CN103265012A - Methods for preparing large-area graphene film and large-area graphene composite films - Google Patents
Methods for preparing large-area graphene film and large-area graphene composite films Download PDFInfo
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Abstract
The invention discloses a method for preparing a large-area graphene film. The method comprises the following steps of pouring a graphene oxide aqueous solution on a paper base material to obtain a uniformly-covering graphene oxide film, carrying out drying curing treatment, and dipping the paper base material with the graphene oxide film into hydroiodic acid for a reduction reaction, wherein in the reduction reaction, the paper base material is hydrolyzed under the acidic condition and simultaneously, reacts with an acid to produce bubbles so that the graphene oxide film is automatically separated from the paper base material and the large-area graphene film product is obtained. The invention also discloses a method for preparing the graphene film or large-area graphene composite films. The methods can realize graphene reduction without a high-temperature or a toxic reduction reagent, can conveniently and fast realize film stripping to produce large-area film products and are 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 method for preparing big area Graphene and laminated film thereof.
Background technology
Along with the development of modern technologies, for satisfying design and the power requirement of flexible could carry electrons device (as display screen, the wearable electronics etc. of can curling), the energy storage device of making ultralight, flexibility, safety is just becoming people's research focus.Graphene film is as a kind of new carbon, 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 energy storage.
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; Though spraying method can prepare the larger area graphene film, 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 other substrates at the synthetic big area graphene film of metal substrate and just can use, 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 big area graphene film and other composite prods 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 method for preparing big area Graphene and laminated film thereof, wherein by adopting paper substrates as the intermediate carrier of graphene oxide and composite film thereof, when it is under the sour environment and carries out reduction reaction by hydroiodic acid HI, can carry out the reduction process of Graphene smoothly, convenient simultaneously, that realizes rete rapidly peels off to obtain required large area 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 large area film is difficult to peel off in the prior art.
According to a first aspect of the present invention, a kind of method for preparing the big area graphene film 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 poured on the paper substrates of tiling with mass concentration, it is flowed and form the rete that one deck evenly covers on the whole surface of paper substrates, carry out baking and curing then and handle;
(b) paper substrates that will carry the graphene oxide rete is immersed in hydrochloric acid, phosphoric acid, acetic acid or the sulfuric acid that volumetric molar concentration is 0.5mol/L～2mol/L, paper substrates issues the unboiled water solution, generates bubble with acid-respons simultaneously at sour environment in this process, impels the graphene oxide rete to break away from paper substrates automatically thus;
(c) the graphene oxide rete after take out breaking away from, and it is immersed in massfraction is to carry out reduction reaction in 45%～55% the hydroiodic acid HI, obtains required big area graphene film product thus.
According to a second aspect of the present invention, a kind of method for preparing the big area graphene film is provided, it is characterized in that this method comprises the following steps: successively
(i) be that the graphite oxide aqueous solution of 0.1mg/ml～10mg/ml is poured on the paper substrates of tiling with mass concentration, it is flowed and form the rete that one deck evenly covers on the whole surface of paper substrates, carry out baking and curing then and handle;
It is to carry out reduction reaction in 45%～55% the hydroiodic acid HI that the paper substrates that (ii) will carry the graphene oxide rete directly is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete to break away from paper substrates automatically thus, and obtain required big area graphene film product.
According to a third aspect of the present invention, a kind of method for preparing big area Graphene/carbon nano-tube coextruded film is provided, it is characterized in that this method comprises the following steps: successively
(1) 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 paper substrates 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;
(2) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/carbon nano-tube compound film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/carbon nano-tube compound film layer to break away from paper substrates automatically thus, and obtain required big area Graphene/carbon nano-tube coextruded film product.
According to a fourth aspect of the present invention, a kind of method for preparing big area graphene/polyaniline laminated film is provided, it is characterized in that this method comprises the following steps: successively
(A) be to add polyaniline nano fiber 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 polyaniline nano fiber is 2:1～4:1, this mixed solution is coated on the paper substrates 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;
(B) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/polyaniline composite film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film to break away from paper substrates automatically thus, and obtain required big area graphene/polyaniline laminated film product.
According to a fifth aspect of the present invention, a kind of method for preparing big area Graphene/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 polypyrrole nano particle is 2:1～4:1, this mixed solution is coated on the paper substrates 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;
(II) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/composite polypyrrole film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/composite polypyrrole film layer to break away from paper substrates automatically thus, and obtain required big area Graphene/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 oxide/Graphene/Graphene composite film, impel rete to peel off and can not cause damage to it; Can realize peeling off 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, when the paper substrates that directly will carry rete was dipped into hydroiodic acid HI, peeling off and reducing of graphene oxide or its composite film can be carried out simultaneously;
3, not only can realize the preparation of big area graphene film and other all kinds of Graphene laminated films 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 be according to the embodiment of the invention 3 prepared big area graphene films section SEM figure;
Fig. 2 is the SEM figure according to the embodiment of the invention 7 prepared big area graphene/polyaniline laminated films.
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 5mg/ml is poured on the commercial A4 printer paper of tiling with the 150ml mass concentration, make graphene oxide flow of solution and form the rete that one deck evenly covers on the whole surface of printer paper with the stainless steel bar rolling method, at room temperature dry curing then naturally;
The printer paper that at room temperature will carry the graphene oxide rete is immersed in the hydrochloric acid that volumetric molar concentration is 1mol/L, paper substrates issues the unboiled water solution, generates bubble with acid-respons simultaneously at sour environment in this process, can strip down from printer paper at an easy rate by the graphene oxide rete in about 10 minutes, and can obtain the graphene oxide film of A4 size after drying; This film possesses good flexibility, and can arbitrarily curl;
Then this graphene oxide film at room temperature can be immersed in again massfraction and be in 45% the hydroiodic acid HI and carry out reduction reaction, obtain required graphene film product thus.
Embodiment 2
Be that the graphite oxide aqueous solution of 10mg/ml is poured on the commercial A4 printer paper of tiling with the 150ml mass concentration, make graphene oxide flow of solution and form the rete that one deck evenly covers on the whole surface of printer paper with the stainless steel bar rolling method, at room temperature dry curing then naturally;
The printer paper that at room temperature will carry the graphene oxide rete is immersed in the acetic acid that volumetric molar concentration is 0.5mol/L, paper substrates issues the unboiled water solution, generates bubble with acid-respons simultaneously at sour environment in this process, can strip down from printer paper at an easy rate by the graphene oxide rete in about 10 minutes, and can obtain the graphene oxide film of A4 size after drying; This film possesses good flexibility, and can arbitrarily curl;
Then this graphene oxide film at room temperature can be immersed in again massfraction and be in 50% the hydroiodic acid HI and carry out reduction reaction, obtain required graphene film product thus.
Embodiment 3
Be that the specification that the graphite oxide aqueous solution of 0.1mg/ml is poured over tiling is the plotting paper of 35cm*35cm 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, carries out the baking and curing processing then;
The plotting paper that at room temperature will carry the graphene oxide rete directly is immersed in the hydroiodic acid HI of massfraction 55% and carries out reduction reaction, in this reduction process, plotting paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete to break away from plotting paper automatically thus, and obtain required big area graphene film product.Prepared big area graphene film section SEM figure as shown in Figure 1.
Embodiment 4
Be that the specification that the graphite oxide aqueous solution of 4mg/ml is poured over tiling is the plotting paper of 35cm*35cm 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, at room temperature dries curing then naturally;
The plotting paper that at room temperature will carry the graphene oxide rete directly is immersed in the hydroiodic acid HI of massfraction 45% and carries out reduction reaction, in this reduction process, plotting paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete to break away from plotting paper automatically thus, and obtain required big area graphene film product.
Embodiment 5
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 of this mixed solution being coated tiling 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;
The kraft paper that at room temperature will carry graphene oxide/carbon nano-tube compound film layer is immersed in the hydroiodic acid HI of massfraction 50% and carries out reduction reaction, in this reduction process, kraft paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/carbon nano-tube compound film layer to break away from kraft paper automatically thus, and obtain required big area Graphene/carbon nano-tube coextruded film product.
Embodiment 6
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;
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 is immersed in massfraction, in this reduction process, kraft paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/carbon nano-tube compound film layer to break away from kraft paper automatically thus, and obtain required big area Graphene/carbon nano-tube coextruded film product.
Embodiment 7
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;
The printer paper that at room temperature will carry graphene oxide/polyaniline composite film layer is immersed in the hydroiodic acid HI of massfraction 50% and carries out reduction reaction, in this reduction process, printer paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film to break away from printer paper automatically thus, and obtaining required big area graphene/polyaniline laminated film product, the SEM figure of this laminated film sample is as shown in Figure 2.
Embodiment 8
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;
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 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 to break away from printer paper automatically thus, and obtain required big area graphene/polyaniline laminated film product.
Embodiment 9
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;
It is to carry out reduction reaction in 55% the hydroiodic acid HI that the enamelled paper that carries graphene oxide/composite polypyrrole film layer is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/composite polypyrrole film layer to break away from paper substrates automatically thus, and obtain required big area Graphene/polypyrrole laminated film product.
Embodiment 10
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;
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 is immersed in massfraction, in this reduction process, enamelled paper generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/composite polypyrrole film layer to break away from enamelled paper automatically thus, and obtain required big area Graphene/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 (7)
1. a method for preparing the big area graphene film 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 poured on the paper substrates of tiling with mass concentration, it is flowed and form the rete that one deck evenly covers on the whole surface of paper substrates, carry out baking and curing then and handle;
(b) paper substrates that will carry the graphene oxide rete is immersed in hydrochloric acid, phosphoric acid, acetic acid or the sulfuric acid that volumetric molar concentration is 0.5mol/L～2mol/L, paper substrates issues the unboiled water solution, generates bubble with acid-respons simultaneously at sour environment in this process, impels the graphene oxide rete to break away from paper substrates automatically thus;
(c) the graphene oxide rete after take out breaking away from, and it is immersed in massfraction is to carry out reduction reaction in 45%～55% hydroiodic acid HI, obtains required big area graphene film product thus.
2. a method for preparing the big area graphene film is characterized in that, this method comprises the following steps: successively
(i) be that the graphite oxide aqueous solution of 0.1mg/ml～10mg/ml is poured on the paper substrates of tiling with mass concentration, it is flowed and form the rete that one deck evenly covers on the whole surface of paper substrates, carry out baking and curing then and handle;
It is to carry out reduction reaction in 45%～55% the hydroiodic acid HI that the paper substrates that (ii) will carry the graphene oxide rete directly is immersed in massfraction, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the Graphene rete to break away from paper substrates automatically thus, and obtain required big area graphene film product.
3. a method for preparing big area Graphene/carbon nano-tube coextruded film is characterized in that, this method comprises the following steps: successively
(1) 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 paper substrates 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;
(2) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/carbon nano-tube compound film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/carbon nano-tube compound film layer to break away from paper substrates automatically thus, and obtain required big area Graphene/carbon nano-tube coextruded film product.
4. a method for preparing big area graphene/polyaniline laminated film is characterized in that, this method comprises the following steps: successively
(A) be to add polyaniline nano fiber 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 polyaniline nano fiber is 2:1～4:1, this mixed solution is coated on the paper substrates 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;
(B) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/polyaniline composite film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel the graphene/polyaniline composite film to break away from paper substrates automatically thus, and obtain required big area graphene/polyaniline laminated film product.
5. a method for preparing big area Graphene/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 polypyrrole nano particle is 2:1～4:1, this mixed solution is coated on the paper substrates 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;
(II) to be immersed in massfraction be to carry out reduction reaction in 45%～55% the hydroiodic acid HI to the paper substrates that will carry graphene oxide/composite polypyrrole film layer, in this reduction process, paper substrates generation hydrolysis generates bubble with the hydroiodic acid HI reaction simultaneously, impel Graphene/composite polypyrrole film layer to break away from paper substrates automatically thus, and obtain required big area Graphene/polypyrrole laminated film product.
6. as any described method of claim 1-5, 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.
7. as any described method of claim 1-6, 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.
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