CN112938957A - Graphene oxide paper and preparation method thereof - Google Patents
Graphene oxide paper and preparation method thereof Download PDFInfo
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- CN112938957A CN112938957A CN202110397449.6A CN202110397449A CN112938957A CN 112938957 A CN112938957 A CN 112938957A CN 202110397449 A CN202110397449 A CN 202110397449A CN 112938957 A CN112938957 A CN 112938957A
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Abstract
The invention discloses a preparation method of graphene oxide paper, which comprises the following steps: step one, pretreatment of filter paper: completely infiltrating the filter paper with a sodium chloride solution; uniformly dripping the graphene oxide solution on the filter paper obtained in the step one to spread the graphene oxide on the filter paper; drying in a thermostat at below 125 deg.C; and step three, stripping the graphene oxide from the filter paper. The preparation method of the graphene oxide paper disclosed by the invention has the advantages that the graphene oxide paper can be easily and integrally stripped from the filter paper when the graphene oxide paper is prepared, the method is simple and feasible, expensive instruments are not involved, the protection of inert gas is not needed, the cost is low, the safety is good, and the preparation method is suitable for large-scale preparation. The graphene oxide paper prepared by the method has good integrity and adjustable size and thickness, and can be applied to the fields of ion screening, energy storage, electromagnetic shielding and the like.
Description
Technical Field
The invention belongs to the field of graphene preparation, and particularly relates to graphene oxide paper and a preparation method thereof.
Background
The fields of use of paper-like or foil-like materials include protective layers, chemical filters, components of batteries or supercapacitors, adhesive layers, electronic or optoelectronic components and molecular storage; inorganic "paper-like" materials based on nanoscale components, such as exfoliated vermiculite or mica platelets, have been extensively studied and commercialized for use as protective coatings, high temperature adhesives, dielectric barriers, and gas impermeable membranes. The graphene oxide paper is a self-supporting film with a layered structure, and is a paper-like material with a layered structure consisting of a plurality of single-layer graphene oxides. The graphene oxide paper has remarkable mechanical strength and excellent flexibility; the reduced graphene oxide paper with good conductivity can be prepared by thermal reduction or chemical reduction of the graphene oxide paper, and the graphene oxide paper and the reduced graphene oxide paper have good mechanical, thermal, optical and electrical properties and good biocompatibility, so that the paper has important application prospects in ion screening, electromagnetic shielding, supercapacitors and biomedical materials.
The existing methods for preparing graphene oxide paper include a vacuum filtration method, an L-B membrane method and a solvent evaporation method. However, these methods often involve the use of vacuum devices, expensive instruments, or complicated steps, and have limitations in low-cost, large-scale production. Chinese patent application CN106865529A discloses a preparation method of microwave-assisted high-quality reduced graphene oxide in a trigger mode, wherein calcium chloride is used for wetting filter paper, a graphene oxide solution is dripped on the filter paper for spreading, and then a 1% calcium chloride solution is dripped on the spread graphene oxide; and then, cleaning the filter paper with the graphene oxide in deionized water, taking out and drying, and finally taking down the lamellar graphene oxide. The lamellar graphene oxide prepared by the method is firmly combined with the filter paper, and the graphene oxide is not easy to be completely separated from the filter paper.
Disclosure of Invention
The purpose of the invention is as follows: the preparation method of the graphene oxide paper is provided, and the graphene oxide paper prepared by the method can be conveniently and completely peeled from the filter paper.
The technical scheme of the invention is as follows:
a preparation method of graphene oxide paper comprises the following steps:
step one, pretreatment of filter paper: completely infiltrating the filter paper with a sodium chloride solution;
step two, coating of graphene oxide
Uniformly dripping the graphene oxide solution on the filter paper obtained in the step one to spread the graphene oxide on the filter paper; drying in a thermostat at below 125 deg.C;
and step three, stripping the graphene oxide from the filter paper.
According to the preparation method of the graphene oxide paper, the filter paper is soaked by the sodium chloride solution, then the graphene oxide is coated on the filter paper, the graphene oxide paper is dried and lightly clamped by the forceps, the graphene oxide paper can be completely separated from the filter paper, the graphene oxide paper is not cracked, and excessive graphene oxide is not bonded on the filter paper. By using the method, the graphene oxide paper with the required size can be prepared by changing the area of the coated graphene oxide paper according to the required area of the graphene oxide paper; the graphene oxide paper with different thicknesses can be obtained by adopting different unit area dripping amounts. The method for preparing the graphene oxide paper is simple and feasible, does not need the protection of a reducing agent and inert gas, does not need a vacuum environment, and does not involve expensive instruments in the whole process; the area and thickness of the graphene oxide paper are adjustable. Because the graphene oxide paper and the filter paper are easy to peel, the graphene oxide paper with a large area and a complete shape can be conveniently obtained. The graphene oxide used in the present invention may be prepared by a Hummer method or a mechanical exfoliation method. The graphene oxide solution is an aqueous dispersion solution. In the method, the drying temperature of the second step is below 125 ℃, and when the drying temperature is higher than 125 ℃, the graphene oxide paper is difficult to completely peel.
Preferably, the mass percentage concentration of the sodium chloride solution is 1-15%. Higher sodium chloride solution concentrations may also be used, but do not bring about a better beneficial effect, and therefore, sodium chloride solutions having a concentration of 1% to 15% by mass are preferred.
Preferably, the graphene oxide solution is a graphene oxide aqueous solution of 2mg/ml or more. The higher the concentration of the graphene oxide solution is, the thicker the prepared graphene oxide paper is; the graphene oxide solution with lower concentration is more accurate in controlling the thickness of the obtained graphene oxide paper, so that the concentration of the graphene oxide solution can be selected and used as required; the preparation efficiency of the graphene oxide aqueous solution with the concentration of less than 2mg/ml is too low.
Preferably, the drying time in the second step is 2 hours or more.
Preferably, the drying temperature in the second step is 75 ℃.
Preferably, the infiltration manner in the first step is as follows: and dripping a sodium chloride solution on the filter paper for soaking. Of course, dip coating or spray coating may be used.
The invention also provides the graphene oxide paper prepared by the method.
The invention has the beneficial effects that:
according to the preparation method of the graphene oxide paper, when the graphene oxide paper is prepared, the graphene oxide paper can be easily and integrally stripped from the filter paper, the method is simple and easy to implement, expensive instruments are not involved, the protection of inert gas is not needed, the cost is low, the safety is good, and the preparation method is suitable for large-scale preparation. The graphene oxide paper prepared by the method has good integrity and adjustable size and thickness, and can be applied to the fields of ion screening, energy storage, electromagnetic shielding and the like.
Drawings
Fig. 1 shows the graphene oxide paper prepared in example 1 and the peeled filter paper.
Fig. 2 is a raman spectrum of the graphene oxide paper prepared in example 1.
Fig. 3 shows the graphene oxide paper prepared in example 2 and the peeled filter paper.
Fig. 4 shows the graphene oxide paper prepared in example 3 and the peeled filter paper.
Fig. 5 shows the graphene oxide paper prepared in example 4 and the peeled filter paper.
Fig. 6 and 7 show the graphene oxide paper prepared in the comparative example and the peeled filter paper.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparing graphene oxide paper.
Step one, pretreatment of filter paper: dropping sodium chloride solution with the mass concentration of 1% onto the filter paper to completely soak the filter paper.
Step two, coating of graphene oxide
Uniformly dripping 2mg/ml of graphene oxide aqueous solution on the filter paper obtained in the step one, and spreading the graphene oxide on the filter paper; the mixture was placed in an incubator and dried at 75 ℃ for 2 hours.
And step three, taking out the graphene oxide from the thermostat, and peeling the graphene oxide from the filter paper by using tweezers. When peeling, the graphene oxide paper was easily peeled from the filter paper, and fig. 1 shows the graphene oxide paper prepared in this example and the peeled filter paper. In the figure, 1 is the peeled filter paper, and 2 is the peeled graphene oxide paper, and as can be seen from fig. 1, the peeled graphene oxide paper is intact, and the filter paper is not adhered to the graphene oxide paper, and the graphene oxide is not excessively adhered to the filter paper.
Fig. 2 is a raman spectrum of the graphene oxide paper prepared in this embodiment, and as can be seen from fig. 2, the prepared graphene oxide paper is graphene oxide.
Example 2
Preparing graphene oxide paper.
Step one, pretreatment of filter paper: and dripping 3% sodium chloride solution on the filter paper to completely soak the filter paper.
Step two, coating of graphene oxide
Uniformly dripping 10mg/ml of graphene oxide aqueous solution on the filter paper obtained in the step one, and spreading the graphene oxide on the filter paper; the mixture was placed in a thermostat and dried at 125 ℃ for 2 hours.
And step three, taking out the graphene oxide from the thermostat, and peeling the graphene oxide from the filter paper by using tweezers. When peeling, the graphene oxide paper was easily peeled from the filter paper, and fig. 3 shows the graphene oxide paper prepared in this example and the peeled filter paper. In the figure, 1 is the peeled filter paper, and 2 is the peeled graphene oxide, and as can be seen from fig. 3, the peeled graphene oxide paper is intact, and the filter paper is not adhered to the graphene oxide paper, and the graphene oxide is not adhered too much to the filter paper.
Example 3
Preparing graphene oxide paper.
Step one, pretreatment of filter paper: and dripping a sodium chloride solution with the mass concentration of 10% onto the filter paper to completely soak the filter paper.
Step two, coating of graphene oxide
Uniformly dripping 5mg/ml of graphene oxide aqueous solution on the filter paper obtained in the step one, and spreading the graphene oxide on the filter paper; the mixture was placed in an incubator and dried at 100 ℃ for 3 hours.
And step three, taking out the graphene oxide from the thermostat, and peeling the graphene oxide from the filter paper by using tweezers. When peeling, the graphene oxide paper was easily peeled from the filter paper, and fig. 4 shows the graphene oxide paper prepared in this example and the peeled filter paper. In the figure, 1 is the peeled filter paper, and 2 is the peeled graphene oxide, and as can be seen from fig. 4, the peeled graphene oxide paper is intact, and the filter paper is not adhered to the graphene oxide paper, and the graphene oxide is not adhered too much to the filter paper.
Example 4
Preparing graphene oxide paper.
Step one, pretreatment of filter paper: the filter paper is dipped and coated by sodium chloride solution with the mass concentration of 15 percent.
Step two, coating of graphene oxide
Uniformly dripping 10mg/ml of graphene oxide aqueous solution on the filter paper obtained in the step one, and spreading the graphene oxide on the filter paper; the mixture was placed in an incubator and dried at 75 ℃ for 3 hours.
And step three, taking out the graphene oxide from the thermostat, and peeling the graphene oxide from the filter paper by using tweezers. When peeling, the graphene oxide paper was easily peeled from the filter paper, and fig. 5 shows the graphene oxide paper prepared in this example and the peeled filter paper. In the figure, 1 is the peeled filter paper, and 2 is the peeled graphene oxide, and as can be seen from fig. 5, the peeled graphene oxide paper is intact, and the filter paper is not adhered to the graphene oxide paper, and the graphene oxide is not adhered too much to the filter paper.
Comparative example
Preparing graphene oxide paper.
Step one, pretreatment of filter paper: and dripping 1% by mass of calcium chloride solution onto the filter paper to completely soak the filter paper.
Step two, coating of graphene oxide
Uniformly dripping 2mg/ml of graphene oxide aqueous solution on the filter paper obtained in the step one, and spreading the graphene oxide on the filter paper; the mixture was placed in an incubator and dried at 75 ℃ for 2 hours.
And step three, taking out the product from the thermostat. The graphene oxide paper is peeled from the filter paper by using a pair of tweezers, and the operation process shows that the graphene oxide paper is difficult to be completely peeled from the filter paper, the graphene oxide paper is broken in the peeling process, and the graphene oxide paper and the filter paper are mutually bonded and are not easy to peel. Fig. 6 shows the graphene oxide paper prepared in this comparative example and the peeled filter paper. In fig. 6, 1 denotes the peeled filter paper, and 2 denotes the peeled graphene oxide. To strip the graphene oxide paper more, it is often necessary to drip water on the back of the filter paper to wet the filter paper, and then strip the paper. Fig. 7 shows the graphene oxide paper obtained by wetting the filter paper with the graphene oxide paper prepared by the method of the present comparative example and peeling the graphene oxide paper and the peeled filter paper, and it can be seen from fig. 7 that the peeling effect is not good, and the graphene oxide paper cannot be completely peeled well. Similar results were obtained with 3%, 10%, 15% and other concentrations of calcium chloride for dip or drop coating of filter paper, or with other depths of graphene oxide aqueous solution: namely, the graphene oxide paper and the filter paper are bonded with each other and are not easy to be completely separated.
The graphene oxide used for preparing the graphene oxide paper is prepared by a Hummer method. The graphene oxide paper can be prepared by the method of the invention no matter what type of graphene oxide prepared does not influence the effect of the invention, and the graphene oxide paper can be easily stripped from the filter paper due to the fact that the filter paper is pretreated by sodium chloride by the method of the invention, and the graphene oxide paper prepared by the method of the invention can be used for continuously preparing reduced graphene oxide paper. The graphene paper prepared by the method can be easily peeled from the filter paper, and the size and the thickness of the graphene paper can be adjusted according to needs, so that the graphene paper can be used for preparing various graphene oxide papers with required large areas so as to meet the requirements of different subsequent processes on the size.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments of the present invention, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Claims (7)
1. A preparation method of graphene oxide paper is characterized by comprising the following steps:
step one, pretreatment of filter paper: completely infiltrating the filter paper with a sodium chloride solution;
step two, coating of graphene oxide
Uniformly dripping the graphene oxide solution on the filter paper obtained in the step one to spread the graphene oxide on the filter paper; drying in a thermostat at below 125 deg.C;
and step three, stripping the graphene oxide from the filter paper.
2. The method for preparing graphene oxide paper according to claim 1, wherein the sodium chloride solution is 1-15% by mass.
3. The method for preparing graphene oxide paper according to claim 1, wherein the graphene oxide solution is a graphene oxide aqueous solution of 2mg/ml or more.
4. The method for preparing graphene oxide paper according to claim 1, wherein the drying time in the second step is 2 hours or more.
5. The method for preparing graphene oxide paper according to claim 1, wherein the drying temperature in the second step is 75 ℃.
6. The method for preparing graphene oxide paper according to claim 1, wherein the first step comprises a soaking mode: and dripping a sodium chloride solution on the filter paper for soaking.
7. Graphene oxide paper, characterized in that it is prepared by the method of one of claims 1 to 6.
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