CN107055515A - A kind of method that atomized molten medium prepares graphene - Google Patents
A kind of method that atomized molten medium prepares graphene Download PDFInfo
- Publication number
- CN107055515A CN107055515A CN201610955866.7A CN201610955866A CN107055515A CN 107055515 A CN107055515 A CN 107055515A CN 201610955866 A CN201610955866 A CN 201610955866A CN 107055515 A CN107055515 A CN 107055515A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon
- atomized molten
- medium
- prepares graphene
- 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
Abstract
A kind of method that atomized molten medium prepares graphene, it is characterised in that regard atomized molten liquid medium as the solvent of monatomic carbon, the liquid medium and substrate of graphene supersaturation precipitation；First with or part carbon source is cracked using the high temperature of liquation, monatomic carbon dissolution is in fused solution medium；The fused solution medium atomization of monatomic carbon will be dissolved with into drop；By cooling the quick supersaturated indigenous graphite alkene of carbon is crystallized in fused solution medium；Normal temperature is down to, fused solution medium crystallizes into solid substrate, while graphene is deposited in above-mentioned solid substrate；Then at normal temperatures, solid substrate is dissolved with solvent and eluted, obtain graphene.The present invention prepares graphene compared with bed of molten salt method prepares graphene, with the functional, speed of growth faster, the characteristics of production efficiency is high, cost is low.
Description
Technical field
The present invention relates to field of new material preparation, the method that specifically a kind of atomized molten medium prepares graphene.
Background technology
Geim in 2004 etc. has been peeled off since graphene is made repeatedly using adhesive tape on native graphite, and graphene is because of it
Unique Two dimensional Crystallization body causes concern in scientific circles, and obtains Nobel Prize in physics, its unique excellent properties with
Huge potential using value is even more to cause whole world extensive concern.It is used as the two-dimentional macroscopic material found at first, its surface
Product has reached unprecedented 2630m2/g.Chemically on bonding pattern, the carbon atom for constituting graphene two-dimensional structure is miscellaneous in sp2 modes
Change, this hybrid form causes carbon atom to form stable C-C keys by σ keys with three adjacent carbon atoms, imparts graphite
The high mechanical property of alkene, Young's modulus 1100GPa, tensile strength 140GPa.Simultaneously a large amount of on graphene planes
The pi-electron delocalization that carbon atom is provided forms big pi bond, and electronics can be moved freely wherein, therefore graphene has excellent lead
Electrically.Such as graphene is a kind of zero band gap conductor, electronics wherein movement velocity up to the 1/300 of the light velocity, graphene current-carrying
Sub- migration rate is up to 2 × 105cm2·V-1·S-1, resistivity only has 10-8Ωm.Graphene also have good optical property,
Thermal property and magnetic performance.Therefore scientific and technological circle and engineering circles generally believe that graphene is contemporary most important new material.
At present, the preparation method of graphene can be divided into method from top to bottom and from bottom to top method, wherein, graphite oxide reduction
It is the main method in method from top to bottom that method, which prepares graphene oxide GO,；Chemical vapor deposition（CVD）Epitaxial growth method is under
And the main method in upper method；The method that bed of molten salt prepares graphene is another method for growing graphene from bottom to top, than
Above two method cost performance is much higher, and its performance is less than graphene oxide GO close to CVD, cost.The above method it is main
Problem is：
1st, graphene oxide GO poor performances, defect is more, and pollution is big.Graphene oxide typically uses improved Hummers methods, even if
After the concentrated sulfuric acid, sodium nitrate and potassium permanganate and graphite vigorous reaction, diluted and reduced with hydrogen peroxide, then it is pure by ion exchange
Change, dry, obtain graphene oxide GO.It is general that redox graphene rGO can be obtained as reducing agent using hydrazine.So
The product of preparation necessarily carries substantial amounts of phenolic group and carboxyl, intrinsic upper with substantial amounts of defect（10~15%）, lose excellent
Good electric conductivity.Defect is more and powdered so that GO mechanical properties are not also high.Stable processing technique is poor, product structure
With uncertainty, production process uses strong acid and strong oxidizer, and environmental pollution is big, and processing cost is high.
2nd, CVD graphene performance is good, but cost is higher, and production efficiency is lower.This method is to be filled with carbon source at high temperature
Gas（Such as methane, ethane, acetylene）, carbon-source gas are decomposed simultaneously forms graphene on substrate.This method can be in substrate
（Such as copper substrate）Upper formation high-quality graphene, but strict, reaction time length, low yield are required to device and working condition
Under, it is with high costs.Particularly, by this method in substrate（Such as copper, nickel, carborundum）The graphene of upper growth is difficult from lining
Shifted on bottom；Generally required during transfer using radical approach such as strong acid burn into high-temperature gasifications, this has resulted in cost height, environment
Pollution is big, and can damage graphene finished product.
The method that bed of molten salt prepares graphene is the liquid phase substrate and carbon deposited using high-temperature molten salt reaction bed as graphene
Solvent, the monatomic carbon dissolution formed after carbon source is cracked is in reaction bed and supersaturation separates out crystallization, uses salt after cooling
Washing is gone, and the graphene of superior performance, thus, its property more much higher than above two method cost performance can be prepared at lower cost
Graphene oxide GO can be less than close to CVD, cost.
3 but very low, the supersaturation for preparing solubility of the method for graphene due to monatomic carbon in fused salt of above-mentioned bed of molten salt
The speed of precipitation is slower, in addition the specific surface area of graphene hundreds of to 2630 m2/ g, required precipitation area is larger, therefore
Production efficiency is not still high.
Therefore, in the urgent need to developing a kind of good product performance, low cost, efficiency high, the improvement fused salt that pollution is small, discharge is few
The method that bed prepares graphene.
The content of the invention
The present invention in view of the shortcomings of the prior art, to achieve the above object, proposes that a kind of atomized molten medium prepares graphite
The method of alkene.
The object of the present invention is achieved like this：The method that a kind of atomized molten medium of the present invention prepares graphene, its
It is characterised by regarding atomized molten liquid medium as the solvent of monatomic carbon, the liquid medium and lining of graphene supersaturation precipitation
Bottom；First with or part carbon source is cracked using the high temperature of liquation, monatomic carbon dissolution is in fused solution medium；List will be dissolved with
The fused solution medium atomization of atomic carbon is into drop；By cooling the quick supersaturated indigenous graphite alkene of carbon is crystallized in fused solution
In state medium；Normal temperature is down to, fused solution medium crystallizes into solid substrate, while graphene is deposited in above-mentioned solid substrate；
Then at normal temperatures, solid substrate is dissolved with solvent and eluted, obtain graphene.
Above-mentioned high-temperature fusion liquid medium, be by under normal temperature in solid-state one or more of materials mixture, in high temperature
Melt to liquid.
Solid matter under above-mentioned normal temperature includes inorganic salts, alkali, metal and alloy.
Above-mentioned inorganic salts at least include sodium salt, sylvite, sulfate, hydrochloride, nitrate, carbonate, phosphate, silicic acid
Salt, manganate, nickelate, one or more of mixtures of cobaltatess.
Above-mentioned alkali refers to the compound that can be ionized out hydroxide ion in aqueous and not produce other anion,
At least include potassium hydroxide, sodium hydroxide, calcium hydroxide.
Above-mentioned carbon source is carbonaceous material, is one or more of carbonaceous material mixtures.
Above-mentioned carbonaceous material, at least including aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbohydrate, carbon containing polyphosphazene polymer
Compound.
Above-mentioned aliphatic hydrocarbon, aromatic hydrocarbon and hydrocarbon derivative, including but not limited to methane, ethane, propane, butane, ethene, third
Alkene, acetylene, cycloalkane, benzene, toluene, naphthalene, methanol, ethanol.
The method at least ultrasonic atomizatio of the above-mentioned fused solution medium atomization that will be dissolved with monatomic carbon, vacuum atomizing,
One kind of aerodynamic atomization.
Further, the fused solution medium is crystallized into before solid substrate, the characteristics of using graphene and lighter carbon black
Buoyancy sorting is carried out, most of fused solution medium circulation is utilized.
Above-mentioned solvent includes the method that solid substrate dissolves elution to be eluted inorganic salts, alkali soluble solution with water；Will with acid
Metal and alloy dissolving elution；Metal and alloy dissolving are eluted with electrochemical erosion method.
Further, the monatomic carbon dissolution is uniformly blended into solid granulates while fused solution medium, is formed molten
There is atomic carbon suspension；It is atomized into drop；By cooling the quick supersaturated indigenous graphite alkene of carbon is crystallized in the solid-state
On grain, graphene composite material is obtained.
The present invention is that the graphene method that is vapor-deposited to existing graphene oxide technical method and in solid substrate is dashed forward
It is broken, it is the improvement and breakthrough that graphene method is prepared to bed of molten salt method, has the following advantages：
1, compared with graphene oxide, graphene performance prepared by the present invention is good, and cost is low, pollutes small, efficiency high, ratio of defects ratio
The low several orders of magnitude of graphene oxide, be it is a kind of can be less than graphene oxide cost large-scale production electron level graphene
Method..
2, compared with CVD graphene, cost of the present invention is low, efficiency high.Due to washing or weak acid, to wash transfer method cheap
Quickly, cost can several orders of magnitude lower than conventional CVD, efficiency then has 100,000 times of raising.In addition, liquid phase and gas phase phase
Than crystalline quality is good, and long crystalline substance speed is fast.
3, particularly compared with than graphene oxide and the more competitive fused salt bed process graphene of CVD graphenes, growth
Faster, production efficiency is higher for speed, and cost is lower.
In addition,
4, the graphene composite material cost of directly supersaturation indigenous graphite alkene is low on solid granulates, graphene and solid granulates
It is firmly combined with, dispersiveness is preferably.
In summary, graphene prepared by the method that the present invention is provided is compared than fused salt bed process graphene, functional, raw
Long speed is faster, production efficiency is higher, cost is lower.
Embodiment
Below by embodiment, the invention will be further described：
The key of the present invention is：One is the supersaturated precipitation of solvent, graphene as monatomic carbon using fused solution medium
Liquid medium and and substrate；Two be fused solution medium atomization into drop, surface tension effect, and the monatomic carbon of dissolving is in liquid
Drip superficial layer enrichment and supersaturated indigenous graphite alkene.
Embodiment one
NaCl is heated up to 1100 DEG C of meltings, carbon source is cracked into monatomic carbon dissolution and melted in NaCl by addition glucose utilization high temperature
Salt；The NaCl fused salts for being dissolved with monatomic carbon are delivered to atomization reative cell；Atomization reative cell is low vacuum state, NaCl fused salts
Sprayed into from atomization reative cell top compression, and using ultrasound fully atomization, NaCl fused salts atomized drop passes through heat exchanger when landing
Continuous cooling, the high steam of heat exchanger production is used for cogeneration；Due to surface tension effect, the monatomic carbon of dissolving exists
NaCl fused salt drops superficial layer is enriched with so that the quick supersaturated indigenous graphite alkene of carbon is crystallized in fused solution medium, most final decline
To normal temperature, NaCl fused salts crystallize into the brilliant substrate of solid salt, and the carbon black that growing has graphene film is mixed therein；With water by NaCl
Dissolving elution, graphene powder is obtained after drying.
Claims (11)
1. a kind of method that atomized molten medium prepares graphene, it is characterised in that using atomized molten liquid medium as monatomic
Liquid medium and substrate that the solvent of carbon, graphene supersaturation are separated out；First with or part carbon source is split using the high temperature of liquation
Solution, monatomic carbon dissolution is in fused solution medium；The fused solution medium atomization of monatomic carbon will be dissolved with into drop；Pass through drop
Temperature causes the quick supersaturated indigenous graphite alkene of carbon to crystallize in fused solution medium；Normal temperature is down to, fused solution medium is crystallized into
Solid substrate, while graphene is deposited in above-mentioned solid substrate；Then at normal temperatures, solid substrate dissolving is washed with solvent
It is de-, obtain graphene.
2. the method that a kind of atomized molten medium according to claim 1 prepares graphene, it is characterised in that the high temperature
Fused solution medium, be by under normal temperature in solid-state one or more of materials mixture, in high-temperature fusion to liquid.
3. the method that a kind of atomized molten medium according to claim 2 prepares graphene, it is characterised in that the normal temperature
Include inorganic salts, alkali, metal and alloy in the material of solid-state down.
4. the method that a kind of atomized molten medium according to claim 3 prepares graphene, it is characterised in that described inorganic
Salt at least include sodium salt, sylvite, sulfate, hydrochloride, nitrate, carbonate, phosphate, silicate, manganate, nickelate,
One or more of mixtures of cobaltatess.
5. the method that a kind of atomized molten medium according to claim 3 prepares graphene, it is characterised in that the alkali is
Refer to the compound that can be ionized out hydroxide ion in aqueous and not produce other anion, at least including hydroxide
Potassium, sodium hydroxide, calcium hydroxide.
6. the method that a kind of atomized molten medium according to claim 1 prepares graphene, it is characterised in that the carbon source
It is one or more of carbonaceous material mixtures for carbonaceous material.
7. the method that a kind of atomized molten medium according to claim 6 prepares graphene, it is characterised in that described carbon containing
Material, at least including aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbohydrate, carbon containing high molecular polymer.
8. the method that a kind of atomized molten medium according to claim 7 prepares graphene, it is characterised in that the fat
Hydrocarbon, aromatic hydrocarbon and hydrocarbon derivative, including but not limited to methane, ethane, propane, butane, ethene, propylene, acetylene, cycloalkane,
Benzene, toluene, naphthalene, methanol, ethanol.
9. the method that a kind of atomized molten medium according to claim 1 prepares graphene, it is characterised in that the melting
Liquid medium is crystallized into before solid substrate, using buoyancy sorting is carried out the characteristics of graphene and lighter carbon black, by most of melting
Liquid medium is recycled.
10. the method that a kind of atomized molten medium according to right wants 1 prepares graphene, it is characterised in that described to use solvent
The method that solid substrate dissolves elution is included to be eluted inorganic salts, alkali soluble solution with water；Metal and alloy dissolving are eluted with acid；
Metal and alloy dissolving are eluted with electrochemical erosion method.
11. the method that a kind of atomized molten medium according to right wants 1 prepares graphene, it is characterised in that described monatomic
Carbon dissolution is uniformly blended into solid granulates while fused solution medium, is formed dissolved with atomic carbon suspension；It is atomized into drop；It is logical
Crossing cooling causes the quick supersaturation indigenous graphite alkene of carbon to crystallize on the solid granulates, obtains graphene composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610955866.7A CN107055515B (en) | 2016-11-03 | 2016-11-03 | A method of atomization melting media prepares graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610955866.7A CN107055515B (en) | 2016-11-03 | 2016-11-03 | A method of atomization melting media prepares graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107055515A true CN107055515A (en) | 2017-08-18 |
| CN107055515B CN107055515B (en) | 2019-04-23 |
Family
ID=59617294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610955866.7A Active CN107055515B (en) | 2016-11-03 | 2016-11-03 | A method of atomization melting media prepares graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107055515B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003689A (en) * | 2019-04-05 | 2019-07-12 | 孙旭阳 | A method of directly growing graphene on carbon black |
| CN110294470A (en) * | 2018-03-22 | 2019-10-01 | 中国科学院上海硅酸盐研究所 | It is a kind of to vulcanize three-dimensional porous grapheme material and preparation method thereof |
| CN111333057A (en) * | 2020-03-08 | 2020-06-26 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
| CN112778823A (en) * | 2021-01-27 | 2021-05-11 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| WO2015121613A1 (en) * | 2014-02-14 | 2015-08-20 | Cambridge Enterprise Limited | Method of producing graphene |
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
-
2016
- 2016-11-03 CN CN201610955866.7A patent/CN107055515B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| WO2015121613A1 (en) * | 2014-02-14 | 2015-08-20 | Cambridge Enterprise Limited | Method of producing graphene |
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
Non-Patent Citations (2)
| Title |
|---|
| JIE WANG ET AL.: "a modified molten-salt method to prepare graphene electrode with high capacitance and low self-discharge rate", 《CARBON》 * |
| XIAOFENG LIU ET AL.: "a facile molten-salt route to graphene synthesis", 《SMALL》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294470A (en) * | 2018-03-22 | 2019-10-01 | 中国科学院上海硅酸盐研究所 | It is a kind of to vulcanize three-dimensional porous grapheme material and preparation method thereof |
| CN110294470B (en) * | 2018-03-22 | 2022-10-14 | 中国科学院上海硅酸盐研究所 | Vulcanized three-dimensional porous graphene material and preparation method thereof |
| CN110003689A (en) * | 2019-04-05 | 2019-07-12 | 孙旭阳 | A method of directly growing graphene on carbon black |
| CN111333057A (en) * | 2020-03-08 | 2020-06-26 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
| CN111333057B (en) * | 2020-03-08 | 2021-10-12 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
| CN112778823A (en) * | 2021-01-27 | 2021-05-11 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107055515B (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107055515B (en) | A method of atomization melting media prepares graphene | |
| Zhang et al. | Controlled growth of single‐crystal graphene films | |
| Liu et al. | Designed growth of large‐size 2D single crystals | |
| Jin et al. | Mass production of high‐quality transition metal dichalcogenides nanosheets via a molten salt method | |
| CN102431999B (en) | Method for preparing high-quality graphene | |
| CN104860298B (en) | The method that graphene is prepared using molten state reaction bed | |
| US20160347617A1 (en) | A preparation method of graphene as well as graphene oxide based on anthracite | |
| CN112758950B (en) | Boron alkene nanosheets and preparation method thereof | |
| CN103708442B (en) | A kind of ionic liquid prepares the method for polymolecularity Graphene | |
| CN107119316A (en) | A kind of temperature-varying zone liquid bed Direct precipitation grows the preparation method of graphene | |
| CN105731440B (en) | A kind of utilization phase change materials peel off the method for preparing graphene microchip | |
| Wang et al. | Large-area synthesis and growth mechanism of graphene by chemical vapor deposition | |
| CN108557813B (en) | Method for preparing oversized single-layer graphene oxide by one-step method | |
| CN107099171A (en) | A kind of graphene strengthens carbon black preparation method | |
| CN113460997B (en) | Preparation method of three-dimensional grid-shaped graphene material | |
| WO2018205761A1 (en) | Method for preparing three-dimensional porous silicon by taking silicate glass as raw material | |
| US20220275476A1 (en) | A method for preparing an elemental material by reduction using monoatomic carbon | |
| EP3216757B1 (en) | Method for preparing graphene by molten state inorganic salt reaction bed | |
| CN110699749A (en) | Method for preparing large-area continuous single-layer single-crystal graphene film | |
| US20180029889A1 (en) | Preparation method of graphene | |
| CN103936000B (en) | A kind of preparation method of Graphene | |
| Chen et al. | Sodium-ion storage mechanisms and design strategies of molybdenum-based materials: A review | |
| CN106986336B (en) | The preparation method of few layer compound between graphite layers | |
| CN108963215A (en) | The fixed porous MoS of N doped graphene flexible substrates with three-dimensional structure2Nano material and its preparation method and application | |
| KR102413334B1 (en) | Manufacturing method of conductive thin film using expandable graphite |
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 |