CN105293477B - A kind of preparation method of big lamella graphene oxide - Google Patents
A kind of preparation method of big lamella graphene oxide Download PDFInfo
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Abstract
A kind of preparation method of big lamella graphene oxide of the present invention, comprises the following steps：(1) intercalation processing is carried out to natural flake graphite with mixed acid solution, obtains intercalated graphite, then intercalated graphite is heat-treated；(2) oxidation reaction is carried out to the intercalated graphite through Overheating Treatment, obtains graphene oxide；(3) solvent is added into graphene oxide, graphene oxide solution fully is made after dissolving, then the pH value of graphene oxide solution is adjusted to ＜ 7, finally big lamella graphene oxide is settled and separated using the method for stewing process or centrifugal treating.The present invention carries out intercalation processing and heat treatment to natural flake graphite raw material in advance, more contacts area can be provided in follow-up oxidation reaction process for strong acid and strong oxidizer, so as to improve oxidation efficiency；When separating big lamella graphene oxide, the complexing of the oxygen-containing functional group on solvent and graphene oxide is improved, and separating effect is notable.
Description
Technical field
The present invention relates to grapheme material field, relates in particular to a kind of preparation method of big lamella graphene oxide.
Background technology
In carbon material family, Univ Manchester UK Geim et al. be found that in 2004 a new star into
Member, graphene.Graphene, single layer of carbon atom is with sp2The bi-dimensional cellular shape material of hydridization, there is high theoretical surface
(2630m2g-1), the electrical conductivity (10 of superelevation3to 104S m-1), outstanding mechanical performance, high thermal conductivity and chemical stability,
Focus is chased in research and application always scientists from all over the world and scholar in terms of chemistry, electronics and material science.
It is well known that the lamella size of graphene has significant impact to the property of graphene and application.For example, big lamella oxygen
Graphite alkene (be more than 5 μm) can apply in many aspects, as three-dimensional grapheme base net network, two-dimensional polymer based composites and
Conductive film in optoelectronic device, compared with the graphene oxide of small lamella, big lamella graphene oxide has less contact
Resistance, thus the film of high conductivity can be prepared.Moreover, the lamella size of general redox graphene, which depends on it, aoxidizes stone
Black alkene presoma lamella size.
At present, preparing the method for graphene mainly has machinery/liquid phase stripping method, epitaxial growth method, chemical vapour deposition technique
And oxidation-reduction method.Compared with first three preparation method, oxidation-reduction method is considered as most economical effectively suitable industrial metaplasia
The method of production.The existing method for preparing graphene oxide mainly includes Hummer ' s methods, Brodie methods and Standenmaier
Method, wherein Hummer ' s methods are the most commonly used.
But graphene oxide size is smaller made from existing method, and yield is not high, and the size of product is complete
Mix, distribution-free rule.
Therefore, the size of control graphene oxide how is realized, and how to be realized the oxygen of different sizes
Graphite alkene separates to obtain large-sized graphene oxide, has become the crucial institute for realizing industrialized production graphene
.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of technique is simple, and cost is low, and yield is high, can effectively increase oxygen
The preparation method of the big lamella graphene oxide of graphite alkene lamella.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of system of big lamella graphene oxide
Preparation Method, comprise the following steps：
(1) intercalation processing is carried out to natural flake graphite with mixed acid solution, intercalated graphite is obtained, then to intercalated graphite
It is heat-treated；
(2) oxidation reaction is carried out to the intercalated graphite through Overheating Treatment, obtains graphene oxide；
(3) solvent is added into graphene oxide, graphene oxide solution fully is made after dissolving, then by graphite oxide
The pH value of alkene solution is adjusted to ＜ 7, is finally settled big lamella graphene oxide using the method for stewing process or centrifugal treating
And separate.
Preferably, the phosphorus content of the natural flake graphite is 80-99.9%, and granularity is 80-500 mesh.
Preferably, the mixed acid solution is the concentrated sulfuric acid and concentrated nitric acid or concentrated phosphoric acid by volume 1-10：1 ratio is mixed
The nitration mixture of gained is closed, the mass ratio of the mixed acid solution and natural flake graphite is 10-100：1.
Preferably, the temperature of intercalation processing be room temperature, the time be 20-24h.
Preferably, the temperature of heat treatment be 1000-1100 DEG C, the time be 12-17s.
Preferably, the solvent be deionized water, tetrahydrofuran, in dimethylformamide any one or it is two or more
Arbitrary volume than mixed liquor.
Preferably, the concentration of the graphene oxide solution is 0.1-10mg/ml.
Preferably, the pH value of the graphene oxide solution is adjusted to 2~6 with watery hydrochloric acid or dilute sodium carbonate solution.
Preferably, for the number of stewing process more than once, the time per treatment is 1~36h.
Preferably, for the number of centrifugal treating more than once, rotating speed per treatment is 4000-10000rpm/min, when
Between be 5-30min.
Compared with prior art, the beneficial effects of the present invention are：
1. the present invention carries out intercalation processing and heat treatment to natural flake graphite raw material in advance, can be anti-in follow-up oxidation
More contacts area are provided for strong acid and strong oxidizer during answering, so as to improve oxidation efficiency, make obtained oxidation
The lamella of graphene is increased, and yield gets a promotion.
2. graphene oxide solution, graphene oxide layer is first made when separating big lamella graphene oxide in the present invention
On the oxygen-containing functional groups such as carbonyl be present, the electrostatic repulsion between graphene oxide layer prevents graphene oxide from gathering in a solvent
Collection, as the oxygen-containing functional groups such as the increase of graphene oxide layer, carbonyl can be reduced therewith, thus the graphene oxide of small lamella
There is higher solubility than the graphene oxide of big lamella.Therefore, the graphene oxide of big lamella can deposit, and small lamella
Graphene oxide rest in supernatant；The present invention adjusts the pH value of graphene oxide solution to ＜ 7 in addition, in pH value ＜
Under conditions of 7, the lamella of graphene oxide will not be destroyed, the complexing of the oxygen-containing functional group on solvent and graphene oxide
It is improved, separating effect is notable.
3. low raw-material cost of the present invention, being easy to get, technique is simple, easy to operate, favorable reproducibility, can carry out heavy industrialization
Production, has extraordinary application prospect.
4. graphene oxide produced by the present invention, compared to the graphene oxide obtained by existing preparation method, its lamella increases
Big multiple may be up to 5-6 times.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of big lamella graphene oxide made from the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope diagram of big lamella graphene oxide made from the embodiment of the present invention 2.
Fig. 3 is the scanning electron microscope diagram of big lamella graphene oxide made from the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope diagram of big lamella graphene oxide made from the embodiment of the present invention 4.
Fig. 5 is the scanning electron microscope diagram of big lamella graphene oxide made from the embodiment of the present invention 5.
Embodiment
Below in conjunction with the accompanying drawings, the invention will be further described for embodiment：
This part carries out general description to the material and test method that are arrived used in present invention experiment.Although it is
Realize that many materials used in the object of the invention and operating method are it is known in the art that still the present invention makees as far as possible herein
It is described in detail.It will be apparent to those skilled in the art that hereinafter, if not specified, material therefor, equipment and operation of the present invention
Method is well known in the art.The mass fraction of the concentrated sulfuric acid used below is 98%, the mass fraction of concentrated nitric acid is 69% and
The mass fraction of concentrated phosphoric acid is 85%.
Embodiment 1
A kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) at room temperature, to take 2g phosphorus content be 99.9%, granularity is 500 mesh natural flake graphites, and it is molten to add 100g mixed acid
Liquid, then intercalation processing 20h under agitation, is filtered by 5 μm of miillpore filters afterwards, and the precipitation of filtering gained is entered
Row drying, intercalated graphite is obtained, intercalated graphite is finally heat-treated 12s under the conditions of 1100 DEG C；
The mixed acid solution is the concentrated sulfuric acid and concentrated nitric acid by volume 5：The nitration mixture of 1 ratio mixing gained；
(2) oxidation reaction is carried out using Hummer ' s methods to the intercalated graphite through Overheating Treatment, obtains graphene oxide；
Hummer ' s methods comprise the following steps that：Under 0 DEG C, stirring condition, add into the intercalated graphite through Overheating Treatment
Enter the concentrated sulfuric acid, be well mixed, add sodium nitrate, be well mixed, then potassium permanganate is slowly added in 50min, be well mixed,
Then 24h is reacted under 40 DEG C, stirring condition, afterwards pours into the mixed liquor for reacting gained in frozen water, under stirring condition slowly
Hydrogen peroxide, last stewing process 12h are added, then the precipitation for standing gained is separated, oxygen is obtained after watery hydrochloric acid cleans
Graphite alkene；
The mass ratio of the intercalated graphite and the concentrated sulfuric acid, sodium nitrate, potassium permanganate and hydrogen peroxide is 1：23：0.5：3：
3.8；
(3) solvent is added into graphene oxide, the graphene oxide solution that concentration is 5mg/ml is fully made after dissolving,
Then the pH value of graphene oxide solution is adjusted to 2 with watery hydrochloric acid, last stewing process 36h sinks big lamella graphene oxide
Drop and separate；
The solvent is deionized water and tetrahydrofuran by volume 1：The mixed liquor of 1 ratio mixing gained.
The scanning electron microscope diagram of big lamella graphene oxide is shown in Fig. 1 made from the present embodiment, and the present embodiment finally obtains
Obtain 1.8 grams, big lamella graphene oxide of the size range at 15-25 μm.
And using identical natural flake graphite as raw material, oxidation reaction is carried out only with above-mentioned Hummer ' s methods, is obtained
The quality of graphene oxide is 1.5 grams, size range is 1-5 μm.
Embodiment 2
A kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) at room temperature, to take 2g phosphorus content be 80%, granularity is 80 mesh natural flake graphites, adds 20g mixed acid solutions,
Then intercalation processing 24h under agitation, is filtered by 5 μm of miillpore filters afterwards, and the precipitation of filtering gained is carried out
Dry, obtain intercalated graphite, intercalated graphite is finally heat-treated 17s under the conditions of 1000 DEG C；
The mixed acid solution is the concentrated sulfuric acid and concentrated phosphoric acid by volume 1：The nitration mixture of 1 ratio mixing gained；
(2) oxidation reaction is carried out using Hummer ' s methods to the intercalated graphite through Overheating Treatment, obtains graphene oxide；
Hummer ' s methods comprise the following steps that：Under 5 DEG C, stirring condition, add into the intercalated graphite through Overheating Treatment
Enter the concentrated sulfuric acid, be well mixed, add sodium nitrate, be well mixed, then potassium permanganate is slowly added in 40min, be well mixed,
Then 2h is reacted under 60 DEG C, stirring condition, afterwards pours into the mixed liquor for reacting gained in frozen water, is slowly added under stirring condition
Enter hydrogen peroxide, last stewing process 24h, then the precipitation for standing gained is separated, aoxidized after watery hydrochloric acid cleans
Graphene；
The mass ratio of the intercalated graphite and the concentrated sulfuric acid, sodium nitrate, potassium permanganate and hydrogen peroxide is 1：23：0.5：3：
3.8；
(3) solvent is added into graphene oxide, the graphene oxide solution that concentration is 2mg/ml is fully made after dissolving,
Then the pH value of graphene oxide solution is adjusted to 6 with dilute sodium carbonate solution, finally use centrifugal treating (rotating speed for
10000rpm/min, time 30min) method big lamella graphene oxide is settled and separated；
The solvent is deionized water and dimethylformamide by volume 3：The mixed liquor of 1 ratio mixing gained.
The scanning electron microscope diagram of big lamella graphene oxide is shown in Fig. 2 made from the present embodiment, and the present embodiment finally obtains
Obtain 1.6 grams, big lamella graphene oxide of the size range at 45-60 μm.
And using identical natural flake graphite as raw material, oxidation reaction is carried out only with above-mentioned Hummer ' s methods, is obtained
The quality of graphene oxide is 0.9 gram, size range is 15-20 μm.
Embodiment 3
A kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) at room temperature, to take 2g phosphorus content be 85%, granularity is 200 mesh natural flake graphites, adds 70g mixed acid solutions,
Then intercalation processing 21h under agitation, is filtered by 5 μm of miillpore filters afterwards, and the precipitation of filtering gained is carried out
Dry, obtain intercalated graphite, intercalated graphite is finally heat-treated 16s under the conditions of 1025 DEG C；
The mixed acid solution is the concentrated sulfuric acid and concentrated nitric acid by volume 10:The nitration mixture of 1 ratio mixing gained；
(2) oxidation reaction is carried out using Hummer ' s methods to the intercalated graphite through Overheating Treatment, obtains graphene oxide；
Hummer ' s methods comprise the following steps that：Under 10 DEG C, stirring condition, add into the intercalated graphite through Overheating Treatment
Enter the concentrated sulfuric acid, be well mixed, add sodium nitrate, be well mixed, then potassium permanganate is slowly added in 30min, be well mixed,
Then 12h is reacted under 50 DEG C, stirring condition, afterwards pours into the mixed liquor for reacting gained in frozen water, under stirring condition slowly
Hydrogen peroxide, last stewing process 6h are added, then the precipitation for standing gained is separated, is aoxidized after watery hydrochloric acid cleans
Graphene；
The mass ratio of the intercalated graphite and the concentrated sulfuric acid, sodium nitrate, potassium permanganate and hydrogen peroxide is 1：23：0.5：3：
3.8；
(3) solvent is added into graphene oxide, it is molten that the graphene oxide that concentration is 10mg/ml is fully made after dissolving
Liquid, then the pH value of graphene oxide solution is adjusted to 3 with watery hydrochloric acid, then carry out first time stewing process, stood for the first time
24h is handled, then separates the precipitation obtained by first time stewing process, the above procedure of repeat step (3) carries out second
Secondary stewing process, second of stewing process 9h, big lamella graphene oxide is settled and separated by stewing process twice；
The solvent is tetrahydrofuran and dimethylformamide by volume 1：The mixed liquor of 4 ratio mixing gained.
The scanning electron microscope diagram of big lamella graphene oxide is shown in Fig. 3 made from the present embodiment, and the present embodiment finally obtains
Obtain 1.7 grams, big lamella graphene oxide of the size range at 35-45 μm.
And using identical natural flake graphite as raw material, oxidation reaction is carried out only with above-mentioned Hummer ' s methods, is obtained
The quality of graphene oxide is 1.1 grams, size range is 7-12 μm.
Embodiment 4
A kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) at room temperature, to take 2g phosphorus content be 90%, granularity is 300 mesh natural flake graphites, and it is molten to add 150g mixed acid
Liquid, then intercalation processing 22h under agitation, is filtered by 5 μm of miillpore filters afterwards, and the precipitation of filtering gained is entered
Row drying, intercalated graphite is obtained, intercalated graphite is finally heat-treated 14s under the conditions of 1050 DEG C；
The mixed acid solution is the concentrated sulfuric acid and concentrated phosphoric acid by volume 8：The nitration mixture of 1 ratio mixing gained；
(2) oxidation reaction is carried out using Standenmaier methods to the intercalated graphite through Overheating Treatment, obtains graphite oxide
Alkene；
Standenmaier methods comprise the following steps that：Under 0 DEG C, stirring condition, to the intercalated graphite through Overheating Treatment
The middle addition concentrated sulfuric acid, concentrated nitric acid, are well mixed, then potassium chlorate are slowly added in 50min, be well mixed, then 40 DEG C, stir
24h is reacted under the conditions of mixing, adds a large amount of deionized waters, stewing process 12h afterwards, then the precipitation for standing gained is separated,
Graphene oxide is obtained after watery hydrochloric acid cleans；
The mass ratio of the intercalated graphite and the concentrated sulfuric acid, concentrated nitric acid and potassium chlorate is 1：15：8：11；
(3) solvent is added into graphene oxide, it is molten that the graphene oxide that concentration is 0.1mg/ml is fully made after dissolving
Liquid, then the pH value of graphene oxide solution is adjusted to 5 with dilute sodium carbonate solution, then carry out first time centrifugal treating, first
The rotating speed of secondary centrifugal treating is 7000rpm/min, time 15min, then separates the precipitation obtained by first time centrifugal treating
Out, the above procedure of repeat step (3) carries out second of centrifugal treating, second of centrifugal treating, second centrifugal treating
Rotating speed is 4000rpm/min, time 5min, and big lamella graphene oxide is settled and isolated by centrifugal treating twice
Come；
The solvent is deionized water.
The scanning electron microscope diagram of big lamella graphene oxide is shown in Fig. 4 made from the present embodiment, and the present embodiment finally obtains
Obtain 1.7 grams, big lamella graphene oxide of the size range at 25-35 μm.
And using identical natural flake graphite as raw material, oxidation reaction is carried out only with above-mentioned Standenmaier methods, is obtained
To graphene oxide quality be 1.2 grams, size range be 7-13 μm.
Embodiment 5
A kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) at room temperature, to take 2g phosphorus content be 95%, granularity is 400 mesh natural flake graphites, and it is molten to add 200g mixed acid
Liquid, then intercalation processing 23h under agitation, is filtered by 5 μm of miillpore filters afterwards, and the precipitation of filtering gained is entered
Row drying, intercalated graphite is obtained, intercalated graphite is finally heat-treated 13s under the conditions of 1075 DEG C；
The mixed acid solution is the concentrated sulfuric acid and concentrated nitric acid by volume 3：The nitration mixture of 1 ratio mixing gained；
(2) oxidation reaction is carried out using Brodie methods to the intercalated graphite through Overheating Treatment, obtains graphene oxide；
Brodie methods comprise the following steps that：Under 0 DEG C, stirring condition, added into the intercalated graphite through Overheating Treatment
Concentrated nitric acid, it is well mixed, then potassium chlorate is slowly added in 50min, is well mixed, is then reacted under 40 DEG C, stirring condition
24h, a large amount of deionized waters, stewing process 12h are added afterwards, then the precipitation for standing gained is separated, cleaned through watery hydrochloric acid
After obtain graphene oxide；
The mass ratio of the intercalated graphite and concentrated nitric acid, potassium chlorate is 1：30：3；
(3) solvent is added into graphene oxide, the graphene oxide solution that concentration is 8mg/ml is fully made after dissolving,
Then the pH value of graphene oxide solution is adjusted to 4 with watery hydrochloric acid, then carries out first time stewing process, first time stewing process
18h, then the precipitation obtained by first time stewing process is separated, the above procedure progress of repeat step (3) is quiet for the second time
Processing is put, second of stewing process 1h, is then separated the precipitation obtained by second of stewing process, repeat step (3)
Above procedure carries out third time stewing process, third time stewing process 1h, by stewing process three times by big lamella graphite oxide
Alkene is settled and separated；
The solvent is tetrahydrofuran.
The scanning electron microscope diagram of big lamella graphene oxide is shown in Fig. 5 made from the present embodiment, and the present embodiment finally obtains
Obtain 1.7 grams, big lamella graphene oxide of the size range at 20-30 μm.
And using identical natural flake graphite as raw material, carry out oxidation reaction, obtained oxygen only with above-mentioned Brodie methods
The quality of graphite alkene is 1.2 grams, size range is 5-11 μm.
Deionized water, tetrahydrofuran, dimethylformamide are identicals to the peptizaiton of graphene oxide in the present invention,
Identical size classification can be obtained under the same conditions, therefore in deionized water, tetrahydrofuran, dimethylformamide
Any one or two or more arbitrary volumes than mixed liquor also there is identical peptizaiton, for the sake of succinct description, no
Separately enumerate in a specific embodiment.
It should be understood that example as described herein and embodiment can be made only for explanation, those skilled in the art according to it
Various modifications or change, in the case where not departing from spirit of the invention, belong to protection scope of the present invention.
Claims (8)
1. a kind of preparation method of big lamella graphene oxide, comprises the following steps：
(1) intercalation processing is carried out to natural flake graphite with mixed acid solution, the mixed acid solution and natural flake graphite
Mass ratio is 35-100：1, the temperature of intercalation processing is room temperature, the time is 20-24h, intercalated graphite is obtained, then to intercalation
Graphite is heat-treated, and the temperature of heat treatment is 1000-1100 DEG C, the time is 12-17s；
(2) oxidation reaction is carried out to the intercalated graphite through Overheating Treatment, afterwards the mixed liquor by graphene oxide from reaction gained
In extract；
(3) solvent is added into graphene oxide, graphene oxide solution fully is made after dissolving, it is then that graphene oxide is molten
The pH value of liquid is adjusted to ＜ 7, and finally big lamella graphene oxide is settled and divided using the method for stewing process or centrifugal treating
Separate out and.
2. the preparation method of big lamella graphene oxide as claimed in claim 1, it is characterised in that：The natural flake graphite
Phosphorus content be 80-99.9%, granularity is 80-500 mesh.
3. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：The mixed acid is molten
Liquid is the concentrated sulfuric acid and concentrated nitric acid or concentrated phosphoric acid by volume 1-10：The nitration mixture of 1 ratio mixing gained.
4. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：The solvent is to go
Any one or two or more arbitrary volumes in ionized water, tetrahydrofuran, dimethylformamide than mixed liquor.
5. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：The graphite oxide
The concentration of alkene solution is 0.1-10mg/ml.
6. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：The graphite oxide
The pH value of alkene solution is adjusted to 2~6 with watery hydrochloric acid or dilute sodium carbonate solution.
7. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：Time of stewing process
For number more than once, the time per treatment is 1~36h.
8. the preparation method of big lamella graphene oxide as claimed in claim 1 or 2, it is characterised in that：Time of centrifugal treating
Number is more than once, and rotating speed per treatment is 4000-10000rpm/min, and the time is 5-30min.
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| CN113213469B (en) * | 2021-05-31 | 2022-12-23 | 杭州高烯科技有限公司 | Equipment for preparing uniform small-size graphene oxide |
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| CN102491318B (en) * | 2011-12-13 | 2013-08-14 | 河北工业大学 | Method for preparing graphene oxide |
| CN102534869B (en) * | 2012-01-05 | 2014-01-08 | 浙江大学 | Method for preparing high-strength conductive graphene fiber by large-size graphene oxide sheet |
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Effective date of registration: 20200927 Address after: 122000 Xingyuan street zhujiayingzi village, Lingyuan City, Chaoyang City, Liaoning Province Patentee after: Liaoning shizhiyuan Carbon Technology Co.,Ltd. Address before: 221000 Qianlou Village, Huangji Town, Tongshan District, Xuzhou City, Jiangsu Province, Team 121 Patentee before: Chen Huanhuan |