CN109264708A - A kind of manufacturing method of two-dimensional material - Google Patents
A kind of manufacturing method of two-dimensional material Download PDFInfo
- Publication number
- CN109264708A CN109264708A CN201811158662.6A CN201811158662A CN109264708A CN 109264708 A CN109264708 A CN 109264708A CN 201811158662 A CN201811158662 A CN 201811158662A CN 109264708 A CN109264708 A CN 109264708A
- Authority
- CN
- China
- Prior art keywords
- dimensional material
- pressure
- gas
- reaction kettle
- manufacturing
- 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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
-
- 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
- C01B32/19—Preparation by exfoliation
-
- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The invention discloses a kind of manufacturing methods of two-dimensional material.The manufacturing method includes the following steps: to ionize intercalation gas: the manufacture raw material of two-dimensional material are put into reaction kettle, raw material and the cathode of direct current pole plate are made to be in contact, then reaction kettle is vacuumized, intercalation gas is passed through to reach certain pressure in kettle, open plasma generator again, by intercalation gas ionization；Then the power supply for opening direct current pole plate discharges, so that being changed into gas molecule after the positive-ion trapping electronics between monolayer species；Obtain two-dimensional material presoma；Ultrasound removing: the dispersion liquid containing interleaving agent being passed through in reaction kettle, intercalation gas is displaced, and is then carried out ultrasonic lift-off processing to two-dimensional material presoma and is heated simultaneously, holding terminates ultrasonic removing after a certain period of time；Optionally, further progress temperature-pressure decomposes, and obtains the mixture of interleaving agent and two-dimensional material；Mixture is finally obtained into two-dimensional material successively by washing, purification and drying steps.Compared with prior art, the present invention beneficial effect is: technique has continuous production, and single layer rate is high, and cost is extremely low, can be mass produced.
Description
Technical field
The invention belongs to material manufacture technical fields, more particularly to a kind of manufacturing method of two-dimensional material.
Background technique
With the reach of science, the manufacture minute yardstick record of material is constantly refreshed, and occurs monatomic or single point recently
Sub- bistable material.Two-dimensional material, definition temporary at present refer to that electronics only can be in the non-nanosize (1-100nm) of two dimensions
The material of upper free movement (plane motion), there are three the essential characteristics of aspect: 1) structurally ordered；2) it is grown in two-dimensional surface；
3) ultra-thin in third dimension.It common are the two-dimensional material of machine class such as: two-dimentional biphenyl class and union II acetylenic substance；Inorganic
Two-dimensional material is such as: graphene and graphite alkane, two-dimentional hexagonal boron nitride, two-dimentional magnesium-yttrium-transition metal oxide sulfide selenides,
Black phosphorus alkene etc..
The representative for the more two-dimensional material studied at present is the two-dimensional material of carbon --- graphene, common several systems
The advantage and disadvantage for making method are listed below:
One, mechanical stripping method: micro-nano manufacture stripping means and device is easy to operate, product quality is high, is currently to produce
The main method and device of single layer high-quality graphene.But its controllability is poor, and graphene size obtained is smaller and exists very
Big uncertainty, while low efficiency, it is at high cost, be not suitable for large-scale production.
Two, epitaxial growth method: quality is preferable, but yield is small, and cost is very high.
Three, graphite oxide reduction method: obtained single layer rate is small, is easy to reunite, leads to the electric conductivity and ratio of graphene
Surface area reduces, its application in optoelectronic device is further influenced, in addition, easily causing graphene in oxidation-reduction process
Crystal structure defects, such as the loss of carbon atom on carbocyclic ring, and production discharge is seriously polluted etc..
Four, chemical gaseous phase deposition CVD method: being exactly the evolution of method two, can only carry out at lower temperatures, thus
The consumption of energy in manufacturing process can be reduced, and graphene and substrate can pass through chemical attack metal process and device
Separation is conducive to subsequent be processed graphene.But yield is small, and post-processing also generates a large amount of pollution.
Five, substance intercalation stripping method: typical such as supercritical carbon dioxide intercalation, what is had adds ultrasonic wave microexplosion, can be with
Realize large-scale production, single layer rate be also it is highest in addition to CVD method, single layer rate is more than 8%.But due in natural material,
Overlapping between fractional monolayer be it is silent, extraneous common substance cannot be introduced into wherein, with improving pressure or other tradition
Method, be helpless to the raising of single layer rate.
Based on above-mentioned defect in the prior art, the industrialization of two-dimensional material at present is the generation of current research and development urgent need to resolve
Boundary's grade problem.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of manufacturing methods of two-dimensional material.The present invention has can
Continuous production, single layer rate is high, at low cost, the advantages that being mass produced.
To achieve the above object, the present invention takes following technical scheme:
A kind of manufacturing method of two-dimensional material, includes the following steps:
(1) intercalation gas is ionized:
The manufacture raw material of the two-dimensional material of certain molal quantity are put into reaction kettle, and make the raw material with connect it is straight
The electrode plate of stream power cathode is in contact, and then vacuumizes to reaction kettle, is passed through intercalation gas and to reach certain pressure in kettle,
Intercalation gas ionization after ionizing a period of time, is closed plasma generator by open plasma generator again；Then it beats
The DC power supply of the electrode plate is opened, and is kept for certain time, so that turning after the positive-ion trapping electronics between monolayer species
Become gas molecule, then stops direct-current discharge；Obtain two-dimensional material presoma；
(2) ultrasound removing:
Dispersion liquid containing interleaving agent is passed through in reaction kettle with the pressure for being higher than air pressure in kettle, is displaced in reaction kettle
Intercalation gas, is then turned on ultrasonic equipment, carries out ultrasonic lift-off processing to the two-dimensional material presoma and heats simultaneously, protects
It holds and closes ultrasonic equipment after a certain period of time, terminate ultrasonic lift-off processing；
Optionally, in step (2), further progress step (3) temperature-pressure is decomposed afterwards:
The substance of reaction kettle after step (2) ultrasound removing is decomposed under certain temperature and pressure, the temperature and
Pressure can make two-dimensional material presoma decompose to obtain the two-dimensional material, then vacuumize removing solvent, be isolated
The concentration mixture of agent and two-dimensional material, i.e. slurry；
Optionally, in step (3), further progress step (4) repeats step (1)~(3) afterwards:
Product after step (1)~(3) are stripped is tested, if not reaching the requirement such as two-dimensional material size, is weighed
Multiple step (1)~(3), until product meets the requirement such as two-dimensional material size.
(5) mixture is obtained into the two-dimensional material successively by washing, purification and drying steps.
The present invention opens cold plasma generator and makes the intercalation gas ionization in reaction kettle can at gas ions, such as hydrogen
As intercalation gas, hydrogen be ionized after ion diameter very little, a diameter of 1.6 × 10-6Nm can be very easy to penetrate into mesh
The molecule of most of substance can be even penetrated into the microcosmic monolayer species gap of the manufacture raw material of preceding all two-dimensional materials
In, then be passed through low-voltage DC and kept for certain time, so that becoming atom after the ion capture electronics of gas, between atom again
It can be combined into gas, such intercalation gas is just between the microcosmic monolayer species for the treatment of material；Then with biggish
Pressure is pumped into the solution containing interleaving agent, by filter net device, displaces the intercalation gas other than microcosmic monolayer species hole,
Due to the damping action of the minim channel between the microcosmic monolayer species for the treatment of material, intercalation gas inside it be not easy by
Displacement；Ultrasonic unit is opened, certain frequency ultrasonic wave has strong cavitation effect, so that inserting between microcosmic monolayer species
Layer gas generates instantaneous expansion, once overcome the Van der Waals force between monolayer species, so that it may the monolayer species are removed, are obtained
There is the dispersion liquid or slurry of the two-dimensional material of the interleaving agent to surface, then product is washed and dried as needed
Deng post-processing.It should be understood that some ions such as hydrogen ion can be sent out after trapped electron becomes atom with the raw material having
Raw reaction, then need further to obtain object by the method for heating, as graphite can be pressed at normal temperature with atomic reaction of hydrogen
Method production of the invention, Primary product is graphite alkane, but if by graphite alkane be heated to the decomposition temperature of graphite alkane with
It goes up and is kept for the corresponding time, graphite alkane will thoroughly be decomposed into graphene and hydrogen, so that final product graphene be made.
Further, the manufacture raw material of the two-dimensional material include graphite, molybdenum disulfide, boron nitride, Transition Metal Sulfur
Compounds of group, metal halide, layered metal oxide, layered bi-metal oxide, oxide, transition metal oxyhalide,
One of stratiform α and γ zirconium phosphate and phosphate, clay, ternary transition metal nitride and carbide are a variety of, preferably
For graphite.The Transition-metal dichalcogenide is WSe2、ZnPS3Or Sb2Se3；The metal halide is PbI2、MgBr2Or
CrCl3；Layered metal oxide is MnO2、WO3Or LaNb2O7；Layered bimetallic oxide is Mg6Al2(OH)16；
The oxide is perovskite, niobates, rutile or Sr2RuO4；The transition metal oxyhalide is VOCl, WO2Cl2Or
FeOCl；The clay is montmorillonite, mica, vermiculitebiotite, phlogopite, fluorophologopite；The carbide is Ti3C2。
Further, the plasma generator includes direct current or pulsed discharge plasma generator, exchange or friendship
Change discharge plasma generator or high-frequency induction discharge plasma generator, direct current or the pulse power: voltage 0.01
~900KV, 0.01~50A of electric current；Exchange or alternating source, voltage are 0.01~900KV, electric current 0.01~50A, and frequency is
1~300KHZ；Induction power supply, frequency is 1~90MHZ.
Preferably, the plasma generator is alternating current discharge plasma generator, and the voltage of power supply is
800KV, frequency 200KHZ, electric current 5A.
Further, it is 1~1000Pa that step (1) reaction kettle, which vacuumizes rear pressure,；Pressure after being passed through intercalation gas
Power is 0.11~100MPa, and ionization intercalation gas time is 0.01~12 hour.
Preferably, it is 10Pa that step (1) reaction kettle, which vacuumizes rear relative degree of vacuum,；Pressure after being passed through intercalation gas
For 7MPa, voltage 10-100KV, the reaction time is 4 hours.
Further, intercalation gas includes carbon dioxide, nitrogen, hydrogen, helium, neon or argon gas in the step (1).
Preferably, the intercalation gas is hydrogen.
Further, the molar ratio of the intercalation gas and manufacture raw material is 1~10000:1.
Further, DC voltage is 0.11-1000V, electric current 0.01-2A in the step (1), when direct-current discharge
Between be 0.01-18 hours.
Preferably, DC voltage is 4V in the step (1), and electric current 0.1A, the direct-current discharge time is 8 hours.
Further, it is described containing mass concentration be 0.01-19% interleaving agent dispersion liquid, be higher than kettle in air pressure pressure
Power is pumped into reaction kettle, and the molar ratio of the manufacture raw material of dispersion liquid and the two-dimensional material is 0.5~900:1.
Preferably, the mass concentration of the isolation agent dispersing liquid is 0.3%, and isolation agent dispersing liquid is pumped into instead with 8MPa pressure
It answers in kettle.
Further, the interleaving agent in the step (2) includes sodium n-alkylbenzenesulfonate (LAS), fatty alcohol polyoxy second
Alkene ether sodium sulfate (AES), fatty alcohol polyoxyethylene ether ammonium sulfate (AESA), sldium lauryl sulfate (K12 or SDS), lauroyl
Glutamic acid, nonylphenol polyoxyethylene ether (TX-10), peregal, diglycollic amide (6501) glycerol stearate monoesters, sulfomethylated lignin
Hydrochlorate, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum sulfonate), dispersing agent NNO, dispersing agent MF, alkyl, polyether (PO-EO
Copolymer), one of fatty alcohol polyoxyethylene ether (AEO-3) or a variety of.
Preferably, interleaving agent described in step (2) is monoethanolamine.
Further, the solvent of the isolation agent dispersing liquid includes water, the oxide of melting, the sulfide of melting, melting
Salt or one of organic solvent or a variety of.
Preferably, the solvent is water.
Further, supersonic frequency is 1~30KHz in the step (2), and 2~400KW of power, heating temperature is room temperature
~180 DEG C, the reaction time is 0.11~30 hour.
Preferably, supersonic frequency is 20KHz in the step (2), and power 3KW, heating temperature is 90 DEG C of room temperature.
Further, step (3) temperature is room temperature~900 DEG C, and pressure is 0.101~90MPa, and the reaction time is
0.11~12 hour, evacuated pressure 0-1000Pa.
Preferably, step (3) temperature is 105 DEG C, pressure 90MPa, and the reaction time is 8 hours, evacuated pressure
For 10Pa.
Further, step (4) drying temperature is room temperature~1500 DEG C
The present invention has following technical characterstic:
1) present invention is suitble to the high-volume continuous production to two-dimensional material, applied widely, easy to operate, at low cost.
2) the two-dimensional material purity is high that the present invention is prepared, single layer rate is high and defect is few.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of 2 product graphene of embodiment.
Fig. 2 is the Raman spectrogram of 2 product graphene of embodiment.
Specific embodiment
Following specific embodiments are the further explanations to method provided by the invention and technical solution, but are not construed as
Limitation of the present invention.
Embodiment 1
Steps are as follows for the manufacturing method of graphite alkane:
(a), after 120 grams of natural flake graphites being put into reaction kettle, each valve is closed, water-tight equipment, opening vacuum pump will
Reaction kettle is evacuated to 8Pa；
(b), using hydrogen as intercalation gas, then steam supply valve is opened, until Hydrogen Vapor Pressure 4MPa in reaction kettle, closes gas supply
Valve；
(c), plasma generator is opened, the time of plasma treatment material is 3 hours, so that ion is inserted into microcosmic list
In the minim gap of layer substance, it is then shut off plasma generator；
(d), it opens low-voltage dc power supply and is kept for certain time, the cathode of direct current is in contact with treating material, directly
The voltage of galvanic electricity is 15V, is kept for 2 hours, so that the ion of hydrogen becomes atom after obtaining electronics, can be combined again between atom
As gas, it is then shut off DC power supply；
(e), having will be pumped into reaction kettle added with the water of 0.9% monoethanolamine with the pressure of 5MPa, pass through filter device
Hydrogen is all displaced into reaction kettle, such hydrogen just between microcosmic monolayer species, is opening ultrasonic unit, ultrasonic wave
Frequency be 20KHz, power 3KW, and heat simultaneously, temperature is 50 DEG C, and the retention time is 3 hours, turns off valve and discharges
Intercalation gas is dispersed in the aqueous solution added with monoethanolamine to normal pressure so that being fully exfoliated between the single layer of raw material, must
There is the two-dimensional material mixed dispersion liquid or slurry not easy to reunite of interleaving agent to the surface；
(f), 100 DEG C of boiling temperature or more of water are heated to, is kept for 1 hour；It vacuumizes and removes water, vacuum pressure is
200Pa, enriched product, just obtaining the surface has the mixing slurry of graphite alkane and interleaving agent not easy to reunite of interleaving agent
Material；
(g), product is washed and is dried as needed, drying temperature range is at 179~220 DEG C, evaporation purification
Pure two-dimensional material, packaging factory is made.
Embodiment 2
Steps are as follows for graphene manufacturing method:
(a), after 130 grams of natural flake graphites being put into reaction kettle, each valve is closed, water-tight equipment, opening vacuum pump will
Reaction kettle is evacuated to 10Pa；
(b), using hydrogen as intercalation gas, then steam supply valve is opened, until Hydrogen Vapor Pressure 7MPa in reaction kettle, closes gas supply
Valve；
(c) plasma generator is opened, the time of plasma treatment material is 2 hours, so that ion is inserted into microcosmic list
In the minim gap of layer substance, it is then shut off plasma generator；
(d), it opens low-voltage dc power supply and is kept for certain time, the cathode of direct current is in contact with treating material, directly
The voltage of galvanic electricity is 10V, is kept for 1 hour, so that the ion of hydrogen becomes atom after obtaining electronics, can be combined again between atom
DC power supply is closed as gas；
(e), having will be pumped into reaction kettle added with the glycerol of 0.5% monoethanolamine with the pressure of 8MPa, be filled by filtering
It sets and hydrogen is all displaced into reaction kettle, such hydrogen just between microcosmic monolayer species, is opening ultrasonic unit, ultrasound
The frequency of wave is 30KHz, power 4KW, and is heated simultaneously, and temperature is 90 DEG C, and the retention time is 2 hours, turns off valve and releases
Intercalation gas is put to normal pressure, so that being fully exfoliated the glycerite being dispersed in added with monoethanolamine between the single layer of raw material, just
Obtain the two-dimensional material mixed dispersion liquid or slurry not easy to reunite that the surface has interleaving agent；
(f), 455 DEG C of decomposition temperature or more of graphite alkane are pressurized to, is kept for 12 hours, maximum pressure 90MPa；Again
It closes valve and is vacuumized after discharging intercalation gas, solvent is removed and recycled by vacuum pressure 200Pa, enriched product, just
Obtaining the surface has the mixed slurry of graphene and interleaving agent not easy to reunite of interleaving agent；
(g), product is washed and is dried as needed, drying temperature range is at 178~210 DEG C, evaporation purification
Pure two-dimensional material, packaging factory is made.Transmission electron microscope photo and Raman spectrogram such as Fig. 1 and Fig. 2 institute of product graphene
Show.
Embodiment 3
Steps are as follows for the manufacturing method of two-dimentional molybdenum disulfide:
(a), after 120 grams of molybdenum disulfide raw materials being put into reaction kettle, each valve is closed, water-tight equipment, opening vacuum pump will
Reaction kettle is evacuated to 16Pa；
(b), using hydrogen as intercalation gas, then steam supply valve is opened, until Hydrogen Vapor Pressure 6MPa in reaction kettle, closes gas supply
Valve；
(c), plasma generator is opened, the time of plasma treatment material is 7 hours, so that ion is inserted into microcosmic list
In the minim gap of layer substance, it is then shut off plasma generator；
(d), it opens low-voltage dc power supply and is kept for certain time, the cathode of direct current is in contact with treating material, directly
The voltage of galvanic electricity is 15V, is kept for 2 hours, so that becoming atom after the ion capture electronics of hydrogen, can be combined again between atom
DC power supply is closed as gas；
(e), having will be pumped into reaction kettle added with the aqueous solution of 0.2% monoethanolamine with the pressure of 7MPa, pass through filtering
Hydrogen is all displaced reaction kettle by device, and such hydrogen just between microcosmic monolayer species, is being opened ultrasonic unit, surpassed
The frequency of sound wave is 25KHz, power 1KW, and is heated simultaneously, and temperature is 70 DEG C, and the retention time is 6 hours, turns off valve simultaneously
Intercalation gas is discharged to normal pressure, is dispersed in the aqueous solution added with monoethanolamine so that being fully exfoliated between the single layer of raw material,
Just obtain the two-dimensional material mixed dispersion liquid or slurry not easy to reunite that the surface has interleaving agent；
(f), 105 DEG C of temperature or more are heated to, is kept for 1 hour, is vacuumized remove water later, vacuum pressure 200Pa,
Enriched product, just obtaining the surface has the mixed slurry of molybdenum disulfide and interleaving agent not easy to reunite of interleaving agent；
(g), product is washed and is dried as needed, drying temperature range is at 175~213 DEG C, evaporation purification
Pure two-dimensional material, packaging factory is made.
Embodiment 4
Steps are as follows for the manufacturing method of two-dimentional hexagonal boron nitride:
(a), after 400 grams of hexagonal boron nitride raw materials being put into reaction kettle, each valve is closed, water-tight equipment opens vacuum pump
Reaction kettle is evacuated to 19Pa；
(b), using hydrogen as intercalation gas, then steam supply valve is opened, until Hydrogen Vapor Pressure 4MPa in reaction kettle, closes gas supply
Valve；
(c), plasma generator is opened, the time of plasma treatment material is 7 hours, so that ion is inserted into microcosmic list
In the minim gap of layer substance, it is then shut off plasma generator；
(d), it opens low-voltage dc power supply and is kept for certain time, the cathode of direct current is in contact with treating material, directly
The voltage of galvanic electricity is 6V, is kept for 3 hours, again can be between atom so that become atom after the ion capture electronics of intercalation gas
It is combined into gas and closes DC power supply；
(e), having will be pumped into reaction kettle added with the aqueous solution of 0.3% monoethanolamine with the pressure of 5MPa, pass through filtering
Hydrogen is all displaced reaction kettle by device, and such hydrogen just between microcosmic monolayer species, is being opened ultrasonic unit, surpassed
The frequency of sound wave is 18KHz, power 5KW, and is heated simultaneously, and temperature is 80 DEG C, and the retention time is 4 hours, turns off valve simultaneously
Intercalation gas is discharged to normal pressure, is dispersed in the aqueous solution added with monoethanolamine so that being fully exfoliated between the single layer of raw material,
Just obtain the surface have interleaving agent monoethanolamine two-dimensional material hexagonal boron nitride mixed dispersion liquid not easy to reunite or
Slurry；
(f), 100 DEG C of boiling temperature or more of water are heated to, is kept for 1 hour；It vacuumizes and removes water, vacuum pressure is
200Pa, enriched product, just obtaining the surface has the mixing of hexagonal boron nitride and interleaving agent not easy to reunite of interleaving agent
Slurry；
(g), product is washed and is dried as needed, drying temperature range is at 176~206 DEG C, evaporation purification
Pure two-dimensional material, packaging factory is made.
The method of the present invention that the above embodiments are only used to help understand and its core concept.It should be pointed out that for
For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention
Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection scope.
Claims (10)
1. a kind of manufacturing method of two-dimensional material, which comprises the steps of:
(1) intercalation gas is ionized:
The manufacture raw material of the two-dimensional material of certain molal quantity are put into reaction kettle, and make the raw material with connect direct current
The electrode plate of source cathode is in contact, and then vacuumizes to reaction kettle, is passed through intercalation gas and to reach certain pressure in kettle, then beats
The plasma generator is opened, by intercalation gas ionization, after ionizing a period of time, closes plasma generator；Then it beats
The DC power supply for opening the electrode plate discharges, and is kept for certain time, so that the positive-ion trapping between monolayer species
It is changed into gas molecule after electronics, then stops electric discharge；Obtain two-dimensional material presoma；
(2) ultrasound removing:
Dispersion liquid containing interleaving agent is passed through in reaction kettle with the pressure for being higher than air pressure in kettle, displaces the intercalation in reaction kettle
Gas is then turned on ultrasonic equipment, carries out ultrasonic lift-off processing to the two-dimensional material presoma and heats simultaneously, keeps one
Ultrasonic equipment is closed after fixing time, and terminates ultrasonic lift-off processing；
Optionally, in step (2), further progress step (3) temperature-pressure is decomposed afterwards:
The substance of reaction kettle after step (2) ultrasound removing is decomposed under certain temperature and pressure, the temperature and pressure
Two-dimensional material presoma can be made to decompose to obtain the two-dimensional material, then vacuumize removing solvent, obtain interleaving agent with
The concentration mixture of two-dimensional material, i.e. slurry；
Optionally, in step (3), further progress step (4) repeats step (1)~(3) afterwards:
Product after step (1)~(3) are stripped is tested, if not reaching the requirement such as two-dimensional material size, repeats to walk
Suddenly (1)~(3), until product meets the requirement such as two-dimensional material size.
(5) mixture is obtained into the two-dimensional material successively by washing, purification and drying steps.
2. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that the manufacture of the two-dimensional material
Raw material include graphite, molybdenum disulfide, boron nitride, Transition-metal dichalcogenide, metal halide, layered metal oxide,
Layered bi-metal oxide, oxide, transition metal oxyhalide, stratiform α and γ zirconium phosphate and phosphate, clay, ternary
One of transition metal nitride and carbide are a variety of.
3. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that step (1) reaction kettle
Vacuumizing rear pressure is 1~1000Pa；Pressure after being passed through intercalation gas is 0.11~100MPa, and ionization intercalation gas time is
0.01~12 hour.
4. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that intercalation in the step (1)
Gas includes one of carbon dioxide, nitrogen, hydrogen, helium, neon or argon gas or a variety of.
5. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that direct current in the step (1)
Piezoelectric voltage is 0.11-1000V, and electric current 0.01-2A, the direct-current discharge time is 0.01-18 hours.
6. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that described to be containing mass concentration
The dispersion liquid of 0.01-19% interleaving agent is pumped into reaction kettle, dispersion liquid and the two-dimensional material with being higher than the pressure of air pressure in kettle
Manufacture raw material molar ratio be 0.5~900:1.
7. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that in the step (2) every
It include sodium n-alkylbenzenesulfonate (LAS), sodium sulfate of polyethenoxy ether of fatty alcohol (AES), fatty alcohol polyoxyethylene ether sulphur from agent
It is sour ammonium (AESA), sldium lauryl sulfate (K12 or SDS), lauroyl glutamate, nonylphenol polyoxyethylene ether (TX-10), average
Add, diglycollic amide (6501) glycerol stearate monoesters, lignosulfonates, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum
Sulfonate), dispersing agent NNO, dispersing agent MF, alkyl, polyether (PO-EO copolymer), in fatty alcohol polyoxyethylene ether (AEO-3)
It is one or more.
8. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that ultrasonic in the step (2)
Frequency is 1~30KHz, and 2~400KW of power, heating temperature is room temperature~180 DEG C, and the reaction time is 0.11~30 hour.
9. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that step (3) temperature is
Room temperature~900 DEG C, pressure are 0.101~90MPa, and the reaction time is 0.11~12 hour, evacuated pressure 0-1000Pa.
10. a kind of manufacturing method of two-dimensional material according to claim 1, which is characterized in that the step (1) it is equal from
Daughter generator includes direct current or pulsed discharge plasma generator, exchange or alternating discharge plasma generator or high frequency
Induction discharge plasma generator, direct current or the pulse power: voltage is 0.01~900KV, 0.01~50A of electric current；Exchange
Or alternating source, voltage is 0.01~900KV, and 0.01~50A of electric current, frequency is 1~300KHZ；Induction power supply, frequency
For 1~90MHZ.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810824172 | 2018-07-25 | ||
| CN2018108241729 | 2018-07-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109264708A true CN109264708A (en) | 2019-01-25 |
| CN109264708B CN109264708B (en) | 2021-03-12 |
Family
ID=65194975
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811158662.6A Active CN109264708B (en) | 2018-07-25 | 2018-09-30 | Method for manufacturing two-dimensional material |
| CN201910145173.5A Pending CN110194448A (en) | 2018-07-25 | 2019-02-27 | A kind of two-dimensional material of graphene coated or the manufacturing method of graphene |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910145173.5A Pending CN110194448A (en) | 2018-07-25 | 2019-02-27 | A kind of two-dimensional material of graphene coated or the manufacturing method of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN109264708B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761232A (en) * | 2019-03-28 | 2019-05-17 | 中国矿业大学(北京) | A kind of device and method preparing compound between graphite layers |
| CN111606312A (en) * | 2020-06-11 | 2020-09-01 | 四川大学 | Method and apparatus for stripping hexagonal boron nitride by arc plasma pretreatment |
| CN113770356A (en) * | 2021-09-06 | 2021-12-10 | 广东工业大学 | Processing technology and system for preparing metal single element two-dimensional topological material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085884A (en) * | 2014-07-11 | 2014-10-08 | 中国科学院等离子体物理研究所 | Method for improving electrochemical performance through reducing graphene oxide (GO) by using hydrogen (H2) and argon (Ar) mixed plasma |
| CN107098321A (en) * | 2017-04-12 | 2017-08-29 | 天津大学 | The method that low temperature plasma prepares two-dimensional structure carboritride |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502604A (en) * | 2011-11-03 | 2012-06-20 | 东南大学 | Preparation method of multifunctional graphene tube |
| CN103224231B (en) * | 2013-04-23 | 2014-11-05 | 北京大学 | Transfer method of graphite film |
| CN103213980B (en) * | 2013-05-13 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of three-dimensional grapheme or its compound system |
| CN105129763B (en) * | 2015-09-09 | 2017-09-26 | 上海大学 | A kind of preparation method of three-dimensional grapheme/mesoporous carbon spheres composite |
| CN106082176A (en) * | 2016-05-25 | 2016-11-09 | 江苏科技大学 | A kind of preparation method of three-dimensional grapheme |
| CN106219521B (en) * | 2016-07-12 | 2018-08-31 | 昆明理工大学 | A kind of preparation method of three-dimensional foam graphene |
-
2018
- 2018-09-30 CN CN201811158662.6A patent/CN109264708B/en active Active
-
2019
- 2019-02-27 CN CN201910145173.5A patent/CN110194448A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085884A (en) * | 2014-07-11 | 2014-10-08 | 中国科学院等离子体物理研究所 | Method for improving electrochemical performance through reducing graphene oxide (GO) by using hydrogen (H2) and argon (Ar) mixed plasma |
| CN107098321A (en) * | 2017-04-12 | 2017-08-29 | 天津大学 | The method that low temperature plasma prepares two-dimensional structure carboritride |
Non-Patent Citations (2)
| Title |
|---|
| RAJESH KUMAR ET AL.: "Pressure-dependent synthesis of high-quality few-layer graphene by plasma-enhanced arc discharge and their thermal stability", 《JOURNAL OF NANOPARTICLE RESEARCH》 * |
| SUNG YEUN CHOI ET AL.: "Large scale production of high aspect ratio graphite nanoplatelets with tunable oxygen functionality", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761232A (en) * | 2019-03-28 | 2019-05-17 | 中国矿业大学(北京) | A kind of device and method preparing compound between graphite layers |
| CN109761232B (en) * | 2019-03-28 | 2020-09-25 | 中国矿业大学(北京) | Device and method for preparing graphite intercalation compound |
| CN111606312A (en) * | 2020-06-11 | 2020-09-01 | 四川大学 | Method and apparatus for stripping hexagonal boron nitride by arc plasma pretreatment |
| CN111606312B (en) * | 2020-06-11 | 2021-01-05 | 四川大学 | Method and apparatus for stripping hexagonal boron nitride by arc plasma pretreatment |
| CN113770356A (en) * | 2021-09-06 | 2021-12-10 | 广东工业大学 | Processing technology and system for preparing metal single element two-dimensional topological material |
| CN113770356B (en) * | 2021-09-06 | 2022-04-08 | 广东工业大学 | Processing method and system for preparing metal single element two-dimensional topological material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110194448A (en) | 2019-09-03 |
| CN109264708B (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108117065B (en) | Method for preparing graphene by adopting alternate current stripping | |
| CN106882796B (en) | Preparation method of three-dimensional graphene structure/high-quality graphene | |
| CN109264708A (en) | A kind of manufacturing method of two-dimensional material | |
| JP7156648B2 (en) | Carbon nanostructured material and method of forming carbon nanostructured material | |
| WO2015184816A1 (en) | Nitrogen-doped graphene sheet and method for preparation and use thereof | |
| CN104386678B (en) | A kind of preparation method of Graphene | |
| JP5649186B2 (en) | Onion-like carbon and method for producing the same | |
| CN103160900B (en) | One prepares Fe in conductive substrates 2o 3the method of nano-tube array | |
| US10815579B2 (en) | Catalyst for water splitting and method for preparing same | |
| CN107492658A (en) | A kind of titanium disulfide nanometer sheet and preparation method thereof | |
| CN104577049A (en) | Hierarchical pore structure silicon-based negative electrode material for lithium battery and preparation method of hierarchical pore structure silicon-based negative electrode material | |
| CN111217361B (en) | Method for preparing graphene nanosheet through electrochemical cathode stripping | |
| CN108622887B (en) | Method for preparing graphene through microwave puffing | |
| CN103484889B (en) | A kind of method preparing the few layer graphene powder of high quality in a large number | |
| CN104979533B (en) | Preparation method of graphene nanoribbon wound germanium nanoparticle composite material | |
| CN103359713A (en) | Preparation method of graphene | |
| CN102605413A (en) | Hydrothermal-electrochemical method for preparing diamond film | |
| CN110371958A (en) | A kind of Microwave reduction method prepares molysite intercalated graphite alkene aeroge | |
| CN109686582A (en) | A method of combination electrode is prepared based on graphene and polyethylene dioxythiophene | |
| CN113148988B (en) | Preparation method of nitrogen-atom-doped graphene quantum dot | |
| CN103950925B (en) | A kind of preparation method of nanoscale graphite flake | |
| CN105417543B (en) | Preparation process of nano porous silicon electrode material | |
| CN103879988A (en) | Boron-doped graphene nano-belt preparation method | |
| CN103879991B (en) | The preparation method of graphene nanobelt | |
| KR100461966B1 (en) | Carbon nano tube electrode electrochemical double layer capacitor using the same and fabricationa method thereof |
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 |