CN113148986A - Preparation method of high-thermal-conductivity self-supporting vertically-oriented graphene film - Google Patents
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Abstract
A preparation method of a high-thermal-conductivity self-supporting vertically-oriented graphene film comprises the following steps: 1) preparing a graphene oxide dispersion liquid; 2) adding long-chain hydrocarbon sulfonic acid, a modified single-walled carbon nanotube and a nonionic surfactant into the graphene oxide dispersion liquid, stirring and performing ultrasonic treatment; 3) under the action of an external magnetic field, taking the mixed solution as an electrodeposition solution, and depositing graphene oxide by adopting an electrochemical deposition method; 4) freezing, freeze-drying, corroding off the matrix, and graphitizing to obtain a vertically oriented graphene film; 5) and (5) pressing the film. The vertically-oriented graphene film layer obtained by the invention can effectively accelerate longitudinal heat conduction and has excellent heat conductivity; by adding the long-chain alkyl sulfonic acid into the electrochemical deposition solution, the surface energy of the graphene oxide is effectively reduced, the graphene can be vertically arranged, meanwhile, the deposition thickness of the film is controllable, the thermal conductivity is remarkably improved, and the large-scale production is easy to realize.
Description
Technical Field
The invention relates to a surface vertical orientation high-thermal conductivity graphene film, in particular to a preparation method of a high-thermal conductivity self-supporting vertical orientation graphene film.
Background
Graphene is used as a novel two-dimensional material, and the unique single graphite atomic layer structure endows the graphene with ultrahigh mechanical strength, excellent electrical conductivity and good chemical and thermodynamic stability, and is widely researched and applied in the fields of heat-conducting coatings, heat-conducting films and the like. The high-thermal-conductivity graphene is a novel thermal-conductivity and heat-dissipation material, can conduct heat in the transverse direction and the longitudinal direction, and has the characteristics of good thermal conductivity, low thermal resistance, light weight and the like. With the development of electronic equipment towards high power and high power consumption, heat dissipation becomes an urgent problem to be solved for electronic products, so that the research and preparation of the high-thermal-conductivity graphene film have important significance.
Due to van der waals force existing between sheet layers of graphene prepared by a traditional chemical method, stacking and agglomeration phenomena are easy to occur during film forming, so that the prepared graphene film has transverse thermal conductivity along graphene sheets and lacks longitudinal thermal conductivity, and meanwhile, the electrical conductivity is reduced, the specific surface area is reduced, and the application of the graphene film in the field of thermal conductivity is limited to a certain extent. For the problem of poor longitudinal thermal conductivity of the graphene film, the longitudinal thermal conductivity is realized by preparing vertically oriented graphene on the surface of a substrate by a Plasma Enhanced Chemical Vapor Deposition (PECVD) method at present, and the prepared film has uniform thickness and components, good film compactness, but high requirements on equipment and harsh preparation conditions. Therefore, the preparation method of the self-supporting vertically-oriented graphene film which is simple, convenient, efficient, low in cost, easy to produce and high in thermal conductivity has important practical significance.
Disclosure of Invention
Aiming at the problems of complex preparation process, high requirement on equipment, low production efficiency and the like of the existing vertical orientation graphene, the invention provides a preparation method of a high-thermal-conductivity self-supporting vertical orientation graphene film, and solves the problems of low production efficiency, insufficient thermal conductivity, high cost, difficulty in self-supporting and limitation on application and commercialization of the existing graphene thermal-conductivity film in the high-thermal-conductivity field to a certain extent.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-thermal-conductivity self-supporting vertically-oriented graphene film is characterized by comprising the following steps:
step 2, adding long-chain alkyl sulfonic acid, a modified single-walled carbon nanotube and a nonionic surfactant into the graphene oxide dispersion liquid obtained in the step 1, stirring and mixing uniformly, and performing ultrasonic treatment to obtain a mixed liquid serving as an electrodeposition liquid; wherein in the electrodeposition solution, the mass ratio of graphene oxide, long-chain hydrocarbon sulfonic acid, modified single-walled carbon nanotube and nonionic surfactant is 10: (2-10): (0.5-5): (0.1 to 0.5);
3, under the action of an external magnetic field, taking the mixed solution prepared in the step 2 as an electrodeposition solution, and depositing graphene oxide on the conductive substrate by adopting an electrochemical deposition method;
and 5, pressing the graphene film obtained in the step 4 to obtain the high-thermal-conductivity self-supporting vertically-oriented graphene film.
Further, in the graphene oxide dispersion liquid in the step 1, the concentration of the graphene oxide is 10-20 mg/mL.
Further, the preparation process of the graphene oxide dispersion liquid in the step 1 specifically comprises the following steps: preparing graphene oxide from graphite powder by a modified Hummers method; and adding the prepared graphene oxide into deionized water, and uniformly stirring and mixing to obtain a graphene oxide dispersion liquid with the concentration of 10-20 mg/mL.
Further, the long-chain alkyl sulfonic acid in the step 2 is a long-chain hydrocarbon substance containing a sulfonic acid group and has a general structural formula of R- (HSO3)n(ii) a Wherein R is a long-chain hydrocarbyl structure with the carbon atom number more than or equal to 10, and n is 1-3.
Further, the long-chain alkyl sulfonic acid in the step 2 is dodecyl sulfonic acid, dodecyl benzene sulfonic acid and the like.
Further, the modifier adopted by the modified single-walled carbon nanotube in the step 2 is Cetyl Trimethyl Ammonium (CTAB), wherein the mass ratio of the single-walled carbon nanotube to the cetyl trimethyl ammonium is 10: (0.5-5).
Further, the nonionic surfactant in step 2 is one of long-chain fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, specifically hexapolyethylene glycol monododecyl ether, dodecyl polyoxyethylene ether, and the like.
Further, magnetic stirring is adopted for stirring in the step 2, the rotating speed is 500-2000 rpm, and the stirring time is 12-24 hours.
Further, the power of the ultrasound in the step 2 is 100-500W, the ultrasound frequency is 40-50 Hz, and the time is 1-10 hours.
Further, the magnitude of the external magnetic field in the step 3 is 0.1-1T, and the direction is vertical to the electrode; during electrochemical deposition, the conductive matrix is copper foil which is used as a working electrode, the thickness of the conductive matrix is 10-20 mu m, the area of the conductive matrix is 5cm multiplied by 5cm, the platinum sheet is used as a counter electrode, the applied constant voltage is 3.0-5.0V, and the electrochemical deposition time is 1-3 hours.
Further, the matrix with the graphene oxide in the step 4 is placed in a low-temperature refrigerator to be rapidly frozen, the freezing temperature is-20 to-30 ℃, and the freezing time is 12 to 24 hours; and then freeze-drying in a freeze dryer at the temperature of between 50 ℃ below zero and 60 ℃ below zero for 24 to 36 hours.
Further, in the step 4, 0.1-1 mol/L of K is adopted2S2O8The solution corrodes the conductive substrate for 5-10 hours, so that the substrate is completely dissolved.
Further, the graphitization treatment in step 4 is as follows: firstly, raising the temperature from room temperature to 1000 ℃ at a temperature raising rate of 1-10 ℃/min, and preserving the temperature for 1-2 hours; and raising the temperature to 1000-3000 ℃, and preserving the heat for 1-2 hours.
Furthermore, the film pressing mode in the step 5 is isostatic pressing, the pressure is 200-400 MPa, and the time is 0.5-2 hours.
According to the preparation method of the high-thermal-conductivity self-supporting vertically-oriented graphene film, the adopted graphene oxide dispersion liquid contains a large number of hydroxyl groups and epoxy groups on the surface of a graphene oxide layer, and a large number of carboxyl groups, carbonyl groups and the like on the edge, the surface of GO in the dispersion liquid is in a negative charge state due to deprotonation of the carboxyl groups, and when an external electric field is added, the GO moves to an anode and is adsorbed on the surface of a conductive matrix; because the high-concentration GO has liquid crystal property and larger diamagnetism, under the action of an external magnetic field, the graphene sheet can respond and align the magnetic field like a ferromagnetic material, so that the oriented orientation of the graphene oxide sheet is realized; meanwhile, long-chain alkyl sulfonic acid can be adsorbed on the surface of graphene oxide through a sulfonic group, and the graphene oxide is vertically oriented by virtue of a rigid long chain; the single-walled carbon nanotube is used as a conductive enhancer to improve the structural stability and conductivity of the electrode; the nonionic surfactant serves to enhance the interaction between the nanosheets, increasing the symmetry of deposition of the graphene sheets.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a high-thermal-conductivity self-supporting vertically-oriented graphene film, which comprises the steps of firstly forming a vertically-oriented compact graphene oxide film layer on the surface of a copper foil by adopting an electrochemical deposition method, and then obtaining the independent self-supporting high-thermal-conductivity graphene film through the processes of etching, graphitization, isostatic pressing and the like; the obtained vertically-oriented graphene film layer can effectively accelerate longitudinal heat conduction and has excellent heat conductivity; by adding the long-chain alkyl sulfonic acid into the electrochemical deposition solution, the surface energy of the graphene oxide is effectively reduced, the graphene can be vertically arranged, meanwhile, the deposition thickness of the film is controllable, the thermal conductivity is remarkably improved, and the large-scale production is easy to realize. Therefore, the preparation method of the high-thermal-conductivity self-supporting vertically-oriented graphene film is simple, efficient, low in cost and environment-friendly.
Drawings
FIG. 1 is a schematic diagram of the deposition of a high thermal conductivity self-supporting vertically oriented graphene film according to the present invention;
fig. 2 is a digital photograph of the high thermal conductivity self-supporting vertically aligned graphene thin film obtained in example 4.
Description of reference numerals: 1. a copper foil substrate; 2. graphene oxide sheets; 3. a dodecylsulfonic acid molecule; 4. a platinum sheet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious 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.
Example 1
Preparing a Graphene Oxide (GO) dispersion liquid with the concentration of 10mg/mL by adopting an improved Hummers method: under the condition of ice bath (0-4 ℃), 1g of graphite powder and 1g of NaNO are mixed3Added to a beaker followed by 46mL of concentrated sulfuric acid H2SO4(not less than 98 wt%) for 10 min. Then 6g KMnO was slowly added4After stirring for 10 minutes, the ice bath was removed, and the mixed solution was stirred for 10 hours at 35 ℃ in an oil bath. Then slowly dropping 80mL of deionized water, heating to 80 deg.C for 30 min, adding 200mL of deionized water after heating, stirring, and adding 6mL of H2O2(30 wt%). And (3) respectively cleaning the mixed solution by using HCl (5 wt%) and deionized water, and centrifuging (6000r/min) until the pH value is 3-4 to obtain the GO dispersion liquid.
Preparing modified single-walled carbon nanotubes: firstly preparing 50mL of CTAB aqueous solution with the mass fraction of 0.1 wt%, adding 1g of single-walled carbon nanotube into the aqueous solution, carrying out ultrasonic treatment for 1 hour under the power of 200W, then centrifuging the aqueous solution for 10 minutes at the rotating speed of 8000r/min, collecting bottom slurry, washing the bottom slurry for 5 times by using deionized water and absolute ethyl alcohol respectively, and finally drying the bottom slurry in an oven at the temperature of 50 ℃ for 12 hours.
Taking 5mL of GO dispersion prepared by the method, adding 10mg of dodecyl sulfonic acid, 2.5mg of modified single-walled carbon nanotube and 0.5mg of hexa-polyethylene glycol monododecyl ether into the GO dispersion, and magnetically stirring the mixture for 12 hours at the rotating speed of 1000 rpm; then the mixture is fully and uniformly mixed by ultrasound (power is 200W, ultrasonic frequency is 40Hz) for 5 hours to be used as the electrodeposition solution. A0.1T magnetic field was applied to both ends of the vertical electrode, a copper foil (10 μm thick) was used as a working electrode, a platinum sheet was used as a counter electrode, and the electrodes were electrochemically treatedThe chemical workstation applied a constant voltage of 3.0V for 1 hour. Then placing the copper foil loaded with the vertical graphene oxide in a low-temperature refrigerator at-20 ℃ for freezing for 12 hours, then placing the copper foil in a refrigerator at-55 ℃ for freeze drying for 24 hours, and then placing the copper foil in K of 0.1mol/L2S2O8Etching the copper foil in the solution for 10 hours, finally heating to 1000 ℃ at the speed of 1 ℃/min, keeping for 1 hour, heating to 3000 ℃ again, keeping for 1 hour, cooling to room temperature, and carrying out isostatic pressing treatment at 200MPa for 1 hour to obtain the self-supporting vertically oriented graphene film with high thermal conductivity.
Example 2
Preparing GO dispersion liquid with the concentration of 15mg/mL by adopting the improved Hummers method in the embodiment 1, taking 4mL of GO solution, adding 12mg of dodecyl sulfonic acid, 3mg of the modified single-walled carbon nanotube prepared in the embodiment 1 and 0.6mg of hexa-polyethylene glycol monododecyl ether into the GO solution, and magnetically stirring the mixture for 24 hours at the rotating speed of 1000 rpm; then the mixture is fully and uniformly mixed by ultrasound (power is 200W, ultrasonic frequency is 50Hz) for 5 hours to be used as the electrodeposition solution. A0.2T magnetic field was applied across the vertical electrodes, a copper foil (15 μm thick) was used as a working electrode, a platinum sheet was used as a counter electrode, and a constant voltage of 3.0V was applied for 2 hours via an electrochemical workstation. Then placing the copper foil loaded with the vertical graphene oxide in a low-temperature refrigerator at-20 ℃ for freezing for 12 hours, then placing the copper foil in a refrigerator at-55 ℃ for freeze drying for 24 hours, and then placing the copper foil in K of 0.5mol/L2S2O8And etching the copper foil in the solution for 8 hours, finally heating to 1000 ℃ at the speed of 1 ℃/min, keeping for 2 hours, heating to 3000 ℃ again, keeping for 1 hour, cooling to room temperature, and carrying out isostatic pressing treatment at 250MPa for 0.5 hour to obtain the self-supporting vertically-oriented graphene film with high thermal conductivity.
Example 3
Preparing GO dispersion liquid with the concentration of 20mg/mL by adopting the improved Hummers method in the embodiment 1, taking 2.5mL of GO solution, adding 50mg of dodecyl sulfonic acid, 12.5mg of the modified single-walled carbon nanotube prepared in the embodiment 1 and 1.25mg of dodecyl polyoxyethylene ether into the GO solution, and magnetically stirring the mixture for 12 hours at the rotating speed of 2000 rpm; then the mixture is fully and uniformly mixed by ultrasound (power is 200W, ultrasonic frequency is 50Hz) for 5 hours to be used as the electrodeposition solution. A 0.4T magnetic field was applied to both ends of the vertical electrode, and a copper foil (thickness: 15 μm) was used as a working electrode and a platinum sheetAs a counter electrode, a constant voltage of 4.0V was applied for 2 hours through an electrochemical workstation. Then placing the copper foil loaded with the vertical graphene oxide in a low-temperature refrigerator at-25 ℃ for freezing for 12 hours, then placing the copper foil in a refrigerator at-55 ℃ for freeze drying for 24 hours, and then placing the copper foil in K of 1mol/L2S2O8Etching the copper foil in the solution for 5 hours, finally heating to 1000 ℃ at a speed of 2 ℃/min, keeping for 1 hour, heating to 3000 ℃ again, keeping for 2 hours, cooling to room temperature, and carrying out isostatic pressing treatment at 300MPa for 1 hour to obtain the self-supporting vertically oriented graphene film with high thermal conductivity.
Example 4
Preparing a GO dispersion solution with the concentration of 20mg/mL by adopting the improved Hummers method in the embodiment 1, taking 5mL of GO solution, adding 100mg of dodecyl sulfonic acid, 50mg of the modified single-walled carbon nanotube prepared in the embodiment 1 and 5mg of dodecyl polyoxyethylene ether into the GO solution, and magnetically stirring the mixture for 24 hours at the rotating speed of 2000 rpm; then the mixture is fully and uniformly mixed by ultrasound (the power is 400W, the ultrasonic frequency is 50Hz) for 10 hours to be used as the electrodeposition solution. A0.8T magnetic field was applied across the vertical electrodes, a copper foil (20 μm thick) was used as a working electrode, a platinum sheet was used as a counter electrode, and a constant voltage of 5.0V was applied for 2 hours via an electrochemical workstation. Then placing the copper foil loaded with the vertical graphene oxide in a low-temperature refrigerator at-30 ℃ for freezing for 12 hours, then placing the copper foil in a refrigerator at-55 ℃ for freeze drying for 24 hours, and then placing the copper foil in K of 1mol/L2S2O8Etching the copper foil in the solution for 5 hours, finally heating to 1000 ℃ at a speed of 2 ℃/min, keeping for 1 hour, heating to 3000 ℃ again, keeping for 2 hours, cooling to room temperature, and carrying out isostatic pressing treatment at 400MPa for 2 hours to obtain the self-supporting vertically oriented graphene film with high thermal conductivity.
The thermal conductivity of the graphene films prepared in examples 1 to 4 is shown in table 1:
TABLE 1
| Name (R) | Density (g/cm)3) | Test temperature | Longitudinal coefficient of thermal conductivity (W/mK) |
| Example 1 | 0.910 | At room temperature | 2.214 |
| Example 2 | 1.293 | At room temperature | 3.291 |
| Example 3 | 1.831 | At room temperature | 4.887 |
| Example 4 | 2.065 | At room temperature | 5.729 |
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a high-thermal-conductivity self-supporting vertically-oriented graphene film is characterized by comprising the following steps:
step 1, preparing a graphene oxide dispersion liquid;
step 2, adding long-chain alkyl sulfonic acid, a modified single-walled carbon nanotube and a nonionic surfactant into the graphene oxide dispersion liquid obtained in the step 1, stirring and performing ultrasonic treatment to obtain a mixed liquid serving as an electrodeposition liquid; wherein in the electrodeposition solution, the mass ratio of graphene oxide, long-chain hydrocarbon sulfonic acid, modified single-walled carbon nanotube and nonionic surfactant is 10: (2-10): (0.5-5): (0.1 to 0.5);
3, under the action of an external magnetic field, taking the mixed solution prepared in the step 2 as an electrodeposition solution, and depositing graphene oxide on the conductive substrate by adopting an electrochemical deposition method;
step 4, freezing and freeze-drying the matrix with the oxidized graphene obtained in the step 3, then corroding the matrix, and then carrying out graphitization treatment to obtain a vertically-oriented graphene film;
and 5, pressing the graphene film obtained in the step 4 to obtain the high-thermal-conductivity self-supporting vertically-oriented graphene film.
2. The method for preparing a highly thermally conductive self-supporting vertically oriented graphene film according to claim 1, wherein in the graphene oxide dispersion liquid in the step 1, the concentration of the graphene oxide is 10-20 mg/mL.
3. According toThe method for preparing a highly thermally conductive self-supporting vertically oriented graphene film according to claim 1, wherein the long-chain alkyl sulfonic acid in step 2 is a long-chain hydrocarbon substance containing sulfonic acid groups and having a general structural formula of R- (HSO)3)n(ii) a Wherein R is a long-chain hydrocarbyl structure with the carbon atom number more than or equal to 10, and n is 1-3.
4. The method for preparing a high thermal conductivity self-supporting vertically oriented graphene film according to claim 1, wherein the long-chain alkyl sulfonic acid in step 2 is dodecyl sulfonic acid or dodecyl benzene sulfonic acid.
5. The method for preparing the high-thermal-conductivity self-supporting vertically-aligned graphene film according to claim 1, wherein the modifier used in the modified single-walled carbon nanotubes in the step 2 is cetyltrimethylammonium, and the mass ratio of the single-walled carbon nanotubes to the cetyltrimethylammonium is 10: (0.5-5).
6. The method for preparing a high thermal conductivity self-supporting vertically oriented graphene film according to claim 1, wherein the nonionic surfactant in step 2 is one of long-chain fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, specifically hexapolyethylene glycol monododecyl ether or dodecyl polyoxyethylene ether.
7. The preparation method of the high-thermal-conductivity self-supporting vertically-oriented graphene film according to claim 1, wherein the magnitude of the external magnetic field in the step 3 is 0.1-1T, and the direction is perpendicular to the electrodes; in the electrochemical deposition, the applied constant voltage is 3.0-5.0V, and the electrochemical deposition time is 1-3 hours.
8. The preparation method of the high-thermal-conductivity self-supporting vertically-oriented graphene film according to claim 1, wherein the substrate with the graphene oxide in the step 4 is placed in a low-temperature refrigerator for quick freezing at the temperature of-20 to-30 ℃ for 12 to 24 hours; and then freeze-drying in a freeze dryer at the temperature of between 50 ℃ below zero and 60 ℃ below zero for 24 to 36 hours.
9. The method for preparing the high thermal conductivity self-supporting vertically oriented graphene film according to claim 1, wherein the graphitization treatment in the step 4 is as follows: firstly, raising the temperature to 1000 ℃ at a temperature rise rate of 1-10 ℃/min, and preserving the temperature for 1-2 hours; and raising the temperature to 1000-3000 ℃, and preserving the heat for 1-2 hours.
10. The method for preparing the high thermal conductivity self-supporting vertically oriented graphene film according to claim 1, wherein the film pressing in the step 5 is performed by isostatic pressing, the pressure is 200-400 MPa, and the time is 0.5-2 hours.
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| CN114717624A (en) * | 2022-04-08 | 2022-07-08 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
| CN115010494A (en) * | 2022-06-01 | 2022-09-06 | 星途(常州)碳材料有限责任公司 | Preparation method of graphene heat conducting sheet for reinforcing longitudinal heat flux transmission |
| CN115709988A (en) * | 2022-11-30 | 2023-02-24 | 广东墨睿科技有限公司 | Graphene superconducting film and preparation method thereof |
| CN115818633A (en) * | 2022-12-29 | 2023-03-21 | 常州富烯科技股份有限公司 | Oriented graphene oxide film and preparation method thereof |
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| CN114717624A (en) * | 2022-04-08 | 2022-07-08 | 广东工业大学 | Vertically oriented graphene and preparation method and application thereof |
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| CN115010494B (en) * | 2022-06-01 | 2023-01-24 | 星途(常州)碳材料有限责任公司 | Preparation method of graphene heat conducting sheet for strengthening longitudinal heat flux transmission |
| CN115709988A (en) * | 2022-11-30 | 2023-02-24 | 广东墨睿科技有限公司 | Graphene superconducting film and preparation method thereof |
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