CN107055515B - A method of atomization melting media prepares graphene - Google Patents
A method of atomization melting media prepares graphene Download PDFInfo
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- CN107055515B CN107055515B CN201610955866.7A CN201610955866A CN107055515B CN 107055515 B CN107055515 B CN 107055515B CN 201610955866 A CN201610955866 A CN 201610955866A CN 107055515 B CN107055515 B CN 107055515B
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Abstract
A method of atomization melting media prepares graphene, it is characterised in that will be atomized fused solution medium as the solvent of monatomic carbon, the liquid medium and substrate of graphene supersaturation precipitation；First with or part using the high temperature of melt carbon source is cracked, monatomic carbon dissolution is in fused solution medium；By the fused solution medium atomization dissolved with monatomic carbon at drop；By cooling so that carbon quickly supersaturated indigenous graphite alkene crystallization in fused solution medium；It is down to room temperature, fused solution medium crystallizes into solid substrate, while graphene is deposited in above-mentioned solid substrate；Then at normal temperature, solid substrate is dissolved with solvent and is eluted, obtain graphene.The present invention prepares graphene compared with bed of molten salt method prepares graphene, have the characteristics that the functional, speed of growth faster, it is high production efficiency, at low cost.
Description
Technical field
The present invention relates to field of new material preparation, specifically a kind of method that atomization melting media prepares graphene.
Background technique
Geim in 2004 etc. has been removed since graphene is made on natural graphite repeatedly using adhesive tape, and graphene is because of it
Unique Two dimensional Crystallization body causes to pay close attention in scientific circles, and obtains Nobel Prize in physics, unique excellent properties and
Huge potential using value is even more to cause whole world extensive concern.As the two-dimentional macroscopic material found at first, surface
Product has reached unprecedented 2630m2/g.Chemically on bonding pattern, the carbon atom for constituting graphene two-dimensional structure is miscellaneous in a manner of sp2
Change, this hybrid form makes carbon atom and three adjacent carbon atoms form stable C-C key by σ key, imparts graphite
The high mechanical property of alkene, Young's modulus 1100GPa, tensile strength 140GPa.Simultaneously perpendicular to a large amount of on graphene planes
The pi-electron delocalization that carbon atom provides forms big pi bond, and electronics can move freely wherein, therefore graphene has excellent lead
Electrically.Such as graphene is a kind of zero band gap conductor, electronics in 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 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 reduction
Method prepares graphene oxide GO as the main method in method from top to bottom；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 performance is lower than graphene oxide GO close to CVD method, cost.The above method it is main
Problem is:
1, graphene oxide GO performance is poor, and defect is more, and pollution is big.Graphene oxide generally uses improved Hummers method,
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.Generally using hydrazine as the available redox graphene rGO of reducing agent.
The product being prepared necessarily has a large amount of phenolic group and carboxyl, intrinsic upper with a large amount of defect (10~15%), loses
Excellent electric conductivity.Defect is more and powdered, so that GO mechanical property is not also high.Stable processing technique is poor, product
Structure has uncertainty, and production process uses 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 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 decomposes and graphene is formed on the substrate.This method can be in substrate
High-quality graphene is formed in (such as copper substrate), but stringent, reaction time length, low yield are required to device and working condition
Under, it is with high costs.In particular, the graphene grown on substrate (such as copper, nickel, silicon carbide) by this method 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 at high cost, 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 use salt after cooling in reaction bed and supersaturation precipitation crystallization
Washing is gone, and can prepare the graphene of superior performance, thus, property more much higher than above two method cost performance at lower cost
Graphene oxide GO can be lower than close to CVD method, cost.
3 but above-mentioned bed of molten salt prepare the method for graphene since solubility of the monatomic carbon in fused salt is very low, supersaturation
The speed of precipitation is slower, and the specific surface area of graphene is hundreds of to 2630 m in addition2/ g, required precipitation area is larger, therefore
Production efficiency is not still high.
Therefore, there is an urgent need to develop a kind of good product performances, the improvement fused salt that at low cost, high-efficient, pollution is small, discharge is few
The method that bed prepares graphene.
Summary of the invention
The present invention in view of the deficiencies of the prior art, to achieve the above object, proposes that a kind of atomization melting media prepares graphite
The method of alkene.
The object of the present invention is achieved like this: the method that a kind of atomization melting media of the invention prepares graphene,
It is characterized in that liquid medium and lining that fused solution medium is precipitated as the solvent of monatomic carbon, graphene supersaturation will be atomized
Bottom；First with or part using the high temperature of melt carbon source is cracked, monatomic carbon dissolution is in fused solution medium；It will be dissolved with single
The fused solution medium atomization of atomic carbon is at drop；By cooling so that carbon quickly supersaturated indigenous graphite alkene crystallization in molten liquid
In state medium；It is down to room temperature, fused solution medium crystallizes into solid substrate, while graphene is deposited in above-mentioned solid substrate；
Then at normal temperature, solid substrate is dissolved with solvent and is eluted, obtain graphene.
Above-mentioned high-temperature fusion liquid medium, be by under room temperature in the mixture of solid one or more of substances, in high temperature
Melt to liquid.
Solid matter under above-mentioned room temperature includes inorganic salts, alkali, metal and alloy.
Above-mentioned inorganic salts include at least sodium salt, sylvite, sulfate, hydrochloride, nitrate, carbonate, phosphate, silicic acid
The mixtures of the one or more of salt, manganate, nickelate, cobaltatess.
Above-mentioned alkali refers to the compound that can be ionized out hydroxide ion in aqueous solution and not generate other anion,
Including at least 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 includes at least aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbohydrate, carbon containing polyphosphazene polymer
Close object.
Above-mentioned aliphatic hydrocarbon, aromatic hydrocarbon and hydrocarbon derivative, including but not limited to methane, ethane, propane, butane, ethylene, third
Alkene, acetylene, cycloalkane, benzene, toluene, naphthalene, methanol, ethyl alcohol.
It is above-mentioned to be at least ultrasonic atomizatio dissolved with the method for the fused solution medium atomization of monatomic carbon, vacuum atomizing,
One kind of aerodynamic atomization.
Further, before the fused solution medium crystallizes into solid substrate, the lighter feature of graphene and carbon black is utilized
Buoyancy sorting is carried out, most of fused solution medium circulation is utilized.
It is above-mentioned with solvent by solid substrate dissolution elution method include with water by inorganic salts, alkali soluble solution elute；It will with acid
Metal and alloy dissolution elution；Metal and alloy dissolution 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 so that carbon quickly supersaturated indigenous graphite alkene crystallization 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 for preparing graphene method to bed of molten salt method, has the following advantages:
1, compared with graphene oxide, graphene performance prepared by the present invention is good, at low cost, pollutes small, high-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 lower than graphene oxide
The method of alkene.
2, compared with CVD method graphene, the present invention is at low cost, high-efficient.Since to wash transfer method cheap for washing or weak acid
Quickly, cost can several orders of magnitude lower than conventional CVD method, 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, especially compared with fused salt bed process graphene more more competitive than graphene oxide and CVD graphene, growth
Faster, production efficiency is higher for speed, and cost is lower.
In addition to this,
4, the graphene composite material of directly supersaturation indigenous graphite alkene is at low cost on solid granulates, graphene and solid-state
Particle is firmly combined, and dispersibility is preferably.
In conclusion the graphene of method preparation provided by the invention is compared than fused salt bed process graphene, it is functional, raw
Long speed is faster, production efficiency is higher, cost is lower.
Specific embodiment
Below by embodiment, the invention will be further described:
Key of the invention is: first is that solvent, graphene supersaturation using fused solution medium as monatomic carbon
The liquid medium of precipitation and and substrate；Second is that fused solution medium atomization is at drop, surface tension effect, the monatomic carbon of dissolution
In the enrichment of droplet surface layer and supersaturated indigenous graphite alkene.
Embodiment one
By NaCl be heated up to 1100 DEG C melting, addition glucose utilization high temperature by carbon source be cracked into monatomic carbon dissolution in
NaCl fused salt；NaCl fused salt dissolved with monatomic carbon is delivered to atomization reaction chamber；Atomization reaction chamber is low vacuum state,
NaCl fused salt is sprayed into from atomization reaction chamber top compression, and using ultrasound sufficiently atomization, logical when NaCl fused salt atomized drop lands
Heat exchanger continuous cooling is crossed, the high steam of heat exchanger production is used for cogeneration；Due to surface tension effect, single original of dissolution
Sub- carbon is enriched in NaCl fused salt drop superficial layer so that carbon quickly supersaturated indigenous graphite alkene crystallization in fused solution medium,
It is finally down to room temperature, NaCl fused salt crystallizes into solid salt crystalline substance substrate, and growth has the carbon black of graphene film to be mixed therein；Use water
NaCl is dissolved and is eluted, obtains graphene powder after dry.
Claims (11)
1. a kind of method that atomization melting media prepares graphene, it is characterised in that using atomization fused solution medium as monatomic
The liquid medium and substrate that the solvent of carbon, graphene supersaturation are precipitated；First with or part using the high temperature of melt carbon source is split
Solution, monatomic carbon dissolution is in fused solution medium；By the fused solution medium atomization dissolved with monatomic carbon at drop；Pass through drop
Temperature makes carbon, and quickly supersaturated indigenous graphite alkene is crystallized in fused solution medium；It is down to room temperature, fused solution medium crystallizes into
Solid substrate, while graphene is deposited in above-mentioned solid substrate；Then at normal temperature, solid substrate dissolution is washed with solvent
It is de-, obtain graphene.
2. a kind of method that atomization melting media prepares graphene according to claim 1, it is characterised in that the high temperature
Fused solution medium, be by under room temperature in the mixture of solid one or more of substances, in high-temperature fusion to liquid.
3. a kind of method that atomization melting media prepares graphene according to claim 2, it is characterised in that the room temperature
It include down inorganic salts, alkali, metal and alloy in solid substance.
4. a kind of method that atomization melting media prepares graphene according to claim 3, it is characterised in that described inorganic
Salt include at least sodium salt, sylvite, sulfate, hydrochloride, nitrate, carbonate, phosphate, silicate, manganate, nickelate,
One or more of mixtures of cobaltatess.
5. a kind of atomization melting media method for preparing graphene according to claim 3, it is characterised in that the alkali is
Refer to the compound that can be ionized out hydroxide ion in aqueous solution and not generate other anion, includes at least hydroxide
Potassium, sodium hydroxide, calcium hydroxide.
6. a kind of method that atomization melting media prepares graphene according to claim 1, it is characterised in that the carbon source
It is one or more of carbonaceous material mixtures for carbonaceous material.
7. a kind of method that atomization melting media prepares graphene according to claim 6, it is characterised in that described carbon containing
Substance includes at least aliphatic hydrocarbon, aromatic hydrocarbon, hydrocarbon derivative, carbohydrate, carbon containing high molecular polymer.
8. a kind of method that atomization melting media prepares graphene according to claim 7, it is characterised in that the fat
Hydrocarbon, aromatic hydrocarbon and hydrocarbon derivative, including but not limited to methane, ethane, propane, butane, ethylene, propylene, acetylene, cycloalkane,
Benzene, toluene, naphthalene, methanol, ethyl alcohol.
9. a kind of method that atomization melting media prepares graphene according to claim 1, it is characterised in that the melting
Before liquid medium crystallizes into solid substrate, buoyancy sorting is carried out using the lighter feature of graphene and carbon black, by most of melting
Liquid medium recycles.
10. a kind of method that atomization melting media prepares graphene according to claim 1, it is characterised in that the use
The method of solid substrate dissolution elution is included being eluted inorganic salts, alkali soluble solution with water by solvent；Metal and alloy are dissolved with acid
Elution；Metal and alloy dissolution are eluted with electrochemical erosion method.
11. a kind of method that atomization melting media prepares graphene according to claim 1, it is characterised in that the list
Atomic carbon is uniformly blended into solid granulates while being dissolved in fused solution medium, formed dissolved with atomic carbon suspension；It is atomized into liquid
Drop；By cooling so that carbon quickly supersaturated indigenous graphite alkene crystallization obtains graphene composite material on the solid granulates.
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| 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 |
| CN111333057B (en) * | 2020-03-08 | 2021-10-12 | 西南交通大学 | Reaction device for preparing graphene and method for preparing graphene |
| 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 |
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| GB2523154B (en) * | 2014-02-14 | 2016-04-27 | Cambridge Entpr Ltd | Method of producing graphene |
| CN104860298B (en) * | 2015-03-25 | 2018-02-16 | 孙旭阳 | The method that graphene is prepared using molten state reaction bed |
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