CN111907096A - Preparation method of graphene heat-conducting film - Google Patents
Preparation method of graphene heat-conducting film Download PDFInfo
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- CN111907096A CN111907096A CN202010667248.9A CN202010667248A CN111907096A CN 111907096 A CN111907096 A CN 111907096A CN 202010667248 A CN202010667248 A CN 202010667248A CN 111907096 A CN111907096 A CN 111907096A
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- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
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Abstract
The invention relates to a preparation method of a graphene heat-conducting film. According to the graphene oxide, a large number of functional groups exist on the surface, and the graphene oxide can be completely and uniformly dispersed in water; according to the invention, the graphene heat-conducting film with stable quality, excellent heat dissipation effect and high flexibility is prepared by self-assembly of nano molecules after graphene oxide is dissolved, high-temperature carbonization, graphitization and calendaring treatment, so that gaps among graphene film layers are reduced, the heat conductivity is effectively improved. The graphene heat-conducting film can be prepared through simple process steps, and is low in cost, controllable in thickness, simple to operate, high in production efficiency and suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of heat conduction materials, in particular to a preparation method of a graphene heat conduction film.
Background
With the rapid development of microelectronic integration and assembly technology and the integrated use of high power density devices, the heat generation amount and the dissipation power density become larger and larger, which seriously affects the stability and the service life of electronic components, so that the heat dissipation problem becomes extremely important. The traditional heat conduction material mainly takes a metal thin film, a graphite rolling film, a graphitized polyimide film and the like as main materials. The metal film has the defects of heavy mass, easy corrosion, low heat conductivity and the like, and the graphite calendered film and the graphitized polyimide film are brittle and easy to fall off powder in the use process, so that the metal film is not suitable for the field of precise instrument management with complex structure and high cleanliness requirement. On the other hand, the traditional graphitized polyimide film is usually produced by batch operation, and a large amount of time (at least 6-10 h of heating time and at least 10h of cooling time) and energy (at least 50-70 KW/h of energy consumption of an experimental furnace) are consumed in the graphitizing process.
The graphene heat conduction film is a novel heat conduction and dissipation material, has high in-plane heat conductivity, can reach 4800W/k.m-5300W/k.m in single-layer in-plane heat conductivity, has excellent characteristics of low density, low thermal expansion coefficient, good mechanical property and the like, and becomes the focus of new heat dissipation materials. Therefore, a preparation method of the graphene heat conduction film is provided.
Disclosure of Invention
The invention aims to provide a preparation scheme of a graphene heat-conducting film, which is simple in process flow, low in energy consumption and low in cost, aiming at one or more of the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a graphene heat conduction film comprises the following steps:
firstly, preparing the graphene oxide powder serving as a precursor from the expanded graphite by adopting an improved Hummers method. Dissolving the prepared graphene oxide powder in water, and performing ultrasonic treatment to disperse the graphene oxide powder uniformly to obtain uniform and stable graphene oxide dispersion liquid, wherein the ultrasonic time is 1 h;
secondly, placing the silica-based ground into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, heating in a water bath, washing with a large amount of deionized water, and placing into a vacuum drying oven for drying for later use;
thirdly, dripping the PEI aqueous solution on the silicon substrate for soaking for 1min, spin-coating the silicon substrate for 1min at the speed of 800r/min by using a spin coater to ensure that the solution is uniformly dispersed, then spin-coating the silicon substrate for 1min at the speed of 1000r/min to ensure that the formed film is thinned, and finally spin-coating the silicon substrate for 1min at the speed of 2000r/min to ensure that the film is dried;
fourthly, placing the silicon substrate obtained in the third step into a glass container with a flat and smooth bottom, slowly dripping the graphene oxide dispersion liquid into the glass container, and ensuring that the solution completely immerses the silicon substrate;
fifthly, placing the glass container obtained in the fourth step into a constant-temperature water bath kettle, and forming a flat GO thin film on a silicon substrate by utilizing a gas-liquid interface self-assembly process;
sixthly, drying the GO thin film prepared by the fifth step in a vacuum drying oven for 2 hours to obtain a dried GO thin film, wherein the drying temperature is 80 ℃;
seventhly, taking down the dried GO film, putting the dried GO film into a tubular furnace, performing carbonization treatment, and naturally cooling;
placing the obtained reduced graphene oxide (rGO) film into a graphitization furnace, performing graphitization atom recombination treatment, and naturally cooling to room temperature to obtain a semi-finished graphene heat-conducting film.
Ninthly, obtaining the graphene heat-conducting film after the semi-finished product of the graphene heat-conducting film is subjected to delay.
Preferably, the concentration of the graphene oxide solution is 0.1% to 3%, and more preferably 1.5%.
Preferably, the volume ratio of the mixed solution of the biological concentrated sulfuric acid and the hydrogen peroxide is 2: 1-4: 1, more preferably 7: 3; the temperature of the water bath is 60-100 ℃, the further optimization is 80 ℃, and the time is 20-50 min, the further optimization is 35 min.
Preferably, the concentration of the PEI aqueous solution is 0.05 mol/L.
Preferably, the temperature of the water bath is 60-100 ℃, and further preferably 80 ℃; the water bath time is 15-60 min, and preferably 40 min.
Preferably, in the carbonization process, the temperature is firstly increased to 200 ℃, the temperature is kept for 20-40 min, further preferably 30min, the temperature is continuously increased to 400 ℃, the temperature is kept for 20-40 min, further preferably 30min, the temperature is continuously increased to 800-1200 ℃, the temperature is kept for 20-40 min, further preferably 1000 ℃, the temperature is kept for 30min, and the temperature increase rate is 5 ℃/min.
Preferably, the graphitization temperature is 2800-3200 ℃, further preferably 3000 ℃, and the heat preservation time is 6-10 hours, further preferably 7 hours.
Preferably, the calendering pressure is 2 to 4 tons, further preferably 3 tons.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the mechanical stripping of graphene, the graphene oxide has the advantages that the graphene oxide is large in sheet diameter and high in single-layer rate, tiny air bags are generated during high-temperature reduction, mechanical performance is good after rolling, graphene is of a six-membered alkene ring structure, energy required by atomic rearrangement repair is less compared with the polyimide graphitization process, and energy consumption is saved.
2. Compared with tape casting coating, the gas-liquid interface nano material self-assembly process is adopted, and the graphene layer with ordered layers can be stacked inside the graphene film, so that the in-plane thermal conductivity can be obviously improved; compared with the pumping filtration method which consumes long time and can not be industrially produced, the self-assembly of the gas-liquid interface nano material has short time and simple process, and can be industrially produced.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention provides a technical scheme that: a preparation method of a graphene heat conduction film comprises the following steps:
example 1
Firstly, preparing the graphene oxide powder serving as a precursor from the expanded graphite by adopting an improved Hummers method. Dissolving the prepared graphene oxide powder in water, and performing ultrasonic treatment to disperse the graphene oxide powder uniformly to obtain a uniform and stable graphene oxide dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid is 1.5%, and the ultrasonic time is 1 h;
secondly, placing the silicon substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, wherein the volume ratio is 7: 3, after heating in water bath at 80 ℃ for 30min, washing with a large amount of deionized water, and drying in a vacuum drying oven for later use;
thirdly, dripping 0.05mol/L PEI aqueous solution on the silicon substrate for soaking for 1min, spin-coating the silicon substrate for 1min at the speed of 800r/min by using a spin coater to ensure that the solution is uniformly dispersed, then spin-coating the silicon substrate for 1min at the speed of 1000r/min to ensure that the formed film is thinned, and finally spin-coating the silicon substrate for 1min at the speed of 2000r/min to ensure that the film is dried;
fourthly, placing the silicon substrate obtained in the third step into a glass container with a flat and smooth bottom, slowly dripping the graphene oxide dispersion liquid into the glass container, and ensuring that the solution completely immerses the silicon substrate;
fifthly, placing the glass container obtained in the fourth step into a constant-temperature water bath kettle at the temperature of 80 ℃, performing water bath for 40min, and forming a flat GO thin film on a silicon substrate by utilizing a gas-liquid interface self-assembly process;
sixthly, drying the GO thin film prepared by the fifth step in a vacuum drying oven for 2 hours to obtain a dried GO thin film, wherein the drying temperature is 80 ℃;
seventhly, taking down the dried GO film, putting the dried GO film into a tubular furnace, carrying out carbonization treatment, heating to 200 ℃, keeping the temperature for 30min, continuing to heat to 400 ℃, keeping the temperature for 30min, finally heating to 1000 ℃, keeping the temperature for 30min, wherein the heating rate is 5 ℃/min, and then naturally cooling;
placing the obtained reduced graphene oxide (rGO) film into a graphitization furnace, carrying out graphitization atom recombination treatment, heating to 3000 ℃, keeping the temperature at the heating rate of 5 ℃/min for 7h, and finally naturally cooling to room temperature to obtain the semi-finished product of the graphene heat-conducting film.
And ninthly, calendering the semi-finished product of the graphene heat-conducting film by 3 tons of pressure to obtain the graphene heat-conducting film.
Example 2
Firstly, preparing the graphene oxide powder serving as a precursor from the expanded graphite by adopting an improved Hummers method. Dissolving the prepared graphene oxide powder in water, and performing ultrasonic treatment to disperse the graphene oxide powder uniformly to obtain a uniform and stable graphene oxide dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid is 1.0%, and the ultrasonic time is 1 h;
secondly, placing the silicon substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, wherein the volume ratio is 7: 3, after heating in water bath at 80 ℃ for 30min, washing with a large amount of deionized water, and drying in a vacuum drying oven for later use;
thirdly, dripping 0.05mol/L PEI aqueous solution on the silicon substrate for soaking for 1min, spin-coating the silicon substrate for 1min at the speed of 800r/min by using a spin coater to ensure that the solution is uniformly dispersed, then spin-coating the silicon substrate for 1min at the speed of 1000r/min to ensure that the formed film is thinned, and finally spin-coating the silicon substrate for 1min at the speed of 2000r/min to ensure that the film is dried;
fourthly, placing the silicon substrate obtained in the third step into a glass container with a flat and smooth bottom, slowly dripping the graphene oxide dispersion liquid into the glass container, and ensuring that the solution completely immerses the silicon substrate;
fifthly, placing the glass container obtained in the fourth step into a constant-temperature water bath kettle at 70 ℃, performing water bath for 20min, and forming a flat GO thin film on a silicon substrate by utilizing a gas-liquid interface self-assembly process;
sixthly, drying the GO thin film prepared by the fifth step in a vacuum drying oven for 2 hours to obtain a dried GO thin film, wherein the drying temperature is 80 ℃;
seventhly, taking down the dried GO film, putting the dried GO film into a tubular furnace, carrying out carbonization treatment, heating to 200 ℃, keeping the temperature for 20min, continuing to heat to 400 ℃, keeping the temperature for 20min, finally heating to 1000 ℃, keeping the temperature for 20min, wherein the heating rate is 5 ℃/min, and then naturally cooling;
placing the obtained reduced graphene oxide (rGO) film into a graphitization furnace, carrying out graphitization atom recombination treatment, heating to 2800 ℃, keeping the temperature for 6 hours at the heating rate of 5 ℃/min, and finally naturally cooling to room temperature to obtain the semi-finished product of the graphene heat-conducting film.
And ninthly, calendering the semi-finished product of the graphene heat-conducting film by 3 tons of pressure to obtain the graphene heat-conducting film.
Example 3
Firstly, preparing the graphene oxide powder serving as a precursor from the expanded graphite by adopting an improved Hummers method. Dissolving the prepared graphene oxide powder in water, and performing ultrasonic treatment to disperse the graphene oxide powder uniformly to obtain a uniform and stable graphene oxide dispersion liquid, wherein the concentration of the graphene oxide dispersion liquid is 3.0%, and the ultrasonic time is 1 h;
secondly, placing the silicon substrate in a mixed solution of concentrated sulfuric acid and hydrogen peroxide, wherein the volume ratio is 7: 3, after heating in water bath at 80 ℃ for 30min, washing with a large amount of deionized water, and drying in a vacuum drying oven for later use;
thirdly, dripping 0.05mol/L PEI aqueous solution on the silicon substrate for soaking for 1min, spin-coating the silicon substrate for 1min at the speed of 800r/min by using a spin coater to ensure that the solution is uniformly dispersed, then spin-coating the silicon substrate for 1min at the speed of 1000r/min to ensure that the formed film is thinned, and finally spin-coating the silicon substrate for 1min at the speed of 2000r/min to ensure that the film is dried;
fourthly, placing the silicon substrate obtained in the third step into a glass container with a flat and smooth bottom, slowly dripping the graphene oxide dispersion liquid into the glass container, and ensuring that the solution completely immerses the silicon substrate;
fifthly, placing the glass container obtained in the fourth step into a constant-temperature water bath kettle at 100 ℃, performing water bath for 60min, and forming a flat GO thin film on a silicon substrate by utilizing a gas-liquid interface self-assembly process;
sixthly, drying the GO thin film prepared by the fifth step in a vacuum drying oven for 2 hours to obtain a dried GO thin film, wherein the drying temperature is 80 ℃;
seventhly, taking down the dried GO film, putting the dried GO film into a tubular furnace, carrying out carbonization treatment, heating to 200 ℃, keeping the temperature for 40min, continuing to heat to 400 ℃, keeping the temperature for 40min, finally heating to 1200 ℃, keeping the temperature for 30min, wherein the heating rate is 5 ℃/min, and then naturally cooling;
placing the obtained reduced graphene oxide (rGO) film into a graphitization furnace, carrying out graphitization atom recombination treatment, heating to 3000 ℃, keeping the temperature at the heating rate of 5 ℃/min for 10h, and finally naturally cooling to room temperature to obtain the semi-finished product of the graphene heat-conducting film.
And ninthly, calendering the semi-finished product of the graphene heat-conducting film by 4 tons of pressure to obtain the graphene heat-conducting film.
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 (8)
1. A preparation method of a graphene heat conduction film is characterized by comprising the following steps:
firstly, preparing the graphene oxide powder serving as a precursor from the expanded graphite by adopting an improved Hummers method. Dissolving the prepared graphene oxide powder in water, and performing ultrasonic treatment to disperse the graphene oxide powder uniformly to obtain uniform and stable graphene oxide dispersion liquid, wherein the ultrasonic time is 1 h;
secondly, placing the silica-based ground into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, heating in a water bath, washing with a large amount of deionized water, and placing into a vacuum drying oven for drying for later use;
thirdly, dripping the PEI aqueous solution on the silicon substrate for soaking for 1min, spin-coating the silicon substrate for 1min at the speed of 800r/min by using a spin coater to ensure that the solution is uniformly dispersed, then spin-coating the silicon substrate for 1min at the speed of 1000r/min to ensure that the formed film is thinned, and finally spin-coating the silicon substrate for 1min at the speed of 2000r/min to ensure that the film is dried;
fourthly, placing the silicon substrate obtained in the third step into a glass container with a flat and smooth bottom, slowly dripping the graphene oxide dispersion liquid into the glass container, and ensuring that the solution completely immerses the silicon substrate;
fifthly, placing the glass container obtained in the fourth step into a constant-temperature water bath kettle, and forming a flat GO thin film on a silicon substrate by utilizing a gas-liquid interface self-assembly process;
sixthly, drying the GO thin film prepared by the fifth step in a vacuum drying oven for 2 hours to obtain a dried GO thin film, wherein the drying temperature is 80 ℃;
seventhly, taking down the dried GO film, putting the dried GO film into a tubular furnace, performing carbonization treatment, and naturally cooling;
placing the obtained reduced graphene oxide (rGO) film into a graphitization furnace, performing graphitization atom recombination treatment, and naturally cooling to room temperature to obtain a semi-finished graphene heat-conducting film.
Ninthly, obtaining the graphene heat-conducting film after the semi-finished product of the graphene heat-conducting film is subjected to delay.
2. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the concentration of the graphene oxide solution is 0.1% -3%.
3. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the volume ratio of the biological concentrated sulfuric acid to the hydrogen peroxide mixed solution is 2: 1-4: 1; the temperature of the water bath is 60-100 ℃, preferably 80 ℃, and the time is 20-50 min.
4. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the concentration of the PEI aqueous solution is 0.05 mol/L.
5. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the temperature of the water bath is 60-100 ℃; the water bath time is 15-60 min.
6. The method for preparing a graphene thermal conductive film according to claim 1, wherein: in the carbonization process, the temperature is firstly increased to 200 ℃, the temperature is kept for 20-40 min, the temperature is continuously increased to 400 ℃, the temperature is kept for 20-40 min, the temperature is continuously increased to 800-1200 ℃, the temperature is kept for 20-40 min, and the temperature increase rate is 5 ℃/min.
7. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the graphitization temperature is 2800-3200 ℃, and the heat preservation is carried out for 6-10 h.
8. The method for preparing a graphene thermal conductive film according to claim 1, wherein: the calendering pressure is 2 to 4 tons.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277503A (en) * | 2021-05-28 | 2021-08-20 | 常州第六元素材料科技股份有限公司 | Preparation method of reduced graphene oxide and graphene heat-conducting film |
| WO2023011646A1 (en) * | 2021-08-06 | 2023-02-09 | 深圳市深瑞墨烯科技有限公司 | Graphene film and preparation method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109318564A (en) * | 2018-09-10 | 2019-02-12 | 成都紫苑华光新材料科技有限公司 | A kind of method that the spraying of self assembly ultrasound prepares graphene heat conducting film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277503A (en) * | 2021-05-28 | 2021-08-20 | 常州第六元素材料科技股份有限公司 | Preparation method of reduced graphene oxide and graphene heat-conducting film |
| WO2023011646A1 (en) * | 2021-08-06 | 2023-02-09 | 深圳市深瑞墨烯科技有限公司 | Graphene film and preparation method therefor |
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