CN106365154B - A kind of preparation method of non high temperature liquid phase method growth graphene - Google Patents
A kind of preparation method of non high temperature liquid phase method growth graphene Download PDFInfo
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- CN106365154B CN106365154B CN201610769878.0A CN201610769878A CN106365154B CN 106365154 B CN106365154 B CN 106365154B CN 201610769878 A CN201610769878 A CN 201610769878A CN 106365154 B CN106365154 B CN 106365154B
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Abstract
A kind of preparation method of non high temperature liquid phase method growth graphene, is technically characterized in that preparation method includes the following steps：Cold plasma is lighted in protective gas; the organic solvent for being operated in non high temperature state is placed in the plasma; then gaseous state or liquid carbon source are introduced into the cold plasma lighted; above-mentioned gaseous carbon source is activated cracking or liquid carbon source evaporation post activation cracking, the carbon after cracking fully dissolve in above-mentioned organic solvent；The aimed thin film of supercooling is immersed into organic solvent so that the carbon dissolved in organic solvent supersaturation on the aimed thin film of supercooling is precipitated, and graphene film is formed on the aimed thin film of supercooling.The present invention a kind of non high temperature liquid phase method growth graphene preparation method, prepared graphene have it is superior in quality, it is at low cost, efficient, pollution less, can be grown directly upon on aimed thin film without transfer.
Description
Technical field
The present invention relates to field of new material preparation, specifically a kind of preparation side of non high temperature liquid phase method growth graphene
Method.
Background technology
Graphene be one kind by carbon atom with sp2Hydridization and the two dimensional crystal with honeycomb lattice formed.2004, English
The An Deliehaimu and Constantine's Nuo Woxiao loves of University of Manchester of state successfully isolate graphene from graphite,
And therefore obtain Nobel Prize in physics in 2010.
Graphene has excellent performance.First, the specific surface area of graphene is very big, up to 2630m2/g.Secondly, stone
Carbon atom in black alkene is with sp2Mode hydridization, each carbon atom three carbon atoms adjacent thereto are formed stable by σ keys
Carbon-carbon bond, thus make graphene that there is high mechanical property, for Young's modulus up to 1100GPa, fracture strength is reachable
130GPa.Again, the pi-electron delocalization in graphene forms big pi bond, and pi-electron can move freely, therefore graphene is with excellent
Electric conductivity, carrier mobility rate may be up to 2 × 105cm2·V-1·S-1, and resistivity only has 10-8Ωm.In addition, stone
Black alkene also has good optical property, thermal property and magnetic performance etc..Therefore, graphene has huge potential application valence
Value, it is considered to be one of the present age most important new material.
Currently, the preparation method of graphene can be divided into method from top to bottom and from bottom to top method, wherein graphite oxide restores
Method is the main method in method from top to bottom；Chemical vapor deposition（CVD）Epitaxial growth method is the main side in method from bottom to top
Method；The method that bed of molten salt prepares graphene is another method for growing graphene from bottom to top.The main problem of the above method
It is：
1, graphene oxide GO poor performances, defect is more, and pollution is big.Graphene oxide generally uses improved Hummers methods,
After using the concentrated sulfuric acid, sodium nitrate and potassium permanganate and graphite vigorous reaction, is diluted and restored with hydrogen peroxide, handed over using ion
Purifying, drying are changed, graphene oxide GO is obtained.Redox graphene rGO generally can be obtained as reducing agent using hydrazine.
The product being prepared necessarily carries a large amount of phenolic group and carboxyl, intrinsic upper with a large amount of defect（10~15%）, lose
Excellent electric conductivity.Defect is more and powdered so that GO mechanical properties are not also high.Stable processing technique is poor, product
There is structure uncertainty, production process to use strong acid and strong oxidizer, and environmental pollution is big, and processing cost is high.
2, CVD method graphene performance is good, but cost is very high, and production efficiency is extremely low.This method is to be filled with carbon source at high temperature
Gas（Such as methane, ethane, acetylene）, carbon-source gas decompose simultaneously form graphene on substrate.This method can be in substrate
（Such as copper substrate）Upper formation high-quality graphene, but stringent, reaction time length, low yield are required to device and working condition
Under, it is with high costs.In particular, by this method in substrate（Such as copper, nickel, silicon carbide）The graphene of upper growth is difficult from lining
It is shifted on bottom；It is generally required when transfer using radical approach such as strong acid burn into high-temperature gasifications, this has resulted in of high cost, environment
Pollution is big, and can damage graphene finished product.
3, bed of molten salt prepares the method for graphene although the graphene of superior performance can be prepared at lower cost, made
At graphene be powder, when application, generally requires to coat film forming after slurry is made, and needs to solve evenly dispersed, is bonded, solidification
Etc. many technological problems.Moreover, the graphene number of plies of this method production, size and quality etc. are more difficult to control, are unable to get high-quality
The graphene film of amount.
Invention content
The purpose of the present invention proposes that a kind of performance quality is excellent aiming at above-mentioned technical problem, cost is relatively low, efficiency compared with
Preparation method high, of reduced contamination, that the non high temperature liquid phase method growth graphene that transfer is not necessarily on aimed thin film can be grown directly upon.
A kind of preparation method of non high temperature liquid phase method growth graphene of the present invention, is technically characterized in that preparation method packet
Include following steps：The cold plasma being placed in protective gas in reative cell is lighted, and work is placed in the plasma
Make the organic solvent in non high temperature state, is then introduced into gaseous state or liquid carbon source in the cold plasma lighted, above-mentioned gaseous state
Carbon source is activated cracking or liquid carbon source evaporation post activation cracking, the carbon after cracking fully dissolve in above-mentioned organic solvent；It will
The aimed thin film of supercooling immerses organic solvent so that the carbon dissolved in organic solvent supersaturation analysis on the aimed thin film of supercooling
Go out, graphene film is formed on the aimed thin film of supercooling.Above-mentioned gaseous state or liquid carbon source include at least aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon
One kind in analog derivative.
The above-mentioned organic solvent for having dissolved carbon also can be in the container by pipeline transportation to another reative cell；By supercooling
Aimed thin film immerses above-mentioned organic solvent so that and the carbon dissolved in organic solvent supersaturation on the aimed thin film of supercooling is precipitated,
Graphene film is formed on the aimed thin film of supercooling.
The gaseous state or liquid carbon source includes at least one kind in aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative.
The protective gas is at least one kind in nitrogen, argon gas, hydrogen, ammonia.
The aimed thin film of the supercooling immerses organic solvent using " roll-to-roll（R2R）" continuous processing mode, the mesh of supercooling
The temperature for marking film is less than the temperature of organic solvent, and aimed thin film puts mode using three stackings, and two outer layers are that macromolecule is organic
Film, middle layer are heat conducting film.
During the carbon dissolution is precipitated, one in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium is at least used
Kind is used as catalyst.
It is less than the boiling point of organic solvent after the catalyst is heated when using higher than the temperature of organic solvent.
It is described to be operated in addition graphene crystal seed in the solvent of non high temperature state.
A kind of preparation method of non high temperature liquid phase method growth graphene of the present invention is to existing using in solid substrate
The breakthrough for the graphene method that is vapor-deposited, and the improvement of graphene method is prepared to bed of molten salt method, there are following three big advantages：
1, compared with graphene oxide, graphene performance prepared by the present invention is good, at low cost, pollutes small, efficient, defect
Rate several orders of magnitude lower than graphene oxide are a kind of cost large-scale production electron level graphite that can be less than graphene oxide
The method of alkene.
2, compared with CVD method graphene, the present invention is at low cost, efficient.Since graphene is grown directly upon aimed thin film
It is upper to shift, solve the graphene transport difficulties of puzzlement scientific research and engineering technological, cost can be lower than conventional CVD method several
A order of magnitude, efficiency then have 100,000 times of raising.In addition, liquid phase, compared with gas phase, crystalline quality is good, long crystalline substance speed is fast.
3, compared with molten-salt growth method graphene, performance is excellent, high-quality, efficient, and pollution is small.Product different from molten-salt growth method is
Powder, prepared by the present invention is the graphene film of high quality, and may be used " roll-to-roll（R2R）" continuous production processes, it is raw
It produces more efficient, eliminates washing removing inorganic salts, the processing steps such as filter centrifugation separation pollute smaller, cost is lower.
Therefore, a kind of preparation method of non high temperature liquid phase method of the invention growth graphene, prepared graphene are realized
Performance quality is excellent, at low cost, efficient, pollution less, the purpose without transfer on aimed thin film can be grown directly upon.
Description of the drawings
Fig. 1 is the flow diagram that non high temperature liquid phase method of the present invention grows graphene embodiment one.
Fig. 2 is the flow diagram that non high temperature liquid phase method of the present invention grows graphene embodiment two.
Specific implementation mode
By embodiment, the invention will be further described below in conjunction with the accompanying drawings：
Embodiment one：
As shown in Figure 1, a kind of preparation method of non high temperature liquid phase method growth graphene of the present invention, is technically characterized in that
Preparation method includes the following steps：A kind of preparation method of non high temperature liquid phase method growth graphene, is technically characterized in that preparation
Method includes the following steps：The cold plasma 3 being placed in protective gas in reative cell 2 is lighted, in the plasma 3
It is placed with the container 4 for the organic solvent 5 for being operated in non high temperature state, then gaseous carbon source 1 is introduced to the cold plasma 3 lighted
In, above-mentioned gaseous carbon source is activated cracking or liquid carbon source evaporation post activation cracking, and the carbon after cracking is in above-mentioned organic solvent 5
Fully dissolving；Device 8 is moved by Volume, the aimed thin film 7 of supercooling is immersed into organic solvent 5 so that the carbon dissolved in organic solvent 5
Supersaturation is precipitated on the aimed thin film 7 of supercooling, and graphene film is formed on the aimed thin film 7 of supercooling.
Specifically, normal pressure microwave is used as described above（2.5GHz）Plasma reactor as reative cell 2, continue with
Argon gas is lighted and is kept as protective gas, by argon plasma 3, and organic solvent will be filled（JS-EPh）5 container 4 is placed in instead
Answer room 2, organic solvent（JS-EPh）5 temperature is not higher than 180 DEG C；Acetylene gas 1 is injected into cold plasma 3 as carbon source
In, acetylene 1 cracks in cold plasma 3；After activation cleavage reaction occurs, the carbon dissolution of cracking is in the organic of container 4
Solvent（JS-EPh）In 5 and reach saturation state；Film 7 is closed in three stackings being wound into a roll, and two outer layers are PET film, intermediate
Layer is graphite guide hotting mask, and supercooling is cooled to 40 DEG C, then moves device 8 by Volume, unreel, and film 7 is immersed the organic molten of container 4
Agent（JS-EPh）In 5；Container 4 place local induction heating and continue keep 200 DEG C copper mesh and nickel screen 6 be used as catalyst, together
When be added that a small amount of single-layer graphene kind is brilliant, the supercooling temperature of film 7 makes the supersaturation on film 7 of the carbon of dissolving be precipitated, from
And graphene film is formed on the aimed thin film 7,8 Volume of device is then moved by Volume and is moved, winding finally obtains and is grown in PET
Graphene on film.
Graphene obtained by the above method is the uniformly continuous graphite crystal film of 1~3 atomic layers thick.
Embodiment two
A kind of preparation method of non high temperature liquid phase method growth graphene of the present invention, is technically characterized in that preparation method packet
Include following steps：A kind of preparation method of non high temperature liquid phase method growth graphene, is technically characterized in that preparation method includes such as
Lower step：The cold plasma 3 being placed in protective gas in reative cell 2 is lighted, and work is placed in the plasma 3
In the container 4 of the organic solvent 5 of non high temperature state, then liquid carbon source 1 is introduced into the cold plasma 3 lighted, above-mentioned gas
State carbon source is activated cracking or liquid carbon source evaporation post activation cracking, the carbon after cracking fully dissolve in above-mentioned organic solvent 5；
The above-mentioned organic solvent 5 for having dissolved carbon is transported to by pipeline 9 in the container 11 of another reative cell 10；By the target thin of supercooling
Film 7 immerses organic solvent 5 so that the carbon dissolved in organic solvent 5 supersaturation on the aimed thin film 7 of supercooling is precipitated, and is being subcooled
Aimed thin film 7 on form graphene film.
Specifically, normal pressure microwave is used as described above（2.5GHz）Plasma reactor is as reative cell 2, with argon gas
As protective gas, argon plasma 3 is lighted and kept；Organic solvent will be filled（TDPH）5 container 4 is placed in reative cell 2,
Organic solvent will be filled simultaneously（TDPH）5 container 11 is placed in reative cell 10, and reative cell 10 is using argon gas and hydrogen as protection gas
Body；With pipeline 9 by container 4 and 11 unicom of container, organic solvent（TDPH）5 temperature is not higher than 190 DEG C；By the second as carbon source
Alcohol 1 injects in plasma 3, and 1 drop of ethyl alcohol is evaporated and cracked in plasma 3；After activation cleavage reaction occurs, split
The carbon dissolution of solution is in the organic solvent of container 4（TDPH）In 5 and reach saturation state；The carbon of dissolving is transported to by unicom pipeline 9
Container 11, the organic solvent in container 4 and container 11（TDPH）5 temperature are equal, and the solubility of carbon is identical；Three layers be wound into a roll
Film 7 is overlapped, two outer layers are PET film, and middle layer is graphite guide hotting mask, and supercooling is cooled to 40 DEG C, then pass through the dynamic dresses of Volume
8 are set, is unreeled, film is immersed to the organic solvent of container 11（TDPH）In 5.Local induction heating is placed in container 11 and continues to protect
The copper mesh and nickel screen 6 for holding 200 DEG C are used as catalyst, while a small amount of single-layer graphene kind crystalline substance is added, and 7 supercooling temperature of film makes
The supersaturation on film 7 of the carbon of dissolving is precipitated, and to form graphene film on the aimed thin film 7, then passes through the dynamic dresses of Volume
8 are set, winding finally obtains the graphene of growth on a pet film.
Graphene obtained by the above method is the uniformly continuous graphite crystal film of 1~2 atomic layers thick.
Above-mentioned graphene is easy to, and such as by thermal transfer, is transferred in the substrate of needs.
Claims (8)
1. a kind of preparation method of non high temperature liquid phase method growth graphene is technically characterized in that preparation method includes following step
Suddenly：The cold plasma being placed in protective gas in reative cell is lighted, and is placed in the plasma and is operated in non-height
Then gaseous state or liquid carbon source are introduced into the cold plasma lighted by the organic solvent of temperature state, above-mentioned gaseous carbon source is lived
Change cracking or liquid carbon source evaporation post activation cracking, the carbon after cracking fully dissolve in above-mentioned organic solvent；By the mesh of supercooling
It marks film and immerses organic solvent so that the carbon dissolved in organic solvent supersaturation on the aimed thin film of supercooling is precipitated, and is being subcooled
Aimed thin film on form graphene film.
2. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that above-mentioned
It has dissolved in container of the organic solvent of carbon by pipeline transportation to another reative cell；The aimed thin film of supercooling is immersed above-mentioned
Organic solvent so that the carbon dissolved in organic solvent supersaturation on the aimed thin film of supercooling is precipitated, in the aimed thin film of supercooling
Upper formation graphene film.
3. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that described
Gaseous state or liquid carbon source include at least aliphatic hydrocarbon, aromatic hydrocarbon, one kind in hydrocarbon derivative.
4. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that described
Protective gas is at least one kind in nitrogen, argon gas, hydrogen, ammonia.
5. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that described
The aimed thin film of supercooling immerses organic solvent using " roll-to-roll（R2R）" continuous processing mode, the temperature of the aimed thin film of supercooling
Less than the temperature of organic solvent, aimed thin film puts mode using three stackings, and two outer layers are macromolecule organic film, and middle layer is
Heat conducting film.
6. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that described
During carbon dissolution is precipitated, at least use a kind of as catalyst in copper, copper-bearing alloy, nickel, nickel-containing alloys, platinum, platinum rhodium.
7. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 6, it is characterised in that described
It is less than the boiling point of organic solvent after catalyst is heated when using higher than the temperature of organic solvent.
8. a kind of preparation method of non high temperature liquid phase method growth graphene according to claim 1, it is characterised in that described
It is operated in addition graphene crystal seed in the solvent of non high temperature state.
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| CN110983302A (en) * | 2019-12-30 | 2020-04-10 | 宁波柔碳电子科技有限公司 | Roll-to-roll graphene film growth equipment and roll-to-roll graphene film growth method |
| CN112778823B (en) * | 2021-01-27 | 2022-08-12 | 九江纳维新材料科技有限公司 | Ultra-high conductivity electronic grade graphene-silver composite conductive UV curing ink and preparation method and application thereof |
| CN115159510B (en) * | 2022-07-11 | 2023-12-29 | 常州二维碳素科技股份有限公司 | Graphene heat conduction film and method for efficiently producing graphene heat conduction film |
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Effective date of registration: 20230104 Address after: 102628 room 064, 4th floor, building 1, No. 9, Keyuan Road, economic development zone, Daxing District, Beijing Patentee after: Beijing shengdaike Technology Co.,Ltd. Address before: Room 405, building 21, Hanlin mansion, linggongtang Road, Jiaxing City, Zhejiang Province, 314001 Patentee before: Sun Xuyang |