CN110240149A - The production method of graphene - Google Patents
The production method of graphene Download PDFInfo
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- CN110240149A CN110240149A CN201910567188.0A CN201910567188A CN110240149A CN 110240149 A CN110240149 A CN 110240149A CN 201910567188 A CN201910567188 A CN 201910567188A CN 110240149 A CN110240149 A CN 110240149A
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- 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
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- 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
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- 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
- C01B2204/32—Size or surface area
Abstract
The invention discloses a kind of production method of graphene, include the following steps: that graphene oxide, dispersing agent, reducing agent and structure reinforcing agent are configured to mixed solution by (1);(2) mixed solution is added drop-wise in solidification solution, obtains graphene hydrogel;(3) graphene hydrogel is passed through into freezing processing and heat treatment, obtains graphene.There is lesser partial size and lower density by the graphene that this method is prepared.
Description
Technical field
The present invention relates to a kind of production methods of graphene.
Background technique
Graphene aerogel is a kind of tridimensional network for being prepared and being formed by graphene, has high-specific surface area, Gao Kong
The advantages that gap rate, high conductivity and good thermal conductivity and mechanical strength, catalysis, absorption, in terms of it is aobvious
Great application potential is shown.Graphene aerogel can any adjustable shape, elasticity is good, lipophilic good, itself weight can be adsorbed
The oil of 300 times of amount or more, is a kind of ideal adsorbent material.
The preparation method of existing graphene aerogel uses collosol and gel and freezing mostly using graphene oxide as raw material
Dry method is prepared.It will appear gap structure during preparing small size graphene aerogel to collapse, aeroge
The problem of density rises, reduces the application performance of aeroge.
CN106517160A discloses a kind of preparation method of isotropic super-elasticity graphene aerogel: (1) restoring
In the presence of agent, graphene oxide aqueous dispersions are stirred at low speed with lauryl sodium sulfate aqueous solution after mixing, then high-speed stirred
Foaming, graphene oxide layer is restored to form tridimensional network;(2) freezing reinforcing graphene sheet layer is formed by hole wall,
Last normal heating is dry, obtains the graphene aerogel of isotropic.This method is unable to get the graphene of small size.
CN109232013A discloses a kind of preparation method of big size graphene cystosepiment: (1) to graphene oxide water
Reducing agent is added in solution and adds surfactant after to be restored dose is completely dissolved, stirs the gas into graphene oxide solution
Bubble, obtains the foaming graphene oxide solution with micron order uniform liquid crystal phase;(2) by the foaming oxygen of micron order uniform liquid crystal phase
Graphite alkene solution, which is transferred in mold, heats reduction, obtains big size graphene hydrogel;(3) large scale hydrogel is cold
Freeze, then melt, obtains the big size graphene hydrogel of freeze thaw processing;(4) by the large scale stone of freeze thaw processing
Black alkene hydrogel naturally dry or the drying at 30~60 DEG C, obtain big size graphene cystosepiment.This method is unable to get small
The graphene of partial size.
CN108147401A discloses a kind of preparation method of graphene aerogel powder: (1) first by graphene-based slurry
Or dispersion liquid carries out cold treatment, obtains frozen samples;(2) frozen samples are crushed and is sieved at low temperature again, obtain ice
Particle;(3) ice particle is freeze-dried, obtains graphene aerogel powder.The graphene gas being prepared by this method
The density of gel powder is larger.
CN107434248A discloses a kind of preparation method of graphene aerogel microballoon: (1) providing graphene oxide water
Dispersion liquid;(2) graphene oxide aqueous dispersions and reducing agent are uniformly mixed to form mixed liquor;It (3) is single by mixed liquor injection
The microlayer model of dispersion, and the microlayer model is accepted with the powder formed by hydrophobic type particle aggregation, obtain graphene oxide moisture
The liquid hoodle of dispersion liquid;(4) liquid hoodle gel is obtained into graphene hydrogel microsphere;(5) it removes and is attached to graphene water-setting
The hydrophobic particle of glue microsphere surface, then by solvent displacement and drying, obtain graphene aerogel microballoon.This method is prepared into
The density of the graphene aerogel microballoon arrived is larger.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of production methods of graphene.What this method was prepared
Graphene has lesser partial size and lower density.
The present invention provides a kind of production method of graphene, includes the following steps:
(1) formed containing graphene oxide, dispersing agent, reducing agent and structure reinforcing agent mixed solution;
(2) mixed solution is added drop-wise in solidification solution, obtains graphene hydrogel;
(3) graphene hydrogel is passed through into freezing processing and heat treatment, obtains graphene.
Method in accordance with the invention it is preferred that containing water in mixed solution;Based on 2000 parts by weight water, the mixing is molten
Liquid includes 3~35 parts by weight graphene oxides, 3~35 parts per weight dispersing agents, 2~20 parts by weight reducing agents and 0.5~5 parts by weight
Structure reinforcing agent.
Method in accordance with the invention it is preferred that the purity of graphene oxide is 95% or more, and piece diameter≤50 μm, piece thickness
Degree≤30nm, specific surface area > 500m2/ g, oxygen carbon molar ratio are 0.15~0.65.
Method in accordance with the invention it is preferred that the concentration of graphene oxide is 0.5~20mg/ml in mixed solution.
Method in accordance with the invention it is preferred that dispersing agent is selected from lauryl sodium sulfate, neopelex, gathers
Ethylene glycol, sodium glycocholate, cetyl trimethylammonium bromide, polyvinylpyrrolidone, polystyrene sulfonate sodium, N, N- diformazan
One of base formamide is a variety of.
Method in accordance with the invention it is preferred that the reducing agent is selected from ascorbic acid, ethylenediamine, gallic acid, dioxygen
One of water, glucose, formaldehyde, citric acid are a variety of.
Method in accordance with the invention it is preferred that structure reinforcing agent be selected from borate, organic siliconresin, phenylenediamine, urea,
Diethyl amino propylamine, diaminodiphenylmethane, diaminodiphenylsulfone, trien, ammonium carbonate, ammonium hydroxide, polyethylene glycol oxide
One of or it is a variety of.
Method in accordance with the invention it is preferred that solidification solution is the chloride solution or liquid nitrogen of alkaline-earth metal.
Method in accordance with the invention it is preferred that in alkaline earth metal chloride solution, alkaline earth metal chloride concentration is 1~
10wt%.
Method in accordance with the invention it is preferred that mixed solution is dripped with the drop that diameter is 0.1~2mm in step (2)
It is added in solidification solution.
The mixed liquor of graphene oxide, dispersing agent, reducing agent, structure reinforcing agent is added drop-wise in solidification liquid in the present invention,
By freezing processing and heat treatment, obtained graphene partial size is small, and has lower density.In currently preferred technical side
In case, solidification solution uses mass fraction for the alkaline earth metal chloride solution of 1~10wt%, can graphene be had in this way
There is lower density.
Detailed description of the invention
Fig. 1 is the graphene hydrogel that the embodiment of the present invention 1 obtains
Fig. 2 is the graphene that the embodiment of the present invention 1 obtains
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, but protection scope of the present invention is not limited to
This.
The production method of graphene of the invention includes the following steps: the step of (1) prepares mixed solution;(2) stone is prepared
The step of black alkene hydrogel;(3) the step of preparing graphene.It is further explained below.
<the step of preparing mixed solution>
Formed containing graphene oxide, dispersing agent, reducing agent and structure reinforcing agent mixed solution.For example, stone will be aoxidized
Black alkene, dispersing agent, reducing agent and structure reinforcing agent are dispersed in water to form mixed solution.For another example, by graphene oxide, dispersion
Agent, reducing agent and structure reinforcing agent are dispersed in water respectively, and dispersion liquid is then mixed to form mixed solution.
Graphene oxide in the present invention can be obtained using conventional method.Including but not limited to pass through Hummers method, liquid
The methods of Xiang Fa, Mechanical Method, electrochemical oxidation process are prepared.A specific embodiment according to the present invention aoxidizes stone
Black alkene is prepared by Hummers method.
In the present invention, for the purity of graphene oxide 95% or more, piece diameter≤50 μm, lamellar spacing≤30nm compares table
Area > 500m2/ g, oxygen carbon molar ratio are 0.15~0.65.Preferably, the purity of graphene oxide is 96% or more.More preferably
Ground, the purity of graphene oxide is 98% or more.For example, can be 99%.Preferably, the piece diameter of graphene oxide is 2~45 μ
m.It is highly preferred that the piece diameter for aoxidizing black alkene is 20~30 μm.Preferably, the lamellar spacing of graphene oxide is 1~10nm.It is more excellent
Selection of land, the lamellar spacing of graphene oxide are 5~10nm.Preferably, the specific surface area > 800m of graphene oxide2/g.It is more excellent
Selection of land, the specific surface area > 1000m of graphene oxide2/g.Preferably, the oxygen carbon molar ratio of graphene oxide is 0.2~0.5.
It is highly preferred that the oxygen carbon molar ratio of graphene oxide is 0.3~0.5.The graphene being prepared can in this way had smaller
Density.
In the present invention, the concentration of graphene oxide is 0.5~20mg/ml in mixed solution.Preferably, graphene oxide
Concentration be 3~15mg/ml.It is highly preferred that the concentration of graphene oxide is 5~10mg/ml.Mixed solution can pass through ultrasound
Method be prepared.It can make mixed solution dispersion so more evenly, the graphene being prepared has smaller density.
It in the present invention, include graphene oxide, dispersing agent, reducing agent, structure reinforcing agent and water in mixed solution.Base
In 2000 parts by weight water, the dosage of graphene oxide is 3~35 parts by weight, preferably 5~25 parts by weight, more preferably 10~20
Parts by weight.Based on 2000 parts by weight water, the dosage of dispersing agent is 3~35 parts by weight, preferably 3~20 parts by weight, more preferably
10~20 parts by weight.Based on 2000 parts by weight water, the dosage of reducing agent is 2~20 parts by weight, preferably 3~15 parts by weight, more
Preferably 5~10 parts by weight.Based on 2000 parts by weight water, the dosage of structure reinforcing agent is 0.5~5 parts by weight, preferably 0.5~
3 parts by weight, more preferably 1~3 parts by weight.
It according to embodiment of the present invention, include 3~35 parts by weight graphene oxides, 3~35 weights in mixed solution
Measure part dispersing agent, 2~20 parts by weight reducing agents and 0.5~5 parts by weight structure reinforcing agent.Another embodiment party according to the present invention
Formula, includes 5~25 parts by weight graphene oxides in mixed solution, 3~20 parts per weight dispersing agents, 3~15 parts by weight reducing agents,
0.5~3 parts by weight structure reinforcing agent.Yet another embodiment according to the present invention includes 10~20 parts by weight in mixed solution
Graphene oxide, 10~20 parts per weight dispersing agents, 5~10 parts by weight reducing agents, 1~3 parts by weight structure reinforcing agent.It in this way can be with
Make the graphene being prepared that there is smaller density.
In the present invention, dispersing agent can be selected from lauryl sodium sulfate, neopelex, polyethylene glycol, sweet
Sodium taurocholate, cetyl trimethylammonium bromide, polyvinylpyrrolidone, polystyrene sulfonate sodium, N,N-dimethylformamide
One of or it is a variety of.Preferably, dispersing agent is in lauryl sodium sulfate, neopelex or polyethylene glycol
It is one or more.It is highly preferred that dispersing agent is lauryl sodium sulfate.It can make graphene oxide dispersion so more evenly, make
The graphene being prepared has lower density.
In the present invention, reducing agent can selected from ascorbic acid, ethylenediamine, gallic acid, hydrogen peroxide, glucose, formaldehyde,
One of citric acid is a variety of.Preferably, reducing agent is selected from one of ascorbic acid, ethylenediamine or gallic acid or more
Kind.It is highly preferred that reducing agent is selected from ascorbic acid.
In the present invention, structure reinforcing agent can be selected from borate, organic siliconresin, phenylenediamine, urea, diethylin third
One of amine, diaminodiphenylmethane, diaminodiphenylsulfone, trien, ammonium carbonate, ammonium hydroxide, polyethylene glycol oxide or
It is a variety of.Preferably, structure reinforcing agent is selected from one of borate, organic siliconresin or phenylenediamine.It is highly preferred that structure enhances
Agent is sodium tetraborate.The mechanical performance that graphene can be enhanced in this way is not in that gap collapses when preparing small particle graphene
It collapses, makes the graphene being prepared that there is lower density.
<the step of preparing graphene hydrogel>
Mixed solution is added drop-wise in solidification solution, graphene hydrogel is obtained.
In the present invention, solidification solution is the chloride solution or liquefied ammonia of alkaline-earth metal.Preferably, solidification solution is alkaline earth
Metal chloride solutions.It is highly preferred that solidification solution is calcium chloride solution or barium chloride solution.One according to the present invention specific
Embodiment, solidification solution be barium chloride solution.
In the present invention, in alkaline earth metal chloride solution, alkaline earth metal chloride concentration is 1~10wt%.Preferably,
Alkaline earth metal chloride concentration is 2~8wt%.It is highly preferred that alkaline earth metal chloride concentration is 3~6wt%.It can make in this way
The graphene being prepared has lower density.
In the present invention, mixed solution is added drop-wise in solidification solution with the drop that diameter is 0.1~2mm.Preferably, liquid
The diameter of drop is 0.25~1.0mm.It is highly preferred that the diameter of drop is 0.3~0.7mm.Mixed solution can be dripped by syringe needle
It is added in solidification solution.It can make the graphene being prepared that there is smaller partial size and lower density in this way.
It in the present invention, can also include heat preservation and washing after the step of mixed solution is added drop-wise to solidification solution
Step.The temperature of heat preservation is 40~150 DEG C.Preferably, the temperature of heat preservation is 60~120 DEG C.It is highly preferred that the temperature of heat preservation is
70~100 DEG C.The time of heat preservation is 3~12h.Preferably, the time of heat preservation is 5~10h.It is highly preferred that the time of heat preservation is 5
~8h.Washing washing lotion used in step can be water or the aqueous solution of ethyl alcohol.Preferably, washing lotion is the aqueous solution of ethyl alcohol.It is more excellent
Selection of land, the content of ethyl alcohol is 1~10vol% in the aqueous solution of ethyl alcohol.
<the step of preparing graphene>
Graphene hydrogel is passed through into freezing processing and heat treatment, obtains graphene.In addition, can be after freezing processing
It is dry under room temperature (15~35 DEG C), then it is heat-treated.
In the present invention, the time of freezing processing is 5~30h.Preferably, the time of freezing processing is 10~25h.It is more excellent
Selection of land, the time of freezing processing are 10~20h.The temperature of freezing processing is -35~-10 DEG C.Preferably, the temperature of freezing processing
It is -30~-10 DEG C.It is highly preferred that the temperature of freezing processing is -20~-10 DEG C.
In the present invention, the temperature of heat treatment can be 800~1300 DEG C, preferably 900~1200 DEG C, more preferably
1000~1100 DEG C.Heat treatment can carry out in the mixed airflow of inert gas and hydrogen.Preferably, inert gas is nitrogen
Or argon gas.It is highly preferred that inert gas is argon gas.
In the present invention, in the mixed airflow of inert gas and hydrogen, the flow-rate ratio of inert gas and hydrogen is 200~
50:1.Preferably, the flow-rate ratio of inert gas and hydrogen is 150~80:1.It is highly preferred that the flow-rate ratio of inert gas and hydrogen
For 120~90:1.It can make the graphene being prepared that there is lower density in this way.
Test method is described below.
Partial size test: to graphene sample grab sample, with the partial size of vernier caliper macroscopic measurement particle.
Density measurement: signified density is the bulk density of graphene sample in this test method.Keep graphene sample logical
It crosses funnel quantitatively freely to fall, after loose filling, with the graphene sample quality fallen divided by packing volume to get graphene sample
The freely settled density of product.Each graphene sample at least measures three times, is averaged.
Embodiment 1
By 10 parts by weight graphene oxides, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, and oxygen carbon molar ratio is
0.4, specific surface area 1200m2/ g), 10 parts by weight lauryl sodium sulfate, 5 parts by weight ascorbic acid, 1 parts by weight tetraboric acid
Sodium is dispersed in 2000 parts by weight of deionized water, ultrasonic disperse, obtains the mixed solution that graphene oxide concentration is 5mg/ml;
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, graphene hydrogel is obtained, referring to Fig. 1.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene, referring to fig. 2.Experimental result is referring to table 1.
Embodiment 2
By 14 parts by weight graphene oxides, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, and oxygen carbon molar ratio is
0.4, specific surface area 1200m2/ g), 14 parts by weight lauryl sodium sulfate, 7 parts by weight ascorbic acid, 1 parts by weight tetraboric acid
Sodium is dispersed in 2000 parts by weight of deionized water, ultrasonic disperse, obtains the mixed solution that graphene oxide concentration is 7mg/ml;
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, obtains graphene hydrogel.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene.Experimental result is referring to table 1.
Embodiment 3
By 20 parts by weight graphene oxides, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, and oxygen carbon molar ratio is
0.4, specific surface area 1200m2/ g), 20 parts by weight lauryl sodium sulfate, 10 parts by weight ascorbic acid, 2 parts by weight tetraboric acids
Sodium is dispersed in 2000 parts by weight of deionized water, ultrasonic disperse, obtains the mixed solution that graphene oxide concentration is 7mg/ml;
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, obtains graphene hydrogel.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene.Experimental result is referring to table 1.
Table 1
Test sample | Partial size (mm) | Density (mg/ml) |
Embodiment 1 | 0.3 | 7 |
Embodiment 2 | 0.4 | 9 |
Embodiment 3 | 0.6 | 10 |
Embodiment 4
Weighing 100mg graphene oxide respectively, (purity 99%, piece diameter are 28 μm, lamellar spacing 8nm, oxygen carbon mole
Than being 0.4, specific surface area 1200m2/ g), 100mg lauryl sodium sulfate, 50mg ascorbic acid, 1mg sodium tetraborate, by it
Be dispersed in water, ultrasonic disperse, prepare obtain graphene oxide concentration be 5mg/ml mixed solution.
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, obtains graphene hydrogel.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene.
Embodiment 5
Weighing 140mg graphene oxide respectively, (purity 97%, piece diameter are 35 μm, lamellar spacing 15nm, oxygen carbon mole
Than being 0.2, specific surface area 900m2/ g), 140mg lauryl sodium sulfate, 70mg ascorbic acid, 1mg sodium tetraborate, by it
Be dispersed in water, ultrasonic disperse, prepare obtain graphene oxide concentration be 7mg/ml mixed solution.
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, obtains graphene hydrogel.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene.
Embodiment 6
Weighing 200mg graphene oxide respectively, (purity 95%, piece diameter are 50 μm, lamellar spacing 15nm, oxygen carbon mole
Than being 0.6, specific surface area 600m2/ g), 200mg lauryl sodium sulfate, 100mg ascorbic acid, 20mg sodium tetraborate will
They are dispersed in water, ultrasonic disperse, prepare and obtain the mixed solution that graphene oxide concentration is 10mg/ml.
With diameter it is the drop of 0.5mm by mixed solution syringe needle, it is molten is added drop-wise to the barium chloride that barium chloride concentration is 5wt%
In liquid, 80 DEG C of heat preservation 6h are warming up to, is then washed with the ethanol water of 2vol%, obtains graphene hydrogel.
Graphene hydrogel is freezed into 12h, drying at room temperature, then at 1000 DEG C, in argon gas and hydrogen under the conditions of -15 DEG C
Gas atmosphere (throughput of argon gas and hydrogen ratio is 100:1) heat treatment, obtains graphene.
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of production method of graphene, which comprises the steps of:
(1) formed containing graphene oxide, dispersing agent, reducing agent and structure reinforcing agent mixed solution;
(2) mixed solution is added drop-wise in solidification solution, obtains graphene hydrogel;
(3) graphene hydrogel is passed through into freezing processing and heat treatment, obtains graphene.
2. the method according to claim 1, wherein containing water in mixed solution;Based on 2000 parts by weight water, institute
Stating mixed solution includes 3~35 parts by weight graphene oxides, 3~35 parts per weight dispersing agents, 2~20 parts by weight reducing agents and 0.5
~5 parts by weight structure reinforcing agents.
3. the method according to claim 1, wherein the purity of graphene oxide is 95% or more, piece diameter≤50 μ
M, lamellar spacing≤30nm, specific surface area > 500m2/ g, oxygen carbon molar ratio are 0.15~0.65.
4. the method according to claim 1, wherein the concentration of graphene oxide is in the mixed solution
0.5~20mg/ml.
5. the method according to claim 1, wherein the dispersing agent is selected from lauryl sodium sulfate, 12
Sodium alkyl benzene sulfonate, polyethylene glycol, sodium glycocholate, cetyl trimethylammonium bromide, polyvinylpyrrolidone, polystyrene benzene
One of sodium sulfonate, N,N-dimethylformamide are a variety of.
6. the method according to claim 1, wherein the reducing agent is selected from ascorbic acid, ethylenediamine, does not eat
One of sub- acid, hydrogen peroxide, glucose, formaldehyde, citric acid are a variety of.
7. the method according to claim 1, wherein the structure reinforcing agent is selected from borate, organosilicon tree
Rouge, phenylenediamine, urea, diethyl amino propylamine, diaminodiphenylmethane, diaminodiphenylsulfone, trien, ammonium carbonate,
One of ammonium hydroxide, polyethylene glycol oxide are a variety of.
8. the method according to claim 1, wherein the solidification solution is the chloride solution of alkaline-earth metal
Or liquid nitrogen.
9. according to the method described in claim 8, it is characterized in that, in the alkaline earth metal chloride solution, alkaline-earth metal
Chloride concentration is 1~10wt%.
10. the method according to claim 1, wherein in step (2), by mixed solution with diameter be 0.1~
The drop of 2mm is added drop-wise in solidification solution.
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