CN110609067B - Alcohol sensor and preparation method thereof - Google Patents
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Abstract
The invention discloses an alcohol sensor, which comprises an acid-modified graphene oxide film used as an electrolyte film, wherein the thickness of the acid-modified graphene oxide film is 3-10 mu m, a set pore structure is distributed in the acid-modified graphene oxide film, and the average diameter of pores is 40-80 nm. Wherein the acid is sulfanilic acid. The alcohol sensor disclosed by the invention has good reliability and high sensitivity, eliminates the potential safety hazard of the existing strong acid electrolyte, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to an alcohol sensor and a preparation method thereof.
Background
Alcohol sensors are generally test tools used to detect whether and how much alcohol a person consumes. The device can be used as a detection tool for detecting the drinking amount of a drinker when the traffic police law enforcement is carried out, so that the occurrence of major traffic accidents is effectively reduced; the method can also be used for detecting the alcohol content in the exhaled air of the human body in other occasions, so that the serious loss of casualties and property is avoided, for example, enterprises forbidden to go on post after drinking in some high-risk fields.
In various countries, with the increasing consumption of alcohol drinks by residents and the frequent occurrence of various traffic accidents caused by drunk driving, alcohol concentration detection instruments play an unprecedented important role in traffic management and resident daily life. In recent years, the development of material technology has promoted the continuous improvement of the related technology of alcohol detectors. Among them, the discovery of graphene oxide materials has attracted global attention. The unique two-dimensional structure of the graphene oxide membrane also endows the graphene oxide membrane with typical anisotropic transport properties including thermal conductivity, electronic conductivity, water permeability and the like, and the graphene oxide membrane serving as a membrane separation material is successfully applied to various important fields.
The ionic conductivity of graphene oxide, mainly proton conductivity and hydroxide ion conductivity, has also been found to be anisotropic, and when used in some practical electrochemical devices, such as fuel cells, its anisotropic ion conductivity properties are not ideal. The fabrication of graphene oxide in porous form is an important strategy to address the proton conducting channels in this application. For example, patent nos: CN106596654A discloses a vertical response type gas sensor based on a three-dimensional porous graphene ultrathin film and a preparation method thereof, wherein a porous graphene dispersion liquid is obtained by carrying out dialysis treatment on a graphene oxide dispersion liquid after ultraviolet treatment. Patent No: CN106290489A discloses a porous graphene gas sensor and a preparation method thereof, which adopts a high-power ultraviolet radiation method and is sensitive to ammonia molecules. The method of the above patent is relatively complicated in process, and the ultraviolet irradiation has a certain damage to human body. As another example. Patent No: CN106430156A discloses preparation of porous graphene, porous graphene obtained therefrom and application thereof, and the method and the obtained porous graphene and application thereof are different from those of the present invention. Patent No: CN104752703A discloses a porous graphene, which is different from the method and application of the present invention.
Based on the currently used pore-forming methods, such as ultraviolet radiation, plasma etching, and the like, process control is complex. In addition, the traditional alcohol sensor still has the problems of strong corrosive strong acid liquid electrolyte leakage, slow response time, poor reliability and the like. Therefore, there is a need to develop a new graphene oxide material with excellent proton conductivity, which can enhance the reliability and sensitivity of the sensor when used in an alcohol sensor, and eliminate the potential safety hazard of a strong acid electrolyte.
Disclosure of Invention
The invention provides an alcohol sensor and a preparation method thereof aiming at the defects in the prior art, wherein the alcohol sensor comprises an acid modified graphene oxide film, the material is prepared by carrying out porous and acidification treatment on graphene oxide through ozone and sulfanilic acid, and the graphene oxide film has excellent proton conductivity when being used as an electrolyte film.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme:
the alcohol sensor comprises an acid-modified graphene oxide film used as an electrolyte film, wherein the thickness of the acid-modified graphene oxide film is 3-10 mu m, a set pore structure is distributed in the acid-modified graphene oxide film, and the average diameter of pores is about 40-80 nm.
The alcohol sensor as described above, wherein the acid is sulfanilic acid.
The purpose of the invention and the technical problem to be solved can also be realized by adopting the following technical scheme:
according to the method of the alcohol sensor provided by the invention, the method sequentially comprises the following steps:
(1) preparing a graphene oxide dispersion liquid;
(2) under the ultrasonic condition, introducing ozone into the graphene oxide dispersion liquid obtained in the step (1) for 0.5-4 hours to obtain a porous graphene oxide dispersion liquid;
(3) adding sulfanilic acid and sodium hydroxide into the porous graphene oxide dispersion liquid obtained in the step (2), mixing, heating to 70-90 ℃, keeping the reaction for 3-12 hours, then sequentially centrifuging and washing to remove residues, and finally exchanging residual metal ions into protons to obtain acid-modified graphene oxide;
(4) dispersing the obtained acid-modified graphene oxide in deionized water, and performing vacuum filtration to obtain an acid-modified graphene oxide film;
(5) and assembling the obtained acid-modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
In the method, in the step (1), the graphene oxide dispersion liquid is prepared through the following steps in sequence:
a. taking a certain amount of graphite powder and sodium nitrate, adding concentrated sulfuric acid, and uniformly mixing;
b. adding potassium permanganate into the mixture obtained in the step a to react for 1-8 h, and keeping the temperature of the whole reaction system not higher than 20 ℃ in the period;
c. c, adding deionized water into the reaction system after the temperature of the reaction system in the step b is restored to room temperature, reacting for 0.5-2 h, continuously adding the same amount of deionized water for dilution, then adding a certain amount of hydrogen peroxide until the reaction system is discolored, and finally cooling to room temperature;
d. and c, adding dilute hydrochloric acid into the reaction system obtained after the reaction in the step c for dilution, then sequentially filtering, washing and removing acid until the pH value of the reaction system is about 2, and finally diluting with deionized water to obtain the graphene oxide dispersion liquid.
The method, wherein in the step a, the particle size D of the graphite powder 50 1 to 15 μm.
In the method, in the step a, the graphite powder, the sodium nitrate and the concentrated sulfuric acid are mixed according to a mass ratio of 2: (0.5-1.5): (40-50) in an amount.
In the method, in the step b, the potassium permanganate is added into the graphite powder according to a mass ratio of potassium permanganate to graphite powder of (2-5): 1 is added.
In the method, in the step c, the volume ratio of the deionized water to the concentrated sulfuric acid is (3-4): 1 is added.
In the method, in the step c, the hydrogen peroxide concentration is 30%, and the mass ratio of hydrogen peroxide to graphite is (15-25): 1 is added.
In the foregoing method, in the step d, the concentration of the hydrochloric acid is 5%, and the volume ratio of the hydrochloric acid to the concentrated sulfuric acid is (35 to 45): 1 is added.
In the method, in the step (1), the graphene oxide dispersion liquid has a dilution concentration of 1-10 mg/mL.
The method, wherein in the step (3), the ratio of the graphene oxide dispersion liquid to sulfanilic acid to sodium hydroxide is 4: (4-20) and (1-5).
In the method, in the step (4), the acid-modified graphene oxide and deionized water are added according to a mass ratio of 1 (1-2).
The invention has the beneficial effects that:
(1) the alcohol sensor adopts the acid modified graphene oxide film as the electrolyte film, wherein the acid modified graphene oxide film is prepared into porous graphene oxide by ozone treatment, and compared with ultraviolet light or plasma etching and the like used in the prior art, the method is simple and effective. And the sulfanilic acid is simply and effectively treated to introduce sulfonic acid groups into the porous graphene oxide nano-sheets, so that the proton conductivity of the membrane can be remarkably improved.
(2) The novel graphene oxide-based solid proton conductor is applied to the alcohol sensor, so that leakage of strong corrosive strong acid liquid electrolyte in the traditional alcohol sensor is effectively reduced, attenuation of corresponding signals is reduced, reliability of the sensor is enhanced, and potential safety hazards of the strong acid electrolyte are eliminated.
(3) The alcohol sensor disclosed by the invention is simple and effective in manufacturing process, is suitable for industrial production, and has a wide application prospect.
Drawings
Fig. 1 is a TEM image of an acid-modified graphene oxide film obtained according to the preparation method in example 1 of the present invention;
fig. 2 is an SEM image of the acid-modified graphene oxide film obtained according to the preparation method in example 1 of the present invention;
fig. 3 is a graph showing a relationship between proton conductivity and temperature of the acid-modified graphene oxide film obtained by the preparation method in example 1 of the present invention;
FIG. 4 is a response curve of the alcohol sensor obtained according to the manufacturing method of examples 1, 2, 3, 4 of the present invention, wherein a, b, c and d represent response curves of the alcohol sensor in example 1, example 2, example 3 and example 4, respectively;
fig. 5 is a response curve of the alcohol sensor according to the manufacturing method of example 1 of the present invention and comparative example 1.
Detailed Description
The present invention is further illustrated by the following figures and examples, which are to be understood as merely illustrative and not restrictive. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
Example 1
2g of graphite powder (particle size D) was taken 50 1-15 μm), 1g of sodium nitrate and 46ml of concentrated sulfuric acid are added and mechanically mixed evenly in an ice bath environment. Then 6g of potassium permanganate was added and stirred for 2 hours, during which the temperature of the reaction system was kept at not higher than 20 ℃. And (3) when the reaction system is returned to the room temperature, slowly adding 140mL of deionized water into the reaction system to oxidize and expand the graphite, carrying out the reaction for 0.5h, then continuously adding 140mL of deionized water for dilution, then slowly adding 40mL of 30% hydrogen peroxide, quickly converting the reaction system from purple red into golden yellow, and keeping stirring until the mixture is cooled to the room temperature. 2L of 5% diluted hydrochloric acid was added to the above reaction system to dilute and dissolve the remaining undissolved manganese dioxide, followed by filtration. And then washing with deionized water, centrifugally separating to remove acid until the pH of the reaction system is about 2, and finally diluting with deionized water to enable the concentration of the graphene oxide dispersion liquid to be 1-10 mg/mL.
And (3) introducing ozone gas into the obtained graphene oxide dispersion liquid with the concentration of 5mg/mL in a fume hood by an ozone generator for 1 hour under the ultrasonic condition to obtain the porous graphene oxide dispersion liquid.
Mixing 50mL of the porous graphene oxide dispersion liquid obtained in the step (1 mg/mL), 150mg of sulfanilic acid and 37.5mg of sodium hydroxide, heating to 80 ℃, keeping the temperature for reaction for 12 hours, then carrying out high-speed centrifugal separation to remove supernatant, repeatedly washing with deionized water and centrifuging for three times to remove residual reactants, dispersing with the deionized water again, exchanging sodium ions into protons by using a strong-acid ion exchange column to obtain acid-modified porous graphene oxide, and finally freeze-drying for later use.
And (3) dispersing 40mg of the obtained acid-modified porous graphene oxide into 40mL of deionized water, and performing vacuum filtration by using a polyether sulfone filter membrane to form a self-supporting acid-modified porous graphene oxide membrane.
And assembling the obtained acid-modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
Fig. 1 is a TEM image of an acid-modified graphene oxide film obtained according to the preparation method in example 1 of the present invention; fig. 2 is an SEM image of the acid-modified graphene oxide film obtained according to the preparation method in example 1 of the present invention. As can be seen from FIGS. 1 and 2, the acid-modified graphene oxide film prepared by the method has a lamellar structure and also has a void structure, wherein the thickness of the lamellar structure is 3-10 μm, and the average diameter of the void is about 40-80 nm.
Fig. 3 is a graph showing a relationship between proton conductivity and temperature of the acid-modified graphene oxide film obtained by the preparation method in example 1 of the present invention. As can be seen from fig. 3, the proton conductivity of the acid-modified graphene oxide membrane gradually increases with an increase in temperature within a certain range.
The alcohol standard solution used for the test was 0.05BAC, i.e., the concentration of alcohol vapor at 34 ℃ was 125ppm, and the test results are specifically shown in the curve a in FIG. 4.
Example 2
2g of graphite powder (particle size D) was taken 50 1-15 μm), 0.5g sodium nitrate and 40ml concentrated sulfuric acid are added and placed in an ice bath environment to be mechanically and uniformly mixed. Then 4g of potassium permanganate was added and stirred for 1 hour, during which the temperature of the reaction system was kept at not higher than 20 ℃. After the reaction system is returned to the room temperature, 120mL of deionized water is slowly added into the reaction system to oxidize and expand the graphite, the reaction is carried out for 2 hours, then 120mL of deionized water is continuously added for dilution, 50mL of 30% hydrogen peroxide is slowly added, and the reaction system is rapidly converted into gold from purple redYellow, stirring was maintained until the mixture cooled to room temperature. 2.25L of 5% diluted hydrochloric acid was added to the above reaction system to dilute and dissolve the remaining undissolved manganese dioxide, followed by filtration. And then washing with deionized water, centrifugally separating to remove acid until the pH of the reaction system is about 2, and finally diluting with deionized water to enable the concentration of the graphene oxide dispersion liquid to be 1-10 mg/mL.
And (3) introducing ozone gas into the obtained graphene oxide dispersion liquid with the concentration of 10mg/mL for 4 hours from an ozone generator in a fume hood under the ultrasonic condition to obtain the porous graphene oxide dispersion liquid.
And mixing 50mL of the porous graphene oxide dispersion liquid obtained in the step of 1mg/mL, 50mg of sulfanilic acid and 62.5mg of sodium hydroxide, heating to 70 ℃, keeping the mixture for reaction for 3 hours, then carrying out high-speed centrifugal separation to remove supernatant, repeatedly washing with deionized water and centrifuging for three times to remove residual reactants, dispersing with the deionized water again, exchanging sodium ions into protons by using a strong-acid ion exchange column to obtain acid-modified porous graphene oxide, and finally freeze-drying for later use.
And (3) dispersing 40mg of the obtained acid-modified porous graphene oxide into 80mL of deionized water, and performing vacuum filtration by using a polyether sulfone filter membrane to form a self-supporting acid-modified porous graphene oxide membrane.
And assembling the obtained acid-modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
The alcohol standard solution used for the test, 0.05BAC, i.e. a concentration of 125ppm of alcohol vapor at 34 ℃ was used, and the test results are shown in detail in the curve b in FIG. 4.
Example 3
2g of graphite powder (particle size D) was taken 50 1-15 μm), 1g of sodium nitrate and 45ml of concentrated sulfuric acid are added and mechanically mixed evenly in an ice bath environment. Then 7g of potassium permanganate was added and stirred for 8 hours while keeping the temperature of the reaction system at not higher than 20 ℃. After the reaction system is returned to the room temperature, 200mL of deionized water is slowly added into the reaction system to oxidize and expand the graphite, the reaction is carried out for 1.25h, then 200mL of deionized water is continuously added for dilution, and then 40mL of 30% hydrogen peroxide is slowly addedThe reaction quickly turned from a purple red color to a gold color, and stirring was maintained until the mixture was cooled to room temperature. 1.4L of 5% diluted hydrochloric acid was added to the above reaction system to dilute and dissolve the remaining undissolved manganese dioxide, followed by filtration. And then washing with deionized water, centrifugally separating to remove acid until the pH of the reaction system is about 2, and finally diluting with deionized water to enable the concentration of the graphene oxide dispersion liquid to be 1-10 mg/mL.
Taking the graphene oxide dispersion liquid with the concentration of 1mg/mL, and introducing ozone gas for 2.25 hours from an ozone generator in a fume hood under the ultrasonic condition to obtain the porous graphene oxide dispersion liquid.
Mixing 50mL of the porous graphene oxide dispersion liquid obtained in the step (1 mg/mL), 250mg of sulfanilic acid and 12.5mg of sodium hydroxide, heating to 80 ℃, keeping the temperature for reaction for 7.5h, then carrying out high-speed centrifugal separation to remove supernatant, repeatedly washing with deionized water and centrifuging for three times to remove residual reactants, dispersing with the deionized water again, exchanging sodium ions into protons by using a strong-acid ion exchange column to obtain acid-modified porous graphene oxide, and finally freeze-drying for later use.
And (3) dispersing 40mg of the obtained acid-modified porous graphene oxide into 60mL of deionized water, and performing vacuum filtration by using a polyether sulfone filter membrane to form a self-supporting acid-modified porous graphene oxide membrane.
And assembling the obtained acid-modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
The alcohol standard solution used for the test was 0.05BAC, i.e., the concentration of alcohol vapor at 34 ℃ was 125ppm, and the test results are specifically shown in the curve c in FIG. 4.
Example 4
2g of graphite powder (particle size D) was taken 50 1-15 μm), 1.5g sodium nitrate and 50ml concentrated sulfuric acid are added and placed in an ice bath environment to be mixed evenly mechanically. Then 10g of potassium permanganate was added and stirred for 4.5 hours, during which the temperature of the reaction system was kept at not higher than 20 ℃. After the reaction system is returned to the room temperature, 160mL of deionized water is slowly added into the reaction system to oxidize and expand the graphite, the reaction is carried out for 1h, and then 160mL of deionized water is continuously addedUpon dilution, 30mL of 30% hydrogen peroxide was slowly added and the reaction rapidly turned from a purple-red color to a golden yellow color, and stirring was maintained until the mixture was cooled to room temperature. 1.83L of 5% diluted hydrochloric acid was added to the above reaction system to dilute and dissolve the remaining undissolved manganese dioxide, followed by filtration. And then washing with deionized water, centrifugally separating to remove acid until the pH of the reaction system is about 2, and finally diluting with deionized water to enable the concentration of the graphene oxide dispersion liquid to be 1-10 mg/mL.
Taking the graphene oxide dispersion liquid with the concentration of 5.5mg/mL, and introducing ozone gas for 0.5 hour in a fume hood from an ozone generator under the ultrasonic condition to obtain the porous graphene oxide dispersion liquid.
Mixing 50mL of the porous graphene oxide dispersion liquid obtained in the step (1 mg/mL), 150mg of sulfanilic acid and 62.5mg of sodium hydroxide, heating to 90 ℃, keeping the temperature for reaction for 12 hours, then carrying out high-speed centrifugal separation to remove supernatant, repeatedly washing with deionized water and centrifuging for three times to remove residual reactants, dispersing with the deionized water again, exchanging sodium ions into protons by using a strong-acid ion exchange column to obtain acid-modified porous graphene oxide, and finally freeze-drying for later use.
And (3) dispersing 40mg of the obtained acid-modified porous graphene oxide into 60mL of deionized water, and performing vacuum filtration by using a polyether sulfone filter membrane to form a self-supporting acid-modified porous graphene oxide membrane.
And assembling the obtained acid-modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
The alcohol standard solution used for the test, 0.05BAC, i.e. a concentration of 125ppm of alcohol vapor at 34 ℃ was used, and the test results are shown in detail in the curve d in FIG. 4.
Comparative example 1
2g of graphite powder (particle size D) was taken 50 1-15 μm), 1g of sodium nitrate and 46ml of concentrated sulfuric acid are added and mechanically mixed evenly in an ice bath environment. Then 6g of potassium permanganate was added and stirred for 2 hours while keeping the temperature of the reaction system at not higher than 20 ℃. After the reaction system is returned to the room temperature, 140mL of deionized water is slowly added into the reaction system to oxidize and expand the graphiteThe reaction was allowed to proceed for 0.5h, then diluted with an additional 140mL of deionized water, followed by the slow addition of 40mL of 30% hydrogen peroxide, the reaction rapidly turned from purple to golden yellow, and stirring was maintained until the mixture cooled to room temperature. 2L of 5% diluted hydrochloric acid was added to the above reaction system to dilute and dissolve the remaining undissolved manganese dioxide, followed by filtration. And then washing with deionized water, centrifugally separating to remove acid until the pH of the reaction system is about 2, and finally diluting with deionized water to enable the concentration of the graphene oxide dispersion liquid to be 1-10 mg/mL.
And (3) taking the graphene oxide dispersion liquid with the concentration of 1mg/mL, carrying out high-speed centrifugal separation to remove supernatant, repeatedly washing with deionized water and centrifuging for three times to remove residual reactants, dispersing with deionized water again, exchanging sodium ions into protons by using a strong acid ion exchange column to obtain porous graphene oxide, and finally freeze-drying for later use.
And (3) dispersing 40mg of the obtained porous graphene oxide into 40mL of deionized water, and performing vacuum filtration by using a polyether sulfone filter membrane to form a self-supporting acid modified porous graphene oxide membrane.
And assembling the obtained acid modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
The alcohol standard solution used for the test was 0.05BAC, i.e., the concentration of alcohol vapor at 34 ℃ was 125ppm, and the test results are specifically shown in FIG. 5.
Comparative example 1 differs from example 1 only in that example 1 uses an acid-modified porous graphene oxide membrane, whereas comparative example 1 uses a normal non-acid-modified non-porous graphene membrane. By observing the test results in fig. 5, it can be seen that the response curve of the alcohol sensor is sensitive to the response of the acid-modified graphene oxide membrane.
Fig. 5 is a response curve of the alcohol sensor according to the manufacturing method of example 1 of the present invention and comparative example 1. As can be seen from FIG. 5, the acid-modified porous graphene oxide membrane alcohol sensor provided by the invention has obviously superior performance in sensitivity compared with the common graphene oxide sensor, so that the acid-modified porous graphene oxide membrane alcohol sensor has wide application prospect.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein 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 claims.
Claims (11)
1. A method of an alcohol sensor, the method comprising the steps of, in order:
(1) preparing a graphene oxide dispersion liquid;
(2) under the ultrasonic condition, introducing ozone into the graphene oxide dispersion liquid obtained in the step (1) for 0.5-4 hours to obtain a porous graphene oxide dispersion liquid;
(3) adding sulfanilic acid and sodium hydroxide into the porous graphene oxide dispersion liquid obtained in the step (2), mixing, heating to 70-90 ℃, keeping the reaction for 3-12 hours, then sequentially centrifuging and washing to remove residues, and finally exchanging residual metal ions into protons to obtain acid-modified graphene oxide;
(4) dispersing the obtained acid-modified graphene oxide in deionized water, and performing vacuum filtration to obtain an acid-modified graphene oxide film;
(5) and assembling the obtained acid modified graphene oxide membrane and a commercial fuel cell electrode into an alcohol sensor.
2. The method according to claim 1, wherein in the step (1), the graphene oxide dispersion liquid is prepared by sequentially carrying out the following steps:
a. taking a certain amount of graphite powder and sodium nitrate, adding concentrated sulfuric acid, and uniformly mixing;
b. adding potassium permanganate into the mixture obtained in the step a to react for 1-8 h, and keeping the temperature of the whole reaction system not higher than 20 ℃ in the reaction period;
c. after the temperature of the reaction system in the step b is restored to the room temperature, adding deionized water into the reaction system for reaction for 0.5-2 h, then continuously adding the same amount of deionized water for dilution, then adding a certain amount of hydrogen peroxide until the reaction system changes color, and finally cooling to the room temperature;
d. and c, adding dilute hydrochloric acid into the reaction system obtained after the reaction in the step c for dilution, then sequentially filtering, washing and removing acid until the pH value of the reaction system is about 2, and finally diluting with deionized water to obtain the graphene oxide dispersion liquid.
3. The method of claim 2, wherein in step a, the particle size D of the graphite powder 50 1 to 15 μm.
4. The method according to claim 2, wherein in the step a, the graphite powder, the sodium nitrate and the concentrated sulfuric acid are mixed according to a mass ratio of 2: (0.5-1.5): (40-50) in an amount.
5. The method according to claim 4, wherein in the step b, the potassium permanganate is mixed according to a mass ratio of potassium permanganate to graphite powder of (2-5): 1 is added.
6. The method according to claim 4, wherein in the step c, the deionized water is mixed with concentrated sulfuric acid according to a volume ratio of the deionized water to the concentrated sulfuric acid of (3-4): 1 is added.
7. The method according to claim 2, wherein in the step c, the hydrogen peroxide concentration is 30% according to a mass ratio of hydrogen peroxide to graphite of (15-25): 1 is added.
8. The method according to claim 2, wherein in the step d, the concentration of the hydrochloric acid is 5%, and the volume ratio of the hydrochloric acid to the concentrated sulfuric acid is (35-45): 1 is added.
9. The method according to claim 1, wherein in the step (1), the graphene oxide dispersion liquid is diluted to have a concentration of 1-10 mg/mL.
10. The method according to claim 1, wherein in the step (3), the graphene oxide dispersion liquid, sulfanilic acid and sodium hydroxide are mixed according to a mass ratio of 4: (4-20) and (1-5).
11. The method according to claim 1, wherein in the step (4), the acid-modified graphene oxide and deionized water are added in a mass ratio of 1 (1-2).
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