CN103265013A - Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film - Google Patents
Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film Download PDFInfo
- Publication number
- CN103265013A CN103265013A CN2013101491241A CN201310149124A CN103265013A CN 103265013 A CN103265013 A CN 103265013A CN 2013101491241 A CN2013101491241 A CN 2013101491241A CN 201310149124 A CN201310149124 A CN 201310149124A CN 103265013 A CN103265013 A CN 103265013A
- Authority
- CN
- China
- Prior art keywords
- graphene
- paper
- film
- substrates
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a preparation method of a flexible substrate-based graphene film. The preparation method comprises the following steps of coating a graphene oxide aqueous solution on a paper base material to obtain a uniform graphene oxide film, carrying out drying curing treatment, coating a polydimethylsiloxane (PDMS) layer on the surface of the graphene oxide film, carrying out curing treatment, and dipping the treated paper base material into hydroiodic acid for a reduction reaction, wherein in the reduction reaction, the treated paper base material undergoes a hydrolysis reaction under the acid conditions and simultaneously, reacts with the acid to produce bubbles so that the graphene oxide film is automatically separated from the paper base material and the flexible substrate-based graphene film product is obtained. The invention also discloses a preparation method of a flexible substrate-based graphene composite film. The methods realize graphene reduction without a high temperature condition or a toxic reduction reagent, conveniently and fast realize film stripping and transfer and are especially suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the Graphene preparing technical field, more specifically, relate to a kind of preparation method of Graphene and the laminated film thereof based on flexible substrates.
Background technology
In recent years, along with the demand of consumption electronic product increases rapidly, relevant flexible, light portable electron device (as display screen, the wearable electronics etc. of can curling) becomes a research focus.Flexible electronic all has good application prospects at aspects such as wearable display element, artificial skin and distributed sensors.Graphene is that carbon atom is with the tightly packed cellular two-dimensional crystal lattice structural carbon nano material that forms of sp2 hybrid systems, because it has features such as the electrochemical properties of bigger serface, high-mechanical property, excellent electron transport ability and relative inertness and lower cost, thereby is expected to obtain widespread use in a plurality of fields such as flexible electronic, energy storage, electrochemical sensing.
In above-mentioned application, Graphene need and be transferred to the enterprising enforcement of flexible substrates and use usually as form of film.Method for the preparation of graphene film mainly comprises spin-coating method, spraying method, suction method and chemical Vapor deposition process (CVD) etc. at present, wherein spin-coating method is as laboratory working method commonly used, can only prepare the less graphene film of area, and the thickness distribution inequality of obtained film, solution is required also relatively harsher; Spraying method operation steps complexity, preparation cost are higher relatively, are unfavorable for large-scale industrial production; Suction method faces suction filtration time length equally, film size is limited by device, is difficult to problems such as large-area preparation; For chemical Vapor deposition process, though can big area synthesizing graphite alkene film, but must adopt metal catalytic layer and synthesizing graphite alkene film on the metal catalytic substrate, synthesis temperature is generally more than 650, like this during actually operating, must transfer on the flexible substrate at the synthetic big area graphene film of metal substrate, correspondingly cause the inconvenience in the actual production.Therefore, in association area, need badly and seek a kind of more perfect preparation method, in order to can obtain graphene film and other composite prods based on flexible substrates in mode simple, that be convenient to control.
Summary of the invention
Above defective or improvement demand at prior art, the invention provides a kind of preparation method of Graphene and the laminated film thereof based on flexible substrates, wherein by adopting paper substrates as the intermediate carrier of graphene oxide and composite film thereof, when it is immersed in the hydroiodic acid HI, not only can carry out the reduction process of Graphene smoothly, and can also make things convenient for, that realizes rete rapidly peels off to obtain required film product, can break away from this way hot conditions or other poisonous dependences of going back original reagent, and solve the technical problem that graphene film in the prior art and laminated film film thereof are difficult to shift.
According to a first aspect of the present invention, a kind of preparation method of the graphene film based on flexible substrates is provided, it is characterized in that this method comprises the following steps: successively
(a) be that the graphite oxide aqueous solution of 0.1mg/ml～10mg/ml is coated on the surface of paper substrates and forms the rete that one deck evenly covers with mass concentration, carry out baking and curing then and handle, obtain graphene oxide paper thus;
(b) on the graphene oxide film surface of graphene oxide paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(c) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the graphene oxide paper that will be coated with the polydimethylsiloxane layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required graphene film product based on the polydimethylsiloxane flexible substrates.
According to a second aspect of the present invention, a kind of preparation method of the Graphene/carbon nano-tube coextruded film based on flexible substrates is provided, it is characterized in that this method comprises the following steps: successively
(i) be to add multi-walled carbon nano-tubes in the graphite oxide aqueous solution of 2mg/ml～8mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～5:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/carbon nano-tube compound film layer thus;
(ii) on the graphene oxide/carbon nano-tube compound film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 45%～55% the hydroiodic acid HI that paper substrates after (iii) will (ii) handling through step is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/carbon nano-tube compound film layer that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required Graphene based on the polydimethylsiloxane flexible substrates/carbon nano-tube coextruded film product.
According to a third aspect of the present invention, a kind of preparation method of the graphene/polyaniline laminated film based on flexible substrates is provided, it is characterized in that this method comprises the following steps: successively
(A) be to add the polyaniline nano particle in the graphite oxide aqueous solution of 2mg/ml～8mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～4:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/polyaniline composite film layer thus;
(B) on the graphene oxide/polyaniline composite film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(C) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates after will handling through step (B), in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required graphene/polyaniline laminated film product based on the polydimethylsiloxane flexible substrates.
According to a fourth aspect of the present invention, the preparation method of a kind of Graphene based on flexible substrates/polypyrrole laminated film is provided, it is characterized in that this method comprises the following steps: successively
(I) be to add the polypyrrole nano particle in the graphite oxide aqueous solution of 3mg/ml～6mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～4:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/composite polypyrrole film layer thus;
(II) on the graphene oxide/composite polypyrrole film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(III) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates after will handling through step (II), in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/composite polypyrrole film layer that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required Graphene based on the polydimethylsiloxane flexible substrates/polypyrrole laminated film product.
As further preferably, described paper substrates is selected from printer paper, plotting paper, kraft paper, water writing paper, blotting paper or enamelled paper or other analogous materials.
As further preferably, adopt stainless steel bar or coating roll to make on the whole surface of paper substrates and form graphene oxide rete or its composite film that evenly covers.
In general, the above technical scheme of conceiving by the present invention compared with prior art mainly possesses following technological merit:
1, by adopting paper substrates as the intermediate carrier of graphene oxide and composite film thereof, when it is in sour environment following time, hydrolysis reaction makes that the degree of crystallinity of paper fiber is destroyed on the one hand, the polymerization degree and intensity lower, its additive that contains can generate many small bubbles with acid-respons on the other hand, these small bubbles act on the interface between paper substrates and the Graphene/Graphene composite film, impel rete to peel off and can not cause damage to it; Can realize peeling off and shifting of rete fast, expediently in this way, and can operate at normal temperatures;
2, by adopting hydroiodic acid HI as the reducing substance of graphene oxide, can break away from hot conditions or poisonous dependence of going back original reagent in the prior art, help the generation of large area film product, in addition, can also solve the technical problem that graphene film in the prior art and laminated film film thereof are difficult to shift well;
3, not only can realize preparation based on graphene film and other all kinds of Graphene laminated films of flexible substrates at normal temperatures according to preparation method of the present invention, and simple to operate, be convenient to control, cost is low, environmentally safe, prepared film product possesses good flexibility and planeness, thereby is particularly useful for large batch of suitability for industrialized production purposes.
Description of drawings
Fig. 1 is the section SEM figure according to the prepared graphene film of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can not make up mutually as long as constitute conflict each other.
Embodiment 1
Be that the graphite oxide aqueous solution of 0.1mg/ml is poured over such as on the commercial printer paper of A4 specification with the 300ml mass concentration, employing stainless steel bar rolling method flows it and forms the rete that one deck evenly covers on the whole surface of plotting paper, carry out baking and curing then and handle, obtain graphene oxide paper thus;
On the graphene oxide film surface of graphene oxide paper, adopt stainless steel bar that polydimethylsiloxane (PDMS) liquid is given roller coating equally and cover, obtain the PDMS layer thus, and it is carried out solidification treatment under the 80-90 degree;
It is to carry out reduction reaction in 45% the hydroiodic acid HI that the graphene oxide paper that at room temperature will be coated with the polydimethylsiloxane layer is immersed in massfraction, in this reduction process, printer paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete that combines with the polydimethylsiloxane layer to break away from printer paper automatically thus, and obtain the required graphene film product based on the polydimethylsiloxane flexible substrates.
Embodiment 2
Be that the graphite oxide aqueous solution of 10mg/ml is poured over such as on the commercial printer paper of A4 specification with the 300ml mass concentration, employing stainless steel bar rolling method flows it and forms the rete that one deck evenly covers on the whole surface of plotting paper, carry out baking and curing then and handle, obtain graphene oxide paper thus;
On the graphene oxide film surface of graphene oxide paper, adopt stainless steel bar that polydimethylsiloxane (PDMS) liquid is given roller coating equally and cover, obtain the PDMS layer thus, and it is carried out solidification treatment under the 80-90 degree;
It is to carry out reduction reaction in 50% the hydroiodic acid HI that the graphene oxide paper that at room temperature will be coated with the polydimethylsiloxane layer is immersed in massfraction, in this reduction process, printer paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete that combines with the polydimethylsiloxane layer to break away from printer paper automatically thus, and obtain the required graphene film product based on the polydimethylsiloxane flexible substrates.
Embodiment 3
Be to add the 50mg multi-walled carbon nano-tubes and carry out ultra-sonic dispersion in the graphite oxide aqueous solution of 2mg/ml to obtain mixed solution after 2 hours to the 40ml mass concentration, the specification that this mixed solution is coated tiling by coating roll is on the kraft paper of 40cm*40cm, and at the composite film that its whole surface formation one deck evenly covers, carry out baking and curing then and handle;
On the graphene oxide/carbon nano-tube compound film laminar surface of this kraft paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 55% the hydroiodic acid HI that the kraft paper that carries graphene oxide/carbon nano-tube compound film layer and polydimethylsiloxane layer is immersed in massfraction, in this reduction process, kraft paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/carbon nano-tube compound film layer that combines with the PDMS layer to break away from kraft paper automatically thus, and obtain the required Graphene based on PDMS/carbon nano-tube coextruded film product.
Embodiment 4
Be to add the 100mg multi-walled carbon nano-tubes and carry out ultra-sonic dispersion in the graphite oxide aqueous solution of 5mg/ml to obtain mixed solution after 2 hours to the 40ml mass concentration, the specification that this mixed solution is coated tiling by coating roll is on the kraft paper of 40cm*40cm, and at the composite film that its whole surface formation one deck evenly covers, carry out baking and curing then and handle;
On the graphene oxide/carbon nano-tube compound film laminar surface of this kraft paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 45% the hydroiodic acid HI that the kraft paper that at room temperature will carry graphene oxide/carbon nano-tube compound film layer and PDMS layer is immersed in massfraction, in this reduction process, kraft paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/carbon nano-tube compound film layer that combines with the PDMS layer to break away from kraft paper automatically thus, and obtain the required Graphene based on PDMS/carbon nano-tube coextruded film product.
Embodiment 5
With the Ammonium Persulfate 98.5 of the aniline solution of 0.3ml and 0.18g be dissolved in 10ml respectively, volumetric molar concentration is in the hydrochloric acid of 1mol/L, vibration is 30 seconds after the short mix, standing and reacting is 2 hours under the room temperature, namely obtains polyaniline nano fiber; Be to add the prepared polyaniline nano fiber of 100mg in the graphite oxide aqueous solution of 5mg/ml to the 40ml mass concentration, and the execution ultra-sonic dispersion obtains mixed solution, this mixed solution is coated by coating roll on the A4 printer paper of tiling and on its whole surface and formed the composite film that one deck evenly covers, carry out baking and curing then and handle;
On the graphene oxide/polyaniline composite film laminar surface of this printer paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 55% the hydroiodic acid HI that the printer paper that at room temperature will carry graphene oxide/polyaniline composite film layer and PDMS layer is immersed in massfraction, in this reduction process, printer paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film that combines with the PDMS layer to break away from printer paper automatically thus, and obtain the required graphene/polyaniline laminated film product based on PDMS.
Embodiment 6
With the Ammonium Persulfate 98.5 of the aniline solution of 0.3ml and 0.18g be dissolved in 10ml respectively, volumetric molar concentration is in the hydrochloric acid of 1mol/L, vibration is 30 seconds after the short mix, standing and reacting is 2 hours under the room temperature, namely obtains polyaniline nano fiber; Be to add the prepared polyaniline nano fiber of 100mg in the graphite oxide aqueous solution of 3mg/ml to the 40ml mass concentration, and the execution ultra-sonic dispersion obtains mixed solution, this mixed solution is coated on the A4 printer paper of tiling and on its whole surface and formed the composite film that one deck evenly covers, carry out baking and curing then and handle;
On the graphene oxide/polyaniline composite film laminar surface of this printer paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 45% the hydroiodic acid HI that the printer paper that at room temperature will carry graphene oxide/polyaniline composite film layer and PDMS layer is immersed in massfraction, in this reduction process, printer paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film that combines with the PDMS layer to break away from printer paper automatically thus, and obtain the required graphene/polyaniline laminated film product based on PDMS.
Embodiment 7
Be to add the polypyrrole nano particle and carry out ultra-sonic dispersion in the graphite oxide aqueous solution of 3mg/ml to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and polypyrrole nano particle is 2:1, the specification that this mixed solution is coated tiling is to form the composite film that one deck evenly covers on the enamelled paper of 30cm*30cm and on its whole surface, carries out baking and curing then and handles;
On the graphene oxide/composite polypyrrole film laminar surface of this enamelled paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 50% the hydroiodic acid HI that the enamelled paper that carries graphene oxide/composite polypyrrole film layer and PDMS layer is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/composite polypyrrole film layer that combines with the PDMS layer to break away from paper substrates automatically thus, and obtain required Graphene based on PDMS/polypyrrole laminated film product.
Embodiment 8
Be to add the polypyrrole nano particle and carry out ultra-sonic dispersion in the graphite oxide aqueous solution of 6mg/ml to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and polypyrrole nano particle is 4:1, the specification that this mixed solution is coated tiling is to form the composite film that one deck evenly covers on the enamelled paper of 30cm*30cm and on its whole surface, carries out baking and curing then and handles;
On the graphene oxide/composite polypyrrole film laminar surface of this enamelled paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 45% the hydroiodic acid HI that the enamelled paper that carries graphene oxide/composite polypyrrole film layer and PDMS layer is immersed in massfraction, in this reduction process, enamelled paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/composite polypyrrole film layer that combines with PDMS to break away from enamelled paper automatically thus, and obtain required Graphene based on PDMS/polypyrrole laminated film product.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the preparation method based on the graphene film of flexible substrates is characterized in that, this method comprises the following steps: successively
(a) be that the graphite oxide aqueous solution of 0.1mg/ml～10mg/ml is coated on the surface of paper substrates and forms the rete that one deck evenly covers with mass concentration, carry out baking and curing then and handle, obtain graphene oxide paper thus;
(b) on the graphene oxide film surface of graphene oxide paper, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(c) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the graphene oxide paper that will be coated with the polydimethylsiloxane layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required graphene film product based on the polydimethylsiloxane flexible substrates.
2. the preparation method based on the Graphene/carbon nano-tube coextruded film of flexible substrates is characterized in that, this method comprises the following steps: successively
(i) be to add multi-walled carbon nano-tubes in the graphite oxide aqueous solution of 2mg/ml～8mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～5:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/carbon nano-tube compound film layer thus;
(ii) on the graphene oxide/carbon nano-tube compound film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
It is to carry out reduction reaction in 45%～55% the hydroiodic acid HI that paper substrates after (iii) will (ii) handling through step is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/carbon nano-tube compound film layer that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required Graphene based on the polydimethylsiloxane flexible substrates/carbon nano-tube coextruded film product.
3. the preparation method based on the graphene/polyaniline laminated film of flexible substrates is characterized in that this method comprises the following steps: successively
(A) be to add the polyaniline nano particle in the graphite oxide aqueous solution of 2mg/ml～8mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～4:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/polyaniline composite film layer thus;
(B) on the graphene oxide/polyaniline composite film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(C) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates after will handling through step (B), in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required graphene/polyaniline laminated film product based on the polydimethylsiloxane flexible substrates.
4. the preparation method of the Graphene based on flexible substrates/polypyrrole laminated film is characterized in that this method comprises the following steps: successively
(I) be to add the polypyrrole nano particle in the graphite oxide aqueous solution of 3mg/ml～6mg/ml and carry out ultra-sonic dispersion to obtain mixed solution to mass concentration, wherein the quality proportioning of graphene oxide and multi-walled carbon nano-tubes is 2:1～4:1, this mixed solution is coated on the surface of paper substrates and forms the composite film that one deck evenly covers, carry out baking and curing then and handle, obtain to carry the paper substrates of graphene oxide/composite polypyrrole film layer thus;
(II) on the graphene oxide/composite polypyrrole film laminar surface of this paper substrates, apply one deck polydimethylsiloxane layer again, and it is carried out solidification treatment;
(III) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates after will handling through step (II), in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene/composite polypyrrole film layer that combines with the polydimethylsiloxane layer to break away from paper substrates automatically thus, and obtain the required Graphene based on the polydimethylsiloxane flexible substrates/polypyrrole laminated film product.
5. as any described method of claim 1-4, it is characterized in that described paper substrates is selected from printer paper, plotting paper, kraft paper, water writing paper, blotting paper or enamelled paper or other analogous materials.
6. as any described method of claim 1-5, it is characterized in that, adopt stainless steel bar or coating roll to make on the whole surface of paper substrates and form graphene oxide rete or its composite film that evenly covers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310149124.1A CN103265013B (en) | 2013-04-26 | 2013-04-26 | Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310149124.1A CN103265013B (en) | 2013-04-26 | 2013-04-26 | Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103265013A true CN103265013A (en) | 2013-08-28 |
| CN103265013B CN103265013B (en) | 2014-12-10 |
Family
ID=49008693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310149124.1A Expired - Fee Related CN103265013B (en) | 2013-04-26 | 2013-04-26 | Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103265013B (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804704A (en) * | 2014-02-17 | 2014-05-21 | 江苏亚宝绝缘材料股份有限公司 | Polyimide composite conductive thin film and preparation method thereof |
| CN104211960A (en) * | 2014-09-30 | 2014-12-17 | 中原工学院 | One-step chemical preparation method for graphene and polyaniline composite materials |
| CN104505148A (en) * | 2014-11-13 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing flexible-substrate three-dimensional conformal graphene film |
| CN105869892A (en) * | 2016-04-05 | 2016-08-17 | 上海交通大学 | High-performance graphene thin film electrode and preparation method thereof |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
| CN106430160A (en) * | 2016-09-09 | 2017-02-22 | 浙江理工大学 | Production method of double-layer reductive graphite oxide film flexible strain sensor |
| CN106430161A (en) * | 2016-09-09 | 2017-02-22 | 浙江理工大学 | Apical impulse sensor based on reduced graphene oxide film with bilayer buckling structure |
| CN106959071A (en) * | 2017-01-19 | 2017-07-18 | 吉林大学 | A kind of bionical strain perceptual structure and forming method thereof |
| CN107324321A (en) * | 2017-07-24 | 2017-11-07 | 济南大学 | Load the preparation method of golden flower three-dimensional redox graphene |
| US20170355879A1 (en) * | 2014-11-14 | 2017-12-14 | Agency For Science, Technology And Research | Hydrophobic coatings (as amended) |
| CN107556508A (en) * | 2017-08-31 | 2018-01-09 | 浙江理工大学 | A kind of preparation method of the fexible film based on the micro- cylindrical-array of graphene |
| CN108425271A (en) * | 2018-03-23 | 2018-08-21 | 齐鲁工业大学 | A kind of paper substrate Flexible graphene film and preparation method thereof |
| CN108688252A (en) * | 2018-03-27 | 2018-10-23 | 武汉纺织大学 | A kind of preparation method of multiple stimulation response driver film |
| CN108763764A (en) * | 2018-05-29 | 2018-11-06 | 南京航空航天大学 | A kind of computational methods of graphene-flexible substrates buckling structure deformation |
| CN109111664A (en) * | 2018-07-11 | 2019-01-01 | 四川羽玺新材料股份有限公司 | A kind of PVDF-PET/ graphene quantum dot composite membrane and preparation method thereof |
| CN110165366A (en) * | 2019-04-22 | 2019-08-23 | 浙江大学 | A kind of graphene antenna of thermal transfer and its preparation method and application |
| CN110696540A (en) * | 2019-09-29 | 2020-01-17 | 东南大学 | Patterned graphene-based electronic tattoo skin and preparation method thereof |
| US10583407B2 (en) | 2014-03-28 | 2020-03-10 | The University Of Manchester | Reduced graphene oxide barrier materials |
| CN111925776A (en) * | 2020-07-11 | 2020-11-13 | 西北工业大学 | Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material |
| CN113074622A (en) * | 2021-03-24 | 2021-07-06 | 北京航空航天大学 | Flexible strain sensor based on graphene-gold composite film cracks and preparation method |
| CN113329528A (en) * | 2021-06-29 | 2021-08-31 | 华南理工大学 | Paper-based graphene flexible heater and preparation method thereof |
| CN114486427A (en) * | 2022-01-05 | 2022-05-13 | 西北工业大学重庆科创中心 | Extensible electrode leveling integration method based on ultrathin viscous silica gel |
| WO2022141180A1 (en) * | 2020-12-30 | 2022-07-07 | 杭州高烯科技有限公司 | Method for stripping graphene oxide nano membrane from substrate |
| CN114750471A (en) * | 2022-04-22 | 2022-07-15 | 成都飞机工业（集团）有限责任公司 | Graphene composite membrane material and preparation method and application thereof |
| CN115073057A (en) * | 2022-06-30 | 2022-09-20 | 浙江大学 | Preparation method of high-strength high-toughness graphene composite film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815043A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method of grapheme and polyaniline composite paper, and products thereof |
| CN103065813A (en) * | 2012-12-20 | 2013-04-24 | 中国科学技术大学 | Preparing method and application of super capacitor electrode |
-
2013
- 2013-04-26 CN CN201310149124.1A patent/CN103265013B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815043A (en) * | 2012-08-02 | 2012-12-12 | 中国科学技术大学 | Preparation method of grapheme and polyaniline composite paper, and products thereof |
| CN103065813A (en) * | 2012-12-20 | 2013-04-24 | 中国科学技术大学 | Preparing method and application of super capacitor electrode |
Non-Patent Citations (1)
| Title |
|---|
| MING HE ET AL.: "Graphene-based transparent flexible electrodes for polymer solar cells", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, 31 December 2012 (2012-12-31), pages 24254 - 24264 * |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804704A (en) * | 2014-02-17 | 2014-05-21 | 江苏亚宝绝缘材料股份有限公司 | Polyimide composite conductive thin film and preparation method thereof |
| CN103804704B (en) * | 2014-02-17 | 2016-08-17 | 江苏亚宝绝缘材料股份有限公司 | The preparation method of a kind of polyimides composite conductive thin film and conductive film |
| US10583407B2 (en) | 2014-03-28 | 2020-03-10 | The University Of Manchester | Reduced graphene oxide barrier materials |
| CN104211960A (en) * | 2014-09-30 | 2014-12-17 | 中原工学院 | One-step chemical preparation method for graphene and polyaniline composite materials |
| CN104505148A (en) * | 2014-11-13 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Method for preparing flexible-substrate three-dimensional conformal graphene film |
| US20170355879A1 (en) * | 2014-11-14 | 2017-12-14 | Agency For Science, Technology And Research | Hydrophobic coatings (as amended) |
| CN105883781B (en) * | 2016-03-09 | 2018-10-30 | 王祉豫 | A kind of preparation method of large area redox graphene film |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
| CN105869892A (en) * | 2016-04-05 | 2016-08-17 | 上海交通大学 | High-performance graphene thin film electrode and preparation method thereof |
| CN106430161A (en) * | 2016-09-09 | 2017-02-22 | 浙江理工大学 | Apical impulse sensor based on reduced graphene oxide film with bilayer buckling structure |
| CN106430160A (en) * | 2016-09-09 | 2017-02-22 | 浙江理工大学 | Production method of double-layer reductive graphite oxide film flexible strain sensor |
| CN106430161B (en) * | 2016-09-09 | 2018-05-22 | 浙江理工大学 | A kind of apex beat sensor of the oxidation graphene film based on double-deck buckling structure |
| CN106959071A (en) * | 2017-01-19 | 2017-07-18 | 吉林大学 | A kind of bionical strain perceptual structure and forming method thereof |
| CN106959071B (en) * | 2017-01-19 | 2019-04-26 | 吉林大学 | A kind of bionical strain perceptual structure and forming method thereof |
| CN107324321A (en) * | 2017-07-24 | 2017-11-07 | 济南大学 | Load the preparation method of golden flower three-dimensional redox graphene |
| CN107556508B (en) * | 2017-08-31 | 2020-01-17 | 浙江理工大学 | Preparation method of flexible thin film based on graphene micro-cylinder array |
| CN107556508A (en) * | 2017-08-31 | 2018-01-09 | 浙江理工大学 | A kind of preparation method of the fexible film based on the micro- cylindrical-array of graphene |
| CN108425271A (en) * | 2018-03-23 | 2018-08-21 | 齐鲁工业大学 | A kind of paper substrate Flexible graphene film and preparation method thereof |
| CN108688252A (en) * | 2018-03-27 | 2018-10-23 | 武汉纺织大学 | A kind of preparation method of multiple stimulation response driver film |
| CN108688252B (en) * | 2018-03-27 | 2020-07-24 | 武汉纺织大学 | Preparation method of multi-stimulus responsive driver film |
| CN108763764A (en) * | 2018-05-29 | 2018-11-06 | 南京航空航天大学 | A kind of computational methods of graphene-flexible substrates buckling structure deformation |
| CN108763764B (en) * | 2018-05-29 | 2022-04-15 | 南京航空航天大学 | Calculation method for buckling deformation of graphene-flexible substrate structure |
| CN109111664A (en) * | 2018-07-11 | 2019-01-01 | 四川羽玺新材料股份有限公司 | A kind of PVDF-PET/ graphene quantum dot composite membrane and preparation method thereof |
| CN110165366B (en) * | 2019-04-22 | 2021-02-19 | 浙江大学 | Thermal transfer printing graphene antenna and preparation method and application thereof |
| CN110165366A (en) * | 2019-04-22 | 2019-08-23 | 浙江大学 | A kind of graphene antenna of thermal transfer and its preparation method and application |
| CN110696540A (en) * | 2019-09-29 | 2020-01-17 | 东南大学 | Patterned graphene-based electronic tattoo skin and preparation method thereof |
| CN111925776B (en) * | 2020-07-11 | 2021-11-30 | 西北工业大学 | Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material |
| CN111925776A (en) * | 2020-07-11 | 2020-11-13 | 西北工业大学 | Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material |
| WO2022141180A1 (en) * | 2020-12-30 | 2022-07-07 | 杭州高烯科技有限公司 | Method for stripping graphene oxide nano membrane from substrate |
| CN113074622A (en) * | 2021-03-24 | 2021-07-06 | 北京航空航天大学 | Flexible strain sensor based on graphene-gold composite film cracks and preparation method |
| CN113329528A (en) * | 2021-06-29 | 2021-08-31 | 华南理工大学 | Paper-based graphene flexible heater and preparation method thereof |
| CN114486427A (en) * | 2022-01-05 | 2022-05-13 | 西北工业大学重庆科创中心 | Extensible electrode leveling integration method based on ultrathin viscous silica gel |
| CN114486427B (en) * | 2022-01-05 | 2023-09-08 | 西北工业大学重庆科创中心 | Extensible electrode leveling integration method based on ultrathin viscous silica gel |
| CN114750471A (en) * | 2022-04-22 | 2022-07-15 | 成都飞机工业（集团）有限责任公司 | Graphene composite membrane material and preparation method and application thereof |
| CN114750471B (en) * | 2022-04-22 | 2023-08-04 | 成都飞机工业（集团）有限责任公司 | Graphene composite film material and preparation method and application thereof |
| CN115073057A (en) * | 2022-06-30 | 2022-09-20 | 浙江大学 | Preparation method of high-strength high-toughness graphene composite film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103265013B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265013B (en) | Preparation methods of flexible substrate-based graphene film and flexible substrate-based graphene composite film | |
| CN103265012B (en) | Methods for preparing large-area graphene film and large-area graphene composite films | |
| Shim et al. | Synthesis of numerous edge sites in MoS2 via SiO2 nanorods platform for highly sensitive gas sensor | |
| US20170260054A1 (en) | Graphene dispersant and application thereof | |
| Lei et al. | Boron carbon nitride nanostructures from salt melts: tunable water-soluble phosphors | |
| Sethi et al. | Superhydrophobic conductive carbon nanotube coatings for steel | |
| Jin et al. | A durable, superhydrophobic, superoleophobic and corrosion-resistant coating with rose-like ZnO nanoflowers on a bamboo surface | |
| CN102275902B (en) | Method for preparing graphene material by reducing graphene oxide | |
| CN103028737B (en) | Method for preparing graphene-metal nano particle composite material | |
| CN103282306A (en) | Graphene film transfer method, and method for manufacturing transparent conductive film | |
| CN110127671A (en) | A kind of general preparative methods of redox graphene group compound film | |
| CN106276862A (en) | A kind of volume to volume shifts the device of Graphene continuously | |
| CN103213980A (en) | Preparation method of three-dimensional graphene or composite system thereof | |
| CN102674321A (en) | Graphene foam with three dimensional fully connected network and macroscopic quantity preparation method thereof | |
| CN102795619A (en) | Graphene thin film transferring method based on physical adsorption | |
| Belkhedkar et al. | Physical properties of nanostructured Mn3O4 thin films synthesized by SILAR method at room temperature for antibacterial application | |
| CN105692595A (en) | Preparation method of layered nanoscale material | |
| Wang et al. | Nonenzymatic glucose sensor using freestanding single-wall carbon nanotube films | |
| CN106158144A (en) | A kind of preparation method of ultra-thin super Flexible graphene conductive film | |
| CN107541709B (en) | A kind of preparation method and graphene film of graphene film | |
| Mahadik et al. | Recoverable and thermally stable superhydrophobic silica coating | |
| Pradhan et al. | One-dimensional and two-dimensional ZnO nanostructured materials on a plastic substrate and their field emission properties | |
| US9546430B2 (en) | Lithium recovery device and recovery method | |
| CN104944402B (en) | Method for quickly and efficiently preparing adjustable-fluorine-content fluoridized graphene | |
| Chen et al. | Robust superhydrophobic surfaces via the sand-in method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170315 Address after: 453000 Xinxiang City, Weihui City Industrial Zone standardization workshop building, building 6, No. Patentee after: Weihui Power Technology Co., Ltd. Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037 Patentee before: Huazhong University of Science and Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20180426 |