CN104445170A - Method for preparing graphene film - Google Patents
Method for preparing graphene film Download PDFInfo
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- CN104445170A CN104445170A CN201410736297.8A CN201410736297A CN104445170A CN 104445170 A CN104445170 A CN 104445170A CN 201410736297 A CN201410736297 A CN 201410736297A CN 104445170 A CN104445170 A CN 104445170A
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Abstract
The invention relates to a method for preparing a graphene film. The method comprises the following steps: coating a graphene oxide acid solution on a magnesium film, drying the magnesium film deposited with graphene oxide, and dissolving the magnesium film by using diluted acid, thereby obtaining the graphene film. The method is simple in process condition, environmental friendly, low in cost and beneficial for large-scale preparation of the graphene film.
Description
Technical field
The present invention relates to technical field of graphene, particularly relate to a kind of method for preparing graphene membrane.
Background technology
Graphene is by a kind of type material of carbon atom tightly packed one-tenth hexagonal lattice structure on two-dimensional space, is the elementary cell of composition zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite.Since the people such as Novoselov in 2004 obtain self-existent Graphene, due to mechanical property and the physicals of its excellence, become rapidly the focus of Materials science research, the research of current Graphene extensively launches in every field, as Graphene can be used for preparing Flied emission transistor (FET) and Field Emission Display, simultaneously at sensor, solar cell, lithium ion battery, ultracapacitor and field of liquid crystal display have potential application prospect, wherein graphene film can substitute polysilicon, ITO etc. are applied in various electronic product, therefore preparing high-quality graphene film is one of its key realizing large-scale application.
The technology preparing graphene film at present mainly contains: chemical vapour deposition (CVD), electrophoretic deposition, the method such as vacuum filtration and spin coating, wherein in the substrate that generally adopts the graphene solution prepared to drip to be coated onto rotation of the method for spin coating and then be separated the graphene film obtained, but the Graphene quality prepared like this depends on Graphene dispersiveness in a liquid, also there is certain difficulty technically in the graphene solution obtaining stable dispersion, as everyone knows, graphite oxide has fabulous wetting ability feature, therefore researchist generally adopts hydrazine hydrate reduction or high-temperature heat expansion graphene oxide film to prepare graphene film, but the wayward property of the condition of the hypertoxicity of hydrazine hydrate and thermal expansion greatly limit practical application.
Summary of the invention
Embodiments of the present invention provide a kind of method for preparing graphene membrane, and its technical process is simple, overcome the problem that Graphene in prior art is not easy to form film, processing condition are difficult to control and easily bring pollution to environment.
In order to achieve the above object, embodiment of the present invention provides a kind of method for preparing graphene membrane, comprising: be coated on magnesium film by graphene oxide acidic solution, by dry for the magnesium film depositing graphene oxide, then with diluted acid, magnesium film is dissolved, obtain graphene film.
In embodiments of the present invention; graphene oxide acidic solution is coated on magnesium film; in this process; MgO protective layer on magnesium film dissolves by H+; magnesium is fully contacted, simultaneously and reactive magnesium generation proton hydrogen [H], because proton hydrogen [H] has stronger reductibility with graphene oxide; graphene oxide is reduced into Graphene by proton hydrogen [H], and reaction equation is as follows:
MgO+2H
+=H
2o+Mg
2+------------------protective layer dissolves
Mg+2H
+=2 [H]+Mg
2+-----------------Mg intermediate reaction
GO+2 [H]=G+H
2the reduction reaction of O-----------------GO
Wherein GO is graphene oxide, and G is Graphene
Above-mentioned method for preparing graphene membrane, includes but not limited to following steps:
(1) graphene oxide water solution is coated on magnesium film;
(2) by dry for the magnesium film depositing graphite oxide;
(3) graphene film is stripped out from magnesium film.In above-mentioned coating step (1), graphene oxide concentration is 0.01-10g/L alternatively, and pH value is 0-5, and the thickness of magnesium film is 0.1-100 μm.
Implement, in coating step (1), described graphene oxide acidic solution to be spun on described magnesium film, or described graphene oxide acidic solution is coated on magnesium film by vacuum filtration.
Implement to be spun in the step on described magnesium film by described graphene oxide acidic solution in coating step (1), in graphene oxide spin coating process, rate of addition controls as 0.1-100mL/h, and time for adding is 0.1-120s;
Be spun in the step on described magnesium film by described graphene oxide acidic solution, magnesium film speed of rotation is 0-10000rpm, and rotational time is 0.1-120s.
Implement filtration procedure described in coating step (1), the height of the graphene oxide acidic solution liquid level distance magnesium film of interpolation is 0.1-100mm, and filtration time is 0.1-12h.
After implementing coating step (1), the support substrates of graphene coated film can be continued according to actual needs.
Implement in drying step (2), the drying means of employing is heating, drying.
Implement in drying step (2), the temperature of heating, drying is 25-120 DEG C, and drying time is 1-48h.
Implement, in strip step (3), dried film to be immersed in dilute hydrochloric acid and to be dissolved by magnesium film, concentration controls as 0.1-10mol/L, and soak time is 1-48h.
Implement, in strip step (3), to adopt the impurity washes clean that deionized water will graphene film remain.
After implementing strip step (3), can according to actual needs, by graphene film drying treatment.
Above-mentioned method for preparing graphene membrane, preparation process condition is simple, and environmental protection is with low cost, is conducive to the extensive preparation of graphene film.
Accompanying drawing explanation
The schema of the method for preparing graphene membrane that Fig. 1 provides for embodiment of the present invention;
The schematic diagram of spin coating proceeding in the graphene film preparation that Fig. 2 provides for embodiment of the present invention;
The signal of vacuum filtration technique in the graphene film preparation that Fig. 3 provides for embodiment of the present invention
Figure.
Embodiment
Below in conjunction with specific embodiment, the preparation method to method for preparing graphene membrane of the present invention is introduced.
What embodiment of the present invention provided prepares the processing step of the preparation method of graphene film as shown in Figure 1, includes but not limited to following steps:
(1) graphene oxide acidic solution is coated on magnesium film;
(2) by dry for the magnesium film depositing graphite oxide;
(3) graphene film is stripped out from magnesium film.
Due to the method adopting hydrazine hydrate to prepare Graphene as reductive agent, the quality that hydrazine hydrate reduction is too strong and cause reacting violent and affect graphene film, the toxicity that hydrazine hydrate is strong simultaneously brings pollution to environment, therefore the waste gas treatment process that the mode of hydrazine hydrate needs through complexity is adopted, and the method adopting Vacuum Heat to expand needs the equipment of high-temperature vacuum, the uppity technical problem of the condition that also exists.In embodiments of the present invention, graphene oxide acidic solution is coated on magnesium film and obtains graphene oxide film, graphene oxide forms Graphene under the reductive action of magnesium, and the reaction product of magnesium comprises magnesium oxide and residual magnesium thereof easily via acid dissolve, therefore, above-mentioned preparation process processing condition are simple, do not need extra gas defence equipment and vacuum high-temperature equipment, only need simple equipment to prepare graphene film.
Alternatively, in one embodiment of the invention, in above-mentioned coating step (1), the concentration of graphene oxide acidic solution is chosen for 0.01-10g/L, pH value is 0-5, and the thickness of magnesium film is chosen for 0.1-100 μm.
In a preferred embodiment, under graphene oxide acidic solution concentration is chosen at the condition of 0.01-10g/L, solution has good dispersiveness, can solve the too high graphene oxide that causes of strength of solution and forms gel and be unfavorable for applying and the too low concentration problem that causes coating time long; In a preferred embodiment, the pH value of graphene oxide solution is chosen for 0-5, can be conducive to the dissolving of magnesium film surface oxide layer like this, promotes the carrying out of reaction.
The thickness of magnesium film is chosen for 0.1-100 μm, all can reach and prepare effect preferably, and the too thin magnesium film of solution is unfavorable for actually operating and too thick magnesium film causes graphene film to peel off the problem of difficulty.In above-mentioned scope, more preferably, the concentration of graphene oxide acidic solution is 1g/L, and the thickness of magnesium film is 10 μm, will reach best effect like this.
Alternatively, in one embodiment, in above-mentioned coating step (1), the mode of spin coating or vacuum filtration is adopted to be coated on magnesium film by graphene oxide.
As shown in Figure 2, in the step adopting spin coating mode to be coated to by graphene oxide on magnesium film:
In spin coating process, graphene oxide acidic solution 201 is added drop-wise on the magnesium film 202 of rotation, moisture in such graphene oxide acidic solution 201 is thrown out of under the influence of centrifugal force, and graphene oxide is then deposited on magnesium film 202 and forms graphene oxide film.
Alternatively, the rate of addition of graphene oxide acidic solution 201 is 0.1-100mL/h, time for adding is 0.1-120s, and magnesium film 202 speed of rotation is 0-10000rpm, and rotational time is 0.1-120s.
Alternatively, can choose and be spin-coated as coating method, mainly consider that spin coating proceeding condition is simple and can prepare the good film of homogeneity simultaneously, wherein the rate of addition of controlled oxidization Graphene acidic solution 201, time for adding, magnesium film 202 speed of rotation and rotational time can regulate and control thickness and the quality of forming film of graphene oxide film, preferably, the rate of addition of graphene oxide acidic solution 201 controls as 10mL/h, time for adding are 10s, magnesium film 202 speed of rotation is 3000rpm, and rotational time is 30s.
Alternatively, vacuum filtration mode can also be adopted to be coated on magnesium film by graphene oxide 301, as shown in Figure 3, first graphene oxide acidic solution 301 is added drop-wise in funnel 304 and forms certain liquid level, filter flask 305 is in subatmospheric state by valve tube 306, moisture in such graphene oxide acidic solution 301 will filter by funnel 304, and graphene oxide is then deposited on magnesium film 302.Alternatively, the height of graphene oxide acidic solution 301 liquid level distance magnesium film is chosen for 0.1-100mm, and filtration time is chosen for 0.1-12h.Within the scope of above-mentioned parameter, the suitable graphene film good with compactness of thickness will be obtained, solve that graphene oxide content is very few causes not easily film forming and graphene oxide content too much and the blocked up problem of film, suitable filtration time solves the bad problem of graphene film compactness.Within the scope of above-mentioned parameter, preferably, the liquid level of graphene oxide acidic solution 301 in funnel is 10mm, and filtration time is 2h, can reach best effect like this.
Alternatively, after step (1), described method also comprises: above graphene oxide film layer, continue other thin film layers of coating, form the graphene film with support substrates, graphene film can be transferred in required device easily like this.
Alternatively, for drying step (2), adopt the mode of heating, drying, in drying course, graphene oxide contacts with magnesium film will be reduced into Graphene, thus form the film of Graphene, solve the problem how graphene oxide film forms graphene film.Suitable bake out temperature and drying time will be conducive to the quality improving graphene film, and alternatively, bake out temperature is chosen for 25 DEG C-120 DEG C, drying time is chosen for 1-48h.In above-mentioned scope, preferably, bake out temperature is 60 DEG C, and drying time is 12h, can reach best effect.In fact, drying mode is not limited to the method for heating, drying, such as can also adopt air-dry, the method such as vacuum-drying and lyophilize.
Alternatively, for strip step (3), dilute hydrochloric acid is adopted to be dissolved by magnesium film, the film of drying is immersed in dilute hydrochloric acid, the concentration of hydrochloric acid will affect the quality of graphene film, when using concentrated hydrochloric acid, generation vigorous reaction causes graphene film to break by magnesium and hydrochloric acid, and too low concentration is unfavorable for actual production by affecting charge stripping efficiency, therefore suitable concentration of hydrochloric acid and the quality for the treatment of time to graphene film have material impact, alternatively, concentration of hydrochloric acid is 0.1-10mol/L, and when magnesium film dissolves, soak time is 2h; Preferably, concentration of hydrochloric acid is 1mol/L, and soak time when magnesium film dissolves is 2h; After graphene film has soaked, magnesium film and hydrochloric acid react and dissolve, in this process, the impurity generating magnesium chloride is attached on graphene film, therefore need graphene film washes clean, here adopt deionized water by residual impurity washes clean, finally obtain graphene film.
Alternatively, after strip step (3), also comprise graphene film graphene film drying treatment being obtained doing.Due to after strip step (3), the graphene film being in moisture state has just prepared, and according to practical use, this moistening graphene film drying treatment can be obtained the graphene film done by us.Here drying treatment mode is heating, drying, but is not limited to heating, drying, can also adopt air-dry, vacuum-drying and cryodesiccated method.In order to form the good graphene film of quality, alternatively, the temperature of heating, drying is chosen for 25-120 DEG C, and drying time is chosen for 1-48h.In above-mentioned scope, preferably, heating, drying temperature is 60 DEG C, and drying time is 24h, can obtain top-quality dry graphene film like this.
Above embodiment is just illustrative for the purpose of the present invention; and nonrestrictive, those of ordinary skill in the art understand, when not departing from the spirit and scope that claims limit; many amendments, change or equivalence can be made, but all will fall within the scope of protection of the present invention.
Claims (13)
1. a preparation method for graphene film, is characterized in that:
Graphene oxide acidic solution is coated on magnesium film, by dry for the magnesium film depositing graphene oxide, then with diluted acid, magnesium film dissolved, obtain graphene film.
2. the method for claim 1, is characterized in that:
The concentration of described graphene oxide acidic solution is 0.01-10g/L, and pH value is 0-5;
The thickness of described magnesium film is 0.1-100 μm.
3. method as claimed in claim 2, is characterized in that:
Adopt the pH value of hydrochloric acid soln adjustment graphene oxide solution.
4. the method for claim 1, is characterized in that:
After the described step be coated to by graphene oxide acidic solution on magnesium film, described method also comprises: the support substrates of graphene coated film on graphene oxide film.
5. the method for claim 1, is characterized in that:
Described the step that graphene oxide acidic solution is coated on magnesium film to be comprised: described graphene oxide acidic solution is spun on described magnesium film, or described graphene oxide acidic solution is coated on magnesium film by the mode of vacuum filtration.
6. method as claimed in claim 5, is characterized in that:
Described graphene oxide acidic solution is being spun in the step on described magnesium film, graphene oxide acidic solution droplets Acceleration Control is 0.1-100mL/h, time for adding is 0.1-120s, and magnesium film speed of rotation is 0-10000rpm, and rotational time is 0.1-120s.
7. the method for claim 1, is characterized in that:
Described diluted acid is hydrochloric acid, and concentration is 0.1-10mol/L; In the step that magnesium film dissolves by described diluted acid, soak time during dissolving is 1-48h.
8. method as claimed in claim 5, is characterized in that:
Be coated to by described graphene oxide acidic solution in the process on magnesium film by the mode of vacuum filtration, the height of the graphene oxide acidic solution liquid level distance magnesium film of interpolation is 0.1-100mm, and filtration time is 0.1-12h.
9. the method for claim 1, is characterized in that:
The drying means of described magnesium film is heating, drying.
10. method as claimed in claim 9, is characterized in that:
The temperature of described heating, drying is 25-120 DEG C, and drying time is 1-48h.
11. the method for claim 1, is characterized in that:
Described obtain graphene film after, described method also comprises: the drying of moistening graphene film is obtained the graphene film done.
12. methods as claimed in claim 11, is characterized in that:
Described drying means is heating, drying.
13. methods as claimed in claim 12, is characterized in that:
The temperature of described heating, drying is 25-120 DEG C, and drying time is 1-48h.
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| CN201410736297.8A CN104445170A (en) | 2014-12-04 | 2014-12-04 | Method for preparing graphene film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040015A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | High-throughput multilayer composite nano-filtration membrane and preparation method thereof |
| CN107579201A (en) * | 2017-09-14 | 2018-01-12 | 珠海格力电器股份有限公司 | A kind of polylayer forest and preparation method thereof |
| IT201600104397A1 (en) * | 2016-10-18 | 2018-04-18 | Fond Bruno Kessler | GRAPHENE-BASED COMPOSITE MATERIAL FOR THE GENERATION OF HYDROGEN AND HEAT IN AQUEOUS ENVIRONMENT AND PROCESS FOR ITS PRODUCTION |
| CN111939658A (en) * | 2020-07-28 | 2020-11-17 | 广东职业技术学院 | Preparation method and application of graphene filter sheet |
| CN112391664A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557013A (en) * | 2010-12-28 | 2012-07-11 | 国家纳米科学中心 | Preparation method for reduced graphene oxide |
-
2014
- 2014-12-04 CN CN201410736297.8A patent/CN104445170A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557013A (en) * | 2010-12-28 | 2012-07-11 | 国家纳米科学中心 | Preparation method for reduced graphene oxide |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106040015A (en) * | 2016-06-29 | 2016-10-26 | 浙江大学 | High-throughput multilayer composite nano-filtration membrane and preparation method thereof |
| IT201600104397A1 (en) * | 2016-10-18 | 2018-04-18 | Fond Bruno Kessler | GRAPHENE-BASED COMPOSITE MATERIAL FOR THE GENERATION OF HYDROGEN AND HEAT IN AQUEOUS ENVIRONMENT AND PROCESS FOR ITS PRODUCTION |
| EP3312138A1 (en) * | 2016-10-18 | 2018-04-25 | Fondazione Bruno Kessler | Graphene-based material for the generation of hydrogen and heat in auqeous environment and process for the production thereof |
| CN107579201A (en) * | 2017-09-14 | 2018-01-12 | 珠海格力电器股份有限公司 | A kind of polylayer forest and preparation method thereof |
| CN107579201B (en) * | 2017-09-14 | 2023-07-18 | 珠海格力电器股份有限公司 | Multilayer body and preparation method thereof |
| CN112391664A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
| CN112391664B (en) * | 2019-08-16 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
| CN111939658A (en) * | 2020-07-28 | 2020-11-17 | 广东职业技术学院 | Preparation method and application of graphene filter sheet |
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