substrate by mechanical stripping to obtain the metal doped graphene composite film.
According to a second aspect of the present invention, there is provided a method for preparing a graphene/carbon nanotube composite film based on a metal substrate, characterized in that the method sequentially comprises the steps of:
(a) Adding multi-wall carbon nano tubes into graphene oxide aqueous solution with mass concentration of 0.1-20 mg/mL, and performing ultrasonic dispersion to obtain mixed solution, wherein the mass ratio of graphene oxide to multi-wall carbon nano tubes is 20:1-10:1.
(B) Immersing a metal plate into the mixed solution obtained in the step (a), and growing a film layer which is uniformly covered and has adjustable thickness on a metal substrate by accurately regulating the reaction temperature to 20-40 ℃ and the time to 5min-24 h;
(c) Taking out the metal plate obtained in the step (b), cleaning the surface with deionized water, and naturally drying;
(d) And (3) separating the film in the step (c) from the metal substrate by mechanical stripping to obtain the metal doped graphene/carbon nano tube composite film.
According to a third aspect of the present invention, there is provided a method for preparing a graphene/carbon nanosphere composite film based on a metal substrate, characterized in that the method sequentially comprises the steps of:
(a) Adding carbon nanospheres into graphene oxide aqueous solution with the mass concentration of 0.1-20 mg/mL, and performing ultrasonic dispersion to obtain mixed solution, wherein the mass ratio of graphene oxide to carbon nanospheres is 20:1-10:1.
(B) Immersing a metal plate into the mixed solution obtained in the step (a), and growing a film layer which is uniformly covered and has adjustable thickness on a metal substrate by accurately regulating the reaction temperature to 20-40 ℃ and the time to 5min-24 h;
(c) Taking out the metal plate obtained in the step (b), cleaning the surface with deionized water, and naturally drying;
(d) And (3) separating the film in the step (c) from the metal substrate by mechanical stripping to obtain the metal doped graphene/carbon nanosphere composite film.
According to a fourth aspect of the present invention, there is provided a method for preparing a graphene/rhodanine/polyvinylpyrrolidone (PVP) composite film based on a metal substrate, characterized in that the method comprises the following steps in order:
(a) Adding rhodanine and PVP into graphene oxide aqueous solution with the mass concentration of 0.1-20 mg/mL, and performing ultrasonic dispersion to obtain mixed solution, wherein the mass ratio of the graphene oxide to the rhodanine to the PVP is 20:1:1-10:1:1.
(B) Immersing a metal plate into the mixed solution obtained in the step (a), and growing a film layer which is uniformly covered and has adjustable thickness on a metal substrate by accurately regulating the reaction temperature to 20-40 ℃ and the time to 5min-24 h;
(c) Taking out the metal plate obtained in the step (b), cleaning the surface with deionized water, and naturally drying;
(d) And (3) separating the film in the step (c) from the metal substrate by mechanical stripping to obtain the metal doped graphene/rhodanine/PVP composite film.
The preparation method can be used for preparing the graphene high-performance heat dissipation film in a large-scale green and efficient manner, and the preparation process of the composite film mainly relates to the types of metal substrates, the concentration of graphene, the components of additives and the like. The metal substrate and the graphene obtain the metal doped graphene composite film, and the mechanical property, the conductivity and the heat dissipation coefficient of the film are improved through the change of the additive.
In some embodiments, the metal substrate comprises primarily pure metal mesh or sheet of iron, cobalt, nickel, copper, zinc, tin, etc., and at least two metal alloy mesh or sheet of copper, iron, cobalt, nickel, zinc, and tin.
In some embodiments, the graphene is predominantly mono-layer and oligolayer graphene.
In some embodiments, the additive is mainly one or more of carbon nanotubes, carbon nanospheres, rhodanine, polyvinylpyrrolidone (PVP), and the like.
According to the preparation method of the graphene high-performance heat dissipation film induced by the metal at low temperature, the components are mixed to form the graphene composite film by controlling the reaction time, the temperature, the concentration and the like, and the high-performance heat dissipation film with controllable thickness is finally formed by means of stripping, drying, annealing (100-300 ℃) and the like.
Example 1
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting the metal plate into a graphene oxide solution with the concentration of 0.1mg/mL, and assembling the graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 5 mu m, and the heat conductivity coefficient is 1620W m -1K-1.
Fig. 2 is a physical diagram (the size is 25cm x10 cm) of the metal doped graphene composite film product in the embodiment 1, and as can be seen from fig. 2, the film prepared by the method has the characteristic of macroscopic scalability and good flexibility.
Fig. 3 is an SEM image of the surface and cross section of the metal doped graphene composite film according to example 1, and as can be seen from fig. 3, the SEM surface proves that the metal oxide nanoparticles are uniformly distributed on the graphene sheets, and the SEM cross section proves that the structure is formed by stacking layers to form a continuous film.
Example 2
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting the metal plate into a graphene oxide solution of 20mg/mL, and assembling the graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 50 mu m, and the heat conductivity coefficient is 1650W m -1K-1.
Example 3
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
Adding multi-wall carbon nano tubes into 0.1mg/mL graphene oxide solution, and performing ultrasonic dispersion to obtain mixed solution, wherein the mass ratio of graphene oxide to the multi-wall carbon nano tubes is 20:1. And inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/carbon nanotube composite film product is obtained through mechanical stripping, wherein the electrical conductivity is 3.9x10 6S·m-1, the thickness is 7 mu m, and the thermal conductivity coefficient is 1760W m -1K-1.
Example 4
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
Adding the multi-wall carbon nano tube into a graphene oxide solution with the concentration of 20mg/mL, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the multi-wall carbon nano tube is 10:1. And inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/carbon nanotube composite film product is obtained through mechanical stripping, wherein the electrical conductivity is 3.9x10 6S·m-1, the thickness is 38 mu m, and the thermal conductivity coefficient is 1780W m -1K-1.
Example 5
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
Adding carbon nanospheres into a graphene oxide solution with the concentration of 0.1mg/mL, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the carbon nanospheres is 20:1. And inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/carbon nanosphere composite film product is obtained through mechanical stripping, wherein the electrical conductivity is 3.9x10 6S·m-1, the thickness is 8 mu m, and the thermal conductivity coefficient is 1800W m -1K-1.
Example 6
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
Adding carbon nanospheres into a graphene oxide solution with the concentration of 20mg/mL, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the carbon nanospheres is 10:1. And inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/carbon nanosphere composite film product is obtained through mechanical stripping, wherein the electrical conductivity is 3.9x10 6S·m-1, the thickness is 35 mu m, and the thermal conductivity coefficient is 1850W m -1K-1.
Example 7
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
Adding rhodanine and PVP into 0.1mg/mL graphene oxide solution, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the rhodanine to the PVP is 20:1:1. and inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/rhodanine/PVP composite film product is obtained through mechanical stripping, the mechanical flexibility is increased, the thickness is 8 mu m, and the thermal conductivity is 1800W m -1K-1.
Example 8
A10 cm by 10cm copper metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And adding the rhodanine and PVP into the 20mg/mL graphene oxide solution, and performing ultrasonic dispersion to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the rhodanine to the PVP is 10:1:1. And inserting a metal plate into the mixed solution, and assembling graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene/rhodanine/PVP composite film product is obtained through mechanical stripping, the mechanical flexibility is increased, the thickness is 30 mu m, and the heat conductivity coefficient is 1830W m -1K-1.
Example 9
10Cm×10cm iron metal plates were immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting an iron metal plate into a graphene oxide solution of 0.1mg/mL, and assembling graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 6 mu m, and the heat conductivity coefficient of the metal doped graphene composite film product is 800W m -1K-1.
Example 10
A10 cm by 10cm cobalt metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting a cobalt metal plate into a graphene oxide solution of 0.1mg/mL, and assembling the graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 6 mu m, and the heat conductivity coefficient is 700W m -1K-1.
Example 11
A10 cm by 10cm nickel metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting a nickel metal plate into a graphene oxide solution of 0.1mg/mL, and assembling the graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 5 mu m, and the heat conductivity coefficient of the metal doped graphene composite film product is 900W m -1K-1.
Example 12
A10 cm×10cm zinc metal plate was immersed in 6mol/mL hydrochloric acid, and after removing the surface oxide layer, washed with deionized water.
And (3) inserting a zinc metal plate into a graphene oxide solution of 0.1mg/mL, and assembling graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 10 mu m, and the heat conductivity coefficient of the metal doped graphene composite film product is 500W m -1K-1.
Example 13
A10 cm by 10cm tin metal plate was immersed in 6mol/mL hydrochloric acid, and after removal of the surface oxide layer, rinsed with deionized water.
And (3) inserting a tin metal plate into a graphene oxide solution of 0.1mg/mL, and assembling graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 8 mu m, and the heat conductivity coefficient of the metal doped graphene composite film product is 500W m -1K-1.
Example 14
A10 cm×10cm nickel-copper alloy metal plate was immersed in 6mol/mL hydrochloric acid, and after the surface oxide layer was removed, it was rinsed with deionized water.
And (3) inserting a tin metal plate into a graphene oxide solution of 0.1mg/mL, and assembling graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 5 mu m, and the heat conductivity coefficient is 1400W m -1K-1.
Example 15
A10 cm×10cm nickel-copper alloy metal plate was immersed in 6mol/mL hydrochloric acid, and after the surface oxide layer was removed, it was rinsed with deionized water.
And (3) inserting a tin metal plate into a graphene oxide solution of 20mg/mL, and assembling the graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 25 mu m, and the heat conductivity coefficient is 1460W m -1K-1.
Example 16
A10 cm×10cm nickel-cobalt-copper alloy metal plate is immersed in 6mol/mL hydrochloric acid, and the surface oxide layer is removed and then washed with deionized water.
And (3) inserting a tin metal plate into a graphene oxide solution of 0.1mg/mL, and assembling graphene oxide on a metal substrate into a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 15 mu m, and the heat conductivity coefficient is 1430W m -1K-1.
Example 17
A10 cm×10cm nickel-cobalt-copper alloy metal plate is immersed in 6mol/mL hydrochloric acid, and the surface oxide layer is removed and then washed with deionized water.
And (3) inserting a tin metal plate into a graphene oxide solution of 20mg/mL, and assembling the graphene oxide on a metal substrate to form a film by accurately regulating and controlling the reaction temperature and time.
And taking the metal plate after the film growth out of the solution, and cleaning the surface of the film with deionized water to remove unreacted graphene oxide solution.
After drying at room temperature, the required metal doped graphene composite film product is obtained through mechanical stripping, the thickness of the metal doped graphene composite film product is 32 mu m, and the heat conductivity coefficient is 1360W m -1K-1.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The application of the metal doped graphene film prepared at low temperature as a heat dissipation film is characterized in that the preparation method of the metal doped graphene film comprises the following steps: immersing a metal plate into an aqueous solution containing graphene oxide, and carrying out oxidation-reduction reaction on the graphene oxide and the metal plate at a low temperature of 20-40 ℃, so that a uniform and continuous reduced graphene oxide film is formed on the surface of the metal plate, and metal oxide nano particles obtained by the oxidation-reduction reaction are spontaneously deposited on the reduced graphene oxide film in situ.
2. Use according to claim 1, wherein the metal plate is a copper plate, an iron plate, a cobalt plate, a nickel plate, a zinc plate or a tin plate, or an alloy plate of at least two metals of copper, iron, cobalt, nickel, zinc and tin.
3. The use according to claim 1, wherein the aqueous solution further comprises an additive.
4. The use according to claim 3, wherein the additive is one or more of carbon nanotubes, carbon nanospheres, rhodanine, polyvinylpyrrolidone.
5. The use according to claim 1, wherein the reaction time is from 5min to 24h.
6. The use according to claim 1, wherein the concentration of graphene oxide in the aqueous solution is between 0.1mg/mL and 20mg/mL.
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