CN113321207A - Method for preparing high-thermal-conductivity graphene film by using metal catalyst - Google Patents
Method for preparing high-thermal-conductivity graphene film by using metal catalyst Download PDFInfo
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- CN113321207A CN113321207A CN202110709022.5A CN202110709022A CN113321207A CN 113321207 A CN113321207 A CN 113321207A CN 202110709022 A CN202110709022 A CN 202110709022A CN 113321207 A CN113321207 A CN 113321207A
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- film
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- graphene oxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000002356 single layer Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000005087 graphitization Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 6
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910021654 trace metal Inorganic materials 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 32
- 239000000725 suspension Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A method for preparing a high-thermal-conductivity graphene film by using a metal catalyst belongs to the technical field of graphene materials, can solve the problem of complex conditions of the existing preparation of the high-thermal-conductivity graphene film, and comprises the following steps: firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode; secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process; and thirdly, placing the film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high heat conductivity coefficient. The invention achieves higher heat conductivity coefficient under the condition of 2800 ℃ lower than the traditional graphitization temperature by low-temperature induced graphitization of a trace metal catalyst.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a method for preparing a high-thermal-conductivity graphene film by using a metal catalyst.
Background
The graphene is formed by a monolayer of carbon atoms passing through sp2The two-dimensional honeycomb crystal structure formed by hybridization, close packing and the like has extremely high thermal conductivity and excellent electrical property and mechanical property, is regarded as one of ideal novel heat conduction materials, and the preparation method of the graphene can be summarized into three categories, namely a mechanical stripping method, a vapor deposition method and a graphite oxidation-reduction method. The redox method is considered to be a very effective method for synthesizing graphene due to its simple and reliable process. The method comprises the steps of oxidizing natural graphite by an improved Hummers method, ultrasonically stripping to obtain uniformly dispersed graphene oxide colloidal suspension, applying directional acting force to the graphene colloidal suspension to obtain a graphene oxide film with high orientation degree, casting the graphene oxide colloidal suspension in a solution to coat the surface of a device with a local complex structure with a highly oriented graphene oxide film, and removing oxygen-containing functional groups on the graphene oxide by heat treatment to obtain the graphene film with high heat conductivity.
The graphene film of macroscopically assembled graphene oxide or graphene nanosheets is the main application form of nanoscale graphene, and common preparation methods are a suction filtration method, a scraping method, a spin-coating method, a spraying method, a dip-coating method and the like. Through further high-temperature treatment, the defects of graphene can be repaired, the conductivity and the thermal conductivity of the graphene film can be effectively improved, and the graphene film can be widely applied to high-heat-dissipation-demand portable electronic equipment such as smart phones, intelligent random hardware, tablet computers and notebook computers.
The graphitization treatment can repair the defects of the graphene material, so that the electric conduction and heat conduction performance of the graphene material is greatly improved, however, the graphitization treatment is strict in requirement and often requires high-temperature treatment above 2500 ℃.
Application number 2017109534972 discloses a method for catalyzing graphitization and a method for preparing a super-flexible high-thermal-conductivity graphene film, and discloses a method for catalyzing graphitization and a method for preparing a high-thermal-conductivity graphene film by using the method.
Disclosure of Invention
The invention aims to provide a method for preparing a high-thermal-conductivity graphene film by using metal catalysis, which achieves a higher thermal conductivity coefficient at a temperature lower than the traditional graphitization temperature of 2800 ℃.
The invention adopts the following technical scheme:
a method for preparing a high-thermal-conductivity graphene film by using a metal catalyst comprises the following steps:
firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode;
secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process;
and thirdly, placing the film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high heat conductivity coefficient.
Further, in the first step, the stirring speed is 1000-10000 r/min, and the stirring time is 1-10 h.
Further, in the second step, the metal salt comprises any one of iron acetate, cobalt acetate and ferric chloride, and the adding amount of the metal salt is 0.1-1% of the mass of the single-layer graphene oxide.
Further, the thickness of the thin film in the second step is 20 to 200 μm.
Further, in the third step, the heating temperature is 1500-2500 ℃, and the heating time is 30-100 min.
The invention has the following beneficial effects:
the invention achieves higher heat conductivity coefficient under the condition of 2800 ℃ lower than the traditional graphitization temperature by low-temperature induced graphitization of a trace metal catalyst.
Detailed Description
Example 1
A method for preparing a high-thermal-conductivity graphene film by using a metal catalyst comprises the following steps:
firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode, wherein the stirring speed is 1000 revolutions per minute;
secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process, wherein the metal salt is ferric acetate, the addition amount of the metal salt is 0.1% of the mass of the single-layer graphene oxide, and the thickness of the film is 30 microns;
and thirdly, placing the film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high thermal conductivity coefficient, wherein the heating temperature is 1500 ℃, and the heating time is 30 min.
The graphene film prepared by the method has a thermal conductivity coefficient of 1360 (W/(m.K).
Example 2
A method for preparing a high-thermal-conductivity graphene film by using a metal catalyst comprises the following steps:
firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode, wherein the stirring speed is 3000 r/min;
secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process, wherein the metal salt is ferric acetate, the addition amount of the metal salt is 0.1% of the mass of the single-layer graphene oxide, and the thickness of the film is 150 microns;
and thirdly, placing the thin film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high thermal conductivity coefficient, wherein the heating temperature is 2000 ℃, and the heating time is 60 min.
The graphene film prepared by the method has the thermal conductivity of 1450 (W/(m.K).
Example 3
A method for preparing a high-thermal-conductivity graphene film by using a metal catalyst comprises the following steps:
firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode, wherein the stirring speed is 10000 revolutions per minute;
secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process, wherein the metal salt is nickel acetate, the addition amount of the metal salt is 10% of the mass of the single-layer graphene oxide, and the thickness of the film is 200 microns;
and thirdly, placing the film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high thermal conductivity coefficient, wherein the heating temperature is 2500 ℃, and the heating time is 100 min.
The graphene film prepared by the method has a thermal conductivity coefficient of 1935 (W/(m.K).
Claims (5)
1. A method for preparing a high-thermal-conductivity graphene film by using a metal catalyst is characterized by comprising the following steps: the method comprises the following steps:
firstly, dispersing graphene oxide to single-layer graphene oxide in a stirring mode;
secondly, adding metal salt serving as a catalyst into the single-layer graphene oxide, and preparing a film through a coating process;
and thirdly, placing the film obtained in the second step into a graphitization furnace, and heating to obtain the graphene film with high heat conductivity coefficient.
2. The method for preparing the graphene film with high thermal conductivity by using the metal catalyst according to claim 1, wherein the metal catalyst comprises: in the first step, the stirring speed is 1000-.
3. The method for preparing the graphene film with high thermal conductivity by using the metal catalyst according to claim 1, wherein the metal catalyst comprises: in the second step, the metal salt comprises any one of ferric acetate, cobalt acetate and ferric chloride, and the adding amount of the metal salt is 0.1-1% of the mass of the single-layer graphene oxide.
4. The method for preparing the graphene film with high thermal conductivity by using the metal catalyst according to claim 1, wherein the metal catalyst comprises: the thickness of the film in the second step is 20-200 microns.
5. The method for preparing the graphene film with high thermal conductivity by using the metal catalyst according to claim 1, wherein the metal catalyst comprises: in the third step, the heating temperature is 1500-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110709022.5A CN113321207A (en) | 2021-06-25 | 2021-06-25 | Method for preparing high-thermal-conductivity graphene film by using metal catalyst |
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| CN202110709022.5A CN113321207A (en) | 2021-06-25 | 2021-06-25 | Method for preparing high-thermal-conductivity graphene film by using metal catalyst |
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| CN113321207A true CN113321207A (en) | 2021-08-31 |
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| CN202110709022.5A Pending CN113321207A (en) | 2021-06-25 | 2021-06-25 | Method for preparing high-thermal-conductivity graphene film by using metal catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115838167A (en) * | 2022-12-29 | 2023-03-24 | 常州富烯科技股份有限公司 | Graphene heat-conducting film and preparation method thereof |
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|---|---|---|---|---|
| CN103801686A (en) * | 2013-12-31 | 2014-05-21 | 深圳市国创新能源研究院 | Graphene nanocomposite and preparation method thereof |
| CN103864065A (en) * | 2014-03-10 | 2014-06-18 | 贵州新碳高科有限责任公司 | Method for improving thermal conductivity of graphene thin film |
| US20150098891A1 (en) * | 2013-10-07 | 2015-04-09 | Korea Institute Of Science And Technology | Method for manufacturing graphene film, graphene film manufactured by same, electronic device comprising the graphene film |
| CN107651671A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of method of catalyzed graphitization and a kind of preparation method of super flexible high heat conduction graphene film |
| CN110127673A (en) * | 2019-06-21 | 2019-08-16 | 宁德师范学院 | A kind of graphene superconduction thermal compound film block and preparation method thereof |
| CN110540193A (en) * | 2019-09-20 | 2019-12-06 | 上海大学 | preparation method of pressure graphitized graphene film |
| CN113353923A (en) * | 2021-06-25 | 2021-09-07 | 太原理工大学 | Method for preparing high-thermal-conductivity graphene film through autocatalytic growth |
-
2021
- 2021-06-25 CN CN202110709022.5A patent/CN113321207A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150098891A1 (en) * | 2013-10-07 | 2015-04-09 | Korea Institute Of Science And Technology | Method for manufacturing graphene film, graphene film manufactured by same, electronic device comprising the graphene film |
| CN103801686A (en) * | 2013-12-31 | 2014-05-21 | 深圳市国创新能源研究院 | Graphene nanocomposite and preparation method thereof |
| CN103864065A (en) * | 2014-03-10 | 2014-06-18 | 贵州新碳高科有限责任公司 | Method for improving thermal conductivity of graphene thin film |
| CN107651671A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of method of catalyzed graphitization and a kind of preparation method of super flexible high heat conduction graphene film |
| CN110127673A (en) * | 2019-06-21 | 2019-08-16 | 宁德师范学院 | A kind of graphene superconduction thermal compound film block and preparation method thereof |
| CN110540193A (en) * | 2019-09-20 | 2019-12-06 | 上海大学 | preparation method of pressure graphitized graphene film |
| CN113353923A (en) * | 2021-06-25 | 2021-09-07 | 太原理工大学 | Method for preparing high-thermal-conductivity graphene film through autocatalytic growth |
Non-Patent Citations (1)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115838167A (en) * | 2022-12-29 | 2023-03-24 | 常州富烯科技股份有限公司 | Graphene heat-conducting film and preparation method thereof |
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Application publication date: 20210831 |
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