CN109134923B - Preparation method of ultra-dispersed porous graphene/nano TiO2 composite material - Google Patents
Preparation method of ultra-dispersed porous graphene/nano TiO2 composite material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 239000011259 mixed solution Substances 0.000 claims abstract description 23
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 238000001556 precipitation Methods 0.000 claims description 5
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention relates to a super-dispersed porous graphene/nano TiO2The preparation method of the composite material comprises the following steps: in an ice-water bath, adding a mixture obtained by mixing graphite powder and sodium nitrate into concentrated sulfuric acid, stirring and mixing, and adding potassium permanganate; then removing the reaction system from the ice-water bath, heating to 33 ℃, and preserving heat for 30-30 min; adding hydrogen peroxide solution, carrying out suction filtration after 2-hour reaction, adding the obtained graphene oxide into a mixed solution of ethanol and water, and then adding TiO2And carrying out ultrasonic reaction on the precursor and a sodium borohydride solution for 12-24 h, and then carrying out suction filtration to obtain the composite material. The method has simple process and low cost, and can be used for batch production.
Description
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to super-dispersed porous graphene/nano TiO2A method for preparing a composite material.
Background
Graphene is the thinnest, the hardest and the strongest novel nano material with electric and heat conducting properties, and the surface of graphene contains more oxidation groups, so that the graphene can achieve a better composite effect with a polymer. After the graphene is used as a novel lubricating material and is doped into the epoxy resin, the friction coefficient of the epoxy resin can be reduced, and the strength, toughness, wear resistance and corrosion resistance of the epoxy resin are effectively improved. However, due to the effect of the van der waals force between the layers, graphene is easy to agglomerate and even stack, and thus the advantages of the ultra-large specific surface area and the two-dimensional structure are lost. Therefore, as a filling material, the exfoliation of graphene itself is a key factor in determining the performance of the material. During the polymerization of epoxy resin, the agglomeration of graphene is also a main reason for affecting the performance of the epoxy resin.
However, most of graphene prepared by manufacturers or laboratories still have a graphite structure with more than ten layers, and the synthesized graphene is easily agglomerated into graphite sheets under the influence of van der waals force or dangling bond effect. Such "graphite sheets" cannot be actually called graphene, and do not have the excellent physical and chemical properties of "true graphene". If the graphene can be well stripped in the preparation process and the single-layer ultra-dispersed graphene is generated in situ in the polymerization process of the epoxy resin, the graphene can have strong interaction with the interface of the epoxy resin, so that the physical and chemical properties of the epoxy resin are effectively improved, and the use standard in the industry is reached.
Therefore, in order to obtain graphene modified epoxy resin with good performance, it is necessary to develop a simple, easy, low-cost, and mass-producible preparation method of ultra-dispersed graphene, so as to achieve uniform distribution of graphene in epoxy resin and ensure strong interface action between graphene and epoxy resin molecules.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a super-dispersed porous graphene/nano TiO2A method for preparing a composite material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a super-dispersed porous graphene/nano TiO2A method of making a composite material, the method comprising the steps of:
(1) mixing graphite powder with sodium nitrate to obtain a mixture;
(2) in an ice water bath, adding the mixture obtained in the step (1) into concentrated sulfuric acid, stirring and mixing, and then adding potassium permanganate;
(3) removing the reaction system obtained in the step (2) from the ice water bath, heating to 33 ℃, and preserving heat for 30-30 min;
(4) adding hydrogen peroxide solution into the reaction system obtained in the step (3), performing suction filtration after reacting for 2 hours, and washing and drying the precipitate to obtain graphene oxide;
(3) adding the graphene oxide into a mixed solution of ethanol and water, and then adding TiO2And carrying out ultrasonic reaction on the precursor and a sodium borohydride solution for 12-24 h, then carrying out suction filtration, washing and drying the precipitate to obtain the composite material.
Preferably, in the step (1) and the step (2), the adding proportion of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is (1-2 g): (1-2 g): (20-23 ml): (2-3 g).
Preferably, in the step (4), the concentration of the hydrogen peroxide aqueous solution is 30 mass%.
Preferably, in the step (3), the volume ratio of ethanol to water in the mixed solution of ethanol and water is 1: 2.
Preferably, in the step (3), after the graphene oxide is added into the mixed solution of ethanol and water, the pH of the mixed solution is adjusted to 7 by using an aqueous solution of NaOH, and then TiO is added2Precursor and sodium borohydride solution.
Preferably, in the step (3), the TiO2The precursor is prepared by the following method: dissolving titanium salt and acyl ketone compounds in alcohol to obtain a solution A, dissolving organic acid in alcohol to obtain a solution B, mixing and stirring A, B solutions until full precipitation is achieved, and aging for 20-30 hours to obtain the TiO2And (3) precursor.
Preferably, in step (3), the titanium salt is titanium tetrachloride, the acylketone compound is acetylacetone, and the organic acid is at least one selected from formic acid, acetic acid, and oxalic acid.
Preferably, in the step (3), the volume ratio of the alcohol to the organic acid is (2-3): (1-2), the mass ratio of the acyl ketone compound to the titanium salt is 1: (8-10).
Preferably, in the step (3), the mass ratio of sodium borohydride to graphene oxide is 1: (3-10).
Preferably, theIn the composite material, nano TiO2The mass ratio of the graphene to the graphene is (0.3-1): 10.
the invention has the beneficial effects that:
aiming at the problems of high cost, easy agglomeration, difficult dispersion in epoxy resin and the like of graphene, the invention provides a super-dispersed porous graphene/nano TiO2A method for preparing a composite material. The method adopts an organic precipitation method to carry out interlayer stripping on graphene, and specifically adopts an organic deposition method to prepare metastable TiO2The precursor is organically combined with the preparation method of the graphene so that the nano TiO2In-situ generation is carried out between graphene layers, so that the graphene is effectively subjected to interlayer peeling, interlayer compounding of the graphene is blocked, and stable ultra-dispersed graphene/nano TiO is prepared2A composite material. The method has simple process and low cost, and can be used for batch production.
Drawings
FIG. 1-1, FIG. 1-2 and FIG. 1-3 show the graphene/nano TiO obtained in example 12Transmission Electron Microscope (TEM) photographs of the composite material at different magnifications.
FIG. 2 shows the graphene/nano TiO obtained in comparative example 12TEM images of the composite material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to super-dispersed porous graphene/nano TiO2A method of preparing a composite material, the method comprising the steps of:
(1) graphite powder was mixed with sodium nitrate to obtain a mixture.
(2) And (2) in an ice water bath, slowly adding the mixture obtained in the step (1) into concentrated sulfuric acid, stirring and mixing, and then slowly adding potassium permanganate, preferably slowly stirring for 20min after adding the potassium permanganate.
In one embodiment of the invention, in the step (1) and the step (2), the adding proportion of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is (1-2 g): (1-2 g): (20-23 ml): (2-3 g).
(3) And (3) removing the reaction system obtained in the step (2) from the ice-water bath, heating to 33 ℃, and preserving the temperature for 30-30 min, wherein the process can be carried out under the condition of oil bath or water bath.
(4) And (4) adding a hydrogen peroxide solution with the mass concentration of 30% into the reaction system obtained in the step (3), and reacting for 2 hours until no bubbles are generated in the system. And (3) carrying out suction filtration on the reaction liquid by adopting a microporous filter membrane, and washing the precipitate obtained by suction filtration for multiple times by using deionized water until no sulfate radical is detected. And drying the precipitate in vacuum to obtain the graphene oxide.
(3) According to the weight ratio of 1 g: (8-10 ml), adding the obtained graphene oxide into a mixed solution of ethanol and water, testing the pH value of the mixed solution, and adjusting the pH value of the mixed solution to 7 by adopting a NaOH aqueous solution if the pH value is less than 7. Then slowly adding TiO into the mixed solution2Performing ultrasonic reaction on the precursor and a sodium borohydride solution for 12-24 h, then performing suction filtration, washing and drying the precipitate to obtain the ultra-dispersed porous graphene/nano TiO2A composite material.
In one embodiment of the present invention, the volume ratio of ethanol to water in the mixed solution of ethanol and water is 1: 2.
Through years of research, the applicant independently develops a method (such as TiO) capable of preparing nano oxide at normal temperature in large batch2、SiO2、ZrO2Etc.) and named as an organic precipitation method, the method can carry out homogeneous deposition in an organic solvent to generate a large amount of high-energy metastable nano-oxide precursors, and then the precursors can be decomposed and self-assembled into monodisperse nano-oxide clusters in one step under specific conditions. According to the reaction characteristics, the nano oxide precursor can be self-assembled into the nano oxide cluster between graphene layers, so that the graphene can be effectively layeredAnd (4) carrying out intercropping to form the ultra-dispersed graphene.
In one embodiment of the invention, the TiO is2The precursor is prepared by the following method: alcohol is used as solvent, acyl ketone compound is used as buffer, titanium salt is used as metal source, and organic acid is used as precipitant. Dissolving titanium salt and acyl ketone compounds in alcohol to obtain a solution A, dissolving organic acid in alcohol to obtain a solution B, mixing and stirring A, B solutions, enabling the organic acid uniformly distributed in the system to react with the alcohol to generate water molecules, utilizing the water molecules to directly perform hydrolysis reaction with metal salt uniformly distributed in the solvent, and continuously stirring until white turbid precipitates are generated by the reaction. Fully precipitating and then aging for 20-30 h to obtain TiO2And (3) precursor.
In one embodiment of the present invention, the titanium salt is titanium tetrachloride, the acylketone compound is acetylacetone, and the organic acid is at least one selected from formic acid, acetic acid, and oxalic acid.
In one embodiment of the invention, the volume ratio of the alcohol to the organic acid is (2-3): (1-2), the mass ratio of the acyl ketone compound to the titanium salt is 1: (8-10). In the above reaction, the more the amount of the organic acid added, the faster the reaction, and the shorter the time for precipitation. The more the alcohol and the acylketone compound are added, the better the solubility of the titanium salt is, and the more the reaction is sufficient. However, the addition of excessive alcohol and organic acid reduces the concentration of the reaction system, so that the energy consumption of subsequent suction filtration is increased, and therefore, the volume of the organic reagent needs to be controlled within a certain range.
In the step (3), sodium borohydride is used as a reducing agent for graphene oxide. In an embodiment of the present invention, the mass ratio of sodium borohydride to graphene oxide is 1: (3-10). The use amount of sodium borohydride is too small, the reduction of graphene oxide is insufficient, and graphene oxide still remains in the product. Too much sodium borohydride can introduce too many sodium ions and borohydride ions, and the impurity content in the product is increased.
In one embodiment of the invention, TiO may be added2The precursor is added into a sodium borohydride solution, and then slowly dropped into a mixed solution of graphene oxide. Due to TiO2The precursor is inCan be decomposed in one step in organic solvent and self-assembled into monodisperse nano TiO2The organic solvent can be mixed with water or uniformly dispersed in the water, so that TiO is reduced and stripped2The precursor can be decomposed in one step and self-assembled into a large amount of nano TiO between the layers of graphene2Clusters of these nano TiO2The cluster forms a compact interlayer between layers of the graphene, so that the graphene is effectively stripped, and the interlayer compounding of the graphene is blocked, thereby preparing the stable ultra-dispersed graphene.
In the final composite material, nano TiO2The mass ratio of the graphene to the graphene is (0.3-1): 10. i.e. nano TiO2The mass of (a) is 3-10% of the mass of graphene.
Example 1
Preparation of ultra-dispersed porous graphene/nano TiO2A composite material comprising the steps of:
(1) 1g of graphite powder was mixed with 1g of sodium nitrate to obtain a mixture.
(2) And (2) in an ice water bath, slowly adding the mixture obtained in the step (1) into 20ml of concentrated sulfuric acid, stirring and mixing, slowly adding 2g of potassium permanganate, and continuing stirring for 20 min.
(3) And (3) removing the reaction system obtained in the step (2) from the ice-water bath, placing the reaction system in the ice-water bath, heating to 33 ℃, and preserving heat for 30 min.
(4) And (4) adding a hydrogen peroxide solution with the mass concentration of 30% into the reaction system obtained in the step (3), and reacting for 2 hours until no bubbles are generated in the system. And (3) carrying out suction filtration on the reaction liquid by adopting a microporous filter membrane, and washing the precipitate obtained by suction filtration for multiple times by using deionized water until no sulfate radical is detected. And drying the precipitate in vacuum to obtain the graphene oxide.
(3) According to the weight ratio of 1 g: and (3) adding the obtained graphene oxide into a mixed solution of 1 volume of ethanol and 2 volumes of water according to a material-liquid ratio of 8ml, testing the pH value of the mixed solution, and adjusting the pH value of the mixed solution to 7 by adopting a NaOH aqueous solution if the pH value is less than 7. Then slowly adding TiO into the mixed solution2Precursor and sodium borohydride solution, sodium borohydride and graphite oxideThe mass ratio of the alkene is 1: 10. performing suction filtration after the ultrasonic reaction is carried out for 12 hours, washing and drying the precipitate to obtain the ultra-dispersed porous graphene/nano TiO2A composite material.
Wherein, TiO2The precursor is prepared by the following method:
10.98ml of titanium tetrachloride and 0.149g of acetylacetone were dissolved in 13ml of absolute ethanol to give a solution A, 20ml of formic acid were dissolved in 13ml of absolute ethanol to give a solution B, and the A, B solutions were mixed and stirred until the reaction produced a white turbid precipitate. Aging at room temperature for 24h to obtain TiO2And (3) precursor.
Example 2
Preparation of ultra-dispersed porous graphene/nano TiO2A composite material comprising the steps of:
(1) 1.3g of graphite powder was mixed with 1.3g of sodium nitrate to obtain a mixture.
(2) And (2) in an ice-water bath, slowly adding the mixture obtained in the step (1) into 23ml of concentrated sulfuric acid, stirring and mixing, slowly adding 3g of potassium permanganate, and continuing stirring for 20 min.
(3) And (3) removing the reaction system obtained in the step (2) from the ice-water bath, placing the reaction system in the ice-water bath, heating to 33 ℃, and preserving heat for 40 min.
(4) And (4) adding a hydrogen peroxide solution with the mass concentration of 30% into the reaction system obtained in the step (3), and reacting for 2 hours until no bubbles are generated in the system. And (3) carrying out suction filtration on the reaction liquid by adopting a microporous filter membrane, and washing the precipitate obtained by suction filtration for multiple times by using deionized water until no sulfate radical is detected. And drying the precipitate in vacuum to obtain the graphene oxide.
(3) According to the weight ratio of 1 g: and (3) adding the graphene oxide obtained in the step (1) into a mixed solution of 1 volume of ethanol and 2 volumes of water according to a material-liquid ratio of 10ml, testing the pH value of the mixed solution, and adjusting the pH value of the mixed solution to 7 by adopting an NaOH aqueous solution if the pH value is less than 7. Then slowly adding TiO into the mixed solution2The preparation method comprises the following steps of 1, preparing a precursor and a sodium borohydride solution, wherein the mass ratio of sodium borohydride to graphene oxide is 1: 8. carrying out suction filtration after ultrasonic reaction for 12h, washing and drying the precipitate to obtain the ultra-dispersed porous graphene/nano TiO2A composite material.
Wherein, TiO2The precursor is prepared by the following method:
10.98ml of titanium tetrachloride and 0.0743g of acetylacetone were dissolved in 30ml of absolute ethanol to give a solution A, 20ml of acetic acid was dissolved in 30ml of absolute ethanol to give a solution B, and A, B solutions were mixed and stirred until the reaction produced a white turbid precipitate. Aging at room temperature for 24h to obtain TiO2And (3) precursor.
Comparative example 1
In step (3), 3g of commercially available nano-sized TiO was slowly added to the mixed solution2The other operation steps are the same as those in example 1.
Comparative example 2
TiO is not added in the step (3)2The other operation steps are the same as those in example 1.
Test example
Transmission electron microscopy testing
For the graphene/nano TiO obtained in example 1 and comparative example 12The composite was subjected to Transmission Electron Microscopy (TEM) testing, and the results are shown in FIGS. 1-1, 1-2, 1-3, and 2. Wherein FIGS. 1-1, 1-2 and 1-3 are electron micrographs at different magnifications of the composite material obtained in example 1, and FIG. 2 is an electron micrograph at different magnifications of the composite material obtained in comparative example 1. As can be seen from the figure, the graphene obtained in example 1 is thin and transparent, can be judged as a single layer, and can be seen in nano TiO2The graphene is uniformly distributed on the surface of the graphene. The graphene obtained in comparative example 1 was stacked more seriously and due to the non-transparency, nano-TiO2Are hardly visible.
The nano TiO is added into the solution as can be seen by combining the electron microscope photograph2Not only the special properties of its nanoparticles are utilized. Because TiO is added in the preparation process of the graphene2Precursor, in the process of reducing and stripping graphene oxide, TiO2The precursor can be decomposed in one step and self-assembled into a large amount of nano TiO between the layers of graphene2Clusters of these nano TiO2The cluster forms a compact interlayer between layers of the graphene, so that the graphene is effectively stripped from each other, and the graphene is blockedThe graphene is compounded between layers, so that the ultra-dispersed graphene which is more fully stripped, has lower lamella thickness and more stable performance can be obtained.
For ethylene oxide production
The ultra-dispersed porous graphene/nano TiO prepared in the examples and the comparative examples2The composite material is used as an additive of epoxy resin, and comprises the following specific steps:
(1) 0.1g of ultra-dispersed porous graphene/nano TiO2The composite material is stirred and dispersed in 28.02g of epoxy chloropropane, then 22g of bisphenol A and the epoxy chloropropane are sequentially added into a 230ml four-necked bottle provided with a stirrer and a thermometer, the temperature is raised to 73 ℃ by water bath heating, and the bisphenol A is completely dissolved by stirring.
(2) Cooling the reaction system to 70 ℃, dropwise adding 40ml of sodium hydroxide solution with the mass concentration of 20%, continuously reacting for 1.3-2h at 73-80 ℃ after dropwise adding, stopping heating, and cooling to room temperature.
(3) Adding 60ml of benzene into the reaction system, stirring, transferring into a separating funnel, standing, removing the lower water layer, washing with distilled water for multiple times, detecting whether the washing water is neutral with pH test paper, and using AgNO to detect the pH value of the washing water3The solution was checked for chloride ion and the organic layer was separated.
(4) Pouring the upper layer benzene solution into a reduced pressure distillation device, distilling off benzene at 73 ℃ under normal pressure, removing all volatile matters in the reduced pressure distillation device after benzene is removed, pouring out the resin while the resin is hot, and storing.
The tensile strength of the epoxy resin prepared above was tested according to national standard GB/T1040.2-2006, and the results are shown in Table 1.
TABLE 1
Examples/comparative examples | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
Tensile Strength test results | 38.3MPa | 39.6MPa | 34.9MPa | 30.3MPa |
From the above test results, it can be seen that examples 1 and 2 both use the ultra-dispersed porous graphene/nano-TiO prepared by the present invention2The tensile strength of the composite material as an additive to epoxy resins is significantly better than that of comparative examples 1 and 2. The composite material is adopted to modify the epoxy resin, so that the mechanical property of the epoxy resin can be obviously improved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. Ultra-dispersed porous graphene/nano TiO2A method for preparing a composite material, the method comprising the steps of:
(1) mixing graphite powder with sodium nitrate to obtain a mixture;
(2) in an ice water bath, adding the mixture obtained in the step (1) into concentrated sulfuric acid, stirring and mixing, and then adding potassium permanganate;
(3) removing the reaction system obtained in the step (2) from the ice water bath, heating to 35 ℃, and preserving heat for 30-50 min;
(4) adding hydrogen peroxide solution into the reaction system obtained in the step (3), performing suction filtration after reacting for 2 hours, and washing and drying the precipitate to obtain graphene oxide;
(5) adding the graphene oxide into a mixed solution of ethanol and water, and then adding TiO2Carrying out ultrasonic reaction on the precursor and a sodium borohydride solution for 12-24 h, then carrying out suction filtration, washing and drying the precipitate to obtain the composite material;
the TiO is2The precursor is prepared by the following method: dissolving titanium salt and acyl ketone compounds in alcohol to obtain a solution A, dissolving organic acid in alcohol to obtain a solution B, mixing and stirring A, B solutions until full precipitation is achieved, and aging for 20-30 hours to obtain the TiO2A precursor; wherein the titanium salt is titanium tetrachloride, the acyl ketone compound is acetylacetone, and the organic acid is at least one of formic acid, acetic acid and oxalic acid; the volume ratio of the alcohol to the organic acid is (2-5): (1-2), the mass ratio of the acyl ketone compound to the titanium salt is 1: (8-10).
2. The preparation method according to claim 1, wherein in the step (1) and the step (2), the adding proportion of the graphite powder, the sodium nitrate, the concentrated sulfuric acid and the potassium permanganate is (1-2 g): (1-2 g): (20-25 ml): (2-3 g).
3. The production method according to claim 1, wherein in the step (4), the concentration of the aqueous hydrogen peroxide solution is 30 mass%.
4. The method according to claim 1, wherein in the step (5), the volume ratio of ethanol to water in the mixed solution of ethanol and water is 1: 2.
5. The method according to claim 1, wherein in the step (5), the graphene oxide is addedAdding into mixed solution of ethanol and water, adjusting pH to 7 with NaOH water solution, and adding TiO2Precursor and sodium borohydride solution.
6. The preparation method according to claim 1, wherein in the step (5), the mass ratio of sodium borohydride to graphene oxide is 1: (5-10).
7. The method according to claim 1, wherein the composite material contains nano TiO2The mass ratio of the graphene to the graphene is (0.5-1): 10.
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