CN109754951B - Cellulose-graphene composite transparent conductive film and preparation method thereof - Google Patents
Cellulose-graphene composite transparent conductive film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose-graphene composite transparent conductive film and a preparation method thereof. According to the invention, firstly, a cellulose alkaline urine solution is prepared, then graphene is added, sodium hydroxide-urea hydrate formed by the alkaline urine solution in a subzero environment can be easily inserted into an interlayer region of the graphene and is attached to a host layer, so that an original hydrogen bond network is destroyed, a new hydrogen bond network is formed, the graphene is peeled layer by layer, a graphene-cellulose solution with uniform dispersion is obtained, then a cross-linking agent is added to form cellulose-graphene gel, and a conductive film is obtained through a hot-pressing forming method. The graphene and the cellulose which are well dispersed in the conductive film form a stable cross-linked structure under the action of the cross-linking agent, the conductivity of the graphene can be fully exerted, meanwhile, the conductive film is additionally endowed with excellent antibacterial property, hot water resistance and antistatic property, the high-transparency multifunctional conductive film is constructed, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of transparent conductive composite materials, and particularly relates to a cellulose-graphene composite transparent conductive film and a preparation method thereof.
Background
With the rapid update of electronic products, light conductive thin film materials with high light transmittance are increasingly widely used. The transparent conductive films are widely applied to displays of electronic products, thin solar cells and photoelectric materials, and have a far-reaching application prospect. At present, the transparent conductive film substrate material in the photoelectric material mainly adopts some organic polymer materials with high transparency and good thermal stability. However, these artificial organic polymer materials are difficult to degrade and can cause damage to the ecological environment. In order to realize sustainable development of resources, the need to replace fossil raw materials with new materials is urgent.
Graphene is the thinnest and toughest material in the world so far, has a plurality of excellent performances such as ultrahigh current density, ultrahigh carrier mobility, chemical inertness, extremely high thermal conductivity, excellent light transmittance, super hydrophobicity, ultrahigh mechanical strength and the like, and is widely applied to the fields of sensors, lithium ion batteries, solar batteries, fuel cells, photoelectricity and the like. In particular, the properties of the transparent conductive film, such as good light transmittance, high conductivity, and good mechanical strength, have recently been receiving attention and research in the field of transparent conductive films. Compared with an Indium Tin Oxide (ITO) film, the graphene transparent conductive film has the characteristics of good light transmission and stability, better flexibility and the like.
Cellulose is used as a cheap natural polymer material, has wide sources, low cost, light weight, reproducibility and biodegradation, and also has larger specific surface area and super-strong adsorption capacity, cellulose membranes prepared by the cellulose are more and more widely concerned, and huge natural reserves of the cellulose can completely meet the requirements of electronic products on conductive films.
In the prior art, related products of graphene composite nanocellulose are more, for example, patent CN103937032A introduces a cellulose nanocrystal/graphene composite color film and a rapid preparation method thereof, and the color film is obtained by preparing a prepared cellulose nanocrystal into a solution, mixing the solution with graphene, performing ultrasonic dispersion, and performing vacuum filtration. In addition, patent CN104910394A describes a method for preparing nanocrystalline cellulose by graphene oxide assisted acid hydrolysis, which describes a related technology that graphene can be combined with nanocellulose to form a composite product, but the problem is that, while a certain amount of graphene is added into the composite product, the graphene particles are not uniformly dispersed in the nanocellulose, the particle size is not uniform, and interlayer aggregation is likely to occur, so that stress concentration points caused by graphene materials with different sheet diameters are likely to break, which affects the performance of the prepared product.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a high-strength high-toughness cellulose-graphene transparent conductive film and a preparation method thereof.
The technical scheme of the invention is as follows, which specifically comprises the following steps:
(1) preparing a graphene-cellulose solution, namely adding 0.01-0.05 g of graphene into a cellulose solution of 100m L, stirring for 10-60 min, and then carrying out low-temperature stripping at-10 to-20 ℃ to obtain the graphene-cellulose solution;
(2) preparing graphene-cellulose gel: adding a cross-linking agent into the graphene-cellulose solution obtained in the step (1), heating to 30-60 ℃, stirring for 0.5-1 h, pouring to form graphene-cellulose gel under the water bath condition of 20-60 ℃, and washing with deionized water until the pH value is 7;
(3) and (3) carrying out hot-pressing molding on the graphene-cellulose gel obtained in the step (2) to obtain a graphene-cellulose membrane. Through the hot-press molding process, the cellulose-graphene gel forms a layer of film, so that the mechanical strength and toughness are improved while the transparency and the conductivity are kept.
The cellulose solution is a cellulose alkaline urine solution prepared by mixing cellulose and an alkaline urine solution, wherein the ratio of the cellulose to the alkaline urine solution is as follows: 2-5: 95-98.
The cellulose alkaline urine solution is prepared by adopting the following method: adding cellulose into an alkaline urine solution, freezing for 0.5-2 h at the temperature of-10 to-20 ℃, continuously stirring for 30-60min for thawing, and centrifuging at the rotating speed of 4000-6000 rpm to obtain the cellulose solution.
The alkaline urine solution is prepared by mixing sodium hydroxide, urea and water, wherein the mass ratio of the sodium hydroxide to the urea to the water is 7: 12: 81.
and (2) the low-temperature stripping time in the step (1) is 10-60 min.
The cross-linking agent in the step (2) is one of N, N-methylene bisacrylamide, epichlorohydrin, dicumyl peroxide and glutaraldehyde, and the dosage of the cross-linking agent is 1.5-2 wt%. The addition of the cross-linking agent enables the graphene and the cellulose to be combined more firmly, and meanwhile, the elasticity and the mechanical strength of the gel are improved. Washing in deionized water is to remove NaOH from the interior of the gel, increasing its transparency.
In the step (2), the pouring thickness of the cellulose-graphene solution is 3-8 mm; the temperature of the water bath is more easily formed into gel under the environment of 20-30 ℃.
The hot-press molding in the step (3) has the following process conditions: the hot pressing time is 0.5-5h, the temperature is 30-100 ℃, and the pressure is 20-100 pa. The cellulose-graphene composite membrane prepared by adopting the hot-press forming principle is stronger and more compact, and the mechanical property of the cellulose-graphene composite membrane is improved.
The alkali urine dissolves the cellulose and peels off the graphene. The cellulose solution is used as a dispersing agent and a stabilizing agent to keep the graphene in a dispersed state. The prepared cellulose solution is not dialyzed against alkaline urine and is used for the next step of stripping the graphene.
The cellulose alkaline urine solution plays a key role in the dispersion of graphene: 1) the alkaline urine destroys hydrogen bonds and Van der Waals force between graphene layers, and the graphene is peeled layer by layer; 2) the stripped graphene does not re-agglomerate due to the existence of cellulose between layers, and meanwhile, the cellulose surface is rich in polar oxygen-containing groups, so that the graphene can generate non-covalent interactions such as hydrogen bond interaction, electrostatic force and the like with the graphene, the graphene layers are stripped, the dispersity of the graphene is improved, and no precipitate is generated even if the graphene is kept still for two weeks.
The invention has the beneficial effects that:
1. the invention utilizes the direct action of the compound formed by NaOH and urea molecules and cellulose to destroy the hydrogen bond of the cellulose, and forms the urea-NaOH-cellulose inclusion compound by self-assembly between solvent micromolecules and cellulose macromolecules under the action of low-temperature induction, so the addition of the alkaline urine promotes the dissolution of the cellulose. Meanwhile, sodium hydroxide/urea hydrate formed in a subzero environment can be easily inserted into an interlayer region of graphene and attached to a host layer, so that an original hydrogen bond network is damaged, a new hydrogen bond network is formed, and the graphene is peeled layer by layer; the existence of the cellulose in the solution enables the stripped graphene not to reunite any more, and meanwhile, the surface of the cellulose is rich in polar oxygen-containing groups, so that the cellulose can generate non-covalent interactions such as hydrogen bond interaction, electrostatic force and the like with the graphene, the graphene layer is stripped, and the dispersibility of the graphene is improved. The invention is a breakthrough in that the alkaline urine solution of cellulose is used for dispersing graphene.
2. In the conductive film prepared by the invention, the dispersed graphene and cellulose form a stable cross-linked structure under the action of the cross-linking agent, the conductivity of the graphene can be fully exerted, the mobility of electrons is improved, meanwhile, the conductive film is additionally endowed with excellent antibacterial property, hot water resistance and antistatic property, and a high-transparency multifunctional conductive film is constructed.
3. In all the processes, any high-temperature link is not involved, so that the method is safe and reliable; according to the invention, low-temperature stripping is adopted, which is beneficial to the generation of new hydrogen bonds between graphene layers by alkali urine and is more beneficial to the dispersion of graphene.
4. According to the method, after the cellulose solution is dissolved, subsequent processes such as alkaline dialysis and the like are not adopted, and meanwhile, the alkaline urine plays a key role in next-step graphene separation, so that the experiment cost is greatly reduced; the zero-surfactant dispersed graphene is environment-friendly and reduces the cost, the sensor prepared at the later stage has fewer impurities, and the purpose of reducing the cost and avoiding secondary pollution to the environment can be achieved without harsh conditions; the addition of the cross-linking agent enables the combination of the graphene and the cellulose to be firmer, so that the mechanical property of the composite membrane is enhanced.
5. According to the invention, the conductive film prepared by compounding the cellulose and the graphene is directly extracted from natural plants such as cotton and hemp, so that the conductive film has the advantages of flexibility, transparency and conductive function, greatly reduces the cost and is beneficial to large-scale application; meanwhile, the conductive film prepared from the selected conductive graphene and the biodegradable cellulose does not cause secondary pollution to the environment and is beneficial to recycling.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparing a cellulose-graphene solution:
adding 3g of cotton into 97g of alkaline urine solution, and freezing for 1h at-15 ℃; thawing with continuous stirring for 30min, and centrifuging (4500rpm, 10min) to obtain cellulose solution. Then 0.01g of graphene is added and stirred for 30min at the temperature of minus 15 ℃.
2) Preparing cellulose gel-graphene gel:
adding 1.6g N, N-methylene bisacrylamide to 100ml of cellulose-graphene solution, heating to 30-60 ℃, stirring for 1h, forming gel under the condition of water bath at 30 ℃, and replacing in deionized water until the pH value is 7.
3) Preparation of cellulose-graphene film:
and (3) preparing the cellulose-graphene gel into a film by a hot-press forming method. And the pressure of the hot press is 50pa, the time is 1h, and the temperature is 60 ℃, so that the transparent cellulose-graphene film is obtained.
Example 2
1) Preparing a cellulose-graphene solution:
adding 3g of cotton into 97g of alkaline urine solution, and freezing for 1h at-15 ℃; thawing with continuous stirring for 30min, and centrifuging (4500rpm, 10min) to obtain cellulose solution. Then 0.01g of graphene is added and stirred for 30min at the temperature of minus 15 ℃.
2) Preparing cellulose gel-graphene gel:
adding 2g of glutaraldehyde into 100ml of cellulose-graphene solution, heating to 40 ℃, stirring for 1h, forming gel under the condition of water bath at 40 ℃, and replacing in deionized water until the pH value is 7.
3) Preparation of cellulose-graphene film:
and (3) preparing the cellulose-graphene gel into a film by a hot-press forming method. The pressure of the hot press is 80pa, the time is 1.5h, and the temperature is 60 ℃, so that the transparent cellulose-graphene film is obtained.
Example 3
1) Preparing a cellulose-graphene solution:
adding 3g of cotton into 97g of alkaline urine solution, and freezing for 1.5h at-12 ℃; stirring continuously for 30min, thawing, and centrifuging (5000rpm, 10min) to obtain cellulose solution. Then 0.01g of graphene is added and stirred for 30min at-12 ℃.
2) Preparing cellulose gel-graphene gel:
adding 2g of epichlorohydrin into 100ml of cellulose-graphene solution, heating to 60 ℃, stirring for 1h, forming gel under the condition of water bath at 30 ℃, and replacing in deionized water until the pH value is 7.
3) Preparation of cellulose-graphene film:
and (3) preparing the cellulose-graphene gel into a film by a hot-press forming method. And the pressure of the hot press is 50pa, the time is 2h, and the temperature is 60 ℃, so that the transparent cellulose-graphene film is obtained.
Example 4
1) Preparing a cellulose-graphene solution:
adding 3g of cotton into 97g of alkaline urine solution, and freezing for 2h at-12 ℃; stirring continuously for 30min, thawing, and centrifuging (5000rpm, 10min) to obtain cellulose solution. Then 0.01g of graphene is added and stirred for 30min at the temperature of minus 20 ℃.
2) Preparing cellulose gel-graphene gel:
2g dicumyl peroxide is added into 100ml cellulose-graphene solution, heated to 60 ℃ and stirred for 1h, gel is formed under the condition of water bath at 30 ℃, and the solution is replaced in deionized water until the pH value is 7.
3) Preparation of cellulose-graphene film:
and (3) preparing the cellulose-graphene gel into a film by a hot-press forming method. And the pressure of the hot press is 50pa, the time is 2h, and the temperature is 60 ℃, so that the transparent cellulose-graphene film is obtained.
Results of the experiment
The experimental results of the present invention are shown in the following table:
| examples | Crosslinking agent | Strength (mpa) | Light transmittance (%) | Resistivity (omega. m) |
| 1 | N, N-methylenebisacrylamide | 3.56 | 90 | 305.44 |
| 2 | Glutaraldehyde | 4.41 | 80 | 405.15 |
| 3 | Epoxy chloropropane | 5.68 | 83 | 389.74 |
| 4 | Dicumyl peroxide | 6.46 | 62 | 588.64 |
As can be seen from the table, the cellulose-graphene film prepared by the method has excellent light transmittance, outstanding mechanical properties and good conductivity. The transparent cellulose-graphene film prepared in embodiment 1 of the present invention has a light transmittance close to that of glass (the light transmittance of ordinary glass is 90%), has an ultrahigh light transmittance, can ensure strength and have a certain flexibility, and can be applied to displays of electronic products, thin solar cells and photoelectric materials.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (4)
1. The preparation method of the cellulose-graphene composite transparent conductive film is characterized by comprising the following steps:
(1) preparing a graphene-cellulose solution, namely adding 0.01-0.05 g of graphene into a cellulose solution of 100m L, stirring for 10-60 min, and then carrying out low-temperature stripping at-10 to-20 ℃ to obtain the graphene-cellulose solution;
(2) preparing graphene-cellulose gel: adding a cross-linking agent into the graphene-cellulose solution obtained in the step (1), heating to 30-60 ℃, stirring for 0.5-1 h, pouring to form graphene-cellulose gel under the water bath condition of 20-60 ℃, and washing with deionized water until the pH value is 7;
(3) carrying out hot pressing molding on the graphene-cellulose gel obtained in the step (2) to obtain a graphene-cellulose membrane;
the cellulose solution is a cellulose alkaline urine solution prepared by mixing cellulose and an alkaline urine solution, wherein the weight ratio of the cellulose to the alkaline urine solution is as follows: 2-5: 95-98.
2. The method for preparing the cellulose-graphene composite transparent conductive film according to claim 1, wherein the alkaline-urea solution is prepared by mixing sodium hydroxide, urea and water, wherein the mass ratio of the sodium hydroxide to the urea to the water is 7: 12: 81.
3. the method for preparing the cellulose-graphene composite transparent conductive film according to claim 1, wherein the low-temperature peeling time in the step (1) is 10-60 min.
4. The method for preparing the cellulose-graphene composite transparent conductive film according to claim 1, wherein the cross-linking agent in the step (2) is one of N, N-methylene bisacrylamide, epichlorohydrin, dicumyl peroxide and glutaraldehyde, and the amount of the cross-linking agent is 1.5-2 wt%; the pouring thickness of the cellulose-graphene solution is 3mm-8 mm.
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