CN103864065A - Method for improving thermal conductivity of graphene thin film - Google Patents
Method for improving thermal conductivity of graphene thin film Download PDFInfo
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- CN103864065A CN103864065A CN201410085269.4A CN201410085269A CN103864065A CN 103864065 A CN103864065 A CN 103864065A CN 201410085269 A CN201410085269 A CN 201410085269A CN 103864065 A CN103864065 A CN 103864065A
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Abstract
The invention discloses a method for improving the thermal conductivity of graphene thin film, and belongs to the field of materials technology. The method comprises the steps of feeding the graphene thin film or the graphene-oxide thin film with thickness of 0.1 to 500 mu m in and density of 0.5 to 2.5g/ cm<3> into a heating furnace with vacuum degree of 1000 to 5000 Pa or a heating furnace filled with the inert gas with the gas pressure equaling to one atmospheric pressure; increasing the temperature of the heating furnace from the room temperature to the target temperature of 1000 to 3000 DEG C at the heating rate of 1 to 30 degree/min; and carrying out furnace cooling. The method disclosed by the invention utilizes high temperature heat treatment to remedy the defects of the graphene powder bodies, so that the graphene thin film powder bodies can be overlapped to form the graphene thin film material and all the graphene powder bodies can be formed into continuously connected big graphene sheets through crystal growing, so as to form an extremely regular layered structure, and then the thermal conductivity is greatly improved.
Description
Technical field
The present invention relates to a kind of method that improves heat sink material thermal conductivity, relate in particular to a kind of method that improves graphene film thermal conductivity; Belong to material technology field.
Background technology
As everyone knows, thermodiffusion material is the important component part that forms heat radiation system; Be generally flat film structure, there is good thermal conductivity at in-plane.The heat that it can produce thermal source becomes a large-area plane heat source from heat point source diffusion, thereby eliminates hot spot, prevents the aging of electron device.The heat-transfer capability of thermodiffusion material determines by its atomic structure, and on nanoscale, the change of crystalline structure can affect the thermal heat transfer capability of thermodiffusion material.
Graphene is a kind of brand-new material with two-dimension plane structure being made up of carbon atom completely, there is high thermal conductivity, be expected to obtain widespread use in fields such as high-performance nano electron device, matrix material, field emmision material, gas sensor, stored energies, be considered to the most promising a kind of thermodiffusion material of electronics of future generation.Although the theoretical value of Graphene thermal conductivity can reach 5000 W/mk, only have the macroscopic material of being prepared into bring into play it in actual central using value.At present, conventionally adopt chemical vapour deposition and oxidation reduction process to prepare Graphene.The Graphene almost Perfect that chemical Vapor deposition process is prepared, but this kind of Graphene macro-size is in the vertical direction very limited, is not suitable for being applied to field of radiating; For example, and the graphene powder that oxidation reduction process prepares after certain art breading (spraying, roller coating etc.) can obtain the above graphene film material of arbitrary dimension of macroscopic view, therefore there is very high application prospect at field of radiating.But graphene powder prepared by oxidation reduction process generally belongs to micron level, even if be prepared into graphene film by certain filming technology again, its internal structure is also the discontinuous structure being formed by the form of physical connection by graphene powder, and therefore its heat dispersion is had a greatly reduced quality to a great extent.
Summary of the invention
For the above-mentioned defect existing in prior art, the present invention aims to provide a kind of method that improves graphene film thermal conductivity, and in its face of graphene film of the inventive method processing, laterally thermal conductivity can reach 500～2000W/mk; Longitudinally thermal conductivity is 10～20W/mk.
To achieve these goals, the present invention by the following technical solutions: be that 0.1～500 μ m, density are 0.5～2.5g/cm by thickness
3graphene-based film or graphene oxide base film to send into vacuum tightness be 1000～5000Pa or send into and be filled with rare gas element and air pressure is in an atmospheric process furnace, by the temperature rise rate of 1～30 DEG C/min, process furnace is risen to the target temperature of 1000～3000 DEG C from room temperature, then furnace cooling.
In technique scheme, the target temperature that the temperature rise rate of process furnace is preferably 10～20 DEG C/min, process furnace is preferably 1500～2100 DEG C, and described rare gas element is argon gas.
In technique scheme, the thickness of graphene-based film or graphene oxide base film is preferably 1～300 μ m; More preferably 5～200 μ m; Most preferably be 10～100 μ m.
Compared with the prior art, the present invention, owing to having adopted technique scheme, utilizes the method for high-temperature heat treatment to repair the defect of graphene powder itself, therefore can make graphene powder overlap joint prepared by redox form graphene film material; Can make every graphene powder grow and form continuous each other large stretch of Graphene by crystal, thereby in the fairly regular laminate structure of the inner formation of graphene film, thermal conductivity is greatly improved.According to test, adopt the interior laterally thermal conductivity of face of the graphene film of the inventive method processing can reach 500～2000W/mk; Longitudinally thermal conductivity is 10～20W/mk.
Brief description of the drawings
Fig. 1 is the electron microscope scanning photo through the cross section of the graphene film of high-temperature heat treatment;
Fig. 2 is the infra-red thermal imaging picture that graphene film that thickness that the inventive method was processed is 50um is covered in 200 ° of C electric heat source surfaces;
Fig. 3 is the electron microscope scanning photo of the cross section of the not graphene film of high-temperature heat treatment;
The graphene film that Fig. 4 is is 50um by the thickness without the inventive method processing is covered in the infra-red thermal imaging picture on 200 ° of C electric heat source surfaces.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the invention will be further described:
Embodiment 1 is that 0.1 μ m, density are 2.5g/cm by thickness
3graphene-based film or graphene oxide base film send in the process furnace that vacuum tightness is 1000Pa, by the temperature rise rate of 30 DEG C/min, process furnace is risen to the target temperature of 1000 DEG C from room temperature, then furnace cooling.
Embodiment 3, the same embodiment of each step
1; Wherein, the thickness of graphene-based film or graphene oxide base film is that 250 μ m, density are 1.5g/cm
3, process furnace vacuum tightness be that 2500Pa, temperature rise rate are that the target temperature of 15 DEG C/min, process furnace is 1500 DEG C.
Embodiment 4 is that 250 μ m, density are 1.5g/cm by thickness
3graphene-based film or graphene oxide base film send in the process furnace that is filled with argon gas, by the temperature rise rate of 10 DEG C/min, process furnace is risen to the target temperature of 2100 DEG C from room temperature, the air pressure of process furnace is a normal atmosphere.
Embodiment 5, each step is with embodiment 4; Wherein, temperature rise rate is that the target temperature of 20 DEG C/min, process furnace is 1500 DEG C.
Embodiment 6, each step is with embodiment 4; Wherein, temperature rise rate is that the target temperature of 15 DEG C/min, process furnace is 1550 DEG C.
Embodiment 7, each step is with embodiment 1; Wherein, the thickness of graphene-based film or graphene oxide base film is that 1 μ m, process furnace vacuum tightness are 3000Pa.
Embodiment 8, each step is with embodiment 1; Wherein, the thickness of graphene-based film or graphene oxide base film is that 300 μ m, process furnace vacuum tightness are 2000Pa.
Embodiment 10, each step is with embodiment 4; Wherein, the thickness of graphene-based film or graphene oxide base film is 5 μ m.
Embodiment 11, each step is with embodiment 4; Wherein, the thickness of graphene-based film or graphene oxide base film is 200 μ m.
Embodiment 12, each step is with embodiment 1; Wherein, the thickness of graphene-based film or graphene oxide base film is that 10 μ m, process furnace vacuum tightness are 4000Pa.
Embodiment 13, each step is with embodiment 1; Wherein, the thickness of graphene-based film or graphene oxide base film is that 100 μ m, process furnace vacuum tightness are 1500Pa.
Fig. 1, Fig. 3 are compared and can be found out, its inside of graphene film without high-temperature heat treatment is the discontinuous structure being formed by the form of physical connection by graphene powder, film inside is more mixed and disorderly, and therefore in its face, transverse heat transfer rate is less than 200W/mk; And its inside of the graphene film of processing through the inventive method can form fairly regular laminate structure, in its face, transverse thermal conductivity can reach 500～2000W/mk.Fig. 2, Fig. 4 are compared and can be found out, be obviously better than the graphene film without high-temperature heat treatment through its heat dispersion of graphene film of the inventive method processing.
Below by the graphene film of the inventive method processing and several groups of data of carrying out contrast test gained without the graphene film of high-temperature heat treatment:
[1] in embodiment 14～15, [2] main reference are as follows: (1) Electrodynamically Sprayed Thin Films of Aqueous Dispersible Graphene Nanosheets:Highly Efficient athodes for Dye-Sensitized Solar Cells. DOI:10.1021/am3005913.（2）Electrospray?deposition?of?a?graphene-oxide?thin?film，its?characterization?and?investigation?of?its?resistive?switching?performance.?DOI：10.3938/jkps.61.470。
No. 5 samples and the original graphene film (without the inventive method processing) chosen in embodiment 14 and embodiment 15 cover respectively under the heat point source of 200 ° of C, observe (seeing Fig. 2, Fig. 4) under thermal infrared imager.As can be seen from the figure there is hot localised points (top temperature reaches 152.2 ° of C) in original graphene film; And there is not hot localised points in No. 5 samples in embodiment 14 and 15, the uniformity of temperature profile of whole film, top temperature is 126.3 ° of C.Illustrate and utilize the Graphene heat radiation film heat transfer efficiency of processing of the present invention higher than original graphene film untreated under same condition.
Embodiment 16, selects different roll coating process
[3]the graphene film of preparation is that raw material is heat-treated, and is filled with argon gas in process furnace, and pressure is a standard atmospheric pressure, gas flow 20ml/min, and the target temperature that heat-up rate is made as 10 ° of C/min, process furnace is 1800 ° of C; Concrete test result is as shown in table 3.The test of thermal diffusivity completes by Netzsch LFA 447 NanoFlash Instrument; Roller coating equipment is purchased from the Hefei MSK-AFA-E300 of Ke Jing company continous way test-type automatic coating machine.
Embodiment 17, selects different roll coating process
[4]the graphene film of preparation is that raw material is heat-treated, and is filled with argon gas in process furnace, and pressure is a standard atmospheric pressure, gas flow 20ml/min, and heat-up rate is that the target temperature of 10 ° of C/min, process furnace is 2100 ° of C; Concrete test result is as shown in table 3.The test of thermal diffusivity completes by Netzsch LFA 447 NanoFlash Instrument; Roller coating equipment is purchased from the Hefei MSK-AFA-E300 of Ke Jing company continous way test-type automatic coating machine.
[3] in embodiment 16～17, [4] main reference are as follows:
（1）A?Facile?Route?to?Polymer?Solar?Cells?with?Optimum?Morphology?Readily?Applicable?to?a?Roll-to-Roll?Process?without?Sacrificing?High?Device?Performance.?DOI：10.1002/adma.201000250。
（2）Roll?to?roll?fabrication?of?polymer?solar?cell.http://www.sciencedirect.com/science/article/pii/S1369702112700196。
[5] main reference in embodiment 18 is as follows:
（1）Processable?aqueous?dispersions?of?graphene?nanosheets.?nature?nanotechnology.?DOI:10.1038/nnano.2007.451。（2）Mechanically?strong,electrically?conductive,and?biocompatible?graphene?paper.?Advanced?materials.?DOI:10.1002/adma.200800757。
Claims (5)
1. a method that improves graphene film thermal conductivity, is characterized in that: be that 0.1～500 μ m, density are 0.5～2.5g/cm by thickness
3graphene-based film or graphene oxide base film to send into vacuum tightness be 1000～5000Pa or send into and be filled with rare gas element and air pressure is in an atmospheric process furnace, by the temperature rise rate of 1～30 DEG C/min, process furnace is risen to the target temperature of 1000～3000 DEG C from room temperature, then furnace cooling.
2. the method for raising graphene film thermal conductivity according to claim 1, is characterized in that: temperature rise rate is that the target temperature of 10～20 DEG C/min, process furnace is 1500～2100 DEG C, and described rare gas element is argon gas.
3. the method for raising graphene film thermal conductivity according to claim 1 and 2, is characterized in that: the thickness of graphene-based film or graphene oxide base film is 1～300 μ m.
4. the method for raising graphene film thermal conductivity according to claim 1 and 2, is characterized in that: the thickness of graphene-based film or graphene oxide base film is 5～200 μ m.
5. the method for raising graphene film thermal conductivity according to claim 1 and 2, is characterized in that: the thickness of graphene-based film or graphene oxide base film is 10～100 μ m.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229783A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene film with high thermal conductivity |
| CN105018041A (en) * | 2015-06-11 | 2015-11-04 | 贵州新碳高科有限责任公司 | Porous graphene film, and phase-changing energy-storing composite material |
| CN105600775A (en) * | 2015-11-05 | 2016-05-25 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuous production of graphene film |
| CN105752963A (en) * | 2016-01-25 | 2016-07-13 | 浙江碳谷上希材料科技有限公司 | Foldable electrothermal film device based on graphene |
| CN108659535A (en) * | 2018-03-09 | 2018-10-16 | 中国电子科技集团公司第三十三研究所 | A kind of heat conduction absorbing material and preparation method thereof for ETC devices |
| CN108997619A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of mesoporous silicon oxide of carbonate and buffer solution duplicate protection and cellulose blending film and its preparation method and application |
| CN109181654A (en) * | 2018-09-13 | 2019-01-11 | 江苏成康石墨烯科技有限公司 | A kind of graphene-based composite heat conduction film and preparation method thereof and its application |
| CN109761224A (en) * | 2018-01-30 | 2019-05-17 | 四川聚创石墨烯科技有限公司 | A kind of method and graphene preparing graphene with graphene oxide |
| CN113213456A (en) * | 2020-01-21 | 2021-08-06 | 常州第六元素材料科技股份有限公司 | Amino acid modified graphene oxide film and preparation method thereof |
| CN113321207A (en) * | 2021-06-25 | 2021-08-31 | 太原理工大学 | Method for preparing high-thermal-conductivity graphene film by using metal catalyst |
| 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 |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229783B (en) * | 2014-09-10 | 2016-04-13 | 浙江碳谷上希材料科技有限公司 | A kind of preparation method of high thermal conductivity graphene film |
| CN104229783A (en) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene film with high thermal conductivity |
| CN105018041A (en) * | 2015-06-11 | 2015-11-04 | 贵州新碳高科有限责任公司 | Porous graphene film, and phase-changing energy-storing composite material |
| CN105018041B (en) * | 2015-06-11 | 2018-09-11 | 贵州新碳高科有限责任公司 | Graphene porous membrane, phase-change energy-storage composite material |
| CN105600775A (en) * | 2015-11-05 | 2016-05-25 | 北京旭碳新材料科技有限公司 | Graphene film and method and device for continuous production of graphene film |
| CN105752963A (en) * | 2016-01-25 | 2016-07-13 | 浙江碳谷上希材料科技有限公司 | Foldable electrothermal film device based on graphene |
| CN105752963B (en) * | 2016-01-25 | 2017-10-31 | 浙江碳谷上希材料科技有限公司 | A kind of foldable electrothermal film device based on graphene |
| CN109761224A (en) * | 2018-01-30 | 2019-05-17 | 四川聚创石墨烯科技有限公司 | A kind of method and graphene preparing graphene with graphene oxide |
| CN108659535B (en) * | 2018-03-09 | 2021-03-05 | 中国电子科技集团公司第三十三研究所 | Heat-conducting wave-absorbing material for ETC device and preparation method thereof |
| CN108659535A (en) * | 2018-03-09 | 2018-10-16 | 中国电子科技集团公司第三十三研究所 | A kind of heat conduction absorbing material and preparation method thereof for ETC devices |
| CN108997619A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of mesoporous silicon oxide of carbonate and buffer solution duplicate protection and cellulose blending film and its preparation method and application |
| CN108997619B (en) * | 2018-08-03 | 2021-03-26 | 武汉工程大学 | Mesoporous silica and cellulose blend membrane doubly protected by carbonate and buffer solution and preparation method and application thereof |
| CN109181654A (en) * | 2018-09-13 | 2019-01-11 | 江苏成康石墨烯科技有限公司 | A kind of graphene-based composite heat conduction film and preparation method thereof and its application |
| CN109181654B (en) * | 2018-09-13 | 2020-10-30 | 常州德维勒新材料科技有限公司 | Graphene-based composite heat-conducting film and preparation method and application thereof |
| CN113213456A (en) * | 2020-01-21 | 2021-08-06 | 常州第六元素材料科技股份有限公司 | Amino acid modified graphene oxide film and preparation method thereof |
| CN113321207A (en) * | 2021-06-25 | 2021-08-31 | 太原理工大学 | Method for preparing high-thermal-conductivity graphene film by using metal catalyst |
| 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 |
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Application publication date: 20140618 |