CN110104632A - A kind of method of room temperature preparation high thermal conductivity graphene film - Google Patents
A kind of method of room temperature preparation high thermal conductivity graphene film Download PDFInfo
- Publication number
- CN110104632A CN110104632A CN201910277061.5A CN201910277061A CN110104632A CN 110104632 A CN110104632 A CN 110104632A CN 201910277061 A CN201910277061 A CN 201910277061A CN 110104632 A CN110104632 A CN 110104632A
- Authority
- CN
- China
- Prior art keywords
- graphene
- thermal conductivity
- film
- graphene oxide
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of methods of room temperature preparation high thermal conductivity graphene film.Large-sized graphene film and small size graphene film are mixed to get the graphene oxide solution prepared by the present invention, prepare oxidation graphene film using wet spinning and hydroiodic acid later.The redox graphene that this method obtains, which needs not move through high-temperature heat treatment just, has quite outstanding thermal conductivity, and can according to need the thermal conductivity for adjusting product in a certain range.The invention has synthesis technology relatively easy, feature low in cost, at the same time, the invention provides a kind of completely new research direction for graphene is applied to heat sink material field: improveing the defect of graphene film interiors of products by sized distribution to improve thermal conductivity, rather than Expenses Cost goes high-temperature heat treatment to eliminate defect, the application for graphene in the integrated circuit heat management direction provides more wide prospect.
Description
Technical field
The present invention relates to the methods of preparing graphene at normal temperature film, specifically a kind of to pass through regulation graphene oxide sheet
The method of high thermal conductivity graphite alkene film was also prepared after layer size distribution originally.
Background technique
With the continuous development of hyundai electronics electric utility, effectively the problem of heat dissipation, is increasingly becoming keeping in check for its development,
Chip industry, effectively heat dissipation, which become, restricts the bottleneck that chip size constantly reduces；In the development of the equipment Industries such as electrical and cable
In, can enhance in the filler or coating of heat dissipation is also preventing the fields such as ageing equipment from seeming more prominent and important；Especially
It is also the key point for determining many equipment performances in field of aerospace heat dissipation problem.In order to solve the problems, such as effectively to radiate,
Various high performance heat sink materials come into being.Wherein carbon material due to its good heat conductivity, chemical thermal stability it is high, light-weight
And to the mankind it is friendly the features such as, be increasingly becoming the ideal material of high-performance cooling fin.And wherein grapheme material is because its is high
Thermal conductivity (up to 5300Wm-1·K-1) and natural two-dimensional structure, have greatly preparing lateral heat dissipation Material Field
Potential.
It is existing preparation high thermal conductivity graphene film a variety of conventional methods, such as liquid stripping method, electronic spraying sedimentation,
Chemical vapour deposition technique etc..But due to cost problem, they are not appropriate for for graphene film is mass produced.In recent years,
The self assembly of graphene oxide, which restores, has proved to be a kind of graphene film of the large-scale production with excellent heat dissipation property
Effective way.However the method usually also needs 1000 to 3000 DEG C of high-temperature post-treatment to lead to obtain height in current research
Hot, this post-processing significantly increases the energy loss and time cost of film preparation, is unfavorable for pushing away for large-scale production
Extensively.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the problems of the above-mentioned prior art, one kind is provided directly normal
The method of the lower preparation high thermal conductivity graphene film of temperature, is not necessarily to high-temperature post-treatment, to simplify preparation, reduces cost, realize batch
Metaplasia produces.
For this purpose, the present invention adopts the following technical scheme that: the method for room temperature preparation high thermal conductivity graphene film comprising step
It is rapid:
1) it prepares graphene oxide solution: being 8-18mg/ml large scale graphene oxide by a part of finely dispersed concentration
Solution carries out the processing of cell Ultrasonic Pulverization, the small size graphene oxide solution of same concentration is obtained, then by the big of another part
Size graphene oxide solution and small size graphene oxide solution uniformly mix, and obtain mixed oxidization graphene solution；
2) the mixed oxidization graphene solution that step 1) obtains is injected in the coagulating bath being made of calcium chloride, second alcohol and water and is carried out
Flocculation, and transmitted by Polyethylene Terephthalates' film, obtain the graphene oxide film handled by coagulating bath；
3) collection step 2) obtained in by coagulating bath processing graphene oxide film be immersed in the aqueous solution of ethyl alcohol clearly
It washes, is then placed in 30-60 DEG C of thermal station, it is 1-3 hours dry, then it is placed in vacuum drying oven 50-80 DEG C of holding, further
It is 3-8 hours dry；
4) product for obtaining step 3) and Polyethylene Terephthalates' film immersion 1-5 hours in deionized water, then
It removes in deionized water, obtains unsupported graphene oxide film, place it in vacuum drying oven again, at 50-80 DEG C
At a temperature of, it is 6-12 hours dry；
5) unsupported graphene oxide film dried in step 4) is immersed in reducing agent reaction, while makes reaction system
It is placed in 60-90 DEG C of water-bath and heats 8-14 hours；
6) saturated sodium bicarbonate solution, deionized water and dehydrated alcohol is successively used to rinse the film after reacting in step 5), so
Film is placed in vacuum drying oven afterwards, it is dry 10-16 hours thin to get the graphene to high thermal conductivity at a temperature of 80-120 DEG C
Film.
A kind of method of room temperature preparation high thermal conductivity graphene film provided by the invention, prepares reduction-oxidation graphite with other
The method of alkene film is compared to advantage: can effectively realize redox graphene by controlling graphene oxide solution concentration
The control of film thickness can also be further realized by control graphene oxide layer size distribution to redox graphene
The control of film heating conduction；In addition, this method be not necessarily to high-temperature post-treatment, have it is easy to operate, low in cost, can give birth on a large scale
The advantages that production, high efficiency.
Further, in step 1), the large scale graphene oxide partial size is 10-15 μm；Small size graphene oxide
Partial size is 2-4 μm.
Further, in step 2, the quality point of the mixed oxidization graphene solution small-medium size graphene oxide
Number is 10-90%, preferably 30-70%, most preferably 50%.
Further, in step 2, the coagulating bath ingredient is that ethyl alcohol and water are added with volume ratio 1:2-1:5 mixed solution
Mass fraction is the calcium chloride of 3-8%.
Further, in step 5), the reducing agent is hydroiodic acid solution, mass fraction 30-50%.
Further, in step 3), in the aqueous solution of the ethyl alcohol, the mass fraction of ethyl alcohol is 90-95%.
The present invention has the advantages that compared with existing preparation high thermal conductivity graphene film method
(1) in the present invention, alternative reducing agent is numerous, common graphene oxide reducing agent such as hydroiodic acid, Vitamin C
Acid etc. can restore graphene oxide film to obtain required high thermal conductivity graphene film；
(2) the adjustable graphene oxide solution concentration of method of the invention, to be conducive to control reduction, to obtain graphene thin
The thickness of film；
(3) method of the invention is not necessarily to large scale equipment, easy to operate, at low cost, and traditional 1000-3000 is not necessarily in reaction process
DEG C high-temperature heating, reduction reaction can be carried out at room temperature, it is safer, high-efficient；
(4) method of the invention can also be widely used in other many oxidation-reduction methodes, such as roller in addition to being suitable for wet-spinning techniques
Coating, vacuum filtration process, in-situ metal reduction method etc., to be conducive to it, industrially large-scale production is promoted.
Detailed description of the invention
Fig. 1 is the conductivity and thermal conductivity and small size graphene of graphene film obtained by the embodiment of the present invention 1 and 2
Relation with contents figure.
In Fig. 2, (a-c) is the graphene of pure large scale, graphene containing small size 50% mass fraction and pure small size respectively
The scanning electron microscopy plan view of film；It (d-f) is pure large scale, 50% mass fraction of graphene containing small size and pure small respectively
The scanning electron microscopy sectional view of the graphene film of size.
Fig. 3 is the Raman map of the resulting graphene film of Example 1 and Example 2 of the present invention.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.Implementation condition used in the examples can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Below with reference to embodiment, the present invention will be described in detail, it should be understood that citing described herein is only used to explain this
Invention, is not intended to limit the present invention.
Embodiment 1
(1) prepared by sample solution, i.e., is that 8mg/ml large scale graphene oxide sample solution carries out carefully by finely dispersed concentration
The processing of born of the same parents' Ultrasonic Pulverization, obtains the graphene oxide solution of the small size of same concentration, then by the solution of two kinds of sizes according to one
It is uniformly mixed than a mass ratio.
(2) by step (1) be uniformly mixed graphene oxide sample solution by syringe pump inject be mixed with calcium chloride,
It flocculates in the coagulating bath of second alcohol and water, and is transmitted by Polyethylene Terephthalates' film.
(3) graphene oxide film obtained in collection step (2), which is immersed in the aqueous solution of ethyl alcohol, cleans, then by it
It is placed on drying 1 hour in 40 DEG C of thermal station, then is placed in vacuum drying oven 60 DEG C of holding and is further dried 4 hours.
(4) film dried in step (3) and Polyethylene Terephthalates' film are impregnated 3 small in deionized water
When, then removing obtains graphene oxide film in water, places it in vacuum drying oven again and is kept for 60 DEG C drying 8 hours.
(5) graphene oxide film dried in step (4) is immersed in hydroiodic acid solution reaction, while makes reactant
System, which is placed in 80 DEG C of water-baths, heats 12 hours.
(6) graphene film after reaction in step (5) is used into saturated sodium bicarbonate solution, deionized water and anhydrous respectively
Ethyl alcohol rinses, and film is then placed in vacuum drying oven and is kept for 100 DEG C drying 12 hours, it is thin that high performance graphene can be obtained
Film.
Embodiment 2, it is same as Example 1, but by 50% small size graphene oxide and 50% large scale graphene oxide
Quality proportioning is changed to 0 and 100%, 10% and 90%, and 30% and 70%, 70% and 30%, 90% and 10%, 100% and 0.
Embodiment 3, it is same as Example 1, but graphene oxide solution concentration is changed to 12mg/ml or 18mg/ml.
Fig. 1 is the conductivity and thermal conductivity and small size graphene relation with contents of graphene film prepared by the present invention
Figure, can be found from figure when small size is mixed with big size graphene conductivity and thermal conductivity to a certain extent than not mixing when
It is improved, especially graphene film obtained by embodiment 1 has up to 1102.62Wm-1·K-1Thermal conductivity and
8982.18S·m-1Conductivity, improve 188.87% He respectively than pure large-size graphene film thermal conductivity
81.41%.Fig. 2 is the scanning electricity of the graphene film of pure large scale, 50% mass fraction of graphene containing small size and pure small size
The micro- plane of son and sectional view, pure large-size graphene film arrangement is preferable as shown in the figure, but with the presence of many holes；And
Pure small size graphene film arrangement is worst, and the warped structures on surface and the hole in section are most；And contain obtained in embodiment 1
The graphene film of 50% mass fraction of small size graphene then arranges most smooth close, and hole is minimum.Fig. 3 is containing different quality
The Raman map of the graphene film of the small size graphene of score, the peak D as shown in the figure and G peak intensity ratio (ID/IG) and by calculation
Defect average headway (the L obtainedD) know that, by incorporation small size graphene, film defects average headway has than not mixing situation
It is promoted, it means that 50% mass fraction of graphene containing small size obtained in the reduction of defects count, especially embodiment 1
Graphene film defects count it is minimum, to illustrate its thermal conductivity and the best reason of conductivity.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of method of room temperature preparation high thermal conductivity graphene film, which is characterized in that comprising steps of
1) it prepares graphene oxide solution: being 8-18mg/ml large scale graphene oxide by a part of finely dispersed concentration
Solution carries out the processing of cell Ultrasonic Pulverization, the small size graphene oxide solution of same concentration is obtained, then by the big of another part
Size graphene oxide solution and small size graphene oxide solution uniformly mix, and obtain mixed oxidization graphene solution；
2) the mixed oxidization graphene solution that step 1) obtains is injected in the coagulating bath being made of calcium chloride, second alcohol and water and is carried out
Flocculation, and transmitted by Polyethylene Terephthalates' film, obtain the graphene oxide film handled by coagulating bath；
3) collection step 2) obtained in by coagulating bath processing graphene oxide film be immersed in the aqueous solution of ethyl alcohol clearly
It washes, is then placed in 30-60 DEG C of thermal station, it is 1-3 hours dry, then it is placed in vacuum drying oven 50-80 DEG C of holding, further
It is 3-8 hours dry；
4) product for obtaining step 3) and Polyethylene Terephthalates' film immersion 1-5 hours in deionized water, then
It removes in deionized water, obtains unsupported graphene oxide film, place it in vacuum drying oven again, at 50-80 DEG C
At a temperature of, it is 6-12 hours dry；
5) unsupported graphene oxide film dried in step 4) is immersed in reducing agent reaction, while makes reaction system
It is placed in 60-90 DEG C of water-bath and heats 8-14 hours；
6) saturated sodium bicarbonate solution, deionized water and dehydrated alcohol is successively used to rinse the film after reacting in step 5), so
Film is placed in vacuum drying oven afterwards, it is dry 10-16 hours thin to get the graphene to high thermal conductivity at a temperature of 80-120 DEG C
Film.
2. the method for room temperature preparation high thermal conductivity graphene film according to claim 1, which is characterized in that in step 1),
The large scale graphene oxide partial size is 10-15 μm；Small size graphene oxide partial size is 2-4 μm.
3. the method for room temperature preparation high thermal conductivity graphene film according to claim 1, which is characterized in that in step 2,
The mass fraction of the mixed oxidization graphene solution small-medium size graphene oxide is 10-90%.
4. the method for room temperature preparation high thermal conductivity graphene film according to claim 3, which is characterized in that in step 2,
The mass fraction of the mixed oxidization graphene solution small-medium size graphene oxide is 30-70%.
5. the method for room temperature preparation high thermal conductivity graphene film according to claim 4, which is characterized in that in step 2,
The mass fraction of the mixed oxidization graphene solution small-medium size graphene oxide is 50%.
6. the method for room temperature preparation high thermal conductivity graphene film according to claim 1, which is characterized in that in step 2,
The coagulating bath ingredient is the calcium chloride of ethyl alcohol and water with volume ratio 1:2-1:5 mixed solution plus mass fraction for 3-8%.
7. the method for room temperature preparation high thermal conductivity graphene film according to claim 1, which is characterized in that in step 5),
The reducing agent is hydroiodic acid solution, mass fraction 30-50%.
8. the method for room temperature preparation high thermal conductivity graphene film according to claim 1, which is characterized in that in step 3),
In the aqueous solution of the ethyl alcohol, the mass fraction of ethyl alcohol is 90-95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910277061.5A CN110104632B (en) | 2019-04-08 | 2019-04-08 | Method for preparing high-thermal-conductivity graphene film at normal temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910277061.5A CN110104632B (en) | 2019-04-08 | 2019-04-08 | Method for preparing high-thermal-conductivity graphene film at normal temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110104632A true CN110104632A (en) | 2019-08-09 |
| CN110104632B CN110104632B (en) | 2020-09-04 |
Family
ID=67483719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910277061.5A Active CN110104632B (en) | 2019-04-08 | 2019-04-08 | Method for preparing high-thermal-conductivity graphene film at normal temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110104632B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125297A (en) * | 2020-09-22 | 2020-12-25 | 杭州高烯科技有限公司 | Preparation method of graphene film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
| CN105084858A (en) * | 2015-08-07 | 2015-11-25 | 常州富烯科技股份有限公司 | Method for preparing graphene film |
| GB2534217A (en) * | 2015-01-19 | 2016-07-20 | Ping Lai Chung | Graphene laminate film with thermal conductivity |
| CN107601468A (en) * | 2017-10-23 | 2018-01-19 | 南京旭羽睿材料科技有限公司 | A kind of preparation method of graphene film |
| CN108976700A (en) * | 2018-08-17 | 2018-12-11 | 厦门凯纳石墨烯技术股份有限公司 | Controllable method for preparing based on the modified high thermal conductivity carbon-plastic alloy of high degree of piling up graphene |
| CN108996491A (en) * | 2018-07-06 | 2018-12-14 | 中国航发北京航空材料研究院 | A kind of preparation method of the derivative graphene perforated membrane of bubble |
-
2019
- 2019-04-08 CN CN201910277061.5A patent/CN110104632B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
| GB2534217A (en) * | 2015-01-19 | 2016-07-20 | Ping Lai Chung | Graphene laminate film with thermal conductivity |
| CN105084858A (en) * | 2015-08-07 | 2015-11-25 | 常州富烯科技股份有限公司 | Method for preparing graphene film |
| CN107601468A (en) * | 2017-10-23 | 2018-01-19 | 南京旭羽睿材料科技有限公司 | A kind of preparation method of graphene film |
| CN108996491A (en) * | 2018-07-06 | 2018-12-14 | 中国航发北京航空材料研究院 | A kind of preparation method of the derivative graphene perforated membrane of bubble |
| CN108976700A (en) * | 2018-08-17 | 2018-12-11 | 厦门凯纳石墨烯技术股份有限公司 | Controllable method for preparing based on the modified high thermal conductivity carbon-plastic alloy of high degree of piling up graphene |
Non-Patent Citations (1)
| Title |
|---|
| JOON-SUK OH ET AL.，: "Chemically-modified graphene sheets as an active layer for eco-friendly metal electroplating on plastic substrates", 《THIN SOLID FILMS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125297A (en) * | 2020-09-22 | 2020-12-25 | 杭州高烯科技有限公司 | Preparation method of graphene film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110104632B (en) | 2020-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10889497B2 (en) | Sheet-shaped nitrogen-phosphorus co-doped porous carbon material and method for preparation thereof and use thereof | |
| CN107857249B (en) | Preparation method of nitrogen-doped annular hollow nano carbon material | |
| CN106099053B (en) | A kind of molybdenum sulfide/selenizing molybdenum composite material and its preparation and application | |
| Gao et al. | A regenerable Cu2O/BiOBr S-scheme heterojunction photocatalysts for efficient photocatalytic degradation of mixed organic pollutants | |
| CN105938908A (en) | Nitrogen-doped three-dimensional graphene catalyst and preparation method thereof | |
| CN106145101B (en) | A kind of bigger serface nitrogen-doped graphene and preparation method thereof | |
| CN105719849B (en) | A kind of graphene/Co (OH) of morphology controllable2The preparation method of composite material | |
| CN106381481A (en) | Preparation method of metal doping molybdenum disulfide thin film | |
| CN102718250A (en) | Method for preparing carbon-material-carrying tin dioxide nanosheet composite material | |
| CN106129377A (en) | The preparation method of a kind of sesquioxide/graphene composite material, lithium ion battery negative, lithium ion battery | |
| CN104787799B (en) | Web-type three-dimensional perforated macroporous-mesoporous-structure titanium dioxide material, and preparation method and application thereof | |
| CN105406042A (en) | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery | |
| CN106563813B (en) | A kind of Ag-CoSe2Nanobelt and its preparation method and application | |
| Shao et al. | Hierarchical porous carbons as a metal-free electrocatalyst of triiodide reduction for dye-sensitized solar cells | |
| CN104198560B (en) | A kind of preparation method of the porous silica titanium compound film of graphene modified | |
| CN104628030B (en) | The floride-free preparation method of class graphene-structured titanium dioxide | |
| CN104752074A (en) | Molybdenum oxide/carbon sphere composite material preparation method | |
| CN109559902A (en) | Derivative cobalt nickel boron sulphide material of a kind of metal organic frame and the preparation method and application thereof | |
| CN104108707B (en) | A kind of sulfur doping Graphene and preparation method thereof | |
| CN110104632A (en) | A kind of method of room temperature preparation high thermal conductivity graphene film | |
| Zhang et al. | The spatially oriented redistribute of photogenerated carriers and photocatalytic hydrogen evolution mechanism research on polymeric carbon nitride Van der Waals homojunction | |
| CN106981650A (en) | A kind of preparation method of nanoscale bismuth with elementary | |
| CN110098337A (en) | A kind of stannic oxide/zinc oxide compound nano wire material and preparation method thereof | |
| CN108057457A (en) | A kind of recyclable flexible monoblock type photochemical catalyst and preparation method thereof | |
| CN105314684A (en) | Preparation method of manganese dioxide nanosheet of two-dimension porous structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |