CN110395717A - A kind of preparation method of fold graphene - Google Patents
A kind of preparation method of fold graphene Download PDFInfo
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- CN110395717A CN110395717A CN201910697726.8A CN201910697726A CN110395717A CN 110395717 A CN110395717 A CN 110395717A CN 201910697726 A CN201910697726 A CN 201910697726A CN 110395717 A CN110395717 A CN 110395717A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The present invention provides a kind of preparation method of fold graphene.The material of oxygen-containing group layer and ferric trichloride alternating intercalated graphite is prepared first, removing oxygen-containing group layer obtains dispersible ferric trichloride intercalation graphene oxide in water, then film forming is filtered, film is immersed in hydrogen peroxide solution, make to generate a large amount of folds inside film, film naturally dry is taken out later, and finally film is immersed in hydroiodic acid solution and is restored, the graphene film of independent self-supporting is obtained.The method of the invention can efficiently prepare high fold graphene film, effectively mitigate graphene sheet layer structural damage, improve the popularity and uniformity of graphene fold, preparation process is simple, requirement to equipment is lower, is suitable for industry or laboratory operation, has huge application prospect.
Description
Technical field
The present invention relates to graphene film preparation field, especially a kind of preparation method of fold graphene film.
Background technique
Graphene is the quasi- two dimension that the thickness that one kind is made of carbon atom completely is only monoatomic layer or several monoatomic layers
Crystalline material, special structure contain abundant and novel physical phenomenon, it is made to show excellent optics, electricity, power
Learn characteristic, materialogy, sea water desalination, micro-nano technology, the energy, biomedicine and in terms of have important application
A kind of prospect, it is considered to be future revolutionary material.One main application form of graphene is by microcosmic oxidation stone
Black alkene or graphene film are assembled into the graphene film of macroscopic view.Fold graphene has unique pleated structure, has excellent
Tensile property, higher specific surface area and mesoporous can be provided, in conjunction with graphene own advantages, the material is made to be expected to become flexibility
Device, filter membrane, high-performance super capacitor and lithium ion battery electrode material, in FPD, anticorrosion, electric heating material
Material, energy storage field, Industrial Catalysis field all have preferable application prospect.But the preparation side of existing high fold graphene
Method mainly passes through chemical vapor deposition or wet-dry change transfer, and complex process, energy consumption are high, and equipment requirement is high, and fold stone
Black alkene technical report it is seldom, need to develop a kind of effective high fold graphene large-scale preparation method.
Graphite oxide is otherwise known as graphite oxide or referred to as graphitic acid, can pass through strong oxidizer and handle graphite preparation
It obtains, the highest product of degree of oxidation is a kind of carbon oxygen ratio of number yellow solid between 2.1 to 2.9, still reservation stone
The laminated structure of black parent, but the spacing (about 0.7nm) of two interlayers is about twice of interlamellar spacing in graphite.In recent years, with
Graphite oxide, which carrys out large-scale industrial production graphene for raw material, becomes main way, a large amount of hydrophilic due to existing in graphite oxide
Group, graphite oxide are easy to form single graphite linings, but graphite oxide itself is insulator or half in aqueous dispersion
Conductor needs to obtain graphene by reduction reaction again.Efficiently removing it can prepare single layer although with graphite oxide method and lack
Layer graphene, but the destruction of graphene sheet layer structure can seriously bring asking for the variation such as graphene film electric conductivity and mechanical property
Topic.
Summary of the invention
The present invention provides a kind of preparation method of fold graphene.From graphite raw material, oxygen-containing group layer is prepared first
With the material of ferric trichloride alternating intercalated graphite, removing oxygen-containing group layer obtains dispersible ferric trichloride intercalation oxidation in water
Then graphene filters film forming.Ferric trichloride in graphene is the key that cause fold, and film is immersed in hydrogen peroxide solution,
Ferric trichloride catalytic hydrogen peroxide dissociation reaction generates gas, makes to generate a large amount of gaps inside film, takes out film later, will be thin
Film naturally dry.Iron ion catalyzing hydrogen peroxide remaining in film point can be utilized by the repeated multiple times immersion hydrogen peroxide solution of film
Solution persistently generates fold, and iron ion is removed also with number increase is impregnated.Finally, film is immersed in hydroiodic acid solution also
Original obtains the graphene film of independent self-supporting.
The present invention adopts the following technical scheme:
A kind of preparation method of fold graphene, includes the following steps:
(1) anhydrous ferric trichloride and graphite Hybrid Heating are prepared into second order graphite intercalation compound with molte-salt synthesis, adopted
Oxidation intercalation is carried out to second order graphene intercalation compound with oxidant and concentrated acid, obtains oxygen-containing group layer and ferric trichloride alternating
The material of intercalated graphite；
(2) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into aqueous solution and are ultrasonically treated, remove oxygen-containing group
Group's layer obtains dispersible ferric trichloride intercalation graphene oxide in water, filters film forming；
(3) film is immersed in hydrogen peroxide solution, takes out film after reaction, by film naturally dry, this process can be more
It is secondary to repeat；
(4) film is immersed in hydroiodic acid solution and is reacted, obtain the graphene film of independent self-supporting.
Molten-salt growth method reaction temperature in step (1) is 400 DEG C, and the reaction time is 4-6 hours, anhydrous ferric trichloride and graphite
Mass ratio is 5: 1.
Oxidant in step (1) includes chlorate, perchlorate, permanganate, bichromate, sodium peroxide, concentrated acid
For the concentrated sulfuric acid or the mixture of the concentrated sulfuric acid and concentrated nitric acid, the oxidation intercalation time is 4-48h, and temperature is 0-80 DEG C.
Ultrasonic time in step (2) is 0.5-2h.
Reaction time in step (3) is 0.5-6h, number of repetition 1-4 times.
Hydroiodic acid solution concentration in step (4) is 10-30%, reaction time 0.5-6h.
The present invention has the advantage that
(1) the method for the invention can efficiently prepare graphene, while the ferric trichloride catalytic peroxide of interlayer from graphite
Change hydroperoxide decomposition reaction and generate gas, makes to generate a large amount of folds inside film, can efficiently prepare high fold graphene film.
(2) graphite flake in the material for oxygen-containing group layer and ferric trichloride the alternating intercalated graphite that the method for the invention obtains
Layer single side oxidation, amount of oxidation reduce half, effectively mitigate graphene sheet layer structural damage, reduce graphite oxide method bring
The variation drawback such as electric conductivity and mechanical property.
(3) ferric trichloride of the method for the invention preparation is evenly distributed on graphene film interlayer, effectively improves graphene
The popularity and uniformity of fold.
(4) iron ion catalyzing hydrogen peroxide decomposes and generates fold and can be repeated several times progress in the method for the invention, iron from
Son also with number of repetition increase and removed.
(5) the method for the invention preparation process is simple, and the requirement to equipment is lower, is suitable for industry or laboratory operation,
With huge application prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the method for the present invention prepares second order graphite intercalation compound.
Fig. 2 is that oxidant and concentrated acid carry out oxidation intercalation to second order ferric trichloride graphite intercalation compound in the method for the present invention
Structural schematic diagram.
Fig. 3 is that removing oxygen-containing group layer obtains dispersible ferric trichloride intercalation graphite oxide in water in the method for the present invention
The structural schematic diagram of alkene.
Fig. 4 is the process schematic that ferric trichloride catalytic hydrogen peroxide dissociation reaction generates fold in the method for the present invention.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg sodium chlorate is put into solution, stirs 12 hours at room temperature, product eccentric cleaning obtains
Replace intercalated graphite to oxygen-containing group layer and ferric trichloride.
(3) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into 50mL aqueous solution and are ultrasonically treated 1h, obtained
Dispersible ferric trichloride intercalation graphene oxide in water, filters film forming.
(4) film is immersed in the hydrogen peroxide solution that mass fraction is 30% and reacts 1h, take out film after reaction, it will be thin
Film naturally dry.
(5) film is immersed mass fraction is to react 1h in 10% hydroiodic acid solution, and the graphene for obtaining independent self-supporting is thin
Film.
Embodiment 2
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg sodium chlorate is put into solution, stirs 12 hours at room temperature, product eccentric cleaning obtains
Replace intercalated graphite to oxygen-containing group layer and ferric trichloride.
(3) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into 50mL aqueous solution and are ultrasonically treated 1h, obtained
Dispersible ferric trichloride intercalation graphene oxide in water, filters film forming.
(4) film is immersed in the hydrogen peroxide solution that mass fraction is 30% and reacts 1h, take out film after reaction, it will be thin
Film naturally dry.
(5) film is again dipped into the hydrogen peroxide solution that mass fraction is 30% and reacts 1h, take out film after reaction,
By film naturally dry.
(6) film third time is immersed in the hydrogen peroxide solution that mass fraction is 30% and reacts 1h, taken out after reaction thin
Film, by film naturally dry.
(7) film is immersed mass fraction is to react 1h in 10% hydroiodic acid solution, and the graphene for obtaining independent self-supporting is thin
Film.
Embodiment 3
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400 DEG C of heating 4h prepare pure second order graphite intercalation compound, graphite intercalation compound are dissolved in dilute hydrochloric acid solution, take out
Filter drying.
(2) graphite intercalation compound is added in 20mL concentrated sulfuric acid solution, is stirred 0.5 hour for (0 DEG C) in ice water, it will
360mg potassium permanganate is put into solution, is stirred 12 hours at room temperature, by product eccentric cleaning, is obtained oxygen-containing group layer and three
Iron chloride replaces intercalated graphite.
(3) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into 50mL aqueous solution and are ultrasonically treated 1h, obtained
Dispersible ferric trichloride intercalation graphene oxide in water, filters film forming.
(4) film is immersed in the hydrogen peroxide solution that mass fraction is 30% and reacts 1h, take out film after reaction, it will be thin
Film naturally dry.
(5) film is immersed mass fraction is to react 1h in 10% hydroiodic acid solution, and the graphene for obtaining independent self-supporting is thin
Film.
Embodiment 4
(1) 300mg anhydrous ferric trichloride is uniformly mixed with 60mg expanded graphite, is vacuumized, be enclosed within 50mL vial
In, 400'C heats 4h, prepares pure second order graphite intercalation compound, graphite intercalation compound is dissolved in dilute hydrochloric acid solution, takes out
Filter drying.
(2) graphite intercalation compound is added in the mixed solution of the 20mL concentrated sulfuric acid and the concentrated nitric acid of 10mL, in ice water
(0 DEG C) is stirred 0.5 hour, and 360mg sodium chlorate is put into solution, stirs 12 hours at room temperature, product eccentric cleaning obtains
Replace intercalated graphite to oxygen-containing group layer and ferric trichloride.
(3) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into 50mL aqueous solution and are ultrasonically treated 1h, obtained
Dispersible ferric trichloride intercalation graphene oxide in water, filters film forming.
(4) film is immersed in the hydrogen peroxide solution that mass fraction is 30% and reacts 2h, take out film after reaction, it will be thin
Film naturally dry.
(5) film is immersed mass fraction is to react 0.5h in 20% hydroiodic acid solution, obtains the graphene of independent self-supporting
Film.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (6)
1. a kind of preparation method of fold graphene, includes the following steps:
(1) anhydrous ferric trichloride and graphite Hybrid Heating are prepared into second order graphite intercalation compound with molte-salt synthesis, using oxygen
Agent and concentrated acid carry out oxidation intercalation to second order graphene intercalation compound, obtain oxygen-containing group layer and ferric trichloride alternating intercalation
The material of graphite；
(2) oxygen-containing group layer and ferric trichloride alternating intercalated graphite are put into aqueous solution and are ultrasonically treated, remove oxygen-containing group layer
Dispersible ferric trichloride intercalation graphene oxide in water is obtained, film forming is filtered；
(3) film is immersed in hydrogen peroxide solution, takes out film after reaction, by film naturally dry, this process can be weighed repeatedly
It is multiple to carry out；
(4) film is immersed in hydroiodic acid solution and is reacted, obtain the graphene film of independent self-supporting.
2. preparation method according to claim 1, which is characterized in that the molten-salt growth method reaction temperature in step (1) is 400
DEG C, the reaction time is 4-6 hours, and anhydrous ferric trichloride and graphite quality ratio are 5: 1.
3. preparation method according to claim 1, which is characterized in that the oxidant in step (1) includes chlorate, high chlorine
Hydrochlorate, permanganate, bichromate, sodium peroxide, concentrated acid are the mixture of the concentrated sulfuric acid or the concentrated sulfuric acid and concentrated nitric acid, and oxidation is inserted
The layer time is 4-48h, and temperature is 0-80 DEG C.
4. preparation method according to claim 1, which is characterized in that the ultrasonic time in step (2) is 0.5-2h.
5. preparation method according to claim 1, which is characterized in that the reaction time in step (3) is 0.5-6h, is repeated
Number 1-4 times.
6. preparation method according to claim 1, which is characterized in that the hydroiodic acid solution concentration in step (4) is 10-
30%, reaction time 0.5-6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172066A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Fe 3+ Induced folded graphene-based capacitive composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172066A (en) * | 2022-06-16 | 2022-10-11 | 宁德师范学院 | Fe 3+ Induced folded graphene-based capacitive composite material and preparation method thereof |
| CN115172066B (en) * | 2022-06-16 | 2023-04-25 | 宁德师范学院 | Fe (Fe) 3+ Induced fold graphene-based capacitance composite material and preparation method thereof |
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Application publication date: 20191101 |